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14 .1 Nomenclature and Isomerism 14 .6 Special Reactions Given by Aromatic Aldehydes and

14 .2 Structure of the Carbonyl Group (Cf. carbon-carbon double Ketones
bond) 14 .7 Analysis of Aldehydes and Ketones
14 .3 Preparation of Aldehydes and Ketones 14 .8 Illustrative Examples
14 .4 Physical Properties EXERCISE
14 .5 Chemical Properties SOLUTIONS

14.1 Nomenclature and Isomerism

Aldehydes and ketones are the compounds containing a carbonyl group, > C=O. They have the same general
formula, CnH2nO. The general structure of aldehydes is R—CHO, except for formaldehyde where R=H ; and that of ketones
is RR¢CO ; the groups R and R¢ may be aliphatic, aromatic or alicyclic.
The common names of aldehydes are derived from the names of the corresponding carboxylic acids by replacing -
ic acid by -aldehyde. In IUPAC system, aliphatic aldehydes are named as alkanals.
O O O O
|| || || ||
H —C— H CH 3CH 2CH 2C — H ClCH 2 CH 2 C — H C 6 H 5 CH 2 C — H
Methanal Butanal 3 -Chloropropanal Phenylethanal
(Formaldehyde) ( n -Butyraldehyde) (b -Chloropropionaldehyde) (Phenylacetaldehyde)
Aldehydes in which the —CHO group is attached to a ring system are named as substitutively by adding the
suffix carbaldehyde.

CHO CHO
CHO

Benzenecarbaldehyde Cyclohexane- 2-Naphthalenecarbaldehyde

(Common name : Benzaldehyde) carbaldehyde

Common name for ketones are obtained simply by adding the word ketone to the name of the two alkyl groups.
In IUPAC system, these are named as alkanones.
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O
||
CH 3 CH2 CCH 3 CH 3 COCH 2 CH=CH 2 C6 H 5 CH 2 COCH 3
Butanone 4-Penten-2-one 1-Phenyl-2-propanone
(Ethyl methyl ketone) (Allyl methyl ketone) (Benzyl methyl ketone)
A ketone in which the carboxyl group is attached to a benzene ring is named as a - phenone.
O

C
COCH3 COCH2CH2CH3 COC6H5
NO2

CH3
Acetophenone n-Butyrophenone Benzophenone 3-Nitro-4¢-methylbenzophenone

When it is necessary to name the —CHO and —COR groups as prefix, these are named as methanoyl (or formyl)
and alkanoyl (or acyl) groups respectively.
COCH3

CHO
COOH

SO3H
2-Methanoylbenzoic acid 4-Ethanoylbenzenesulphonic acid
(o -Formylbenzoic acid) (p-Acetylbenzenesulphonic acid)

Aldehydes show chain and functional isomerism.

Chain isomers. CH 3 CH2 CH 2 CHO (CH 3 )2 CHCHO
n -Butanal 2-Methylpropanal (iso-Butanal)
Functional isomers.
CH3CH2CHO CH3COCH3 CH2 = CHCH2OH CH 3CH—CH2 CH2 = CH.O.CH3

O
Propanal Acetone Allyl alcohol a, b-Propylene oxide Methyl vinyl ether
Ketones show chain, functional and metamerism. Examples of functional isomerism is given above in aldehydes.
O O
|| ||
Chain isomers. CH 3 CH2 CH 2 — C — CH 3 (CH 3 ) 2 CH — C — CH 3
Methyl propyl ketone Methyl isopropyl ketone

O O
|| ||
Metamers. CH 3 CH2 CH 2 — C — CH 3 CH 3CH 2 — C — CH 2CH 3
Methyl propyl ketone Diethyl ketone

1. Give IUPAC names of the following compounds :

CH3O
CHO
(a) OHC CHO (b) (c) HO CHO (d) CH2COCH2
C6H5

(e) CH.CHO (f) CHO (g) C6H5CH=CHCOC 6H5

CHO
2. Write down the structural formulas for (a) the seven carbonyl compounds of formula C5H10O, (b) the five carbonyl compounds of
formula C8H8O having a benzene ring.
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14.2 Structure of the Carbonyl Group (Cf. carbon-carbon double bond)

Like the carbon-carbon double bond of alkenes, the carbon-oxygen double bond of the carbonyl group is composed
of one s and one p bond.
In the carbonyl group, carbon atom is in a state of sp2 hybridisation. The C—O s bond is
R 120°
produced by overlap of an sp2 orbital of carbon with a p orbital of oxygen. On the other hand, the C—
O p bond is formed by the sideways overlap of p orbitals of carbon and oxygen. The remaining two sp3 C=O
120°
orbitals of carbon form s bonds with the s orbital of hydrogen or sp2 orbital of carbon of the alkyl group.
Now since the three s bonds of the carbonyl carbon utilize sp2 orbitals, they lie in one plane and are R 120°
120° apart (similarity with C = C).
However, it is important to note that the carbon-oxygen double bond is different from carbon-carbon double
bond. Due to greater electronegativity of oxygen atom, the p electron cloud is attracted towards oxygen. Consequently,
oxygen attains a partial negative charge and carbon a partial positive charge. This polar nature of the carbonyl group
causes intermolecular attraction in aldehydes or ketones and hence accounts for their higher boiling points than that of
hydrocarbons and ethers of comparable molecular weight. Moreover, polar nature of the carbonyl group also explains the
dipole moment in aldehyde and ketones. However, the high values of dipole moments (2.3 – 2.8 D) of aldehydes and
ketones can’t be accounted for only by inductive effect ; this can be accounted for if carbonyl group is a resonance hybrid
of the two structures.
+ –
d d + –
C = O: ¬ ¾ ® C—O :

: :
C=O

:
Polarity due to inductive effect Polarity due to resonance

Other important difference in carbon-oxygen and carbon-carbon double bonds lies in the fact that the carbonyl
group undergoes nucleophilic addition reactions, while olefinic bond undergoes electrophilic addition reactions.

14.3 Preparation of Aldehydes and Ketones

1. By oxidation of primary and secondary alcohols. Discussed in the chapter on “Monohydric Alcohols”.
pyridinium chlorochromate, CH 2 Cl 2
RCH2OH ¾¾¾¾¾¾¾¾¾¾¾¾¾® RCHO
OH PCC, CH2Cl2 H
¾¾¾¾¾®
1-Heptanol
Heptanal
O

OH CrO3 in glacial acetic acid

O
¾¾¾¾¾¾¾¾¾¾®
or K2Cr2 O7 + H2SO4

Cyclohexanol Cyclohexanone

Since ketones are oxidised with difficulty, so these can be easily prepared by oxidizing 2° alcohols with acidic
dichromate (difference from aldehyde preparation).
Recall that solution of chromic anhydride in pyridine is known as Sarett’s reagent, while solution of chromic
anhydride in water, acetone and sulphuric acid is known as Jone’s reagent.
Primary and secondary alcohols may also be oxidised to aldehyde and ketones respectivley by heating with
copper at about 250–300°C (dehydrogenation of alcohol).
Ketones can also be prepared by oxidizing 2° alcohols with aluminium tert-butoxide (Oppenauer oxidation).
R R
(tert-BuO)3Al
CHOH ¾ ¾ ¾ ¾ ¾ ® CO
R R

¾¾¾¾¾®
OH O
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1. Can an aldehyde be prepared by oxidation of a 1° alcohol with acid dichromate ? If, yes mention the condition.

2. By reduction of acid chlorides, esters, and nitriles (only for aldehydes). Theoretically, we may think that
aldehydes can be prepared by reducing carboxylic acids with lithiumaluminium hydride (LiAlH4 or LAH).
However, LAH is a very powerful reducing agent and hence aldehydes formed as intermediate are very readily
further reduced to primary alcohols.
LiAlH 4 LiAlH 4
RCOOH ¾¾® [RCHO] ¾¾® RCH2OH
However, a modified version of the reaction is used for preparing aldehydes. For this,
(i) a derivative of a carboxylic acid, which is more easily reduced than the carboxylic acid itself is taken as a starting
material. Three such acid derivatives are acid chlorides, esters and nitriles ; which in turn are easily prepared
from carboxylic acids.
(ii) a less reactive aluminium hydride derivative than LiAlH4 is used. Two such derivatives are lithium tri-tert-
butoxyaluminium hydride (LBAH) and diisobutylaluminium hydride (DBAH).
–
OC(CH3)3
CH2CH(CH3)2
+
Li H—Al—OC(CH3)3
Al
OC(CH3)3 H CH2CH(CH3)2
Lithium tri-tert -butoxyaluminium hydride Diisobutylaluminium hydride

These two hydrides are less reactive than LiAlH4 as they are much more sterically hindered and, therefore, face
difficulty in transferring hydride ions. Reduction by these reagents is brought about by the transfer of a hydride
ion from the aluminium atom to the carbonyl carbon (in case of acid chlorides and esters) or the nitrile carbon (in
case of nitriles). Subsequent hydrolysis of the intermediate liberates the aldehyde.
–
O O Al (OCMe3)3 O
LiAlH (OCMe3)3 + H2O
(a) R— C ¾ ¾ ¾ ¾ ¾ ¾ ® R—C—H Li ¾ ¾ ® R—C—H + LiCl + Al(OCMe3)3
ether, – 78°C
Cl Cl

(i) LiAlH (OBu-t )3

O2N COCl ¾¾¾¾¾¾¾® O2N CHO
(ii) H2O

Acid chlorides may also be reduced to aldehydes by catalytic hydrogenation (H2/Pd)

Pd/BaSO 4
RCOCl + H2 ¾¾¾¾® RCHO + HCl
over deactivated (by sulphur or quinoline) palladized barium sulphate or carbonate. (Rosenmund reduction).

Pd/BaSO 4
RCOCl + H2 ¾¾¾¾¾® RCHO
S or quinoline

Partial deactivation of the catalyst is necessary to check further reduction of the product aldehyde.

O OAl(iso-Bu)2
(iso-Bu)2AlH H2O
(b) CH3(CH2)10 C ¾¾¾¾¾® CH3(CH2)10 CH ¾ ¾ ¾ ® CH3(CH2)10CHO
hexane, – 78°C
OC2H5 OC2H5

NAl(iso-Bu)2
||
( iso - Bu)2 AlHH2 O
(c) CH3CH=CHCH2CH2CºN ¾¾¾¾® CH3CH=CHCH2CH2 CH ¾® CH3CH=CHCH2CH2CHO
hexane

Ketones can’t be prepared by this method.

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3. By hydration of alkynes (Discussed in alkynes).

H 2SO 4 , Hg 2+
HC º CH ¾¾¾¾® CH2 = CHOH CH3CHO

H 2SO 4 , Hg 2+
CH3CH2C º CH ¾¾¾¾® CH3CH2COCH3
4. Hydroboration of alkynes (Discussed in alkynes). Hydroboration of terminal alkynes followed by oxidation of
the intermediate (vinylboranes) with alkaline hydrogen peroxide gives aldehydes.
–
BH3.THF H2O2/OH
CH3C º CH ¾ ¾ ¾ ® [CH3CH = CH ]3 B ¾ ¾¾ ¾ ® CH3CH = CHOH CH3CH2CHO
Propyne Vinylborane Propanal

Similar reaction with non-terminal alkynes gives ketones

BH3.THF H2O2
CH3C º CCH3 ¾ ¾ ¾ ® [CH3CH=C ]3 B ¾ ¾ –® CH3CH = COH ¾ ¾ ® CH3CH2COCH3
OH
Butyne-2 Butanone-2
CH3 CH3

To get good yield of vinylboranes and hence aldehydes, sterically hindered alkylboranes should be used instead
of borane itself.
R 2 BH.THF 2 2 H O /OH -
CH 3C º CH ¾¾¾¾® (CH3CH = CH)BR2 ¾¾¾¾® CH3CH = CHOH CH 3CH 2CHO

1. Write structures for A and B in the following reactions :

LBAH LAH
B ¬¾¾ CH3CH(CH3) COCl ¾¾® A
0° C

2. Prepare CH3CH2CH2CHO from (a) an ester, (b) a nitrile, and (c) an acid chloride.
3. Give an outline of the scheme for preparing 3-phenylpropanal from benzene and oxirane.
4. Use hydroboration method for preparing following aldehydes or ketones.
(a) Pentanal (b) Cyclohexanone (c) n-Butyl cyclopentyl ketone (d) Dicyclohexyl ketone.

5. From organometallic compounds.

(a) Aldehydes are obtained by the reaction of (i) Grignard reagent with hydrogen cyanide, or (ii) Grignard reagent
with alkyl formate in equimolar amounts. For details, consult chapter on Grignard reagents.

MgBr HC = NMgBr CHO

ether H2O
(i) HC º N + ¾¾® ¾¾® + MgBrNH2

–
O O O
+
H3O –
(ii) H—C—OC2 H5 + CH3MgBr ¾ ® H—C—OC2H5 ¾ ¾ ® CH3—C—H + C2H5O

CH3

(b) Ketones from Grignard reagents (Details discussed earlier).

R¢ R¢
ether H2O
(i) R—C º N + R¢ MgX ¾ ¾ ® R—C = NMgX ¾ ¾ ® R—C = O
A nitrile
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O
(i) ether
CH3C º N + —MgBr ¾¾¾® —C—CH3
(ii ) H2O

Cyclohexyl methyl ketone

(i) ether
(ii) RCOCl + CH3MgBr ¾¾¾®
+ RCOCH3 + MgBrCl
(ii) H3O
An acid chloride

– 70°C
(iii) (RCO)2O + CH 3MgBr ¾ ¾ ¾ ® RCOCH3 + RCOOMgBr
An acid anhydride

(i) ether
(iv) CH3COOC2H5 + C2H5MgBr ¾¾¾®
+ CH3COC2H5
(ii ) H3O
Ethyl ethanoate

(c) Ketones from organolithium compounds

(i) ether
CH3C º N + CH3CH2CH2Li ¾ ¾ ¾ ®
+ CH3COCH2CH2CH3
(ii) H3O

Even though a nitrile has a triple bond, addition of the Grignard or lithium reagent takes place only once
because addition of second molecule of the reagent would place a double negative charge on the nitrogen.

R¢
R¢Li – +
R¢ Li 2– +
RC º N ¾ ¾ ® R—C = N Li ¾ ¾ ¾ ® R—C—N 2Li

R¢ R¢

Alternatively, organolithium reagents react with carboxylic acids in the following way to form ketones.

O O O -Li+ é OH ù O
|| || ê | ú - H2 O ||
LiOH R'Li
| H 3O +
R - C - OH ¾¾¾® R - C - O - Li + ¾¾¾
® R - C - O - Li + ¾¾¾¾
® ê R - C - OH ú ¾¾¾¾ ® R - C- R '
| |
ê ú
R' ë R' û

é OH O-Li+
ù O
ê | |ú - H2 O ||
- + H 3O +
® R - C - O Li ¾¾¾¾
Or RCOOH + 2R 'Li ¾¾ ® ê R - C - OH ú ¾¾¾¾ ® R - C- R '
| |
ê ú
R' ë R' û

(d) Ketones from lithium dialkylcuprates, also known as Gilman reagent (Organocopper compounds).

ether
R 2 CuLi + R ¢COCl ¾¾® R¢COR + RCu + LiCl
Lithium – 78° C
dialkylcuprate

ether
(CH3)2CuLi + —COCl ¾ ¾ ¾ ® —COCH3 + CH3Cu + LiCl
– 78°C

Cyclohexyl methyl ketone

Li CuI 2(CH3 )2 CHCOCl

n-C4H9Br ¾® n-C4H9Li ¾® (n-C4 H 9 )2 CuLi ¾¾¾¾¾¾® 2 n-C 4 H9 COCH(CH 3 )2
Lithium di-n-butylcuprate 2 - Methyl-3-heptanone
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Organocopper reagents (lithium dialkylcuprate) are less reactive than Grignard reagents and organolithium
compounds toward the carbonyl group of ketones, hence the reaction stops at the ketonic stage whereas in other
reagents, tert-alcohols are usually formed because ketones are more reactive than acid chlorides. Although
organocopper compounds are more reactive than Grignard reagents toward alkyl halides, however, these do not
react with many of the functional groups (e.g. —NO2, —CN, —CO—, —COOR, etc.) with which Grignard reagents
and organolithiums do react. In short, organocopper compounds are highly selective toward different functional
groups.
CH 3OOC.CH2CH 2COCl + [(CH 3)2CHCH 2CH 2]2CuLi ® CH 3OOC.CH 2CH 2COCH 2CH 2CH(CH 3)2
Lithium diisopentylcuprate Methyl-4-oxo-7-methyloctanoate
(e) Ketones from organocadmium compounds
RCOCl + R¢—Cd—R¢ ¾¾® RCOR¢ + R¢CdCl
Dialkyl cadmium
Like organocopper compounds, organocadmium compounds are also less reactive than Grignard reagents and
organolithiums.

1. Account for the difference in behaviour of RMgX and R2CuLi.

2. (a) Identify the compounds A and B.

(i) Br— O + (CH 2=CH)2CuLi ¾® A (ii) O N—

2
— COCl + B ¾ ® O2N— —COCH2CH 3 .

(b) Would it be feasible to prepare p-nitroacetophenone in the following way ?

O2N— — CuLi + CH3COCl ¾® O2N— —COCH3

2

Lithium di (-p-nitrophenyl) cuprate p-Nitroacetophenone

6. Ozonolysis of alkenes. Alkenes and ozone react readily at low temperatures to yield ozonides which on
decomposition with a reducing agent yield aldehydes or ketone depending upon the structure of the alkene.

O
O3 H2O, Zn
RCH = CH2 ¾ ® R—CH CH2 ¾¾¾® RCHO + CH2O

O O

(i) O 3 CHO
CH 2 = CH CH=CH 2 ¾¾¾® | + 2HCHO
(ii) H 2 O/Zn
1, 3-Butadiene CHO
Glyoxal

(i) O 3
(CH3)2C = CHCH3 ¾¾¾¾® (CH3)2CO + CH3CHO
(ii) H 2 O/Zn

7. By the hydrolysis of gem-dihalides.

OH -
CH3CH2CHCl2 ¾® CH3CH2CH(OH)2 ¾¾® CH3CH2CHO + H2O

OH -
CH3CCl2CH3 ¾® CH3C(OH)2CH3 ¾¾® CH3COCH3 + H2O
8. By the reduction of nitriles. This method is used only for aldehydes.
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SnCl2 H 2O
(a) CH3C º N ¾¾® CH3CH = NH ¾® CH3CHO (Stephen reduction)
HCl

( i ) (iso - Bu)2 AlH 2 , – 40° C

(b) CH3C º N ¾¾¾¾¾¾¾¾¾® CH3CHO
( ii ) H3 O+

9. By dry distillation of calcium salts of fatty acids. Calcium formate, on pyrolysis, gives formaldehyde ; calcium
formate mixed with calcium salt of any other fatty acid gives aldehydes; calcium salts of fatty acids other than
calcium formate yield ketones.

H COO O OCH
Ca + Ca ¾¾® 2HCHO + 2CaCO3
H COO O OCH

Calcium formate (2 moles) Formaldehyde (2 moles)

CH3CHO
CH3COO OOCH
Ca + Ca ¾¾® + + 2CaCO3
CH3COO OOCH CH3CHO
Cal. acetate Cal. formate Acetaldehyde

CH3.CO.CH3
CH3COO OOCCH3
Ca + Ca ¾¾® + + 2CaCO3
CH3COO OOCCH3 CH3.CO.CH3
Calcium acetate (2 moles) Acetone (2 moles)

When calcium salts of dicarboxylic acids are heated, cyclic ketones are formed.

O
–
O 2+ heat
Ca ¾¾® O + CaCO3
O–

O
Calcium succinate Cyclopropanone

–
COO heat
2+
– Ca ¾¾® O + CaCO3
COO
Calcium adipate Cyclopentanone

Instead of using calcium salts of an acid, vapours of acid or mixture of acids can be passed over heated MnO at
300°C.
MnO
CH3COOH + HCOOH ¾¾® CH3CHO + CO2 + H2O
300° C
2CH3COOH ¾¾® CH3COCH3 + CO2 + H2O
CH3COOH + CH3CH2COOH ¾¾® CH3COCH2CH3 + CO2 + H2O

PREPARATION OF AROMATIC ALDEHYDES

1. Gattermann aldehyde synthesis.

CHO

3 AlCl
+ HCN + HCl ¾¾¾¾ ®
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Mechanism

AlCl +
H - C º N + HCl ¾¾
® ClCH º NH ¾¾¾¾
3
® C H = NH + AlCl -4
Electrophile

H CH = NH CH = NH CHO
+ + +
CH = NH –H HO
¾¾¾® ¾¾¾® ¾ ¾2¾ ®

2. Gattermann Koch aldehyde synthesis.

CHO

3 AlCl
+ CO + HCl ¾¾¾¾ ®

3. Oxidation of toluene.

ù
CH3 CHO ú
CrO2 Cl2
¾¾¾® ú
ú
ú
ú Etard reaction
CH2CH3 CH2CHO ú
CrO Cl
2 2 ú
¾¾¾ ® ú
ú
û

Industrial methods.
(a) Formaldehyde, a starting material for a number of plastics, is prepared by oxidation of methanol over a silver or
iron oxide-molybdenum oxide catalyst at elevated temperature.

1 Catalyst
CH3OH + O ¾¾¾® HCHO + H2O
2 2 500° C

(b) Acetaldehyde can be prepared by (i) hydration of acetylene, or (ii) more economically by aerial oxidation of
ethylene in presence of palladium chloride and copper (II) chloride as catalysts (Wacker process).

1 PdCl 2 , CuCl 2
CH2 = CH2 + O ¾¾¾¾¾® CH3CHO
2 2 H 2O

PdCl , CuCl
Similarly, CH 3 CH = CH2 ¾¾¾¾¾¾
2 2
® CH 3 CH 2 CHO
H2O

O
P
CH 3 CH = CHCH3 ¾¾
® CH3 - C - CH 2 CH 3

(c) Aldehydes can also be prepared by hydroformylation, a reaction in which alkenes are converted to aldehydes
containing an additional carbon atom by reaction with carbon monoxide and hydrogen in presence of a suitable
cobalt– or rhodium-based catalyst.

Co 2 (CO)8
RCH = CH2 + CO + H2 ¾¾¾¾® RCH 2 CH 2 CHO + R — CH. CHO
(Major) |
CH 3
(Major)
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14.4 Physical Properties

(i) The carbonyl group is a polar group, therefore, the dipole-dipole attractive forces between molecules are stronger
and hence aldehydes and ketones have higher boiling points than hydrocarbons (non-polar) of comparable
molecular weight. However, aldehydes and ketones cannot have strong hydrogen bonds between their molecules,
hence they have lower boiling points than the corresponding alcohols.
(ii) The carbonyl oxygen atom of aldehydes and ketones form hydrogen bonds to water molecules, hence lower
aldehydes and ketones show appreciable solubility in water.
(iii) Formaldehyde is a gas (b.p. – 21°C), and is handled either as an aqueous solution (formalin), or as one of its solid
polymers : paraformaldehyde, (CH2O)n, or trioxane, (CH2O)3. When dry formaldehyde is desired (as in reaction
with a Grignard reagent), it is obtained by heating paraformaldehyde or trioxane. Similarly, acetaldehyde is
usually generated by heating its higher-boiling trimer with acid.

O O +
H2C CH2 CH3CH CHCH3 H
—CH2 OCH2OCH2O— 3CH3CHO
O O O O
Paraformaldehyde CH2 CH
Trioxane CH3
Paraldehyde

1. Identify A to C in the following reactions :

CO, H 2 O 2 , PdCl 2 CO, H 2

(a) [B] ¬¾¾¾ CH3CH = CH2 ¾¾¾¾® A (b) (CH3)2C = C(CH3)2 ¾¾® C
CuCl2 , H 2 O

2. Which of the components of each of the following pair has higher boiling point ?
(a) Hexane or hexanal (b) Hexanal or 1-hexanol (c) 2-Pentanol or 2-pentanone
(d) Benzaldehyde or benzyl alcohol (e) 2-Phenylethanol or acetophenone.
3. n-Butanol boils at 118°C and n-butanal boils at 76°C, although their molecular weights are nearly similar. Explain.

14.5 Chemical Properties

The carbonyl group, C = O governs the chemistry of aldehydes and ketones in two ways : (a) by providing a site for
nucleophilic addition, and (b) by increasing the acidity of the hydrogen atoms attached to the alpha carbon. Both of these
effects is due to the ability of oxygen to accommodate a negative charge.

(A) Carbonyl group as a site for nucleophilic addition

The mobile p electrons of the carbon-oxygen double bond are pulled strongly towards
oxygen, which makes carbonyl oxygen electron-rich and carbonyl carbon electron-deficient. R¢ d+ d–
: :

C==O
Further, since carbonyl group is flat, it is relatively open to attack from above or below. R
The positive charge on the carbonyl carbon atom means that it is especially susceptible to attack by a nucleophile. On the
other hand, the negative charge on the carbonyl oxygen atom means that nucleophilic addition is susceptible to acid
catalysis.
Thus nucleophilic addition to the carbon-oxygen double bond occurs in either of two general ways.
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1. When the reagent is a strong nucleophile, addition usually takes place in the following way, in which trigonal
planar aldehyde or ketone is converted into a tetrahedral product.
:Z Z Z Z
R¢ H2O
C=O ¾® R¢ C ¾® R¢ C ¾ ¾¾ ¾ ¾ ® R¢ C
R R Od– R O– or nucleophile R OH
Reactant Transition state * Product
(Trigonal) (Becoming tetrahedral) (Tetrahedral)

Note that as the nucleophile is forming a bond through its electron pair with the carbonyl carbon atom, the
electron pair of the carbon-oxygen p bond shifts out to the carbonyl oxygen (as indicated by full negative charge
on oxygen) and thus oxygen gets a negative charge which it can accommodate easily. Thus the ability of oxygen
to carry a negative charge is the real cause of reactivity of carbonyl group toward nucleophiles. (The polarity
of the carbonyl group is not the cause of the reactivity, it is simply another manifestation of the electronegativity
of oxygen).
2. When the reaction is acid-catalysed, nucleophilic addition on carbonyl group takes place in the following way.
:Z Z Z
R¢ H
+
R¢ +
C=O ¾® C=O H ¾ ® R¢ C d+ ¾® R¢ C
R
¾® R R R OH
OH
An oxonium cation

(i) The oxonium cation is highly reactive toward nucleophilic attack at the carbonyl carbon atom because the
carbonyl carbon atom carries more positive charge than it does in the unprotonated compound.
(ii) Prior protonation of the carbonyl group lowers the Eact for nucleophilic attack, because it permits oxygen to
acquire the p electrons without having a negative charge.
(iii) This mechanism operates when carbonyl compounds are treated with strong acids (sometimes Lewis acids)
in presence weak nucleophiles.

Relative reactivity of aldehydes and ketones toward nucleophilic addition. The reactivity of the carbonyl
group toward the nucleophilic addition reactions depends upon the magnitude of the positive charge on the carbonyl
carbon atom (electronic factor) and also on the crowding around the carbonyl carbon atom in the transition state (steric
factor). Both these factors predict the following order
O O O
H— C—H > R— C—H > R— C—R
(i) Formaldehyde has no alkyl group, whereas other aldehydes and ketones contain one and two alkyl groups
respectively. Since an alkyl group is larger than the hydrogen atom, greater the number of alkyl or aryl group
more will be crowding in the transition state which has four groups on C (sp3) and lesser will be its stability.
(ii) Aldehydes have only one electron-releasing group to partially neutralize, and thereby stabilize, the positive
charge at their carbonyl carbon atom. Ketones have two electron-releasing groups and are thus stabilized more.
Greater stabilization of the ketone (the reactant) relative to the product means lesser reactivity.
d– d– d–
O O O
d+ d+ d+
C C C
–

–
–

H H R H R R
®

¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾®
Carbonyl carbon atom becomes lesser positive,
successively increasing stability of the compound

In short, any substituent in the carbonyl compound that decreases the positive charge on the carbonyl carbon
will increase the stability (or decrease the reactivity) of the molecule toward nucleophilic addition and vice versa.
Thus, the decreasing order of reactivity of certain carbonyl compounds is
(a) NO2CH2CHO > ClCH2CHO > CH3CHO > CH3CH2CHO
O O O
|| || ||
(b) CH 3COCH3 > CH 3 — C — C 2H 5 > CH3 — C — CH(CH 3 ) 2 > CH3 — C — C(CH 3 ) 3

* Note that this transition state is relatively roomy as compared to the transition state for an SN2 reaction in which carbon is pentavalent.
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(iii) An alkyl group releases electrons, and thus destabilizes the transition state by intensifying the negative charge
developing on oxygen.
(iv) An aryl group has an electron-withdrawing inductive effect, and thus it is expected to destabilize the reactant or
stabilize the transition state and thus should speed up the reaction. However, it seems to stabilize the reactant
even more, by resonance and thus causes net deactivation.
– – – –

: :

: :

: :

: :
R—C = O : R—C—O : R—C—O: R—C—O : R—C—O:

+ +
¬® ¬® ¬® º +

Addition of water, alcohols, hydrogen cyanide, sodium bisulphite, ammonia derivatives, hydride ion (in the
form of LiAlH4 and NaBH4), organometallic compounds, etc. are examples of nucleophilic addition on carbonyl group.
1. Addition of water (gem-diol formation). Aldehydes and ketones react with water in presence of acid or base in
a rapidly reversible equilibrium.

O OH
fast
R—C—R ¢ + H 2O R—C—R¢
OH
Like the general nucleophilic additions, hydrate formation follows the following order :
HCHO > CH3CHO > (CH3)3CCHO > CH3COCH3
% of hydrate formed 99.96 50 19 0.14

1. Arrange the following compounds in decreasing order of reactivity toward nucleophilic addition.
(a) RCHO, CH2O, R2CO and RCOY : (b) R2CO, Ar2CO, ArCOR and ArCH2COR.
2. In contrast to negligible hydration of acetone, hexafluoroacetone is completely hydrated. Explain.
3. Account for the isolation of CH3CO 18CH3 from a solution of CH3CO 16CH3 in excess of H2O18.
4. Ninhydrin has three ketonic groups, which one of them is likely to be hydrated easily ?

O
a
b
O
c

O
5. Arrange the following in decreasing ease of hydration to form gem-diol.
O O O O
(a) MeO —C— NO2 —C— O2N —C— NO2 MeO —C— OMe

A B C D
(b) CH3CH2CHO CH3CHFCHO CH3CHClCHO CH2ClCH2CHO
A B C D

2. Addition of alcohols (Acetal formation). Anhydrous alcohols add to the carbonyl group of aldehydes in the
presence of anhydrous hydrogen chloride to form acetals via hemiacetals.
+
R dry HCl R OH R¢ OH, H R OR¢
C = O + R¢ OH C C
H H OR¢ H OR¢
Hemiacetal Acetal (an ether)
(an alcohol, as well as an ether) (stable to alkalies)
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(i) With a few exceptions, open-chain hemiacetals are too unstable to be isolated. However, cyclic hemiacetals
with five- or six-membered rings are usually much more stable.
(ii) All steps in the formation of an acetal from an aldehyde are reversible.
(iii) Acetal formation is not favoured when ketones are treated with simple alcohols and gaseous HCl (remember
that the usuage of hemiketals and ketals have been replaced by hemiacetals and acetals respectively).
However, cyclic acetal formation is favoured when a ketone is treated with an excess of a 1, 2-diol and a
trace of acid.
R¢ HOCH2 H
+
R¢ O—CH2 H2O/H
+
R¢ CH2OH
C=O + ¾® C ¾¾¾® C=O+
R HOCH2 R O—CH2 R CH2OH
(excess) Cyclic acetal

(iv) Like ethers, acetals are cleaved by acids and are stable toward bases. However, acetals differ from ethers, in
the extreme ease with which they undergo acidic cleavage, actually acetals are rapidly converted into
aldehydes and alcohols by dilute mineral acids even at room temperature. Thus acetal formation may be
used to protect the aldehydic and ketonic group against undesired reactions in basic solutions.
Thus we can reduce only ester group in the following group by protecting ketonic group.
O O
O
O HA (i) LiAlH4, ether
OC2H5 ¾¾¾¾¾® O OC2H5 ¾ ¾ ¾ ¾ ¾ ¾ ®
HOCH2CH2OH (ii) H2O

Ketonic group protected

O +
CH2OH H3 O O CH2OH
¾¾®
O H2O

Several other examples have been discussed in ethylene glycol in the chapter on “Polyhydric Alcohols”.

OH O
+ CH2I2 ¾¾ ® CH2
1.
OH O
Answer the following with reference to above reaction.
(a) The above reaction is an example of which familiar synthesis ?
(b) To what family of compounds does the product belong ?
(c) Give the reaction of the product with acid, and base.
2. Account for the fact that anhydrous acids bring about formation of acetals while aqueous acids bring about hydrolysis of acetals.
3. Give the structure of the acetal formed in each of the following reactions.
CH2OH
(a) O+ (b) Butanal + 1, 3-propanediol (c) BrCH2CH2COCH3 + CH2OH.CH2OH.
CH2OH
4. Give steps involved in the conversion of each of the following.
O O

(a) CH2=CHCHO ¾® CH2(OH)CH(OH)CHO (b) ¾®

H3C CH3 H3C CH3
O OH

(c) HOCH2CH2CH2CH2CHO ¾¾®

O OCH3
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3. Addition of hydrogen cyanide. Hydrogen cyanide adds to the carbonyl groups of aldehydes and most ketones to
form cyanohydrins. Ketones in which carbonyl group is highly hindered do not undergo this reaction.
OH
C = O + HCN ¾ ® C
CN
(i) Addition of hydrogen cyanide itself takes place very slowly because HCN is a poor source of the nucleophile,
CN–. However, addition of potassium cyanide, or any base that can generate cyanide ions from the weak acid
HCN, causes a dramatic increase in the rate of reaction. The cyanide ion, being a stronger nucleophile, is able
to attack the carbonyl carbon atom much more rapidly than HCN itself, and this is the source of its catalytic
effect. Bases stronger than cyanide ion catalyze reaction by converting HCN (pKa = 9) to cyanide ion.
(ii) Liquid hydrogen cyanide can be used for this reaction (HCN is a gas at room temperature), but since HCN
is a very toxic and volatile, it is generally produced in the reaction mixture for which an acid (generally
H2SO4) is added to a solution of the aldehyde or ketone and aqueous sodium or potassium cyanide.
Cl Cl
NaCN, ether, water,
Cl— —CHO ¾¾¾¾¾¾¾¾® Cl— —CHC º N
then HCl
OH
2, 4-Dichlorobenzaldehyde 2, 4-Dichlorobenzaldehyde cyanohydrin

O OH
NaCN, H2O,
CH3—C—CH3 ¾¾¾¾¾® CH3—C—CH3
then H2SO4
CN
Acetone Acetone cyanohydrin

Cyanohydrins are useful intermediates in organic synthesis. A cyano group may be hydrolysed to an a-
hydroxy carboxylic acid or to an a, b-unsaturated acid (depending upon the condition used) or may be
reduced to a primary amine.

CH3 CH3 CH3

– +
CN , H HCl, H2O
CH3CH2—C = O ¾ ¾ ¾ ® CH3CH2—C—CN ¾ ¾ ¾ ® CH3CH2—C—COOH
heat
2-Butanone
OH OH
½ Conc. H2SO4, 2-Hydroxy-2-methylbutanoic acid
¯ heat

CH3 CH3
CH3CH2—C—COOH ¾¾¾® CH3CH=C—COOH
2-Methyl-2-butenoic acid
OH

O OH OH
HCN (i) LiAlH4
¾¾® CN ¾ ¾¾ ¾ ® CH2NH2
(ii ) H2O

A b -amino alcohol

1. Arrange the following compounds in decreasing ease of formation of cyanohydrin.

COCH3 CH2CHO COCH3 COCH3

NO2 OCH3
I II III IV
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2. Can you draw a scheme for converting acetone to methacrylonitrile, CH2=C(CH3)CN, an industrial chemical used in the production
of plastics and fibres ?
3. Following compounds are converted into their corresponding cyanohydrins. Predict the number of fraction and their optical
activity status in each case.
(a) CH3CHO (b) (CH3)2CO (c) R –(+)– CH2OHCHOHCHO (d) (±)– CH2OHCHOHCHO.
4. (a) In cyanohydrin formation, an optimum pH of 9—10 is recommended. Explain.
(b) Which is the more favourable equilibrium situation for cyanohydrin formation ?
RCHO + NaCN or RCHO + HCN (both in water).

4. Addition of sodium bisulphite. Aldehydes, methyl ketones and cyclic ketones (not aromatic) react with sodium
bisulphite in presence of ethanol to give solid adduct.
– +
R + –
R + 2– +
R SO3 Na
C = O + Na HSO3 ¾® C—OH + : SO3 + Na ¾ ® C
H H H OH
Sodium bisulphite (adduct)
(solid)
NOTE.

(i) A C—S bond is formed rather than C—O because S has more nucleophilic site than O.
(ii) Sulphite ion, SO32– is a large ion and hence reacts only if C = O is not sterically hindered ; as in the case for
RCHO, RCOCH3, and cyclic ketones.

The solid adduct is filtered from the ethanolic solution and then decomposed by acid or base to regenerate the
carbonyl compound. Hence this reaction is used for the purification and separation of carbonyl compounds.
– +
R SO3 Na +
H (or OH )
– R 2–
C ¾¾¾¾¾® C = O + SO2 (or SO3 )
H OH H
(Extracted with ether)

Separation of RCHO from unreacted RCH2OH.

NaHSO 3 H+
RCH2OH ¾® RCHO ¾¾¾® RCH(OH) SO 3 Na ¯ ¾® RCHO
C2 H 5 OH Separated from
unreacted RCH 2OH

5. Addition of derivatives of ammonia. Certain compounds related to ammonia (such as hydroxylamine, NH2OH;
phenylhydrazine, H2NNHC6H5 ; and semicarbazide H2NNHCONH2, etc.) react with carbonyl compounds to
form compounds, having carbon-nitrogen double bond, known as imines. The reaction is acid catalyzed and
involves two stages : addition of the ammonia derivative to form carbinolamine followed by dehydration to yield
imine which is a mixture of E- and Z-isomers
+
H —H O
C = O + H2NG ¾ ¾ ¾ ® C—NHG ¾ ¾ ¾2¾ ® C = NG
(addition) (elimination)
OH Imine

Like ammonia, these derivatives of ammonia are basic and hence form salts with acids, viz. hydroxylamine
hydrochloride N +H 3OHCl – , phenylhydrazine hydrochloride, C 6H 5NHNH 3 +Cl – ; and semicarbazide
hydrochloride, NH2CONHNH3+Cl–. These salts are less easily oxidized by air than the free bases, and hence
these ammonia derivatives are best used in the form of their salts. When used, the parent reagents are liberated
from their salts in the presence of the carbonyl compound by adding a base, generally sodium acetate.

GNH 3 + Cl – + CH 3 COONa GNH 2 + CH3 COOH + NaCl

Stronger acid Stronger base Weaker base Weaker acid

Imine formation requires a moderate pH (between 4–5), because very low as well as very high pH retards the
reaction. To know why it is so, we must know the steps involved during the reaction
:NH2G (free base) +
+
H + OH OH 2 +
C=O C = O H ¾® C +
¾® C ¾ ® C = NG + H3O
N H 2G NG

H
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From the above steps, it is obvious that an acid is essential to protonate the carbonyl oxygen which makes
carbonyl carbon more susceptible to nucleophilic attack. Hence protonation of the carbonyl group is favoured by
..
high acidity. However, in presence of strong acid, the ammonia derivative (H2 N —G) can also undergo protonation
to form the ion, H3N+—G lacking the unshared electrons which thus will no longer be nucleophilic. Hence the
addition of reagent (H2NG) will be favoured by low acidity. Thus optimum acidity is the compromise between the
two steps to carry out the reaction successfully, i.e. the solution must be acidic enough for an appreciable fraction
of the carbonyl compound to be protonated, but not so acidic that the concentration of the free nitrogen compound
is too low. The exact conditions used depend upon the basicity of the reagent, and upon the reactivity of the
carbonyl compound.
Reaction of aldehydes and ketones with derivatives of ammonia, (H2NG)

C = O + H2N—G ¾ ® C = NG

Reagent H2NG and its name Name of product with specific example

C 2H 5 C2H5
H2NC2H5
H2NR, 1° Amine C=O ¾¾¾® C=NC2H5
CH3 CH3
An Imine
(A Schiff ’s base)

CH3 CH3
H2NOH, Hydroxylamine C=O H2NOH C = NOH
¾¾¾® H
H
Acetaldoxime oxime

CH 3 CH 3
C=O H2 NNH2
H2NNH2, Hydrazine ¾¾¾® C = NNH2
CH 3 CH 3
Acetone hydrazone

C 6H 5 H2NNHC6 H5
C6H5
H2NNHC6H5, Phenylhydrazine C=O ¾¾
+ ¾¾¾® C=NNHC6H5
CH 3 H3O , CH3COOH CH3
Acetophenone
phenylhydrazone

CH 3 2, 4-Dinitro- CH3
H2NHN— —NO2 , C=O ¾¾¾¾¾® C = NNH— —NO2
phenylhydrazine
H H

NO2 NO2
Acetaldehyde
2, 4-dinitrophenylhydrazone

O H2NNHCONH2
H2NNHCONH2, Semicarbazide ¾¾¾¾¾¾® NNHCONH2

Cyclohexanone semicarbazone

The products of the reaction of aldehydes and ketone with hydroxylamine, phenylhydrazine, 2, 4-
dinitrophenylhydrazine and semicarbazide are usually insoluble solids with sharp characteristic melting points.
Moreover, oximes and hydrazones when refluxed with dil HCl, they regenerate the parent aldehyde or ketone.
Hence, formation of oximes and hydrazones is used for the detection and purification of aldehydes and ketones
HCl
C = O + H2NOH ¾ ® C = NOH ¾¾® C = O + NH2OH.HCl
reflux

HCl
C = O + H2NNHPh ¾ ® C = NNHPh ¾¾® C = O + H2NNHPhHCl
reflux
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Unlike, 2, 4-dinitrophenylhydrazones, simple hydrazones have low melting points and are hence occasionally
used to identify carbonyl compounds. However, they form the basis for a useful method to reduce carbonyl
group to methylene group (Wolf-Kishner reduction).
base
C = O + H 2NNH 2 ¾¾® C = NNH2 ¾¾® CH2 + N2
heat
Hydrazone

Ammonia reacts with formaldehyde, other aldehydes and ketones in different ways.
6HCHO + 4NH3 ¾¾® (CH2)6N4 + 6H2O
Hexamethylene tetramine
(Urotropine)

CH3 CH3 OH
C = O + NH3 ¾ ¾ ® C
H H NH2
Acetaldehyde ammonia

CH3 HNH2 CH3 NH2

C=O + ¾¾® C
CH3 HCH2COCH3 CH3 CH2COCH3
Diacetoneamine

Secondary amines, R2NH add to aldehydes and ketones to form carbinolamines which are dehydrated easily to
form enamines

OH
C = O + R2NH ¾¾® C ¾¾® C = NR2
NR2
Enamine

O + HN ¾¾® —N + H2O

Cyclopentanone Pyrrolidine N-(1-Cyclopentenyl)-pyrrolidine

6. Addition of organometallic compounds. Organometallic compounds, such as Grignard reagents, alkyllithiums

and organozinc compounds provide nucleophile which add on carbonyl group to form alcohols.

d– d+ R +
R
R:M – + H3O
C = O ¾¾¾® —C—O: M ¾¾¾®
: :

— C—O—H

Such reactions with Grignard reagents and alkyllithiums have already been discussed at length, so here we will
confine only to addition of organozinc compounds.
In short, it can be summarised that Grignard reagents (M = MgX) or alkyllithium (M = Li) react with formaldehyde,
other aldehydes and ketones to form 1°, 2° and 3° alcohols respectively.
Addition of organozinc compounds (The Reformatsky reaction). Reformatsky reaction involves the reaction of
an aldehyde or ketone with an a-bromoester in presence of zinc metal to form b-hydroxy ester.

OZnBr +
OH
Zn H3O b a
C = O + BrCH2COOR ¾¾¾® —C—CH2COOR ¾¾¾® —C—CH2COOR
benzene
a-Bromoester b-Hydroxy ester

Actually an organozinc compound is first formed as an intermediate which then adds to the carbonyl group in
a manner analogous to that of a Grignard reagent.

benzene d+ d –
BrCH2COOC2H5 + Zn ¾¾¾® BrZ n CH 2 COOC 2 H 5
Organozinc compound
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Since organozinc reagent is less reactive than a Grignard reagent, it does not add to the ester group.

OH
(i) Zn |
CH3CH2CH2CHO + BrCH2COOC2H5 ¾¾¾® CH 3 CH 2 CH 2 CHCH 2 COOC2 H 5
(ii) H 3 O + b -Hydroxy ester

The b -hydroxy esters produced in the reaction are easily dehydrated to a, b-unsaturated esters because the
resulting product contains a more stable conjugated system.

OH
| O
H 3 O+ ||
CH 3 CH 2 CH 2 CHCH 2 COOC2 H 5 ¾¾® CH3CH2CH2CH = CH— C —OC2H5 + H2O
heat

1. What are Schiff bases. Give the structure of the product of the following reactions :
(a) Cyclohexanone + tert-Butyl amine (b) CH3COCH3 + H2NCONHNH2
(c) 2-Butanone + [H3N+OH]Cl–, CH3COONa (d) Acetophenone + Cyclohexyl amine

(e) CH3COCH2C6H5 and HN (f) CH3CH2COCH2CH3 + HN

O O NH2 CHO
(g) + (h) +
N NH2 CHO
H
2. Explain the following :
(i) Reaction of hydroxylamine with acetone gives a single oxime, while similar reaction with an aldehyde or a methyl ethyl ketone
forms two isomeric oximes.
(ii) Oximes are more acidic than hydroxylamine.
(iii) Although semicarbazide has two NH2 groups, only one of them reacts with an aldehyde or ketone.
3. (a) How would you prepare following compounds using Reformatsky reaction ?
OH OH
|
(i) (CH3)2 CCH 2 COOCH2CH3 (ii)
CHCOOCH2CH3
CH3
(b) Why is Mg or Cd not used in place of Zn in the Reformatsky reaction ?

7. Cannizzaro reaction. Aldehydes containing no a-hydrogen atom, when treated with concentrated alkali, (aqueous or
alcoholic), undergo self oxidation-reduction (also known as disproportionation) to yield a mixture of an alcohol and a
salt of a carboxylic acid. This reaction, known as Cannizzaro reaction, is carried out at room temperature ; remember
that under these conditions, aldehydes having a-hydrogen atom undergo aldol condensation.
50% NaOH
2HCHO ¾¾¾¾® CH 3 OH + HCOONa
Methanol Sodium formate

50% NaOH
2(CH3)3CCHO ¾¾¾¾® (CH3)3CCH2OH + (CH3)3CCOONa
In general, a mixture of two aldehydes (each having no a-hydrogen atom) undergo Cannizzaro reaction to form
a mixture of all possible products. However, if one of the aldehydes is formaldehyde, reaction always yields
sodium formate as one of the products and the alcohol (second product) corresponding to the other aldehyde.
Cannizzaro reaction between different aldehyde molecules is known as crossed Cannizzaro reaction.
conc. NaOH
C6H5CHO + HCHO ¾¾¾¾® C6H5CH2OH + HCOONa
Benzaldehyde Formaldehyde Benzyl alcohol Sod. formate
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Mechanism.
The reaction involves two successive nucleophilic addition, of course at different carbonyl groups.
H H
– –
Step 1. Ar—C = O + OH Ar—C—O
OH
I

H H H
–
Step 2. Ar—C = O + Ar—C—O– ¾® Ar—C—O + Ar—C = O
OH H OH
(Second molecule) +
I

¾®
+

¾®
H –H
–
ArCH2OH ArCOO

Intramolecular or Internal Cannizzaro reaction

O OH
CHO conc. NaOH CH2OH conc. NaOH
¾¾¾¾¾® ; —C—CHO ¾¾¾¾¾® —CH—COONa
CHO COONa
Remember that keto group can only be reduced, not oxidised, in internal Cannizzaro reaction.
Although aldehydes having a-hydrogen atom do not undego Cannizzaro reaction, they along with all their
aldehydes can be made to undergo such reactions in presence of aluminium ethoxide. The reaction is now
known as Tischenko reaction and here esters are isolated instead of alcohol and carboxylic acids.
Al(OC2H5 )3
2RCHO ¾¾¾¾® [RCH2OH + RCOOH] ¾® RCOOCH2R
Ester

8. Addition of ylides (The Wittig reaction). An ylide is a neutral molecule having a negative carbon adjacent to a
positive hetero atom (e.g. P or S), each atom has an octet of electrons and directly bonded to each other. Aldehydes
and ketones react with phosphorus ylides to yield alkenes and triphenylphosphine oxide. The reaction, known
as Wittig reaction, has proved to be a valuable method for synthesizing alkenes.

R + – R R
C = O + (C6H5)3P = C or (C6H6)3P—C ¾® C=C + O = P(C6H5) 3
R¢ R¢ R¢
Phosphorus ylide Alkene Triphenylphosphine oxide

Thus the net result of the reaction is the replacement of carbonyl oxygen, = O, by the group = CRR ¢. The reaction
is carried out under mild conditions and in presence of solvents like tetrahydrofuran (THF) and dimethyl
sulfoxide (DMSO).
+ – DMSO + –
O + (C6H5)3P— CH 2 ¾ ¾ ¾ ® CH2 + (C6H5) 3P —O

Wittig reaction has a great advantage over most other alkene syntheses in that no ambiguity exists as to the location
of the double bond in the product.
Mechanism. The ylide acting as a nucleophile attacks the carbonyl carbon of the aldehyde or ketone to form an
unstable intermediate betaine followed by oxaphosphetane which then spontaneously loses triphenylphosphine
oxide to form an alkene. The driving force for the Wittig reaction is the formation of the very strong P—O bond
(DH° = 540 kJ mol–1).

R R
R R¢
– R
C :C ¾® —C—C—R¢ ¾® —C—C—R¢ ¾® C=C + :O = P(C6H5)3
+ R¢
:

+ – +
O: P (C6H5)3 :O: P(C6H5)3 : O —P(C6H5)3
:

Betaine Oxaphosphetane Alkene Triphenylphosphine oxide

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1. Give the structure of the product(s) obtained in each of the following reactions.

conc. NaOH conc. NaOH

(a) ¾¾¾¾® (b) conc. NaOH
C6H5COCHCl2 ¾ (c) ArCDO ¾ ¾ ¾ ¾ ®
¾¾¾®
O CHO

D D –
– OH
OH ¾®
(d) D— C = O ¾® (e) D— C = O
2. In the crossed Cannizzaro reaction, formaldehyde is always oxidised. Explain.
3. Which of the following intermediate (I or II) is considered as a better hydride donor to an aldehyde ?

H H
– –
R—C—O R—C—O

OH O–
I II

4. Identify the alkene produced in each of the following Wittig reactions :

-
..
+
(a) Benzaldehyde + Ph3P+ –
(b) Butanal + Ph 3 P C HCH = CH 2

-
..
(c) Cyclohexyl methyl ketone + Ph 3 P+ = C H 2

5. Give the structure of an ylide and a carbonyl compound from which each of the following could be prepared.

(a) CH3CH2CH2CH = C(CH3)CH2CH3 (b) C6H5CH = CHC6H5 (c) CHCH3

(B) Acidity of a-hydrogens of carbonyl compounds

In addition to nucleophilic addition reactions, carbonyl compounds exhibit the unusual acidity of a-hydrogen
atoms. Actually, in the first type of properties carbonyl group acts as a functional group, while in the second type carbonyl
group acts as a substituent and exerts its effect on the adjacent (alpha) carbon atoms.

O
R—C—C—C—
H H
a-Hydrogen, acidic b-Hydrogen, not acidic
(pKa = 19 – 20) (pKa = 40 – 50)

The unusual acidity of the a-hydrogens of carbonyl compounds is due to its strong electron-withdrawing nature
which in turn makes a-carbon also electron-withdrawing. Hence in presence of base, it easily loses hydrogen as proton
and itself converted into carbanion. Once the anion (carbanion) is formed, it is stabilized by resonance.

–
B: H
– BH – – d– d–
C—C = O: ¬® C = C—O: º
:

: :

C—C = O C—C—O
Carbanion Enolate anion
(larger contribution)

Resonance stabilized anion

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Thus the carbonyl group affects the acidity of a-hydrogens in just the same way it affects the acidity of carboxylic
acids, i.e. by helping to accommodate the negative charge of the anion.

– –
O O O O +
+
—C —C ¬¾® —C +H or —C +H
O—H O– O O
Resonance stabilized carboxylate anion
(Equivalent contributing structures)

– –
O O O O
+ +
—C —C – ¬¾® —C +H or —C +H
C—H C C C
Resonance stabilized enolate anion
(Non-equivalent contributing structures)

Although a-hydrogen atoms of an aldehyde or ketone are very weakly acidic than the hydrogen atom of a —
COOH group, they are considerably more acidic than hydrogen atoms anywhere else in the molecule and they are acidic
enough for producing carbanions in significant concentration. It is interesting to note that the two important properties of
a carbonyl group : (a) susceptibility to nucleophilic attack, and (b) acidity of a-hydrogens, is due to the ability of oxygen to
accommodate the negative charge.

1. Account for the following facts.

(a) (+) —C6H5CH(CH3)CHO undergoes reacemization, when treated with base.
(b) The diketone 2, 4-pentanedione is almost as acidic as phenol, and much more acidic than acetone.
(c) g-Hydrogens of a, b-unsaturated carbonyl compounds are acidic.
2. Write down the structure of the product in the following reactions.
CH3 O
KOD
(a) O + 4 D2O ¾ ¾ ® (b) CH3—C = CH—C—CH3 + NaCN (aqueous) ¾®

Reactions of carbonyl compounds due to acidic hydrogen atom, i.e. due to enols and enolate anions.
9. Aldol condensation. Two molecules of an aldehyde or a ketone, containing at least one a-hydrogen atom, when
treated with dilute base (like NaOH, Ba(OH)2, K2CO3, etc.) at room temperature (or below) combine to form a b-
hydroxyaldehydes or b-hydroxyketones. This reaction is called aldol condensation. In every case, it is the a-
carbon and a-hydrogen atoms of one molecule that add to the carbonyl carbon and oxygen atoms respectively of
the second molecule.
H –
H
OH
(i) CH3—C = O + CH3.CHO ¾¾® CH3—C—CH2CHO

OH
3-Hydroxybutanal

H –
H
b a OH
(ii) CH3CH2—C = O + H3C—CH2—CHO ¾¾® CH3CH2—C—CH—CHO
Propionaldehyde (2 moles)
OH CH3
3-Hydroxy-2-methylpentanal

CH3 CH3 O
–
OH
(iii) CH3—C = O + CH3.CO.CH3 ¾¾® CH3—C—CH2—C—CH3

OH
4-Hydroxy-4-methyl-2-pentanone
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Mechanism.
–
Step 1. CH3CHO + OH– [CH2CHO] + H2O
Carbanion, I

H H
–
Step 2. CH3—C = O + [CH2CHO] CH3—C—CH2CHO
I (Nucleophile)
O–
Alkoxide ion, II

H H
–
Step 3. CH3—C—CH2CHO + H2O CH3—C—CH2CHO + OH
O– OH
Remember that presence of a-hydrogen in aldehyde or ketone is the essential condition for aldol condensation,
since only such carbonyl compounds can form carbanions, the actual nucleophile, which then attacks the
carbonyl carbon to form the product. Hence, aldehydes or ketones, not having a-hydrogen atom, do not undergo
aldol condensation.

dilute
ArCHO, HCHO, (CH3)3CCHO, ArCOAr, or ArCOCR3 ¾¾®
- No reaction
OH

However, in presence of concentrated base, above compounds undergo Cannizzaro reaction.

Dehydration of aldol products. The b-hydroxy aldehydes and b-hydroxy ketones obtained from aldol condensation
are very easily dehydrated, on heating, to form a, b-unsaturated carbonyl compound (conjugated system).

H H H H
+ –
H or OH
CH3—C—CH—C = O heat
CH3—C = CH—C = O + H2O
2-Butenal
OH H
Aldol

Dehydration under acidic conditions follows a mechanism similar to those of other acid-catalyzed alcohol
dehydration. The steps involved in base-catalyzed dehydration of aldol are summarised below.
O – O O
OH, (–H2 O) .–. –
CH3 – CH – CH – CH CH3 – CH – CH – CH CH3 – CH = CH – CH + OH
OH H OH
Enolate ion Conjugated system

Note that in the second step, hydroxide ion which is not a good leaving group in an E2 elimination is removed.
However, here OH– can serve as a leaving group in a strongly exothermic step leading to a highly stable
(conjugated) compound.
In some cases, especially when the double bond produced is conjugated with an aromatic ring, dehydration of
the aldol product occurs so readily that we cannot isolate the product in the aldol form.

CH3
C2H5ONa
—C—CH3 + CH3—C— ¾ ¾¾ ¾ ® —C—CH—C—
O O OH H O
Acetophenone (Hypnone)
CH3
—H2O
¾¾¾® —C = CH—C—
O
1, 3-Diphenyl-2-buten-1-one (Dypnone)
(a fully conjugated system)
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Synthetic applications. (i) Aldol reaction is a general reaction given by aldehydes and ketones having an a-
hydrogen atom.
(ii) Further, aldol reaction gives us a product by introducing a new carbon-carbon bond between two molecules.
(iii) Aldol products contain two functional groups, —OH and —CHO, each of which can be used to carry out
a number of subsequent reactions.

–
OH OH
OH NaBH4
2RCH2CHO ¾ ¾ ® RCH2CH—CHCHO ¾ ¾ ¾ ® RCH2CHCHCH2OH

R R
Aldehyde An aldol A 1, 3-diol

¾¾®
+
H , (—H2O)

H2 /Ni LiAlH4
RCH2CH2CHCH2OH ¬¾ ¾ RCH2CH = CCHO ¾ ¾ ¾ ® RCH2CH = CCH2OH
high P
R R R
A saturated alcohol An a, b -unsaturated aldehyde An allylic alcohol

¾¾® H2, Pd—C

RCH2CH2CHCHO

R
A saturated aldehyde

Acid-catalyzed aldol condensations. Aldol condensation can also be brought about with acid catalysts. The
enol serves as a weak nucleophile to attack an activated (protonated) carbonyl group. Steps involved in the acid-
catalyzed aldol condensation of acetaldehyde are given below.

+ .. +
OH : OH OH OH OH O–H
+
CH3 – CH + CH2 = CH CH3CH – CH 2 CH CH3CH – CH 2 – CH
protonated enol form of
acetaldehyde acetaldeyde

OH O +
O
ROH H
+
CH3CH – CH2CH CH3CH = CHCH + H2O
RO H2
Aldol

Similarly acetone, when treated with hydrogen chloride gives 4-methyl-3-penten-2-one. Here, the aldol formed
undergoes dehydration to form 4-methyl-3-penten-2-one.

O OH O O
|| | || ||
HCl
2CH 3 - C CH 3 ¾¾¾
® CH 3 CCH 2 C CH 3 ¾¾¾
® CH 3 C = CH C CH 3
| ( - H 2 O) |
CH3 CH3
Acetone (2 mole) Diacetone alcohol 4 - Methyl - 3 - penten - 2 - one
(Mesityl oxide)

Mesityl oxide may further undergo crossed aldol condensation to form phorone as final product.

O O OH O CH3 O CH3
—H2O
CH3C = CHCCH3 + CH3CCH3 ¾ ¾¾ ¾ ¾® CH3CCH2CCH = CCH3 ¾ ¾ ® CH3C = CHCCH = CCH3
Crossed aldol
(3rd mole)
CH3 condensation
CH3 CH3
2, 6-Dimethyl-2, 5-heptadien-4-one (Phorone)
Crossed aldol condensation. An aldol condensation between two different carbonyl compounds each having at
least one a-hydrogen atom (crossed aldol condensation) gives a mixture of the four possible products, hence it
is not always feasible in the laboratory. For example, reaction of acetaldehyde and propanal in presence of dilute
NaOH gives a mixture of four products.
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–
OH OH CH3
OH
CH3CHO + CH3CH2CHO ¾ ¾ ® CH3CHCH2CHO + CH3CH2CH CHCHO
Ethanal Propanal 3-Hydroxybutanal 3-Hydroxy-2-methylpentanal

¾¾®
– (from 2 molecules of ethanal) (from 2 molecules of propanal)
OH

OH CH3 OH
CH3CH CHCHO + CH3CH2CHCH2CHO
3-Hydroxy-2-methylbutanal 3-Hydroxypentanal
(from 1 molecule of ethanal and 1 molecule of propanal)
(Ethanal as a carbonyl group (Propanal as a carbonyl group
and propanal as a nucleophile) and ethanal as a nucleophile)

Intramolecular aldol condensation (Cyclization via aldol condensation). A dialdehyde, a keto aldehyde, or a diketone
undergoes aldol condensation to form five and six-membered (sometimes even longer) cyclic compounds, e.g.
O O
–
OH
OHC ¾¾®

1-Cyclopentenyl methyl ketone

In the above keto aldehyde, three different enolates are possible, however it is the enolate from the ketone side of
the molecule that adds to the aldehyde group leading to the product. The reason being greater reactivity of
aldehydes toward nucleophilic addition than the ketones due to electronic as well as steric factors.

1. Write structural formulas for the products obtained by the aldol condensation of following compounds:
CHO
(a) O (b) —COCH3 (c) — CHO +

O
O
(d) (e) C6H5CHO + —C—CH3

Other reactions related to aldol condensation

There are large number of condensations that are closely related to the aldol condensation, each of these reactions
has its own name, viz. Claisen-Schmidt, Knovenagel, Perkin (given only by aromatic aldehydes), etc. At first
glance each may seem to quite different from the others, closer examination shows that each of these involves
attack by a carbanion on a carbonyl group. In each case carbanion is generated like that in aldol condenstion, i.e.,
hydrogen a-to the carbonyl group is abstracted by base.
(a) Claisen-Schmidt reaction. A crossed aldol condensation in which an aromatic aldehyde reacts with an
enolizable aldehyde, ketone or ester, eg CH3COOC2H5 to form a, b-unsaturated carbonyl compound is
known as Claisen-Schmidt reaction.

–
RO
OH
C6H5CHO + RCH2COR¢ ¾¾® C6H5CH = C CR¢ + H2O
(R¢ = H or alkyl) a , b -Unsaturated carbonyl compound
O –
O
OH
C6H5CHO + (CH3)3CCCH3 ¾ ¾ ® C6H5CH = CHCC(CH3)3
4, 4-Dimethyl-1-phenyl-1-penten-3-one
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(b) Knoevenagel reaction. Condensation between an aldehyde or ketone with compound containing active
methylene group* in the presence of ammonia, amines, pyridine, piperidine etc. to form a, b-unsaturated
compound is known as Knoevenagel reaction.

heat
(i) CH3CHO + H2C(COOH)2 ¾¾® CH3CH = C(COOH)2 ¾¾® CH3CH = CHCOOH
—CO 2

Malonic acid Crotonic acid

(i) heat
(ii) C6H5CHO + H2C(COOH)2 ¾¾¾® C6H5CH = CHCOOH
(ii) —CO 2

Cinnamic acid
Note that in Knoevenagel reaction, enol (or enolate ion) is provided by molonic acid and not by aldehyde.

1. Give the structure of the mixed aldol condensation product of the following.

O
CHO
(a) C6H5CHO + C6H5COCH3 (b) — CHO + O = (c) +

2. Give the final product in each case.

KOH C2 H 5ONa
(a) CH3CHO + CH3NO 2 ¾¾® (b) C6H5CHO + C6H5CH2CN ¾¾¾¾®
NH 3
(c) C6H5CHO + CH3COCH2COOC2H5 ¾¾®

10. a-Halogenation of aldehydes and ketones. Aldehydes and ketones having a-hydrogen atom react with halogens
to form a-haloaldehyde or ketone.
H O X O
acid or
—C— C— + X2 ¾¾¾® — C— C— + HX
base

The reaction is regiospecific for substitution of an a-hydrogen.

O O
Cl
H2O
+ Cl2 ¾¾® + HCl

Cyclohexanone 2-Chlorocyclohexanone

CHO CHO
CHCl3
+ Br2 ¾¾¾® Br + HBr

Cyclohexanecarbaldehyde 1-Bromocyclohexanecarbaldehyde

C6H5COCH3 + Cl2 ¾¾® C6H5COCH2Cl

Acetophenone Phenacyl chloride
Phenacyl chloride is a relatively harmless but powerful lachrymator or tear gas and is used by police to disperse
mobs.
* A methylene group flanked on both sides by negative groups is known as active methylene group, e.g.,
COOH COCH3 CN
CH2 CH2 CH2
COOH COOC2H5 COOC2H5
Malonic acid Ethyl acetoacetate Ethyl cyanoacetate
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(i) a-Halogenation of aldehydes and ketones can be carried out in a variety of solvents like water, chloroform,
acetic acid and diethyl ether.
(ii) The reaction is quite different from the free-radical halogenation of alkanes and involves the formation of
resonance stabilized enols.
(iii) Unlike ketones, aldehydes are easily oxidized, and since halogens are strong oxidizing agents, halogenation
of aldehydes usually results in oxidation to carboxylic acids.

O O
|| ||
R C H + X 2 + H2 O ¾¾
® R - C - OH + 2HX

(iv) Since one of the reaction products is hydrogen halide, the process when catalyzed by acids is said to be
auto-catalytic. However, halogenation promoted by base is more important and discussed here.
Mechanism. The rate of reaction depends upon the concentration of acetone and of base, but is independent of
bromine concentration.

– slow –
Step 1. CH3—C—CH3 + : B CH3—C—CH2 ¬ ¾ ® CH3—C = CH2 + H : B
O O O–

.–. fast
Step 2. CH 3 C C H 2 + Br – Br ¾ ¾¾® CH 3 C CH 2 B r Br
|| ||
O O

Since base is not regenerated during the reaction, halogen of ketones in presence of base is called base-promoted,
rather than base-catalyzed reaction. As we will discuss below in haloform reaction, multiple halogenation of
aldehydes and ketones having more than one a – H occurs.
Mechanism of acid catalyzed a-halogenation of ketones. The ketone is dissolved in acetic acid, which serves
as both the solvent and the acid catalyst. In contrast with basic halogenation, acidic halogenation can selectively
replace just one hydrogen or more than one if appropriate amounts of the halogen are used.
In the first step, the carbonyl oxygen is protonated to form enol which reacts with the halogen (electrophile).

+ OH
+ ||
H Base
CH 3 - C - CH 3 ¾¾¾
® CH 3 - C - CH 3 ¾¾¾¾® CH 3 - C = CH 2
|| (say H 2 O) |
O OH
enol

Br - Br + Br -
¾ ¾ ¾¾
® CH 3 - C - CH 2 Br ¬¾® CH 3 - C - CH 2 Br ¾¾ ¾
® CH 3 - C - CH2 Br + HBr
- | || ||
( - Br )
:OH
.. + O- H O

11. Haloform reaction. When methyl ketones (or acetaldehyde) react with halogen in the presence of base, multiple
halogenation of the a -methyl group takes place because introduction of the first halogen (due to its
electronegativity) makes the remaining a hydrogens on the methyl carbon more acidic. Actually, introduction of
the first halogen is slowest, while that of last (i.e. third) is fastest.

O –
O –
O
X2 , OH X2, OH
CH3—C—CH2X ¾¾¾® CH3—C—CHX2 ¾¾¾® CH3—C—CX3

In short,

O O
– base –
CH3—C—CH3 + 3X2 + 3OH ¾¾® CH3—C—CX3 + 3X + 3H2O
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When methyl ketones react with halogens in aqueous sodium hydroxide (i.e. hypohalite solutions), an additional
reaction takes place. Hydroxide ion attacks the carbonyl carbon atom of the trihaloketone (nucleophilic addition) and
causes a cleavage of the carbon-carbon bond between the carbonyl group and the trihalomethyl group (:CX3–), the latter,
being a good leaving group*, departs easily forming a carboxylic acid and the trihalomethyl anion.

:
O: :O :

:
–
O
OH –
CH3—C—CX3 ¾ ¾® CH3—C—CX3 ¾ ¾ ® CH3—C + : CX3
OH OH

¾¾®

¾¾®
–
OH H2O

O
–
CH3—C—O HCX3
Carboxylate anion Trihalomethane

Since haloform (CHCl3, CHBr3 or CHI3) is produced in the reaction, it is known as haloform reaction (reaction of
methyl ketones with alkaline halogen to form haloform, CHX3).
Importance of haloform reaction.
1. Haloform reaction is used as a means of preparing carboxylic acids from methyl ketones. For this, chlorine
and bromine are most commonly used as the halogen component because resulting haloform (chloroform
and bromoform) are water immiscible liquids and hence are easily separated from the aqueous solution
containing the carboxylate anion.
O
–
(CH3)3C—C—CH3 + Br2 + OH ¾ ¾ ® (CH3)3C—COOH + CHBr3
3, 3-Dimethyl-2-butanone 2, 2-Dimethylpropanoic acid

2. Haloform reaction, particularly iodoform reaction is used as a laboratory test for identifying methyl ketones,
acetaldehyde and methyl secondary alcohols which are first oxidized to methyl ketones under the reaction
conditions.

H –
I2 3I2 + 3OH –
—C—CH3 ¾® —C—CH3 ¾¾¾¾® —C—CI3 + 3I + 3H2O
OH O O
Methyl sec. alcohol Methyl ketone Triiodoketone
or acetaldehyde
– –
—C—CI3 + OH ¾ ¾ ® —C—O + CHI3 ¯
O O Yellow precipitate

1. Give the product of the reaction of 1 equivalent of Br 2 in H3O+ with

(a) propanal (b) acetophenone (c) cyclopentanone.
2. Arrange the following in decreasing ease of bromination.
CH3COCH3, CH3COCH2Br, CH3COCH2Cl, CH3COCHBr2.
3. Explain the following.
(a) Ketone I undergoes racemization in basic solution, but ketone II does not.
CH 3

C6H5 — C CH C 6 H5 C6H5 — C¾ C C 6H5

½½
O CH3 O C2 H 5
I II
(b) ArCHO, HCHO and RCH2CHO (R ¹ H) do not undergo haloform reaction.
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(C) Other reactions of aldehydes and ketones.

12. Oxidation. Aldehydes are much more easily oxidized, than ketones, to carboxylic acids. Aldehydes are oxidized
not only by the same reagents that oxidize primary and secondary alcohols, viz. permanganate and dichromate,
but also by the very mild oxidizing agent as silver ion. Oxidation by silver ion requires an alkaline medium
under which conditions it forms insoluble silver oxide, hence to dissolve this oxide a complexing agent ammonia
is added, which brings silver ion as diamminosilver (I) ion, Ag(NH3)2+. This alkaline solution of silver nitrate in
presence of ammonia is commonly known as Tollen’s reagent.

O – O + O
KMnO4, OH –
H3O
R—C—H ¾¾¾¾¾¾¾¾® R—C—O ¾¾¾® R— C—OH
or K2Cr2O7 + H2 SO4

O – O + O
Ag2O, OH –
H3O
R—C—H ¾¾¾¾® R—C—O ¾¾¾® R—C—OH
Note that in the above reactions, aldehydes lose the hydrogen that is attached to the carbonyl carbon atom, and
since ketones do not have such hydrogen, they are resistant to oxidation.
Oxidation by Tollen’s reagent is accompanied by colour change (due to reduction of Ag+ ion to metallic silver),
hence the reagent is commonly used for detecting the presence of an aldehyde in laboratory.
RCHO + Ag(NH3)2+ ¾¾® RCOO– + Ag
Colourless solution Silver mirror
Since Tollen’s reagent is a mild oxidising agent, it does not attack carbon-carbon double bond, hence it is used
for the synthesis of unsaturated acids from unsaturated aldehydes which are easily obtained from aldol condensation.
Ag(NH 3 )2 +
OH - heat
CH 3 CHO ¾¾® CH 3 CHOHCH 2 CHO ¾¾® CH 3 CH = CHCHO ¾¾¾¾® CH 3 CH = CHCOOH
Acetaldehyde Aldol Crotonaldehyde Crotonic acid

Aldehydes (except benzaldehyde) also reduce Fehling’s solution (an alkaline solution of cupric ion complexed
with tartarate ion) and Benedict’s solution, in which complexing agent is citrate ion.

O O
2+ – – +
R—C—H + 2Cu + 3OH ¾ ¾¾ ® R—C—O + 2Cu ¯ + H2O
(deep blue colour) (red ppt.)

Oxidation of ketones requires breaking of carbon-carbon bonds, and hence (except for haloform reaction) takes
place only under vigorous conditions. It is the double bond of the enol form that is cleaved during oxidation of ketones,
thus where structure permits oxidation may occur on either end of the carbonyl group to form a mixture of carboxylic
acids.

H OH O OH H

—C—C = C— —C—C—C— —C = C — C—

H H H H
Enol Keto Enol

O
oxidation
oxidaton
¾¾¾® RCH2COOH + R¢COOH
(b route) (a route)
b a

Methyl ketones are oxidized smoothly by means of hypohalite (NaOH or KOH + halogen) to form carboxylate
ion and haloform, and hence the reaction is commonly known as haloform reaction. (Details discussed earlier).
O O
|| ||
R— C —CH3 + 3X2 + 4OH– ¾¾® R— C —O– + CHX3 + 3X– + 3H2O

H CH3 O H CH3
| | || | |
Oxidation
C6 H 5 — C = C — C — CH 3 ¾¾¾¾® C6H5 — C = C — COO + CHX3
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Aldehydes and ketones having a methyl or methylene group adjacent to the carbonyl group are oxidised by
selenium dioxide.
SeO 2 2 SeO
CH 3 CHO ¾¾® CHO.CHO ; CH 3 COCH 3 ¾¾® CH 3 COCHO
Ethanal Glyoxal Propanone Methylglyoxal

Baeyer-Villiger oxidation. Both aldehydes and ketones are oxidised by peroxy acids. This reaction, called
Baeyer-Villiger oxidation, is however especially useful with ketones, because it converts them to carboxylic esters.
O O O O
R—C—R¢ + R² —C—O—OH ¾ ® R—O—C—R¢ + R² —C—OH
Ketone Peroxy acid Ester Carboxylic acid

Note that an oxygen from the peroxy acid is inserted between the carbonyl carbon and carbon atom of one the
alkyl groups of the ketone. In case of mixed ketones, oxygen insertion occurs between the carbonyl carbon and
the larger of the two alkyl groups of the ketone
O O
C6H5CO3H
—C—CH3 ¾ ¾ ¾ ¾ ¾ ® —O—C—CH3

Cyclohexyl acetate

C6H5CO3H
¾¾¾¾¾®
O
O O
Mechanism, taking the example of cyclopentanone.
H O O
O HO O–O–C–R HO O–O–C–R
H O +
+
–H
+ O–O–C–R

+
OH
+
HO O–O–C–R H–O O
+ O O
+ –H
H –RCOOH

The tendency of a group to migrate (migratory aptitude) in all reactions where the group migrates with its
electron pairs (i.e. as anions) follows the order :
H > phenyl > 3° alkyl > 2° alkyl > 1° alkyl > methyl

1. Give the products of reaction for

(a) Benzaldehyde + Tollen’s reagent (b) CH3CHO + dil. KMnO4
(c) 3-Hexanone + Strong oxidant (d) Cyclohexanone + HNO3, heat
(e) Propanol + Ag(NH3)2+ (f) Methyl ethyl ketone + HNO 3, heat
2. Give the products of the reaction of I2 in KOH
(i) CH3CH2CHO (ii) CH3CH2OH (iii) C6H5CHO (iv) C6H5CH2COCH3
(v) Me 3C.COCH3 (vi) CH3CH2COCH2CH2COCH3 (vii) C6H5CH2OH.
3. What is the product of the reaction of each of the following ketones with peroxybenzoic acid ?

O NO2

(a) C6H5COC6H5 (b) (c) —CHO (d) O

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13. Reduction.
(a) Aldehydes and ketones can be reduced to primary and secondary alcohols respectively by a variety of reagents.
Catalytic hydrogenation over a metal catalyst and reduction with lithium aluminium hydride or sodium
borohydride are common methods and have been discussed in detail in the chapter on “Monohydric Alcohols”.
Sodium in ethanol is useful for reduction of ketones.
H2/Ni or
C = O ¾¾¾¾ ¾¾® CHOH
LiAlH4 or NaBH4

Benzaldehyde undergoes coupling reaction with Na/C2H5OH, so it can be reduced into alcohol by Na/C2H5OH.

(i) LiAlH , or NaBH H /Ni

4 4
CH 3 CH = CHCH 2 OH ¬¾¾¾¾¾¾¾¾ ¾ CH 3 CH = CHCHO ¾¾¾¾
2 ® CH 3 CH 2 CH 2 CH 2 OH
+
(ii) H

LiAlH4
O ¾ ¾¾
+ ® —OH
H
Cyclopentanone Cyclopentanol

Remember that reduction of carbonyl compounds to alcohols by LiAlH4 or NaBH4 is an example of nucleophilic
addition reactions in which hydride ion, H :– (from LiAlH4 or NaBH4) is transferred from the metal to the
carbonyl carbon.

H H
– – 3 C=O –
C = O + H— AlH3 ¾ ¾ ® —C—OAlH3 ¾¾¾¾® —C—O Al
4
Tetraalkyloxyaluminate

H
4H2O –
¾ ¾ ® 4 —C—OH + Al (OH)4

(b) Aldehydes and ketones can be reduced to hydrocarbons by the action (i) of amalgamated zinc and
concentrated hydrochloric acid (Clemmensen reduction), or (b) of hydrazine (NH2NH2) and a strong base
like NaOH, KOH or potassium tert-butoxide in a high-boiling alcohol like ethylene glycol or triethylene
glycol (Wolf-Kishner reduction).
Zn(Hg), HCl
C = O ¾¾¾¾¾¾¾¾¾® CH2
or NH2 NH2, KOH, glycol

Both these methods reduce neither carboxylic acid nor the carbon-carbon double or triple bonds (however,
remember that Zn and HCl reduces —NO2 to —NH2 group).

2 NH NH
2
O ¾¾ ¾®
base
Cyclopentanone Cyclopentane

OH OH OH

CH3(CH2)4COOH Zn(Hg)
¾¾¾¾¾¾® ¾¾¾®
ZnCl2 HCl
OH OH OH
Resorcinol
CO(CH2)4 CH3 CH2(CH2)4CH3
4-n-Hexylresorcinol
(a constituent of dettol )
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(c) Aldehydes and ketones can be reduced to hydrocarbons through thioacetal formation too.

R HA R S—CH2CH3
C = O + 2CH3CH2SH ¾¾® C + H2O
R¢ R¢ S—CH2CH3
Aldehyde Ethanethiol Thioacetal
or ketone

R HSCH2 BF3 R S—CH2

C=O+ ¾¾® C + H2O
R¢ HSCH2 R¢ S—CH2

Aldehyde Ethane-1, 2-dithiol Cyclic thioacetal

or ketone

R S—CH2 Raney Ni R
C ¾¾¾¾® CH2 + CH3CH3 + 2NiS
H2
R¢ S—CH2 R¢

(d) Many aldehydes and ketones are converted into amines by reductive amination (reduction in presence of
ammonia). Reduction can be done catalytically or by sodium cyanohydridoborate, NaBH 3CN. Reaction
involves reduction of an intermediate imine.

R R H2, Ni or R
C = O + NH3 ¾ ¾ ® C = NH ¾¾¾¾® CHNH2
R¢ R¢ NaBH3CN R¢
An aldehyde or ketone An imine 1° Amine

(e) Reduction of ketones to pinacols in presence of magnesium has already been discussed in the chapter on
“Polyhydric Alcohols”

CH3 CH3
Mg/benzene
2CH3COCH3 ¾ ¾¾ ¾ ¾ ® CH3—C——C—CH3
Acetone
OH OH
Pinacol

14. Formation of dihalides. Aldehydes and ketones react with PCl5 and sulphur tetrafluoride to form corresponding
dihalide.

PCl5 Cl
O ¾¾® + POCl3
Cl

O F
SF4
¾¾® F + SOF2

1. Write down the structure and IUPAC name of the products in each of the following reactions.

(a) 4, 4-Dimethylcyclohexanone + NH2NH2, OH– (b) Pent-3-enal + NH2NH2, OH–

(c) Acetylacetic acid + Zn(Hg) and HCl (d) Pent-2-enal + Zn(Hg) and HCl.
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2. Give structures of the compounds A to D.

dry HCl Raney

(a) C6H5CHO + HSCH2CH2SH ¾¾¾® [A] ¾¾® [B]
Ni

(i) BH 3/THF NaBH 4

(b) [D] ¾¾¾¾¾®
-
O CH2 ¾¾® [C].
(ii) H 2 O2 , OH

3. (a) Write structures for the products of the reaction of PCl5 with
(i) propanal (ii) propanone (iii) benzophenone
(b) Give the products in the following reactions :

heat
(i) C6H5CHO + SF4 ¾® (ii) O + MoF6 ¾ ®

15. Polymerisation. Lower aldehydes undergo polymerisation to form different products under different conditions.
evaporate to dryness
nHCHO (CH2O)n
(n = 6 to 50) Paraformaldehyde
room temp.
3HCHO (CH2O)3
Metaformaldehyde
(6-membered cyclic compound)
conc. H2SO 4
3CH 3CHO (CH3CHO)3
Paraldehyde
(6-membered cyclic compound)
conc. H2SO4, 0°C
4CH 3CHO (CH3CHO)4
Metaldehyde
(8-membered cyclic compound)
CH3

conc. H2SO4
3CH 3COCH3 ¾¾ ¾¾ ¾ ¾®
heat
H3C CH3
Mesitylene

14.6 Special Reactions Given by Aromatic Aldehydes and Ketones

1. Reaction with ammonia. Benzaldehyde reacts with ammonia to form hydrobenzamide, recall that aldehydes
other than formaldehyde give aldehyde ammonia, while formaldehyde forms hexamethylenetetramine, commonly
known as urotropine, an important urinary antiseptic.

C6H5CH = O H2NH C6H5CH = N

+ + O = CHC6H5 ¾ ¾ ® CHC6H5
C6H5CH = O H2NH C6H5CH = N
Hydrobenzamide

2. Benzoin condensation. Aromatic aldehydes, when heated with aqueous ethanolic NaCN or KCN, undergoes
self condensation to form benzoins. For example,
OH
KCN, heat
½
oxi. benzil-benzilic acid
2C6H5CHO ¾¾¾¾® C6H5CHOHCOC6H5 ¾® C6H5COCOC6H5 ¾¾¾¾¾¾¾® C6H5 ¾ C— COOH
C2H 5 OH rearrangement
½
C 6 H5
Benzoin Benzil Benzilic acid
(An a-hydroxyketone)
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3. Perkin reaction. Condensation of an aromatic aldehyde with an acid anhydride in presence of sodium salt of the
same acid to form a, b-unsaturated acid is known as Perkin reaction.

(i ) CH 3 COONa
(i) C6H5CHO + (CH3CO)2O ¾¾¾¾¾® C6H5CH = CHCOOH
(ii ) H+

Benzaldehyde Acetic anhydride Cimmanic acid

CH 3
(i ) CH3 CH 2 COONa ½
(ii) C6H5CHO + (CH3CH2CO)2O ¾¾¾¾¾¾¾® C6H5CH = CCOOH
(ii ) H+
Benzaldehyde Propanoic anhydride a-Methylcinnamic acid
Remember that it is the a-carbon atom of the anhydride that reacts with the aldehydic group, observe (ii) example.
4. Reaction with benzene nucleus. Aromatic aldehydes and ketones undergo electrophilic substitutions in the
meta position. However, these reactions are slow because of deactivating influence of the carbonyl group. Moreover,
certain side reactions like oxidation make the yield poor.

14.7 Analysis of Aldehydes and Ketones

1. Aldehydes and ketones can be differentiated from non-carbonyl compounds through their reactions with
semicarbazide, 2, 4-dinitro-phenylhydrazine, and hydroxylamine with which they form precipitates.
Semicarbazones and oximes are colourless, while 2, 4-dinitrophenylhydrazones are usually orange. The melting
points of these derivatives can also be used in indentifying specific aldehydes and ketones.
2. Aldehydes are differentiated from ketones through their ease of oxidation. They give a positive test with Tollen’s
reagent, while ketones do not. However, a positive Tollen’s test is also given by few other easily oxidisable
compounds, e.g. a-hydroxy ketones, certain phenols and hydroxylamines.
3. Schiff’s test is a highly sensitive test for aldehydes. An aldehyde reacts with the fuchsin-aldehyde reagent to
form a characteristic megenta colour.
4. Aldehydes are easily oxidised by cold, dilute, neutral KMnO4 and by CrO3 in sulphuric acid.
5. Aliphatic aldehydes and ketones having a-hydrogen react with bromine in CCl4 (caution this is also a test for
unsaturation).
6. Methyl ketones, acetaldehyde, ethyl alcohol and methyl secondary alcohols give positive iodoform test. In
general, iodoform test is given by following groupings.

O O
|| ||
(a) —C — CH3 present in ethanal, H —C — CH3 and all methyl ketones

OH
½
(b) —C — CH3 present in ethanol and all secondary methyl ketones.
½
H

O
P
(c) R - C - CH2 X since these products are formed during holoform reaction.

X
|
(d) R - CH - CH3 since these on hydrolysis with aq. NaOH give 2° alcohols having methyl group.
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1. What happens when an aldehyde or a ketone is treated with the following reagents ?
Conc. H2SO 4, cold dil., neutral KMnO4, CrO3 in H2SO 4, and Br2 in CCl4.
2. By rapid test tube reactions distinguish between
(a) 2-Pentanol and 2-pentanone (b) Pentanal and diethyl ketone
(c) C6H5COCH2CH3 and C6H5CH(OH)CH2CH2CH3 (d) C6H5CH = CHCH2OH and C6H5CH = CHCHO.

14.8 Illustrative Examples

Example 1 :
Give various steps involved in the following conversions :
C6H5CH = CHCHO to C6H5CHBrCHBrCH2Cl.
Solution :
Conversion involves two main reactions, viz. addition of Br2 on C = C and conversion of —CHO to —CH2Cl. Since
bromine oxidizes —CHO to —COOH, so —CHO first be converted to CH2Cl before adding bromine.

(i) NaBH 4 PCl5 Br2

C6H5CH = CHCHO ¾¾¾¾® C6H5CH = CHCH2OH ¾¾® C6H5CH = CHCH2Cl ¾® C6H5CHBrCHBrCH2Cl.
(ii) H 2 O

Example 2 :
Write structures of the compounds from A to I.

HF (i) BH3 /HF CrO 3 (i) CN -

(a) C6H6 + CH2 = CHCH2OH ¾® [A] ¾¾¾¾¾® [B] ¾¾® [C] ¾¾¾® [D]
(ii) H 2O 2 /OH - Pyridine (ii) H3 O +

Zn CrO 3 3
HOCH 2 CH2 OH LiAlH 4 H O+
(b) CHO + BrCH2COOC2H5 ¾® [E] ¾¾¾® [F] ¾¾¾¾¾¾® [G] ¾¾¾® [H] ¾¾® [I].
Pyridine

Solution :
(a) [A] is C6H5CH2CH = CH2, [B] is C6H5CH2CH2CH2OH,
(obtained by Friedel-craft alkylation) (obtained by anti-Markovnikov hydration)
[C] is C6H5CH2CH2CHO ; [D] is C6H5CH2CH2CHOHCOOH

OH O
O O
(b) COOC2H5 COOC2H5 COOC2H5

[E] (Perkin reaction) [F] [G] (Protection of keto group)

O
O O CH2OH
CH2OH

[I] (Regeneration of keto group)

[H] (Reduction of ester)
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Example 3 :
Write structures for A to D in the following.

CN - H 3O+ H2SO 4 (i) BH 3 /THF

(CH3)2CO ¾® [A] ¾¾® [B] ¾¾® [C] ¾¾¾¾¾® [D].
heat (ii) H2 O 2 , OH -

Solution :

OH OH
CH3—C—CN CH3—C—COOH CH2 = C—COOH HOCH2—CH—COOH
CH3 CH3 CH3 CH3
[A] [B] [C] [D]

Example 4 :
Identify A to C in the following :

2NBS H 3O+ NaOCl

C6H5CH2CH3 ¾¾® [A] ¾¾® [B] ¾¾® [C] + [D]
Solution :
C6H5CBr2CH3, C6H5COCH3, C6H5COO–Na+ + CHCl3
[A] [B] [C] and [D]

Example 5 :
Identify A to C in the following reactions.

CH2 OHCH 2 OH NaBH 4 H 3O+

O ¾¾¾¾¾¾® [A] ¾¾¾® [B] ¾¾® [C]
OHC H+ CH3 OH

Solution :
Aldehydes are more reactive than ketones, hence acetal formation at first step will be with the —CHO group ; this
is done to protect the aldehydic group.

H
O OH
O O H
OH
O O
OHC
[A] [B] [C]

Example 6 :
Complete the following reactions.

C2 H5MgBr (i) CO 2 H2 SO4 , Hg 2∗

(a) CH º CH ¾¾¾¾↑ [A] ¾¾¾↑ B ¾¾¾¾¾↑ C
CrO
¾¾↑ [D]
3
∗ H2 SO 4
(ii) H

NBS NaCN (i) C6H11MgBr

(b) C6H5CH3 ¾¾↑ E ¾¾↑ F ¾¾¾¾¾↑ G
(ii) H3 O∗
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Solution :
C 2H5 MgBr (i) CO 2 H SO , Hg 2+
(a) CH º CH ¾¾¾¾↑ HC º CMgBr ¾¾↑ HC º C ¾ COOH ¾¾¾¾¾↑
2 4
(—C2 H6 ) +
[A] (ii) H [B]

tautomerises CrO 3
HOCH = CHCOOH ¾¾¾¾↑ OHCCH 2 COOH ¾¾↑ HOOCCH 2 COOH
anti -Markownikov hydration [C] [D]
due to —I effect of —COOH

CH3 CH2Br CH2CN CH2COC6H11

NBS NaCN C6 H11MgBr

(b) ¾¾® ¾¾¾® ¾¾¾¾®

[E] [F] [G]

Cyclohexyl benzyl
ketone

Example 7 :
Give steps involved in the following conversions.
(a) Acetaldehyde to 2, 3-dibromopentanoic acid (b) Acetaldehyde to a-hydroxypropanoic acid (lactic acid)
(c) Benzene to p-chlorobenzaldehyde (d) Cyclopentane to cyclopentanecarbaldehyde.
Solution :
OH, heat
(a) 2H3CHO ¾↑ CH3CHOHCH2CHO ¾↑ CH3CH = CHCHO

[Ag(NH 3 )2 ]∗ Br2
¾¾¾¾↑ CH3CH = CHCOOH ¾↑ CH3 CH CH COOH
½ ½
Br Br

NaCN H+
(b) CH3 CHO ¾¾↑ CH3 CHOHCN ¾↑ CH 3 CHOHCOOH
Lactic acid

(i) Br2 , Fe (i) CH2O Cl 2 , Fe

(c) C6 H6 ¾¾¾¾↑ C6 H5 MgBr ¾¾¾¾↑ C6 H5 CH2 OH ¾¾↑ p-Cl.C6H4CH2OH
(ii) Mg, ether (ii) H3 O+

CrO 3 , Pyridine
¾¾¾¾¾↑ p-ClC6H4CHO

Cl MgCl CH2OH CHO

Cl2 Mg, ether (i) CH2 O CrO3

(d) ¾® ¾¾¾¾® ¾ ¾ ¾ ¾+ ® ¾¾¾®
hv (ii) H3O Pyridine

Example 8 :
Perform each of the following transformations :

O CHO CHO

(a) ¾¾¾® (b) ¾¾¾®

COOH CHO
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H
O
H
(c) ¾¾®
O
O
Solution :
O Cl Cl

PCl 5 2NaNH2
(a)

O
CHO CH O O
CHO
O O O +
HOCH2CH 2OH SOCl2 H2 and Pd H3O
(b) ¾¾¾¾® ¾¾®
protection of —CHO BaSO4

COOH COOH COCl CHO CHO

O OH
NaBH4 conc. H2SO4 (i) O3
(c) CHO
heat (ii) Zn CHO

Example 9 :
Illustrate the following series of reactions by providing structure to each of the intermediate.

AlCl 3 Zn /Hg HF Zn /Hg Pd/C

C6H6 + ¾¾↑ [A] ¾¾↑ [B] ¾↑ [C] ¾¾↑ [D] ¾¾↑ [E]
O O O HCl HCl

Solution :
O O

AlCl3 Zn/Hg
+ O ¾¾® ¾¾®
HCl
HOOC
O [A]

HF Zn/Hg Pd/C
¾¾® ¾¾® ¾¾®
(—H2O) HCl
HOOC [D] [E]
[B] [C] O

Example 10 :
Give steps involved in the following conversions.
(a) 14CH OH to CH 14CH OH (b) 14CH OH to 14CH CH OH
3 3 2 3 3 2
(c) 14CH CH OH to 14CD CHO (d) 14CH CHO to 14CH CHDOH.
3 2 3 3 3
Solution :

Cu (i) CH3 MgBr

(a) 14CH OH
3
¾¾↑ H214C = O ¾¾¾¾↑ CH314CH2OH
300↓C (ii) H 3O +
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HBr Mg (i) CH2 O

(b) 14CH OH ¾↑ 14 CH Br ¾¾↑ 14 CH MgBr
¾¾¾↑ 14 CH CH OH
3 3 3 3 2
ether (ii) H 3 O+

Cu D 2 O, OD, (trace)
(c) 14CH CH OH
3 2 ¾↑ 14CH
3CHO ¾¾¾¾¾¾↑ 14CD
3CHO
D 2 /Pt or H2 O
(d) 14CH CHO
3 ¾¾¾↑ 14 CH CHDOD
3 ¾↑ 14CH CHDOH.
3
LiAlD 4

Example 11 :
How will you carry out following transformations ?

O O
(a) to (b) CHO to
O O O Ph Ph

+
H
(c)
H2O
CHO OH
OH

Solution :
The sterically unhindered keto group in (a) and the more reactive aldehyde group in (b) are more easily effected.

HSCH2CH2SH Raney + HS SH
(a)
Ni
O O OS S O

O O O
S
(b) CHO HSCH2CH2SH
¾ ¾¾ ¾ ¾ ® S ¾¾®
Ph Ph Ph

+
H 2 HO
(c) H ¾® H ¾ ¾® H ¾¾ ®
+
(—H )
O OH OH OH
+ + OH

Example 12 :
Write down the steps involved in the following reactions, each involves aldol condensation.
O
O
COOH ¾¾®
(a) ¾¾® (b) H OH
H

OH OH
O OH O

(c) ¾¾® (d) ¾¾®

H OH H

OH OH
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Solution :
O
–
(i) OH CHO (i) CH3CHO
(a) 2 H ¾(¾ ¾¾¾®
ii ) (—H O)
¾¾¾¾¾®
(ii) —H2O
2

CHO mild oxidation COOH

¾ ¾ ¾ ¾ ¾+®
[Ag(NH3 )2]
Sorbic acid ( food preservative)

O OH
–
OH CHO heat
(b) 2 H ¾¾® ¾¾¾®
(—H2O)

CHO H2/Pt
¾¾¾®
OH

2-Ethyl-1-hexanol

OH
OH
– H2/Pt
CHO OH CHO ¾ ¾ ¾ ®
(c) 2 ¾¾® OH

2-Ethyl-1, 3-hexanediol
(an insect repellant )

H CH2OH CH2OH
Ca(OH) 2 CH2O –
(d) H—C—CH = O + 3CH2 = O ¾ ¾ ¾ ¾ ¾ ¾ ¾ ® HOCH2—C—CHO ¾ ¾ –® HOCH2—C—CH2OH + HCOO
(aldol condensation) OH

H CH2OH CH2OH
Acetaldehyde Pentaerythritol (a humectant )

Example 13 :
Give steps involved in the following conversion.

O
OH CH3
OH
H2SO4
——C—CH3 ¾¾¾® C6H5

C6H5

Solution :

OH OH O
OH
OH + OH +
CH3 —H+ CH3 CH3
H + ring : CH2
——C—CH3 ¾ ¾ ® ——C—CH3 C6H5 ¾ ¾ ® C6H5 C6H5
(—H2O) shift
C6H5 C6H5 (Enol) (Keto)
3° Carbocation
(conjugated with Ar—)
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Example 14 :
Identify the final product formed in each case and explain its formation.

(i) NaNH 2 OH H
+
(a) CH3COCH3 + CH º CH ¾¾¾¾® (b) (CH 3) 2C ¾®
(ii) H + CH2OH

Me 3 COK CN -
(c) O + CH2ClCOOCH2CH3 ¾¾¾® (d) + NH3 ¾®
O

Solution :

HC º CH
¾¾®

NaNH2

– –
CH3 : C º CH CH3 O H
+ CH3 OH
(a) C=O ¾¾¾® C ¾® C
CH3 CH3 C º CH CH3 C º CH

+ +
OH H O H2
(b) (CH3)2 C ¾ ® (CH3)2 C ¾¾¾®
CH2OH CH2OH (—H2O)

3° alcohol is more basic than 1°

+ —H + tautomerization
(CH3)2 CCH 2 OH ¾¾® [CH3)2C = CHOH] ¾¾¾¾¾¾® (CH3)2CHCHO

Me3 CO - –
(c) CH2ClCOOCH2CH3 ¾¾¾® C HClCOOCH 2 CH 3

Cl
–
O O CHCOOC2H5 O—–CHCOOC2H5
–
CHClCOOC2H5
¾¾¾¾¾¾® ¾ ¾ ¾– ®
(—Cl )

CN CN
–
CN H2O
+ NH3 ¾ ¾ ® ¾¾® ¾¾®
(d)
O NH NH NH2
–

Example 15 :
Predict the product and explain its formation in each of the following reactions.

O O
– –
OH OH
(a) + CH2 = CHCN ¾ ¾® (b) + CH3CH2NO2 ¾ ¾ ®
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Solution :
O O O – O

:
– – CH2CHCN
OH : CH2 = CHCN CH2CH2CN
¾¾® ¾¾¾¾¾¾® H2O
(a) ¾ ¾® –
(CN is —I group) + OH

CH3 CH3
O OH CH C
H NO2
– NO2
OH
(b) + H—C—NO2 ¾ ¾ ® ¾ ¾®
CH3

Example 16 :
Can you suggest a proper mechanism for the following reaction ?

H+
2C6H6 + (CH3)2CO ¾® (C6H5)2C(CH3)2.
Solution :

CH3
OH
+
O OH C—CH3 + C—CH3 C—C6H5
+ H C6H6
H C6H6 ¾ ¾® ¾¾®
CH3—C—CH3 CH3—C—CH3 ¾ ¾ ® CH3 CH3
+ CH3 (—H2O)
An electrophile Another electrophile

Example 17 :
Semicarbazide (1 mol) is added to a mixture of cyclohexanone (1 mol) and benzaldehyde (1 mol). If the product
is isolated immediately, it consists almost entirely of the semicarbazone of cyclohexanone, if the product is
isolated after several hours, it consists almost entirely of the semicarbazone of benzaldehyde. Explain.
Solution :
Semicarbazone formation is reversible. Cyclohexanone reacts more rapidly because its C = O group is not sterically
hindered (its R groups are tied back into a ring), but benzaldehyde gives the more stable product,
C6H5CH = NNHCONH2, because of conjugation. Hence, initially the rate controlled product (cyclohexanone
semicarbazone) is formed ; later, after equilibrium is established the equilibrium controlled product (i.e. the more
stable benzaldehyde semicarbazone) is formed.

Example 18 :
An organic compound of the formula C5H8O2 reduces Tollen’s reagent and also responds iodoform test. It reacts
with hydroxylamine hydrochloride to form a dioxime and can be reduced to n-pentane. Deduce the structure of
the compound.
Solution :
Positive test with Tollen’s reagent indicates the presence of —CHO group, while positive iodoform test indicates the
presence of —COCH3 grouping. Two carbonyl groups is also indicated by the formation of dioxime. Reduction of
the compound to n-pentane indicates the presence of 5 carbon atoms in a continuous chain. Hence the compound
should be CH3— C CH2CH2CHO.
||
O
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Example 19 :
Compound X, C9H10O, is inert to Br2 in CCl4. Vigorous oxidation with hot alkaline permanganate yields benzoic
acid. X gives a precipitate with semicarbazide hydrochloride and with 2, 4-dinitrophenylhydrazine (DNPH). Write
all possible structures for X. How can these isomers be distinguished by using simple chemical tests ?
Solution :
Formation of benzoic acid, on oxidation of the compound X, indicates that X is having only one side chain. The
formula reveals five degree of unsaturation, four for the benzene ring indicated by the formation of benzoic acid and
hence fifth must be present in the side chain. The side unsaturation must be due to C = O group, indicated by
reaction with DNPH. Thus the possible structures for the compound X are

CH 3
½
C6 H 5 COCH 2 CH 3 C6 H 5 CH 2 COCH 3 C 6 H 5 CH 2 CH 2 CHO C 6 H 5 CHCHO
I II III IV
Difference between I, II, III and IV. Aldehydes III and IV undergo oxidation by cold KMnO4 and CrO3 in H2SO4;
while compound II undergoes iodoform reaction.

Example 20 :
The Grignard reagent of an alkyl halide (I) reacts with propanal to give a secondary alcohol (II). II is converted into
another alkyl halide (III), Grignard reagent of (III) is hydrolyzed to form an alkane (IV). Compound IV can be
produced by coupling alkyl halide (I). Establish the structure of I and explain the reactions involved.
Solution :
Let us translate the given description into chemical equations.
R
Mg (i) CH 3CH 2 CHO HBr ½
RBr ¾¾® RMgBr ¾¾¾¾¾¾® CH 3 CH 2 CH(OH)R ¾® CH3CH2CH Br
I ether (ii) H 3 O+ II
III

R
½
Mg, ether H 2O
¾¾¾¾® CH3CH2 CH MgBr ¾® CH3CH2CH2R
IV
Since IV is formed by coupling of I, it must be symmetrical, i.e. R should be CH3CH2CH2—. Hence compound
I is CH3CH2CH2Br and thus the various reactions can be written as below.
CH 2 CH3
Mg, ether (i) CH 3CH2 CHO ½
CH 3 CH 2 CH 2 Br ¾¾¾® CH 3 CH 2 CH 2 MgBr ¾¾¾¾¾¾® CH3CH2CH2 CHOH
I II (ii) H 3O+

CH 2 CH3 CH 2 CH 3 CH2 CH3

HBr
½ Mg, ether ½ ½ Na
¾® CH3CH2CH2CHBr ¾¾¾® CH3CH2CH2 CHMgBr ¾¾®HOH
CH3CH2CH2 CH 2 ¬¾¾¾ 2BrCH 2 CH2 CH3
(coupling) I
III

Example 21 :
Glycerol and ethanal are treated in equivalent amounts. Predict the number of isomeric acetals formed.

CH 2 OHCHOHCH 2 OH + CH 3 CHO ¾¾
®
Solution :
Cyclic acetal may be formed by the reaction of CH3CHO (a) with the 1- and 2- OH groups, and (b) with 1- and 3- OH
groups. The former possibility creates two chiral centers, hence two pairs of enantiomers will be formed, one pair is the
cis- and the other is trans.
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O H O
OH CH3
CH2 C CH2
CH2 H H H C
+
+ O=C C CH3 C H
CH OH CH3 O O
HOH2C HOH2C
CH2OH cis trans

Reaction of CH3CHO with 1- and 3- OH groups will give cis- and trans- isomers, none of which is chiral. These
isomers are diastereomers.

OH
CH2
H O H O CH3
H H
CHOH + O = C +
OH CH3 OH H
CH3 O O
CH2
cis trans
OH

Thus, on the whole six isomers will be formed.

Example 22 :
The three isomeric dioxanes; 1,2-dioxane, 1,3-dioxane and 1,4-dioxane; behave differently. One of these acts
like an ether and is used as an excellent solvent for Grignard reactions, the other isomer when heated explodes,
and the third quickly hydrolyzes in dil. acid. Predict which one is which, and explain the difference.
Solution :
O O O
O
O
O
1,2-Dioxane, 1,3-Dioxane, 1,4-Dioxane,
I II III

The isomer I has an peroxide linkage (–O–O–) which decomposes on heating to give radicals. In the presence of
organic compounds, radical reactions can be explosive. The isomer II behaves like an acetal which hydrolyzes in
dil. acid to alcohol and HCHO, while the III isomer behaves like a simple ether, the two oxygens are far enough apart
to act independently.

Example 23 :
Acetone, when dissolved in water having labelled oxygen (O18) gives CH3CO18CH3, and this conversion is catalyzed
by traces of strong acids and strong bases. Devise a mechanism for this.
Solution :
Acid catalyzed reaction :
+
O +
OH 18
OH +
OH
|| H || H2 O | –H |
CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3
+ 18 +
–H –H2O |+ H |
18 OH 18 OH
2

+ OH
2 +
+
H | –H2O + –H
CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3
| +
+ | || H ||
–H +H2O
.. - H
18 OH :O 18 OH 18 O
+
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Base-catalyzed reaction :
– 18 18 –
OH + H2O H2O + OH

O O- OH
|| | H2O |
CH 3 - C - CH 3 + 18
OH - CH 3 - C - CH3 CH 3 - C - CH 3
| – |
18 OH OH 18 OH

–
OH –
OH | –OH
CH 3 - C - CH 3 CH 3 - C - CH3
| – ||
H2O OH
18 O
- 18 O

Example 24 :
Bisphenol A, an important constituent of many polymers like polyurethanes, polycarbamates, and epoxy resins, is
synthesized from phenol and acetone in presence of HCl. Propose a mechanism for this reaction.

CH3
HCl
2HO + (CH3)2C = O 2HO C OH

CH3
Bisphenol A

Solution :

CH3
.. HO
HCl + + ..
(CH 3 )2 C = O : ¾¾¾ ® (CH3 )2 C = O C – OH
.. H ¬¾® (CH 3 )2 C - O
..
H HO
+ H CH3

CH3 CH3
–
Cl HCl +
HO C – OH – HO C
  (–Cl )
CH3 CH3

OH CH3 CH3
–
Cl
HO C OH HO C OH
H
CH3 + CH3
Bisphenol A

Example 25 :
H
O + OH
N(CH3)2 H3O +
O + (CH ) NH
3 2 2
H
(a) Propose a mechanism for the above hydrolysis of aminoacetals.
(b) Although aminoacetals are easily and quickly hydrolyzed by dilute acids, the nucleosides (having an
aminoacetal functional group) which are building blocks of DNA are not easily hydrolysed. Explain.
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Solution :
H ..
O .. O O
NMe2 + NMe2 ..
H3O + +
(a)
Resonance stabilized
carbocation

H
.. H .. +
O
.. + O
.. + O
H2 O O–H –H OH H O–H
+

H H
H
O .. O H +. . O H
O H2O
+ .. – H O–H O HO CHO

(b) In the nucleosides the lone pair of electrons on nitrogen (forming a part of aminoacetal functional group) is
involved in aromatic sextet, hence not easily available for protonation with dilute acids. Protonation may
occur with extremely strong acids.

Example 26 :
Complete the following by supplying structures to compounds A and B

cold dil. HNO (i) OH - OH

C6 H 5 CH = CHC6 H5 ¾ ¾ ¾ ¾® [A] ¾ ¾ ¾3¾
® [B] ¾ ¾ ¾ ¾® (C6 H 5 )2 C
KMnO 4 + COOH
(ii) H

Propose mechanism for the conversion of compound (B) to the final product.
Solution :
OH OH O O
| | || ||
C6 H 5 CH - CHC6 H 5 C6 H 5 - C - C - C6 H5
(A) (B)

–
O O O O O- O
|| ||
OH - ||
benzilic
| | ||
H+ OH
C6 H 5 - C - C - C6 H 5 ¾ ¾ ¾® C6 H5 - C - C - OH ¾ ¾ ¾ ¾ ¾® C6 H 5 - C - C - OH ¾ ¾¾
® (C6 H 5 )2 C
(B), Benzil | acid | COOH
C6 H5 rearrangement C6H5
Benzilic acid

Example 27 :
Identify compounds A, B, C and D through the structure of the compound Z.

(i) BuLi
S S [ ] [B]
(ii) A
Hg

3
O

2S

CH3
3)
2+
H3

(i)

H
O
,

(C
+

OH OH
)
(ii

CH3 (i) C
Z
(i) D
+ +
(ii) H3O (ii) H3O CH3

[E] [F] O
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Solution :
The structure of compound Z can be established with the help of the known structure of the compounds E and F with
the help of following facts.
(a) Both are 3° alcohols and formed by identical reaction which seems to be Grignard reagent. Further both E and F
have CH3CH2CH2CH2– group as common, so the compound Z can be a Grignard reagent or a ketone with
n-butyl group as one alkyl group.
(b) Further the formation of Z from A and B suggests that Z is a ketone rather than the Grignard reagent.
Thus the compound Z is hexa-2-one which explains all reactions.

MgBr
OH
MgBr
CH3 CH3
(i) C (i) O
D
O
+ +
(i) H3O (i) H3 O
O O
E Z F
Formation of Z from A and B separately :
2+ R
BuLi n–C4H9Br Hg (i) O3
S S S S (A) S S H3O
+ (ii) (CH3)2S R
– O
H CH3 n-C4H9 CH3 Z (B)
CH3

Example 28 :
Give steps involved in each of the following conversions.
CH=CHCH3 CH2CH2NH2 O OH

(a) (b) +

OCH3 OCH3 O OH
Anethole Tyramine

Solution :

CH=CHCH3 CHO CH=CHNO2 CH2 CH2NH2 CH2CH2NH2

(i) O3, Zn CH3NO2 H2 / Ni (i) HI, heat

(a) (ii) CH3COOH – (ii) neutralize
OH

OCH3 OCH3 OCH3 OCH3 OH

O O O OH

Diels-Alder NaBH4
(b) + reaction (Diels-Alder
reaction)
O O O OH
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EXERCISE 14.1 (MCQ - ONE option correct)

7. An organic compound A of the molecular formula C5H10Cl2 is
1. has its IUPAC name as hydrolyzed to compund B, C5H10O which gives an oxime with
hydroxylamine and yellow precipitate with a mixture of iodine
and sodium hydroxide. The compound A should be
(a) divinyl ketone (b) 1, 4-pentdien-3-one (c)
1, 3-penten-2-one (d) 1, 4-pentandione-3. (a) CH3CH2CCl2CH2CH3
2. In the following reaction, the compound A is (b) CH3CH2CH2CCl2CH3
H 2SO 4 , HgSO 4 (c) CH3CH2CH2CH2CHCl2
[A] ¾¾¾¾¾® CH3CH2COCH3 (d) CH3CH2CH2CHClCH2Cl.
(a) HC º CCH2CH3 (b) CH3C º CCH3
8. Identify the nature of the reagent in the following reaction.
(c) Either of the two (d) CH3CH2CH = CH2
?
Hg 2+ / H + C6H5CH = C(CH3)COCH3 ¾® C 6H5CH = C(CH3)COOH
3. C6H5C º CCH3 ¾¾¾® A. Here A is
(a) alk. KMnO4 (b) conc. HNO3
O C6H5 (c) NaOI, H+ (d) any of the three.
(a) C6H5 (b)
O 9. Identify the compound X in the following reaction.
OH –

OH C6H5COCHO ¾® X
(c) C6H5 (d) OH (a) C6H5COCH2OH (b) C6H5CHOHCH2OH
(c) C6H5CHOHCOO – (d) C6H5COO– + CH3OH.
HCl
4. Carbonyl compounds show two types of important properties : 10. CH3CHO + H2O18 ¾® Acetaldehyde. The structure of the
nucleophilic addition and acidity of a-hydrogen atoms. Which
product acetaldehyde is
factor is most useful in explaining these two ?
(a) Presence of carbon-oxygen double bond (a) CH3CHO (b) CH3CHO18
(b) Resonance in carbonyl group (c) A mixture of (a) & (b) (d) Reaction is not possible.
(c) Ability of oxygen to accommodate negative charge 11. Observe the following two reactions, here the products (A) and
(d) All are equally important. (B) are
5. Identify the end product in the following series of reactions (i) CH3CHO + LiAlD4 ¾¾® [A]
AlCl 3 Mg
Pt
C6H6 + CH3CH2COCl ¾¾® [B] ¾¾® End product (ii) CH3CHO + D2 ¾® [B]
ether
(a) C6H5COCH2CH2Mg (a) CH3CD2OD (b) CH3CHDOD
(c) CH3CH2OD (d) CH3CHDOH.
OH

(b) C6H5— C CH2 CH3

H 2O, H +
12. Identify P in the reaction, ¾¾¾® P
CH 2CH 3

C6 H 5 C6 H5 (a) HOCH2CH2CH2CH2CH2CH2OH + C2H5OH

(b) OHC.CH2CH2CH2CH2CHO
(c) CH3CH2— C C CH2 CH3 (c) HOCH2CH2CH2CH2CHO + C2H5OH
(d) No reaction.
OH OH
13. Identify the product, if any, in the following chemical equation
OC 2 H5 KOD
+ 4D2O ¾¾®
reflux
(d) C6H5— C CH2 CH3

OC 2 H5
6. Identify the nature of the compound (Z).
(a) (b)
CrO3/Pyridino
CH 3 CH 2 CH 2 CH 2 OH ¾¾¾¾¾® [X]
n-Butyl alcohol

(CH 3 )2 CHCH 2 MgBr CrO 3

¾¾¾¾¾¾¾® [Y] ¾¾¾® [Z]
Pyridine

(a) 2CH3CH2CH2COOH
(c) (d) No reaction takes place.
(b) CH3CH2CH2COOH + (CH3)2CHCOOH
(c) CH3CH2CH2COCH2CH(CH3)2
(d) CH3CH2CH2CHOHCH2CH(CH3)2.
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14. The most likely acid-catalysed aldol condensation products of
each of the two aldehydes I and II will respectively be
16. is formed by intramolecular aldol condensation
CHO (I) and (II)
of

(a) (b)
(a) and

(c) (d)

(b) and

(i) NaOH / 100° C

17. ¾¾¾¾¾® Major product is
+
(ii) H /H 2O

(c) and

(a)
(d) and

C 2 H 5 MgCl
Identify A : (b)
15. ¾¾¾® A

(a)

(c)

(b)

(c)
(d)

(d)
18. Which of the following will undergo hydration most readily ?
(a) CH3COCH3 (b) CH3COCCl3
(c) CCl3COCCl3 (d) CF3COCF3.
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19. In the following reactions [A] and [B] respectively are 24. The enol form of acetone, after treatment with D2O gives
OD O
| ||
(a) CH3— C = CH 2 (b) CD3— C — CD3

OH OD
½ ½
(c) CH2 = C — CH2D (d) CD2 = C — CD3
25. How many a hydrogens are present in benzyl methyl ketone,
(a) 3 (b) 4 (c) 5 (d) No
26. In the Cannizzaro reaction, given below,
(a) and
OH -
2C 6H5CHO ¾® C 6H5CH2OH + C6H5COO–
the slowest step is
(a) the attack of OH– at the carbonyl group
(b) the transfer of hydride to the carbonyl group
(b) and (c) the abstraction of proton from the carboxylic acid
(d) the deprotonation of C6H5CH2OH.
27. Among the following compounds, which will react with acetone
to give product containing >C = N –.
(a) C6H5NHCOCH3 (b) (CH3)3N
(c) C6H5NHC 6H5 (d) C6H5NHNH2.
(c) and H+
28. C6H5CH(OH)CH(OH)CH3 ¾® [A]. Here [A] is
(a) C6H5CH = CHCH3 (b) C6H5CH = C(OH)CH3
(c) C6H5COCH2CH3 (d) C6H5CH2COCH3.
(i) Mg, ether CH 3 CH 2 COCl
29. C6H11Cl ¾¾¾¾¾¾® [A] ¾¾¾¾¾® [B].
(d) and (ii) Li, (iii) CuLi

The compund B is
20. Acetic acid on heating gives OH
(a) methane (b) ethane
(c) methyl radical (d) ketene. (a) C6H11— C— CH2 CH3 (b) C6H11COCH2CH3
21. Which one is the best method for reducing 3-bromopropanal to
1-bromopropane ? CH 2 CH3
BrCH2CH2CHO ¾¾® BrCH2CH2CH3
(c) C6H11CH2COCH3 (d) C6H11CH2CH2CHO.
(a) Wolf-Kishner reduction
(b) Clemmensen reduction 30. Which of the following compunds is oxidised to prepare methyl
(c) Either of the two ethyl ketone ?
(d) None of the two. (a) 2-Propanol (b) 1-Butanol
22. The appropriate reagent for the following transformation (c) 2-Butanol (d) tert-Butyl alcohol.
31. The product formed by the reaction of chlorine with C 6H5CHO
in the absence of catalyst is
(a) chlorobenzene (b) benzyl chloride
(c) benzoyl chloride (d) o-chlorobenzaldehyde.
is
32. Which alkene is formed from the following ylide carbonyl pair ?
CH3CH2CH2CH = PPh3 + 2-Butanone
(a) 3-Methyl-3-heptene (b) 4-Methyl-3-heptene (c)
(a) Zn (Hg), HCl (b) NH2NH2,OH– 5-Methyl-3-heptene (d) 1-Methyl-5-heptene.
(c) H2/Ni (d) NaBH4. 33. An organic compound A has the molecular formula C3H6O. It
23. Aldehydes when treated with alcohols form first hemiacetals undergoes iodoform test. When saturated with HCl it gives B of
and then acetals in the following way molecular formula C9H14O ; A and B respectively are
(a) propanal and mesitylene
H H
H+ ½
(b) propanone and mesityl oxide
½ H+
R¢— C = O + ROH ¾¾® R¢— C — OR ¾¾® (c) propanone and 2, 6-dimethyl-2, 5-heptadien-4-one
(- H 2O) (d) propane and mesitylene oxide.
½
OH 34. Compound A (molecular formula C3H8O) is treated with acidified
A hemiacetal dichromate to form a product B (molecular formulae C3H6O). B
forms a shining silver mirror on warming with ammonical silver
H H H nitrate.B when treated with an aqueous solution of
½+ ½ + (i) ROH ½ H2NCONHNH2HCl and sodium acetate gives a product C.
R ¢ — C— OR ¬¾ ® R ¢ — C = OR ¾¾¾® R¢— C — OR
(ii) — H + Identify the structure of C
I II ½
OR (a) CH3CH2CH = NNHCONH2
In the above reaction, which of the two cations is more stable? (b) (CH3)2C = NNHCONH2
(a) I (b) II (c) (CH3)2C = NCONHNH2
(c) Both are equally stable (d) None is stable. (d) CH3CH2CH = NCONHNH2.
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35. Identify the final product (D). 40. Which of the following forces explain the boiling point of aldehydes
AlCl 3 Zn / Hg and ketones?
C6H5CH3 + (CH2CO)2 O ¾¾® [A] ¾¾¾® (a) Hydrogen bonding (b) Vander waal
HCl
(c) Dipole-dipole attraction (d) Any other
HF (i) CH 3 MgI
[B] ¾® [C] ¾¾¾¾® [D] 41. Which of the following will give yellow precipitate with I2/NaOH?
(ii) H 3O + (a) ICH2COCH2CH3 (b) CH3COOCOCH3
(c) CH3CONH2 (d) CH3CH(OH)CH2CH3
CH3
42. Which of the following reactants on reaction with conc. NaOH
followed by acidification gives adjacent lactone as the product?

(a) (b) O

OH C
O
CH3
CH2

COOCH3 COOH
(a) (b)
(c) (d) COOH CHO
H3C COOH CHO
CH3 OH
(c) (d)
COOH CHO
36. Identify the final product [E] 43. The smallest ketone and its next homologue are reacted with NH2OH
Br2 / Fe (CH 3CO) 2 O,AlCl 3
C6H6 ¾¾¾® [A] ¾¾¾¾¾¾® [B] to form oxime
(a) Two different oximes are formed
CH 3 OH / HCl (i) Mg H3O +
(b) Three different oximes are formed
¾¾¾¾¾® [C] ¾¾¾® [D] ¾¾® [E]
(ii) D 2O (c) Two oximes formed are optically active
(d) All oximes formed are optically active
44. Cyclohexene on ozonolysis followed by reaction with zinc dust
and water gives compound E. Compound E on further treatment
(a) (b) with aqueous KOH yields compound F. Compound F is

(a) CHO (b) CHO

CO 2 H
(c) COOH (d)
CO 2 H
45. In the following reaction sequence, the correct structures of E, F
(c) (d) and G are
O O
Heat I
¾¾¾
®[E] ¾¾¾®
2
NaOH
[F] + [G]
Ph OH
37. Identify the final product D in the following reaction. *
[* implies 13C labelled carbon)
C 6 H 6 , HF H 2 / Pt NBS alc. KOH
¾¾¾¾® [A] ¾¾® [B] ¾¾® [C] ¾¾¾® [D]. O O
E= * F= * G = CHI3
(a)
– +
Ph CH3 Ph O Na

O O
(a) (b)
E= F= * G = CHI3
(b) – +
*
(c) Both (d) None. Ph CH3 Ph O Na
38. Which compound(s) does(do) not undergo Cannizzaro
condensation? O O
(a) Methanal (b) Trichloroacetaldehyde *
(c) Benzaldehyde (d) Ethanal E= F= G = CHI3
(c)
39. Treatment of propionaldehyde with dil. NaOH solution gives * – +
Ph CH3 Ph O Na
(a) CH 3 CH 2 COOCH 2 CH 2 CH 3
O O
(b) CH 3 CH 2 CH(OH).CH(CH 3 ).CHO
*
E= F= G = CH3 I
(c) CH 3 CH 2 CHOHCH 2 CH 2 CHO (d)
* – +
Ph CH3 Ph O Na
(d) CH 3 CH 2 COCH 2 CH 2 CHO
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721
To distinguish between the above isomeric hydrocarbons
O
molecules, which will work best ?
(a) Bromine water test
46. + Ph 2P = CH 2 ¾¾
® (X) (b) O3/H2O, heating and passing evolved gas through lime
water
Product (X) is (c) O3/H2O, D, I2/NaOH
(d) Tollen’s test
PPh3 CH2 51. Which of the following sequence of reagents can best be utilized
for the given transformation ?
(a) (b) O O
R– C R– C
H D
(a) Cl2, AcOH; D2O; LiAlH4/H2O
(c) (d)
(b) D2O/D3O+, Cl2, AcOH; NaBH4/H2O

– H 2 C - SH
HgSO 4 dil.OH
¾¾¾¾® (B) (c) | , base; D2O and then HgCl2/CdCO3 – H2O
47. HC º CH ¾¾¾¾ ® (A)
H 2SO4 5°C H 2 C - SH
Give the IUPAC name of “B” is
(a) 2-butenal (b) 3-hydroxybutanal H 2 C - SH
(c) 3-formyl-2-propanol (d) 4-oxo-2-propanol (d) Base, | , HgCl2/CdCO3 – H2O and then D2O
H 2 C - SH
O 52. In a Cannizzaro reaction, the intermediate that will be the best
hydride donor is
C – Cl
H
(i) CdMe 2
¾¾¾¾¾ ® – –
48. (ii) H 2O O O
(a) (b) –
OH O

CHO
H H
Product is – –
O O
(c) – (d) –
O O O
OH H3CO O2N
53. Which will form(s) stable gem-diol ?
(a) (b)
I. Ph - C - C - C - Ph II. CCl3CHO
P P P
O O O
OH OH
O
O
OH C
III. O IV. Ph - C - C - Ph
C P P
(c) (d) O O
O
O O O
P
O V. H - C- H
(a) I, II, III, V only (b) I, II, III, IV only
Mg/Hg H3 /PO 4 (c) II, III, IV only (d) II, III,
49. ¾¾¾¾® A ¾¾¾¾¾ ®B
H 2O D
54. In Cannizaro reaction which species is best hydride donor (in
O conc. alkaline medium)
B is
O O-
(a) Bicyclo-[4, 4, 0] deca-1, 6-diene P |
(b) Cyclodecanone (a) H - C - O- (b) H - C -H
(c) Spiro-[4, 5]-decan-6-one |
(d) Bicyclo-[4, 4, 0] deca-1, 5-diene OH

O- O-
| |
(c) H -C-H (d) H 5 C6 - C - H
50. | |
O- O-
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55. The Keq. value in HCN addition to the following aldehydes are in – –
CHO COO COO
the order : 61. 2 OH– +
–
COOH CH2OH COO
O The above reaction can said be to an example of
(a) intramolecular Cannizzaro reaction
O C H CHO (b) intermolecular Cannizzaro reaction
(c) crossed Cannizzaro reaction
H (d) Tischenko reaction
62. Which of the following complex hydride is a stronger reducing
H3CO agent ?
(I) (II)
CHO (a) Li+ [AlH 4 ]- (b) Li + [Al(OCMe 3 )3 H]-
(III)
(c) Al(CH2 CHMe 2 )2 H (d) All are equal
(a) I > II > III (b) III > II > I O
O
(c) III > I > II (d) II < I > III –
56. The major product obtained in the reaction : 63. H OH

O CH 3 O
P | OD -
H 5 C6 - C - CH - CH 3 + D 2 O ¾¾¾¾¾¾ ® The above reaction involves
room temp.
O O
is –
H H
(a) (b)
O CD 3 O CD 3 –
P | P | O O
(a) H 5C6 - C - CHCH 3 (b) H 5 C6 - C - CD - CD 3 O O
H H
O –
(c) (d)
P CH2 –
(c) H 5 C6 - C - CD - CH 3 (d) None of these O O
| Ca(OH)
CH 3 64. CH 3 CHO + 4HCHO ¾¾¾¾¾
2®

1
C(CH 2OH)4 + (HCOO)2 Ca
2
–
57. The reacion OH is an example of the above reaction is an example of
O O (a) aldol condensation (b) Cannizzaro reaction
CHO (c) both (d) none
65. Which of the following can’t be prepared by the direct of
(a) oxidation reaction (b) reduction Reimer –Tiemann reaction ?
(c) both (d) aldol condensation
OHC
58. A new carbon - carbon bond is formed in
(a) (b)
Aldol condensation Kolbe's reaction
I II N CHO N
| |
Reimer-Tiemann reaction Wurtz-Fittig reaction H
III H
IV
(a) I, III (b) II, III OH
(c) I, III, IV (d) All the four COOH
59. The correct stability order of the following three quinones is (c) (d)
S CHO
O O 66. Cannizzaro reaction between formaldehyde molecules involves
O the formation of
O O -
OH O
| |
O (a) H- C -H (b) H - C -H
|- |-
I II III O O
(a) I > III > II (b) I = III > II
(c) Both (a) and (b) (d) none
(c) I = II > III (d) III > I > II
60. Ninhydrin has three keto groups, which of the keto group is OH -
67. O+ ¾¾¾®
O
expected to be hydrated most easily?
O O
3
2
O
1
O This reaction is an example of
(a) 2 (b) 3 (a) Aldol condensation (b) Cannizzaro reaction
(c) 1 (d) all equal (c) Claisen condensation (d) Wittig reaction
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EXERCISE 14.2
7. Predict the nature of products
DIRECTIONS for Q. 1 to Q. 50 : Multiple choice questions with
one or more than one correct option(s).

1. Which of the following statement is true regarding the following

chemical reaction ?
HCN
CH3CHO ¾¾® CH3CHOHCN
(a) The product on hydrolysis gives a mixture of two COO – K
+
COO – K
+

compounds :
(b) The product is a mixture of two compounds which can be
separated by fractional distillation. (a) (b)
(c) The product is a mixture of two compounds which can’t
be separated by fractional distillation. OH Cl
(d) The product on hydrolysis gives a single compound.
2. One mole of C6H5COCH2CH3 is treated with one mole of Br2 in CH 2OH CH 2OH
basic solution, the product(s) formed is (are)
(a) 1 mole of C6H5COCBr2CH3
(b) 1 mole of C6H5COCHBrCH2Br (c) (d)
(c) 0.5 mole of C6H5COCBr2CH3
H Cl
(d) 0.5 mole of unreacted C6H5COCH2CH3.
3. Pentaerythritol, an important industrial chemical, is prepared 8. Which of the following can be used for the preparation of
by the following reaction chloroform?
(a) C6H5CHCl2 (b) CH3CHO
CH2 OH (c) CD3COCH3 (d) CCl3CHO
½Ca[OH] 2 9. The product of acid hydrolysis of P and Q can't be distinguished
4CH2O + CH3CHO ¾¾¾® CH2OH— C — CH2OH by
½
CH2 OH
Pentaerythritol (P) (Q)
This reaction involves
(a) Cannizzaro reaction (b) aldol condensation
(c) Crossed Cannizzaro (d) crossed aldol condensation (a) Lucas reagent (b) 2, 4-DNP
4. A mixture of cinnamaldehyde and crotonaldehyde is treated (c) Fehling solution (d) NaHSO3.
with concentrated alkali, 10. Acetaldehyde is obtained in the reactions
b a g b a OH – 1. O
C6H5 CH = CHCHO + CH 3CH = CHCHO ¾¾® (a) CH 2 = CH - CH 2 - CH = CH 2 ¾¾ ¾3¾®
2. Zn , H 2O
which statement is not true about the above reaction ?
(a) Aldol condensation takes place and a-carbon atom of 1. O 3
crotonaldehyde provides the carbanion, (b) CH3 CH 2. Zn, H2O
(b) Aldol condensation takes place and b-carbon atom of
crotonaldehyde provides the carbanion. HgSO
(c) HC º CH + H 2O ¾¾ ¾¾
4®
(c) Aldol condensation takes place and g-carbon atom of H 2SO4
crotonaldehyde provides the carbanion. Pd - BaSO 4
(d) CH 3COCl + H 2 O ¾¾ ¾¾¾ ®
(d) Aldol condensation takes place and a-carbon atom of
cinnamic aldehyde provides the carbanion. 11. Which of the following statements are correct about a carbonyl
5. Which of the following undergoes Cannizzaro reaction ? group?
(a) (CH3)3C.CHO (b) (CH3)3CCDO (a) The carbonyl carbon is sp2–hybridized
(c) C6H5CH2Cl (d) CH3CHO (b) The carbonyl carbon is sp3–hybridized
6. Each of the following two ketones is treated with a base (KOH) (c) The three groups attached to the carbonyl carbon lie in
different planes
O CH3
|| | OH -
(d) The three groups attached to the carbonyl carbon lie in the
(+) – C6H5— C — CH — C6 H5 ¾¾® PI ; same plane
I
12. Phosphorus pentachloride reacts with
(a) alcohols (b) ketones
O CH 3 (c) ethers (d) amines
|| | OH -
13. Which of the following aldehydes undergo aldol condensation?
(+) – C6H5— C — C — C6 H5 ¾¾® PII
½ (a) CH3CHO (b) C6H5CHO
C2 H5 (c) C6H5CH2CHO (d) p–ClC6H4CHO
14. Which of the following do not undergo base catalysed aldol
II
condensation?
Which of the following statement is false regarding above reactions? (a) Benzaldehyde
(a) Both PI as well as PII are racemic mixtures (b) 2,2, dimethyl propionaldehyde
(b) Both PI as well as PII are optically pure enantiomers (c) 2-methyl propionaldehyde
(c) PI is optically pure while PII is a racemic mixture (d) p-methylbenzaldehyde
(d) PI is a racemic mixture while PII is optically pure.
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15. Which of the following statements are correct about the
C = O bond? 28. O ; This change can be carried out using:
(a) It is made up of one p-bond and one s-bond
(b) It is used the sp2-hybrid orbital of carbon for its formation (a) NH2NH2, glycol/OH– (b) Sn(Hg)/conc. HCl
(c) It is planar in nature (c) P/HI (d) NH3/LiAlH4
(d) It undergoes addition reactions 29. In which cases products formed are not according to reaction?
16. Which compound(s) undergoes (undergo) aldol condensation?
(a) Acetaldehyde (b) Benzaldehyde OH + HNO3
H2SO 4
NO2
(a)
(c) Phenylacetaldehyde (d) Ethylmethyl ketone
17. Dry distillation of a mixture of calcium acetate and calcium
formate can form H2SO 4
(b) OH+ HNO3 ONO 2
(a) acetone (b) formaldehyde
(c) acetaldehyde (d) propanone
18. Which of the following are generally used for preparing derivatives (c) CH 2 = CH - CHO + LiAlH 4 ¾¾
® CH 3 CH 2 CH 2 OH
of aldehydes and ketones?
(a) Hydroxylamine hydrochloride (d) Cl + CH3 ONa O – CH 3
(b) 2,4-Dinitrophenylhydrazine
(c) Phenylhydrazine hydrochloride 30. Which of the following compounds will give haloform test?
(d) Hydrogen cyanide O
19. Base catalysed aldol condensation occurs with : ||
(a) CH 3 - C - CH 2 I (b) CH 3 - CH - CH 3
(a) propionaldehyde |
(b) benzaldehyde Cl
(c) 2-Methyl propionaldehyde (c) C CH3 (d) CH3CH2Br
(d) 2, 2-Dimethyl propionaldehyde
O
20. Which of the following compounds will give a yellow precipitate
with iodine and alkali? reaction R
(a) 2-Hydroxy propane (b) Acetophenone 31. O or reagent R ; R can be :
(c) Methyl acetate (d) Acetamide
21. Which of the following compounds will react with ethanolic KCN? (a) Wolf Kischner reduction(b) Clemmensen reduction
(a) Ethyl chloride (b) Acetyl chloride (c) (P + HI) mixture (d) Rosen mund reduction
(c) Chlorobenzene (d) Benzaldehyde 32. Cannizzaro reaction will be given by :
22. Keto-enol tautomerism is observed in
(a) CHO (b) —CHO
O O
|| ||
(a) H 5C 6 -C - H (b) H 5 C6 - C -CH3
(c) —CHO (d) CCl3CHO
O O
|| ||
(c) H 5C 6 -C -C6H5 (d) H 5 C6- C -CH 2 -CH 2 - CH 3 O
23. Which of the following are the examples of aldol condensation? ||
SeO 2
33. CH 3 - C - CH 3 ¾¾¾® A; A will :
dil. NaOH
(a) 2CH3CHO ¾¾¾¾
¾® CH3CHOHCH2CHO (a) reduce Tollens reagent (b) give iodoform test
(b) 2CH3COCH3 ¾¾¾¾
dil. NaOH
¾® (CH3)2COHCH2COCH3 (c) form dioxime (d) give Cannizzaro reaction
dil. NaOH O
(c) 2HCHO ¾¾¾¾
¾® CH3OH || conc. H 2 SO 4
dil. NaOH 34. 3CH 3 - C - CH 3 ¾¾¾¾¾¾ ®A; which is/are correct
(d) C6H5CHO + HCHO ¾¾¾¾ ¾® C6H5CH2OH
24. A new carbon-carbon bond formation is possible in statement(s) about A :
(a) A is an aromatic compound
(a) Cannizzaro reaction (b) Friedel–Crafts alkylation (b) A can be oxidised to carboxylic acid
(c) Clemmensen reduction(d) Reimer–Tiemann reaction (c) A can undergo free radical as well as electrophilic
25. Which of the following will undergo aldol condensation? substitution reaction
(a) Acetaldehyde (b) Propanaldehyde (d) A contains two carbonyl group
35. Identify the set from the following which contains the two
(c) Benzaldehyde (d) Trideuteroacetaldehyde
compounds each of which can form acetone in a single-step reaction:
26. Among the following compounds, which will react with acetone
(a) CH3CH(OH)CH3, (CH3)2C = CH2
to give a product containing > C = N –bond ?
(b) (CH3COO)2Ca, (CH3)2C = CH2
(a) C6H5NH2 (b) (CH3)3N
(c) (CH3COO)2Ca, CH3C º CH
(c) C6H5NHC6H5 (d) C6H5NHNH2.
(d) CH3C º CH, CH3C(Cl)2CH3
27. Select correct statements :
HgSO 4 /H 2 SO 4 reaction R
36. CH º CH ¾¾¾¾¾¾¾ ® B ¬¾¾¾¾ ¾A. A, B and
(a) OH and OH both give colour with reaction R are :
O
neutral FeCl3 solution ||
(b) 2-Pentanone and 3-pentanone are position isomers as well (a) CH 3 - C - Cl, CH 3 CHO, Rosenmund (Pd/BaSO4, H2)
as metamers
(c) When benzaldehyde reacts with hydroxylamine product (b) CH3COOH, LiAlH4, hydroboration oxidation
formed shows geometrical isomerism (c) CH3CN, CH3CHO, Stephen (SnCl2 / HCl)
(d) 1, 2-Dibromocyclohexane shows geometrical and optical (d) CH º CH, CH3CHO, hydroboration oxidation
isomerism
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37. Which is/are correct statement(s)? conc. NaOH
(a) In presence of conc. H2SO4, CH3CHO changes to cyclic 46. HCHO ¾¾¾¾¾¾
® MeOH + HCOONa
D
trimer-paraldehyde which is a hypnotic True about the above reaction is/are :
(b) At room temperature, HCHO forms cyclic trimer-trioxan (a) it is Cannizzaro reaction
(c) In presence of Ba(OH)2, HCHO forms hexose (b) it is redox reaction
(d) Bakelite is the polymer of HCHO and urea (c) it is a bimolecular reaction
NaOH (d) it is a disproportionation reaction
38. 3HCHO + CH 3 CHO ¾¾¾¾ ® A ; A formed can :
47. Which of the following will give yellow precipitate with
(a) reduce Tollen’s reagent NaOH/I2
(b) give Cannizzaro reaction
(c) react with Na (a) Ph - CH - Me (b) CH3CHO
|
(d) give green colour with Cr2O72– / H+
OH
39. A formed in previous question further reacts with NaOH to give:
(c) Me - C - C - OH (d) EtOH
CH2 OH P P
|
O O
(a) HOH 2 C - C - CH 2 OH by reduction
|
–
CH 2OH KMnO4/ H , D
I Y
30%H2SO4
CH 2OH 48. HO W + X
| (minor) (major)
HOH 2 C - C - COONa by oxidation O
(b) –
| KMnO4/ H , D
CH 2OH Z
II Of the 4 compounds listed above, more than one will :
(c) only I (d) only II (a) exhibit resonance due to conjugation in their structure
40. Which are correct statements : (b) show NaHCO3 test
(a) Cannizzaro reaction is proton-hydride transfer reaction (c) have a cyclic structure
(d) show 2, 4-DNPH precipitation
(b) Hofmann-degradation of acid amide involves
49. Which of the following compounds will give yellow crystals of
intramolecular migration of alkyl/aryl group from C to N
iodoform on reaction with aq. NaOH + I2 ?
(c) Fries migration is intramolecular
(d) Cannizzaro reaction is disproportionation O OH
41. m-Chlorobenzaldehyde on reaction with conc. KOH at room P |
temperature gives (a) CH 3 - C - CH 3 (b) CH 3 - C - CH 3
(a) potassium m-chlorobenzoate |
CH 3
(b) m-hydroxy benzaldehyde
(c) m-chlorobenzyl alcohol
(d) m-hydroxybenzyl alcohol Cl
42. A mixture of benzaldehyde and formaldehyde on heating with |
aqueous NaOH solution gives (c) Ph - CO - CH3 (d) CH 3 - CH - CH 3
(a) benzyl alcohol (b) sodium benzoate 50. Compound (X), molecular formula C8H8O, is water insoluble
(c) sodium formate (d) methyl alcohol and gives yellow ppt. with I2/NaOH. It reacts with H2NOH in
43. Which of the following reactants on reaction with conc. NaOH presence of NH4Cl/NH4OH to give two geometrical isomers,
followed by acidification gives following lactone as the product? which do not undergo dehydration but can go for rearrangement
O with acids. Compound (X) can be
O
C
O (a) (b) H5C6 CHO
H5C6 CH3
CH2
OH
COOCH3 COOH O
(c) (d)
(a) (b) H5C6 CH3 H3C
COOH CHO
COOH CHO
(c) (d) INSTRUCTION for Q. 51 to 82 : Read the passages given below and
COOH CHO answer the questions that follow.
44. The smallest ketone and its next homologue are reacted with
NH2OH to form oxime
PASSAGE 1
(a) Two different oximes are formed
(b) Three different oximes are formed O O
(c) Two oximes formed are optically active OH–
(d) All oximes formed are optically active CHO
45. MeCHO and PhCHO will give different type of reaction with
(a) NaOI (b) Brady’s reagent
(c) MeMgBr (d) KOH, D
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51. The reaction is an example of
(a) aldol condensation PASSAGE 3
(b) crossed aldol condensation In the following reaction sequence, product I, J and L are formed.
(c) intramolecular aldol condensation K represents a reagent.
(d) none of the three
52. How many carbanions are possible in this case ? 1.Mg / ether
1.NaBH 2.CO K
(a) 1 (b) 2 Hex - 3 - ynal ¾¾¾¾
2.PBr
4
® I ¾¾¾¾¾
2
+ ® J ¾¾®
(c) 3 (d) 4 3 3.H3O
53. Which of the functional group is acting as nucleophile ?
(a) Aldehyde (b) Ketone
(c) Either of the two (d) None of the two Cl H
Me ¾¾¾¾¾¾¾ 2
Pd/ BaSO quioline
®L
4
PASSAGE 2
The carbonyl group C = O governs the chemistry of aldehydes O
and ketones in two ways (a) : by providing a site for nucleophilic
addition, and (b) by increasing the acidity of the hydrogen atoms at- 59. The structure of the product I is –
tached to the alpha carbon.
The mobile p electrons of the carbon-oxygen double bond are (a) Me Br
pulled strongly towards oxygen, which makes carbonyl oxygen elec-
(b) Me
tron-rich and carbonyl carbon electron-deficient. Further, since carbo-
nyl group is flat, it is relatively open to attack from above or below. The Br
positive charge on the carbonyl carbon atom means that it is especially
susceptible to attack by a nucleophile. On the other hand, the negative Me
(c) Br
charge on the carbonyl oxygen atom means that nucleophilic addition
is susceptible to acid catalysis. (d) Me Br
In addition to nucleophilic addition reactions, carbonyl com-
pounds exhibit the unusual acidity of alpha-hydrogen atoms. The
60. The structures of compound J and K, respectively, are
unusual acidity of the alpha-hydrogen of carbonyl compounds is due
to its strong electron-withdrawing nature which in turn makes alpha- (a) Me COOH and SOCl2
carbon also electron-withdrawing. Hence in presence of base it easily
loses hydrogen as proton and itself converted into carbanion.
OH
54. The carbonyl carbon is more reactive toward the nucleophile
(b) and SOCl2
(a) in presence of acids Me
(b) in absence of acids O
(c) equally reactive in both cases
(d) in presence of base (c) Me
55. The yield of hydrate is maximum in COOH
(a) CH3CHO (b) HCHO
(d) Me COOH and CH3SO2Cl
(c) O2NCH2CHO (d) CH3COCH3
56. Which of the following reactions of aldehydes is due to nucle-
ophilic addition on carbonyl group as well as due to acidic nature 61. The structure of product L is
of the a-carbon atom? Me CHO
(a) Reformatsky reaction (b) Aldol condensation (a)
(c) Cannizzaro reaction (d) Wittig reaction
57. The final product obtained during aldol condensation of propanal
is reduced in two ways. (b) Me CHO
CH3 CHO
H , Pd / C
|
LiAlH (c) Me
[B] ¬¾2¾ ¾
¾¾ CH 3CH 2 CH = C CHO ¾¾¾¾
4 ® [A]

Which of the above reactions is a nucleophilic addition?

(d) Me CHO
(a) Reaction leading to [A] (b) Reaction leading to [B]
(c) Both (d) None
58. The compounds A and B in the above question are PASSAGE 4
CH3 CH3 A tertiary alcohol H upon acid catalysed dehydration gives a
| | product I. Ozonolysis of I leads to compounds J and K. Compound J
(a) CH 3CH 2 CH = C CH 2 OH, CH 3CH 2CH 2 C HCH 2 OH
upon reaction with KOH gives benzyl alcohol and compound L, whereas
CH3 CH3 K on reaction with KOH gives only M.
| |
(b) CH 3CH 2 CH = C CH 2 OH, CH 3CH 2CH 2 C HCH O O

CH3 CH3 H3 C
| | Ph
(c) CH3CH 2CH = CCH 2OH, CH 3CH 2 CH = COH M=
CH3 CH3
| | H
(d) CH 3CH 2 CH 2 C HCH 2OH, CH 3CH 2 CH 2 C HCH 2 OH Ph
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62. Compound H is formed by the reaction of
O
O
H
(c) ,
(a) + PhMgBr CHO
Ph CH3 Me Et
Me Et
O
Me O
(b) + PhCH2MgBr
CH3
Ph CH3 (d) ,
CHO
O Me Me Et
67. The structure of the product S is
(c) + PhCH2MgBr
Ph H O
O O
(a) (b)
(d) + O
Me Me
Ph H Ph MgBr Me
63. The structure of compound I is
O O
Ph CH 3 H 3C Ph Me
(a) (b) (c) (d)
H Ph H Ph
Ph Me Me
C H3 H 3C CH3
(c) (d)
H CH 2Ph Ph H PASSAGE 6
64. The structure of compounds J, K and L respecitvely, are –
(a) PhCOCH3, PhCH2COCH3 and PhCH2COO–K+
(b) PhCHO, PhCH2CHO and PhCOO–K+
(c) PhCOCH3, PhCH2CHO and CH3COO–K+
(d) PhCHO, PhCOCH3 and PhCOO–K+

PASSAGE 5
A carbonyl compound P, which gives positive iodoform test, 68. Which of the following statement is correct about P4 ?
undergoes reaction with MeMgBr followed by dehydration to give an (a) It will not give yellow/orange or red colour with 2, 4-DNP
olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which (b) It will give red colour with ceric ammonia nitrate
undergoes intramolecular aldol reaction to give predominantly S. (c) It will not give Fehling test
(d) It will give Bielstien test
1. MeMg Br 1. O 1. OH
– 69. Which of the following statement is correct abot P7 ?
P ¾¾¾¾¾
+ ® Q ¾¾¾¾
3
® R ¾¾¾® S (a) It will not give mustard oil reaction
2.H , H O 2. Zn,H O 2. D
2 2
3.H 2SO4 , Δ (b) It will not give carbylamine test or isocyanide test
(c) It will decolourize bromine water
65. The structure of the carbonyl compound P is (d) It will give base soluble product with Hinsberg reagent
Me 70. Which of the following reaction will be useful for conversion of
P3 to P4.
(a) (b)
(a) Clemmensen’s reduction
O Me O Me (b) Oppenauer oxidation
(c) Meerwin Pondorff Verely reduction
O
(d) Tischenko reaction

(c) (d) PASSAGE 7

O Et Me
66. The structures of the products Q and R, respectively, are
OH
H+ O (1) Mg(Hg)
O ¾¾¾
® P-1 ¾¾¾¾¾
3 ® P-2 ¾¾¾¾¾® P-3
D Zn/H2 O (2) H2 O
H Me
(a) Me ,
COMe
Me Me Me Me Br2/ CCl4

O P4

H 71. If methyl group is in axial position in product (P-4), then what is

(b) ,
the position of Br atoms on C1 and C2 respectively.
Me CHO (a) axial, equatorial (b) equatorial, axial
Me
Me Me (c) axial, axial (d) equatorial, equatorial
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72. Correct sequence of reagents to convert P-4 into P-3.
(a) (i) Zn, D; (ii) dil. H2SO4 PASSAGE 9
An optically active organic compound ‘A’ has molecular formula
(b) (i) Na/Et2O; (ii) B2H6; (iii) NaOH, H2O2
C11H16O2 and it neither forms salt with NaOH nor decolourises
(c) (i) Mg (excess)/Et2O; (ii) O2 (excess); (iii) NH4Cl (excess) bromine water, but evolves a gas on treatment with CH3MgBr.
(d) (i) Mg (1 eq.); (ii) Hg(OAc)2 + H2O; (iii) NaBH4 A on treatment with HI gives another optically active compound
73. Which of the following will produce same visual change as P-1 B(C9H10I2). B on treatment with aqueous KOH yields another
with Br2 water ? optically active compound C(C9H12O2). C on treatment with
PCC yields D(C9H8O2) which gives positive iodoform test as
well as positive Tollen’s test. D is optically inactive and on
(a) (b) treatment with Cl 2/AlCl 3 gives one and only one possible
monochloro derivative E(C9H7O2Cl)
Based on the above information answer the fllowing questions :
(c) (d) None of these
77. The compound (A) is
H3C
PASSAGE 8 H3C
(a) CH CH2OH
Citral or 3, 7-dimethyl-2, 6-octadienal is a mixture of a pair of
terpenoids having molecular formula C 10H 16O. The two OCH3
compounds are double bond isomers. The E-isomer is known as
geranial (citral – a). The Z-isomer is known as neral H3C
(citral – b), whereas geranial has a strong lemon odour, neral
H3C
enjoys a mild lemony fragrance. Citral therefore finds applications (b) CH CH2OH
in making deodorants and soaps.
CH2OH

CHO H
H3CH2C
(c) CH CH2OH
H CHO
OCH3
Citral - a Citral - b

Citral, when subjected to reductive ozonolysis forms H3C

three compounds – X, Y and Z (decreasing molar mass, (d) CH CH2OH
X > Y = Z) OC2H5
78. Conversion of B into C mainly follows
74. Identify the ‘false’ statement :
(a) SN1 mechanism only
(a) Citral – a and b are diastereomers (b) SN2 mechanism only
(b) All fragments obtained on reductive ozonolysis of reduced (c) SN1 at one site and SN2 at other site
citral (Wolf-Kishner reduction) undergo haloform reaction (d) SNi only
(c) Y and Z cannot be distinguished by Fehling’s reagent 79. The compound ‘E’ is
(d) Citral is an isoprene – based natural polymer (dimer) Cl
75. X when reacted with 5% hot and dilute baryta water will form Cl
which major product;
H3C
(a) C CHO (b) H3C
C CHO
O O
CH3 O
(a) (b) C Cl
O H3C H3C
(c) C CHO (d) C CHO
O O Cl
O O
(c) (d)
OH PASSAGE 10
Two aliphatic aldehydes P and Q react in the presence of aqueous
76. 100 ml of an aqueous sample of Z when successfully titrated K2CO3 to give compound R, which upon treatment with HCN
with Ag(NH3)2+ followed by rapid and excess addition of hot provides compound S. On acidification and heating, S gives the
product shown below.
and conc. H2SO4 evolves a mixture of gases which when passed
over red hot charcoal occupy a volume of 6.72 ml at NTP. The H3C OH
molarity of the initial sample is H3C
(a) 10 –1 (b) 10 –2
(c) 10 –3 (d) 10 –4 O
O
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80. The compounds P and Q respectively are : 84. Column I Column II
CH3 OH
CH H H3C H
and (A) (a) aldol condensation
(a) H3C C O
C
O O CHO
CH3 (B) (b) Cannizzaro reaction
CH H H H
and OHC CHO
(b) H3C C C
O O (C) (c) haloform reaction
H3C CH2 H H3C H
CH O
C and C
(c) (D) (d) reaction with chlorine
CH3 O O
H3C CH2 H H H 85. Column I Column II
(d) CH C (A) Schiff’s reagent (a) Elimination reaction
and C
(B) Alcoholic KOH (b) colourless solution
CH3 O due to SO2
O
81. The compound R is : (C) Ammonical AgNO3 (c) Aldehydes
O (D) Benedict solution (d) Chloroform
O
86. Column - I Column - II Column - III
H3C C H3C C OH
C C H |
H
(a) H3C (b) H3C CH A. CH 3 CHO p. (CH 3 )2 CH w. Clemmensen
CH2
H3C OH Zn/Hg. HCl
¾¾¾¾¾¾
® reduction
OH
CH3 O CH3 O OH OH
| |
CH C CH C CH3 COCH3 q. (CH 3 )2C - C (CH3 )2 x. LiAlH4
B.
(c) H3C CH H (d) H3C CH H
[H] reduction
CH2 ¾¾¾ ®
CH
C. CH3COCH3 r. CH3 CH2 CH3 y. Pinacol
OH H3C OH
82. The compound S is : NH NH , OH - reduction
¾¾¾¾¾¾¾
2 2 ®
O D. CH3COCH3 s. CH3 CH3 z. Wolf-Kishner
CH3 O Mg/HCl
H3C C ¾¾¾¾¾ ® reduction
CH C C H 87. Match the column :
(a) H3C CH H (b) H3C Column-I Column-II
CH2
CH2 (Reactions) (products)
CN O
CH3 CN
CN CN
CH CH H3C CH HCN
A. ¾¾¾¾¾¾®(A) (a) Formation of six
(c) trans.of KOH
H3C CH OH (d) C OH
membered ring takes
CH2 H3C CH ¾¾
®(B) ¾¾
®(C)
2
OH O place
OH
Instructions for Q. 83 to Q. 88 : Following questions are Multiple
Matching type Questions : B. (b) Final product is ketone

NH OH or a, b-unsaturated
53. — CHO > C = O ¾¾¾¾
2 ¾
®(A) ¾¾
®(B)
ketone.
Column I Column II
O O
O P P
C. H 3C - C - CH2 - CH 2 - CH2 - C - H (c) Final product formed
(A) OHC + OH – (a) Cyclization
OH- will give positive
+ C6H 5CO 3H ¾¾¾® (A)
(B) (b) Aldol condensation D
Tollen’s test.
O Ph
(C) (c) Ring expansion CH3
D. (sd) Final product formed
+H
+ OH OH
CHO will react with 2, 4-DNP
H+
¾¾¾
® (A)
D
(e) Ring expansion takes
(D) HOCH 2 CH 2 CH 2 CH 2 Cl + OH - (d) Williamson synthesis place
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88. Column I Column II

(A) (a) Nucleophilic substitution

(B) (b) Electrophilic substitution

(C) (c) Dehydration

(D) (d) Nucleophilic addition

O O
Instructions for Q. 89 to 100 : Following questions are Assertion
95. Statement-1 : Acetoacetic ester, CH3 C CH2COC2H 5 will give
and Reasoning Type Questions : iodoform test
Note : Each question contains STATEMENT-1 (Assertion) and
O
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c),
(d) and (e) out of which ONLY ONE is correct. Statement-2 : It contains CH3 C group .
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct 96. Statement-1 : Crossed Cannizzaro reaction between
explanation for Statement-1. formaldehyde and benzaldehyde gives benzyl alcohol and
(b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a formate ion.
correct explanation for Statement-1. Statement-2 : Formaldehyde is a better hydride donor than
(c) Statement -1 is True, Statement-2 is False. benzaldehyde.
(d) Statement -1 is False, Statement-2 is True. 97. Statement-1 : Protonation of a carbonyl group increases its
electrophilic character.
(e) Statement -1 is False, Statement-2 is False.
Statement-2 : Protonation of a carbonyl group involves addition
of an electrophile on nucleophilic oxygen.
89. Statement 1 : Acetaldehyde on treatment with alkali gives aldol. O
Statement 2 : Acetaldehyde molecule contains hydrogen atom.
C – CH3 CH3
90. Statement 1 : Acetylene on treatment with alkaline KMnO4 98. Statement-1 :
produce acetaldehyde.
HO HO
Statement 2 : Alkaline KMnO4 is a reducing agent. This conversion is favoured with, Wolf-Kishner reduction, but
91. Statement 1 : Hydroxyketones are not directly used in Grignard unfavoured with Clemmensen’s reduction.
reaction. Statement-2 : Clemmenson reduction is base sensitive reaction,
Statement 2 : Grignard reagents react with hydroxyl group. whereas Wolf-Kishner reduction is acid sensitive.
92. Statement 1 : Isobutanal does not give iodoform test. 99. Statement-1 : Formaldehyde can’t be prepared by Rosenmund’s
Statement 2 : It does not have a-hydrogen reduction method.
93. Statement 1 : Cyclohexanone forms cyanohydrin in good yield Statement-2 : Formyl chloride is unstable
but 2, 4, 6-trimethyl cyclohexanone does not. 100. Statement-1 : The aldol condensation product is
Statement 2 : The formation of cyanohydrin involves the C6 H 5 - CH - CH - CHO whcn propanal is slowly added to excess
| |
nucleophilic attack by CN– ion on the carbonyl carbon. OH CH 3
94. Statement 1 : There are two – NH2 groups in semicarbazide. of benzaldehyde.
Statement 2 : One group is involved in the formation of Statement-2 : On slow addition self aldol condensation of
semicarbazones. propanal can be prevented.

EXERCISE 14.3 (Subjective Problems)

1. Give IUPAC names for the following : 2. Give the structural formula of
(a) Trimethylacetaldehyde
(b) a, g-Dimethylcaproaldehyde
(a) C6H5CH = CHCHO (b) (c) p, p¢-Dimethylbenzophenone.
3. What are the expected H—C—O and H—C—H bond angles in
CH2O ?
4. Compare the polarities of the C = O and C = C bonds. How
(c) (d) does this difference influence the reactivity of each bond as a
nucleophilic site for reaction ?
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5. Account for the following : CHO
(a) The boiling points of 2-propanol, propanone, and 2- Br
methylpropene differ very much, although they have ap-
proximately same molecular weight. (b)
(b) Carbonyl compounds are more soluble in water than the
corresponding alkanes but less than the corresponding
18. (a) Write down the structure of the product(s) obtained by treat-
alcohols.
ing each of the following aldehyde with conc. OH–
(c) 2-Butanone has a lower DH° of combustion than butanol. (i) Benzaldehyde (ii) Trimethylacetaldehyde
6. What is a ketene ? Give the structural formula and atomic
orbital representation of ketene. (iii) (iv) Benzal chloride
7. (a) How will you prepare an aldehyde by the reduction of a
carboxylic acid ester ?
(b) Give the product of the reaction of cis-1, 2-cyclohexanediol (v) tert-Butyldichloromethane
with periodic acid. Why is the trans-glycol almost inert to (b) Write down the structure of the product(s) obtained by
this reagent ? treating each of the following with conc. NaOH.
8. Give reagent(s) used for preparing (CH3)2CHCH2COCH3 from (i) C6H5CH2CHO (ii) CH3CH = CHCHO
(a) an alkyne (b) an alcohol (iii) C6H5CH = CHCHO + CH3CH = CHCHO
(iv) CH3CHO + 4 HCHO.
(c) an acid chloride + organocopper compound
19. Identify A to D in the following series of reactions :
(d) a carboxylic acid
(e) an acid chloride + organocadmium compound
(f) a nitrile. (i) CH 3 MgI H 2SO4 (i) O 3/H 2 O/Zn OH -
9. Write the organometallic compound and other chemical com- ¾¾¾¾® [B] ¾¾¾¾¾® [C] ¾¾® [D]
¾¾¾¾® [A]
pound (a carbonyl compound) used for preparing following (ii) H 2 O heat
alcohols. 20. Complete the following reactions :
(a) 1-Phenyl-1-propanol (b) 2-Phenyl-2-propanol (a) C6H5COCH2CH3 + SO2Cl2 ¾¾®
(c) 1-Phenyl-2-propanol (d) 3-Phenyl-1-propanol
(e) 1-Methylcyclohexanol (f) Cyclohexylmethanol (b) Me 2 + NBS ¾¾®
(g) 1-Cyclohexylethanol (h) 1-Pentyn-3-ol
(i) 3-Pentyn-2-ol (j) 1-(p-tolyl) ethanol. 21. Describe a simple chemical test that can be applied for
10. Write down the structure of the compound obtained when phe- distinguishing between
nyl acetaldehyde or cyclohexanone is treated with each of the (a) phenylacetaldehyde and benzyl alcohol
following reagents ? (b) 2-pentanone and 3-pentanone
(a) Tollen’s reagent (b) CrO3/H2SO4 (c) cyclohexanone and cyclohexyl methyl ether
(c) Cold dil. KMnO4 (d) Acidic KMnO4, heat (d) diethyl acetal and n-valeraldehyde
(e) H2, Ni, pressure (f) NaBH4 (e) diethyl acetal and di-n-propyl ether
(g) C6H5MgBr, H2O (h) Me 2CHMgCl, H2O (f) methyl m-tolyl ketone and propiophenone
(i) HC º CLi, H2O (j) Semicarbazide (g) 2-pentanone and 2-pentanol
(k) ethyl alcohol, dry HCl (gas) (l) tert-Butyl amine (h) paraldehyde and diisobutyl ether
(m) C2H5SH, H+. (i) dioxane and trioxane.
11. Convert propanal into following 22. Identify compounds [A] to [D] and explain their formation.
(a) n-Propanol (b) a-Hydroxybutanoic acid
(c) sec-Butyl alcohol (d) 1-Phenyl-1-propanol PCl 3 AlCl 3
(e) 2-Methyl-3-pentanol. ¾¾® [A] ¾¾® [B]
C 11H 13OCl C 11H 12 O
12. Name the reagent used to convert 2-methyl-2-pentenal to
(a) 2-methyl-2-pentenol (b) 2-methylpentanol
(c) 2-methylpentane (d) 2-methylpentanal. NH 2 NH 2 , OH - AlCl 3
13. A carbonyl group can be reduced to methylene group by three ¾¾¾¾¾® [C] ¬¾¾¾¾ [D]
heat C11H 14 or Conc. C10 H 13CH 2OH
methods : Clemmensen, Wolf -Kishner and Raney Ni
H2 SO 4
desulphurization. How would you decide which method should
23. Identify the compounds [A] to [E] in the following reactions.
be applied for a particular carbonyl compound?
LiNH 2 CH 2ClCH 2CH 2 Br (i) Mg
14. Select the best way for reducing the carbonyl group to methyl-
n-C 5H11C º CH ¾¾¾® [A] ¾¾¾¾¾¾¾® [B] ¾¾¾®
ene in each of the following : (ii) R ¢ CHO
(a) BrCH2CH2CHO (b) (CH3)2C (OH) CH2CH2COCH3 H 2 , Lindlar CrO 3
(c) C6H5CHOHCH2COC2H5 (d) [C] ¾¾¾¾® [D] ¾¾® [E]
catalyst
24. Identify [A] in the following reaction.
15. Identify the reduced product. H+ C6 H 5Cl
Cl + CCl3CH(OH)2 ¾® [Intermediate] ¾¾¾® [A]
H+
Pt, 1 eq. H 2 25. Give the possible product(s) obtained in each of the following
(a) ¾¾¾¾® [A] reactions.
Et
+
CHO base N CH2COC6H5 base
(a) (b)
CHO N CH COC H
1 eq. NaBH 4 2 6 5
(b) ¾¾¾¾¾® [B] 26. Complete the following explaining each step
CH 3 OH
O
16. How will you convert C6H5CH = CHCOCH3 to +
(a) CH3OCH=PPh3 H , H2O
(a) C6H5CH = CHCOOH (b) C6H5CH = CHCHOHCH3 [A] [B]
(c) C6H5CH2CH2COCH3 (d) C6H5CH = CHCH2CH3
(e) C6H5CH2CH2CH2CH3. (i) O 3 base
17. Arrange the following in decreasing ease of hydration : (b) [C] [D]
(ii) Zn, CH3COOH
(a) CH3CHO, (CH3)2CO, HCHO, CH2ClCOCH3, CH2ClCHO
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EXERCISE 14.1
6 (c) 11 (b) 16 (b) 21 (b) 26 (b) 31 (c) 36 (c) 41 (d) 46 (b) 51 (c) 56 (c) 61 (b) 66 (c)
7 (b) 12 (c) 17 (c) 22 (b) 27 (d) 32 (a) 37 (b). 42 (d) 47 (b) 52 (c) 57 (d) 62 (a) 67 (a)
8 (c) 13 (c) 18 (d) 23 (b) 28 (c) 33 (c) 38 (d) 43 (b) 48 (b) 53 (a) 58 (d) 63 (b)
9 (c) 14 (d) 19 (b) 24 (b) 29 (b) 34 (a) 39 (b) 44 (a) 49 (c) 54 (c) 59 (d) 64 (c)
10 (b) 15 (c) 20 (d) 25 (c) 30 (c) 35 (c) 40 (c) 45 (c) 50 (c) 55 (b) 60 (a) 65 (b)

1. Theoretical
H 2 SO 4
2. HC º CCH2CH3 or CH3C º CCH3 ¾¾¾®
2+ CH3CH2COCH3
Hg

H+ +
3. C6H5C º CCH3 ¾¾® C H C = CHCH ¾¾®
6 5 3
Benzylic type carbocation
(more stable)

+
OH2 OH
½ – H+ ½ tautomerises
C6H5 C = CHCH 3 ¾¾® C6H5 C = CHCH3 ¾¾¾¾¾® C6 H 5COCH 2CH 3
( a)
4. Theoretical

C6H 5C6H5
AlCl 3 Mg, ether ½ ½
5. C6 H6 + C 2 H 5 COCl ¾¾® C 6 H 5 COC 2 H 5 ¾¾¾¾¾¾¾¾® C 2 H 5 — C — C — C2H5
(bimolecular reduction)
½ ½
OH OH

CrO3 Me 2CHCH 2 MgBr CrO 3 / Pyridine

6. n-C 3H7CH2OH ¾¾¾® n-C 3H7CHO ¾¾¾¾¾¾® n-C 3H7CH(OH)CH2CHMe2 ¾¾¾¾¾® n-C3H7COCH2CHMe2
Pyridine

I 2 / OH -
7. CH3CH2CH2CCl2CH3 ¾¾® [CH 3 CH 2 CH 2 C(OH)2 CH 3 ] ¾¾® CH3CH2CH2COCH3 ¾¾¾® CHI3¯
unstable
8. Alk. KMnO4 and conc. HNO3 can’t be used because they oxidize the C = C bond too. Since the compound has —COCH 3 grouping, it
can easily be oxidised by alkaline halogen (NaOX) ; haloform reaction.
9. It is an example of internal crossed—Cannizzaro reaction.
OH -
C6H5COCHO ¾¾® C 6H5CH(OH)COO– Na+

10. CH3CHO + H2O18 LMCH CHO

3
18
H OP CH3CHO18 + H2O
MM ½OH PP
N Q
Hydrate

The unstable half-labelled hydrate loses H2O but not H2O18 because C—O18 bond is strong as compared to C—O16, hence relatively
difficult to cleave.
11. >C = O + D2/Pt (or LiAlD4) ¾¾® >CDOD

OH
OC2 H5 OC2H5
+
CHO
H , H2O
12. O ¾¾¾¾® OH ¾¾¾¾® + C2H5OH
OH
 www.crackjee.xyz
733

13.

Reaction is repeated till all other a-hydrogen atoms are replaced.

OH
+ OH
H –H O
CHO ¾¾® CHO ¾¾
2
® CHO
14. or CHO

I Conjugated system (stable)

2 . It does not lose water because

the double bond so formed will be isolated.

It does not lose water because the double bond so formed will be isolated.

15.

3° alcohol
16. Since the product is having an aldehydic group, the reactant should be a dialdehyde because —CHO are more reactive than ketones
so in a ketoaldehyde the final product should have a ketonic group.
17. It is an example of intramolecular Cannizzaro reaction followed by cyclization.
18. Presence of electron-withdrawing group on the carbonyl carbon atom increases nucleophilic addition.
19. Halogenation of carbonyl compounds takes place in a-position ; since aldehydes are easily oxidisable so here CHCl3 is used and not
water.
heat
20. CH3COOH ¾¾® CH2 = C = O + H2O. This is an industrial method for the preparation of ketene, another method is
700 °
CH3COCH3 ¾¾® CH2 = C = O + CH4.
Zn (Hg)
21. BrCH2CH2CHO ¾¾® BrCH2CH2CH3
HCl
Wolf-Kishner reduction will cause dehydrobromination (—HBr) because it involves alkaline conditions.
22. Zn(Hg), HCl is not used here, because the acidic medium of the reagent may cause dehydration.
23. II cation (oxonium ion) is more stable because here every atom has an octet of electrons
H H
½+ .. ½ +
R— C — OR
.. ¬® R— C = OR
..
I II
(+vely charged C has six electrons) (each atom, except H, has eight electrons)
24. Recall that a H’s of carbonyl compounds are easily replaced by D of D2O.

25.

26. Consult mechanism of Cannizzaro reaction.

27. Only C6H5NHNH2 has —NH2 group.
H+ —H +
+
28. C6H5 CH — CHCH3 ¾¾® ¾¾® C 6H5CH2— C CH3 ¾¾® C6H5CH2COCH3
—H 2 O
½ ½ ½
OH OH OH
Benzylic 2° carbocation 3° carbocation
(i) Mg, ether CH 3 CH 2 COCl
29. C6H11Cl ¾¾¾¾¾¾® [C6H11]2 LiCu ¾¾¾¾¾¾® C 6H11COCH2CH3
(ii) Li, (iii) CuCl
[A] [B]
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30. Methyl ethyl ketone (a C4 compound) can’t be prepared from 2-propanol (a C3 compound) ; tert-butyl alcohol, being 3° alcohol, is not
oxidised easily, 1-butanol, a 1° alcohol will form aldehyde. Thus 2-butanol should be the answer.
OH
½ Oxidation
CH3 CHCH 2CH3 ¾¾¾® CH3COCH2CH3
Cl 2 , hv
31. C6H5CHO ¾¾¾® C 6H5COCl
CH3
½ Wittig
32. CH3CH2CH2CH = PPh3 + CH3COCH2CH3 ¾¾¾® CH3CH2CH2CH = CCH2 CH 3
reaction
3-Methyl-3-heptene
33. Since the compound A has the molecular formula C3H6O and undergoes iodoform test, it should be CH3COCH3. Further reaction of
A with HCl gives C9H14O having three times the number of carbon atoms in A, hence B should be trimer of acetone, i.e., it should be
phorone.
(CH3)2C = O + H3CCOCH3 + O = C(CH3)2 ¾¾® (CH3)2C = CHCOCH = C(CH3)2
Acetone (3 moles) 2, 6-Dimethyl-2, 5-heptadien-4-one (phorone)

K Cr O 2 2 H NCONHNH HCl
C3 H8 O ¾¾¾¾¾
2 2 7 ® C H O ¾¾¾¾¾¾¾¾¾
3 6 ®C
34. H 2 SO 4 CH3 COONa
(A) (B)

½
½ Ammonical AgNO3
B
Silver mirror
Since B reduces ammonical silver nitrate, it should be an aldehyde and hence A is primary alcohol, which should be C 2H5CH2OH.
Hence
K Cr O , H SO H 2 NCONHNH 2
2 2 7 2 4
CH3CH2CH2OH ¾¾¾¾¾¾¾® CH3CH2CHO ¾¾¾¾¾® CH3CH2CH = NNHCONH2
(A) (B) (C)

O
½½
(CH3CO)2O Zn/Hg HF
35. ¾¾¾¾¾® ¾¾¾¾¾® ¾¾¾ ®
AlCl3 H Cl
H 3C H 3C HOC H 3C HOC H 3C
½½
½½ ½½ O
O O
[C]
[A] [B]

(i) CH3MgI
¾¾¾¾¾®
+
( ii) H3O
H 3C
OH CH3
[D]

36.

37.
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735
56. (c) Under basic conditions only the protons at carbon atom
O CH2
µ to the carbonyl group are replaced by deuterium.
57. (d) It is an example of intramolecular aldol condensation. The
46. (b) + Ph 2P = CH 2 ¾¾
® (Wittig reaction)
carbon atom labelled as a acts as a nucleophile.

HgSO dil.NaOH a
47. (b) CH º CH ¾¾¾¾
4 ® CH - CHO ¾¾¾¾¾
3 ® –
H2 SO 4 5° C O OH O
H H
O
OH O O
| OH
CH 3 - CH - CH 2 - CHO (3-hydroxybutanal)
48. (b)
–H2O
O
OH OH O
Mg/ Hg Å
H 58. (d) Aldol condensation :
49. (c)
H2O
Å OH New C–C bond
OH OH
–
O 2CH3CHO H3C–C–CH2CHO
H
OH
Å O Kolbe reaction :
Å –H
ONa
ONa OH New C–C bond
COOH
50. (c) Both molecules will respond to A and B; neither will respond CO
CO2 ,140ºC
,140ºC
to D. Pressure
Pressure

51. (c) Aldehyde is first converted into cyclic thioacetal and then
strong base like PhLi is used to generate carbanion and Reimer-Tiemann reaction :
then treated with D2O. Finally, the aldehyde is regenerated.
52. (c) The methoxy group being electron-releasing group makes New C–C bond
OH OH
the release of hydride group more easy.
CHO
CHCl3
CHCl
H H + 3KCl + 2H2O
3KOH
3KOH
O O O O
Wurtz-Fittig reaction :
53. (a) Ph —C —C —C —Ph Cl —C — C —H

O O Cl HO Na
H3CCl + 2Na + Cl
H
(I) (I)

H3C + 2NaCl
H H
O New C–C bond
O O
C 59. (d) The keto group has considerable resonance energy ; hence
C H —C —H
C more the number of keto groups in a compound, higher is
O O its stability. However, here all the three compounds have
O
H H same (two) number of keto groups. Compound II is least
(III) (V) stable because two adjacent keto groups destabilize the
molecule due to positive charge on the adjacent carbon
atoms. Relative stability of I and III can be ascertained by
O- H O-
| ..
-
- | the stability of their fully reduced forms (phenols), since
OH OH
54. (c) ˆˆˆˆ
†
H- C- H ‡ˆˆˆ ˆˆˆˆ† H- C- H
ˆ H- C- H ‡ˆˆˆˆ fully reduced form of III has two benzene rings, it will be
P | | more stable than the I whose reduced form has only one
O O- O-
benzene ring. Thus

The dianion will clearly be a much powerful hydride donor. –

d
55. (b) III > II > I O O –
d
In I, –OCH3 is electron donating group (+M) so will decrease d
+
d
+
O
the electron deficiency of carbonyl carbon to the most. O O > >
In II, there is no electron donating group.
In III, electron withdrawing group is present which will O
increase electron deficiency at carbonyl carbon. III I II
 EBD_7090
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O H O
||
Ca ( OH )
C O CH 3CHO + H - C- H ¾ ¾ ¾ ¾
¾2 ®
Ethanal Methanal ( crossed aldol )
(no a - H) condensation
.
60. (a) C (3a - hydrogen)

C HCHO , Ca (OH )
O CH 2 OH . CH 2 CHO ¾ ¾ ¾ ¾ ¾ ¾¾2 ®
(crossed aldol )
O H ( Two a - H )
61. (b) Two molecules of the same aldehyde are reacting in CH2OH CH2OH
presence of alkali to form sodium salt of the acid and an HCHO, Ca(OH) 2
alcohol, hence it is an example of intermolecular CH – CH2OH HOH2C – C – CH2OH
(crossed aldol)
Cannizzaro reaction. CHO CHO
62. (a) Lithium tri-tert-butoxyaluminium hydride (LBAH) and (1 a – H) (No a –H)
diisobutyl-aluminium hydride (DBAH) are less reactive
than LAH because they are much more sterically hindered HCHO, Ca(OH) 2 1
and hence face difficulty in transferring their hydride ions. C(CH 2 OH) 4 + (HCOO ) 2 Ca
63. (b) The reaction is an example of intramolecular aldol (crossed Cannizzaro) 2
condensation. In this keto aldehyde, three different 65. (b) Reimer-Tiemann reaction develops – CHO or – COOH
enolates are possible corresponding to the following three group in ortho position to the OH group in phenols or to
carbanions. the hetero atom in pyrrole and thiophene.
66. (c) Consult mechanism of Cannizzaro reaction.
O O
H H 67. (a) Condensation of aldehydes/ketones having a - H in
presence of base to form a, b -unsaturated carbonyl
O O compound (aldol condensation).
I II
O
O O O O
H
H OH -
CH2 ¾¾¾®
O
III
However, carbanion II is formed preferentially because
aldehydes are more reactive towards nucleophilic addition O O
than the ketones due to electronic as well as steric factors. OH
64. (c) First three HCHO molecules react with acetaldehyde via OH -
crossed aldol condensation, while the fourth HCHO H O ¾¾¾®
¾¾2¾® ( - H 2O )
molecule reacts via crossed Cannizzaro reaction.

EXERCISE 14.2
1 (a,c) 2 (c,d) 3 (a,b) 4 (a,b,d) 5 (a,b,c) 6 (a,b,c) 7 (b,d) 8 (b,c,d)
9 (a,b,d) 10 (b, c, d) 11 (a, d) 12 (a, b, c) 13 (a, c) 14 (a, b, d) 15 (a,b,c,d) 16 (a, c, d)
17 (a, b, c) 18 (a, b, c) 19 (a,c) 20 (a, b) 21 (a, b, d) 22 (b, d) 23 (a, b) 24 (b, d)
>1 CORRECT
25 (a, b, d) 26 (a, d) 27 (a,b,c,d) 28 (a, b, c) 29 (a, c, d) 30 (a,b,c,d) 31 (a, b, c) 32 (b, c, d)
OPTION
33 (a,b,c,d) 34 (a, b, c) 35 (a,b,c,d) 36 (a, c, d) 37 (a, b, c) 38 (a,b,c,d) 39 (a, b) 40 (a,b,c,d)
41 (a, c) 42 (a, c) 43 (d) 44 (b) 45 (a, d) 46 (a, b, c, d) 47 (a, b, c, d) 48 (a, c, d)
49 (a, c, d) 50 (a, d)
PASSAGE 1 51 (c) 52 (c) 53 (b)
PASSAGE 2 54 (a) 55 (b) 56 (b) 57 (a) 58 (b)
PASSAGE 3 59 (d) 60 (a) 61 (c)
PASSAGE 4 62 (b) 63 (a) 64 (d)
PASSAGE 5 65 (b) 66 (a) 67 (b)
PASSAGE 6 68 (c) 69 (d) 70 (b)
PASSAGE 7 71 (d) 72 (c) 73 (b)
PASSAGE 8 74 (c) 75 (a) 76 (c)
PASSAGE 9 77 (d) 78 (a) 79 (b)
PASSAGE 10 80 (b) 81 (a) 82 (d)
83 (A)- a, b ; (B) –c ; (C) - a ; (D) - a, d
84 (A)-a, c, d ; (B)-b ; (C)- a, b, d ; (D)- a, c, d
MATCH THE 85 (A) – b, c; (B) – a; (C) – c, d; (D) – c
FOLLOWING 86 (A) – s, w; (B) – p, x; (C) – r, z; (D) – q, y
87 (A) – a, b, d, e; (B) – a, e; (C) – a, b, d; (D) – a, b, d, e
88 (A) – c, d, e; (B) – a, d; (C) – c, d; (D) – b, e
89 (a) 90 (e) 91 (e) 92 (c) 93 (a) 94 (b)
A/R
95 (d) 96 (a) 97 (b) 98 (a) 99 (a) 100 (d)
 www.crackjee.xyz
737
1. Since the product, CH3CHOHCN has a chiral carbon and is a mixture of two enantiomers (racemic mixture) which can’t be separated
by fractional distillation. By fractional crystallisation from a suitable solvent they can be separated.
2. Substitution by one mole of Br gives C6H5COCHBrCH3 ; the electron-withdrawing Br increases the acidity of the remaining a hydrogen
which reacts more rapidly than the hydrogens on the unsubstituted ketones.
Less acidic More acidic
B
C H COCH CH
0.5 mole Br2 B
¾¾¾¾® [C6H 5COCHBrCH3 ] ¾¾¾¾® C6H 5COCBr2CH 3
0.5 mole Br2
6 5 2 3
0.5 mole OH - (0.5 mole, but not isolated) OH - 0.5 mole
3. Acetaldehyde having three a-hydrogen atoms undergo aldol condensation with three moles of CH2O. The product formed now
undergoes intermolecular Cannizzaro reaction with the fourth mole of CH2O to form pentaerythritol.
CH 2OH CH 2OH
H
½ Ca(OH) 2 ½ CH 2 O, OH - ½
H— C — CHO + 3CH2O ¾¾¾¾¾¾¾® CH2OH— C — CHO ¾¾¾¾® CH2OH— C — CH 2OH + HCOO –
(aldol condensation) Cannizzaro
½ ½ reaction ½
H CH 2OH CH2OH
4. Removal of g-hydrogen of crotonaldehyde provides more stable allylic carbanion, hence here g-carbon (not a) provides the carbanion
(nucleophile) for carbonyl carbon of cinnamaldehyde.
LM H H OP
½
OH -
¾¾® MMH ×× C = O ¬® H 2C = CH — CH = C — O – PP
N 2 C — CH = CH — Q
5. Only the first three compounds give Cannizzaro reaction ; C 6H5CHCl2 is converted into C6H5CHO, under the Cannizzaro conditions,
hence it also responds the reaction.
6. Carbonyl compounds having aH form carbanion on treatment with a base, carbanion being flat can be attacked by proton on either side
of the face forming racemic mixture. Only ketone I has a H, so it will form carbanion while ketone II does not form such carbanion.
7. It is an example of Cannizzaro reaction.
8. Only b, c and d will undergo haloform reaction, but not a because on hydrolysis by alkali it gives C 6H5CHO, having no aH.
9.

Acetone and propanal can be distinguished by Fehling solution, and not by others.

48. (a, c, d) O HOOCCH2 H3C

KMnO4 heat
+ O O
H
HOOCCH2 H3C
W Y
O
O
KMnO4 heat
+ HO O
H O O
O H
X O O O
Z
49. (a, c, d)
æ O ö
ç P ÷
(a) and (c) have methyl keto è CH 3 - C - ÷ø group.
ç

(d) forms CH 3 - CH - CH 3 , on reaction with aq. NaOH, which then gives iodoform test.
|
OH
50. (a, d) Compound (X) gives positive haloform test. Hence [X should be (a), (c) and (d).] However, c does not react with NH 2OH to give two
oximes.
O
O
O3 KOH H2N – NH2 CrO3
Sol. (68-70) : Zn/ H2O EtONa
CHO OH O
P1 P2 P4
O OH
P3
KOH H2/ Pd HBr NH3
D excess excess
Br NH2
P5 P6 P7

71. (d)
eq
Br eq Br
Me
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Mg(excess) MgBr
72. (c) ¾¾¾¾¾® O (excess) OMgBr NH Å (excess) OH
Br Br Et 2O MgBr ¾¾¾¾¾
2 ® ¾¾¾¾¾¾®
4
OMgBr OH
Me

73. (b) gives addition reaction and decolourises Br 2 water.

Sol. (74-75) :

O3 O CHO
O
+ +
CHO CHO CHO
X Y Z
Citral (Molecular (58) (58)
mass = 100) (Yand Z can be distinguished
by Fehling reagent)
(i) Wolf-Kishner –
reduction OH
–CHO ® –CH3
(ii) O3
H2O
O O

OH

CHO O
O
+ +
CHO CH3
All undergo haloform reaction
CHO [Ag(NH ) ]+ COOH conc.H SO *
76. (c) | 3 2
¾¾¾¾¾¾® | ¾¾¾¾¾¾2 4
® CO+ CO22CO = 3CO(6.72ml)
CHO COOH
(Z) C

6.72 CHO
Moles = = 3 ´ 10-4 \ Moles of | =10–4 (in 100 ml) = 10–3 M
22400 CHO
Sol. (77-79) :
HI aq. KOH
H3C H3C H3C
CH CH2OH CH CH2I CH CH2OH

OC2H5 (A) I (B) OH (C)

Cl PCC

Cl2
H3C AlCl3 H3C
C CHO C CHO
O (E) O (D)
Sol. (80- 82)
Let us summarize the given facts of the problem.
H3C OH
aq.K 2CO3 HCN H + / H 2O
P + Q ¾¾¾¾¾ ® R ¾¾¾® S ¾¾¾¾ ¾® HC
Heat 3
(2aldehydes)
O O
Structures of P, Q, R and S can be established on going backward from the known final product.

H3C OH H3C
OH
H3 C H3C
– H 2O O
O O
HO OH
H +/H2O

Unstable
Heat

H3C H3C
O OH
HCN
H3C H3C
H C N
aq. K2 CO3

OH HO
(R) (S)

H3C O H
+ H
H3C H O

(P & Q)
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739
87. A - (p, q, s, t); B - (p, t); C - (p, q, s); D - (p, q, s, t)
OH O N – OH
OH LiAlH4 H2NOH PCl5
(A) O
HCN
–
(B) NH
OH CH2 – NH2 Beckmann
CN rearrangement
(A) (B) (A) (B) O
..
..
OH
NaNO2
OH +
+
NaNO2 + HCl
HCl CH2 – N2

..+
O –H O

+
–H
(C)
O O
..
–
O
H2C– C – CH2 H2C——C O
CH2 – C
(C) Intramolecular aldol condensation H CH2 CH2 –H2O
– HO – HC CH2
OH HC – C – CH2 H – C – CH2 – CH2
CH2 – CH2
O O
.. O
OH
.. – H
O
Ph Ph + Ph + Ph
+ Å –H
CH3 H CH3
(D) Pinacol – Pinacolone rearrangement CH3 CH3
..
OH ..
OH
..
..
88. (A) – c, d, e ; (B) – a, d ; (C) - c, d; (D) – b, c

aq/NaOH
(Carbanion)

(Nucleophilic addition)

O O

OH /D
dehydration
OH

CH3MgI
Nucleophilic
addition

97. (a) The given conversion is unfavoured with Clemmensen reduction because with highly acidic medium, it will attack on –OH group of
the given compound.
100. (d) C6 H 5 - CH = C - CHO is the condensation product.
|
CH 3
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EXERCISE 14.3
1. (i) 3-Phenylpropenal (ii) 4-Methyl-3-penten-2-one (iii) 4-Methyl-3-hexanone
(iv) 4-Ketopentanoic acid (—COOH group has a higher priority over —CO group).
CH 3 CH 3
½ ½
2. (a) (CH3)3CCHO (b) CH3CH2 CHCH 2 CHCHO (c)

3. H2C = O is a planar molecule, i.e., its C is sp 2 hybridised (theoretically, its bond angle should be 120°). However, the H—C—O bond
angle is slightly greater (121.8°) than the expected 120°, while the H—C—H angles are 116.5°, slightly less than 120°.
d+ d-
4. The C = O bond is polarised ( C = O ) due to more electronegative nature of oxygen, while the C = C bond is nearly non-polar. The p bond
of C = C is an electron source, and is a nucleophilic site, while in C = O, the nucleophilic site is O.
5. (a) 2-Propanol has highest boiling point due to intermolecular H—bonding, since propanone and 2-methylpropene have no hydrogen
on oxygen, they can’t undergo association. However, the dipole-dipole attractive forces of carbonyl compounds are responsible for
their higher boiling point than those of alkenes.
(b) Oxygen of C = O forms H—bond with the H of water making the former to dissolve in the latter (water) ; such hydrogen bond
formation is not possible in an alkene as it has no oxygen. However, carbonyl group has no H atom which can form H—bond with
the O of H2O, hence these are less water soluble than alcohols.
(c) Alkyl substituents stabilize C = O as they do C = C by releasing electrons towards the sp 2 hybridized C. The enthalpy of the ketone
is lower because it has two R groups, while the aldehydes have only one.
6. Ketenes have the general formula, R2C = C = O. Structural formula for the ketene is H2C = C = O,

7. (a) Reduction of RCOOR with LiAlH4 gives RCH2OH, since the intermediate aldehyde RCHO is generally susceptible to further
reduction. Hence one equivalent of the less reactive diisobutyllithium aluminium hydride (DBAH) is used at —70°C followed by
hydrolysis ; when aldehyde is obtained in good yield.

(b)

cis-1, 2-Cyclohexanediol Hexan-1, 6-dial

The corresponding trans-form does not form transition state easily, hence it is not oxidised by periodic acid.
8. (a) (CH3)2CHCH2C º CH + H2O in HgSO4, H2SO 4
(b) (CH3)2CHCH2CHOHCH3 + KMnO4 or a Cr(VI) reagent
(c) (CH3)2CHCH2COCl + (CH3)2CuLi (from CH3MgI + Li, then Cu)
(d) (CH3)2CHCH2COOH + 2CH3Li
(e) (CH3)2CHCH2COCl + (CH3)2Cd (from CH3MgI + CdCl2)
(f) (CH3)2CHCH2C º N + CH3MgI or CH3Li.
9. In such cases, proceed backward i.e., first write down the structure of the required compound and then apply your memory for getting
the two required components for its preparation.
OH
½
(a) C6H5 CHCH 2CH3 ¬¾¾ C6H5MgBr + CH3CH2CHO or C6H5CHO + CH3CH2MgBr
A 2° alcohol

OH
½
(b) C6H5— C — CH 3 ¬¾¾ C6H5MgBr + (CH3)2CO or C6H5COCH3 + CH3MgBr
½
CH 3
A 3° alcohol
(c) C6H5CH2CHOHCH3 ¬¾¾ C6H5CH2CHO + CH3MgBr (d) C6H5CH2CH2CH2OH ¬¾¾ C6H5CH2CH2MgBr + HCHO
1-Phenyl-2-propanol, a 2°alcohol 3-Phenylpropanol, a 1° alcohol

(e) ¬¾¾ + CH3MgBr (f) ¬¾¾ + CH2O

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(g) ¬¾¾ + CH3CHO or

(h) CH3CH2CHOHC º CH ¬¾¾ CH3CH2CHO + HC º CLi

A 2° alcohol
(i) CH3CHOHC º CCH3 ¬¾¾ CH3CHO + CH3C º CLi
A 2° alcohol
(j) p-CH3C6H4CHOHCH3 ¬¾¾ p-CH3C6H4MgBr + CH3CHO or p-CH3C6H4CHO + CH3MgBr

10. Reagent Product fromC6H5CH2CHO Product from

(a) Tollen’s reagent C6H5CH2COO–Ag+ No reaction

(b) CrO3/H2SO 4 C6H5CH2COOH No reaction
(c) Cold dil KMnO4 C6H5CH2COOH No reaction
(d) KMnO4, H+, heat C6H5COOH HOOC(CH2)4COOH
(e) H2, Ni, Pressure C6H5CH2OH C6H11CHOH
(f) NaBH4 C6H5CH2OH C6H11CHOH

(g) C6H5MgBr, H2O C6H5CH2CHOHC6H5

(h) Me2CHMgCl, H2O C6H5CH2CHOHCHMe2

(i) HC º CLi, H2O C6H5CH2CHOHC º CH

(j) NH2CONHNH2 C6H5CH2CH = NNHCONH2 C6H10 = NNHCONH2

(k) C2H5OH, HCl C6H5CH2CH(OC2H5)2

(l) Me3CNH2 C6H5CH = NMe3 C6H10 = NCMe3

(m) C2H5SH, H+

Where C6H11— is , C 6H10– is ; C6H10 = is

11. Write down the structure of the compound to be prepared.

LiAlH 4 H 2O, H + CN –
(a) CH3CH2CH2OH ¬¾¾¾ CH3CH2CHO (b) CH3CH2 CHCOOH ¬¾¾¾ CH3CH2 CHCN ¬¾¾ CH3CH2CHO
or H , Ni 2 ½ ½ H+
OH OH
(c) CH3CH2 CHCH3 ¬¾¾ CH3CH2CHO + CH3MgBr (d) CH3CH2 CHC6 H 5 ¬¾¾ CH3CH2CHO + C6H5MgBr
½ ½
OH OH
(e) CH3CH2 CHCH(CH 3 ) 2 ¬¾¾ CH3CH2CHO + (CH3)2CHMgBr
½
OH
12. 2-Methyl-2-pentenal, CH3CH2CH = C(CH3)CHO to
CH3 CH3
½ ½
(a) CH3CH2CH = C — CH2OH (b) CH3CH2CH2 CHCH 2OH
(reduction of only —CHO to —CH2OH, (reduction of —CHO to —CH2OH as well as
hence NaBH4 is used) C = C, hence H2/Pt is used)

CH 3 CH 3
½ ½
*(c) CH3CH2CH2 CHCH3 **(d) CH3CH2CH2 CHCHO
(reduction of —CHO to (reduction of only C = C, hence
>CH2 and also of C = C) —CHO must be first protected)
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CH 3 CH3 CH3
½ NH 2 NH 2 , OH - , heat ½ H 2 / Pt ½
*(c) CH3CH2CH = CCHO ¾¾¾¾¾¾¾¾® CH3CH2CH = CCH3 ¾¾¾® CH3CH2CH2 CHCH3
Wolf -Kishner reduction

CH 3 CH 3 CH 3
½ CH 3OH ½ (i) H 2 / Pt ½
**(d) CH3CH2CH = CCHO ¾¾¾® CH3CH2CH = CCH(OCH3 ) 2 ¾¾¾¾¾® CH3CH2CH CHCHO
HCl (ii) HCl, H 2O
13. If a carbonyl compound has some other functional group which is stable to acids but react with strong base, then Clemmensen method
(Zn/Hg + HCl) should be used. In case, the carbonyl compound is sensitive to acid but stable in base, then Wolf-Kishner method
(NH2NH2, OH–) should be used. Raney Ni desulfurization occurs under neutral conditions : however it can’t be used with reactants
with good leaving groups because —SH is an excellent nucleophile.
14. (a) BrCH2CH2CHO ¾¾® BrCH2CH2CH3. It should be carried out by Clemmensen reduction because strong base (used in Wolf-
Kishner method) causes dehydrohalogenation. Desulfurisation by Raney Ni can’t be used because HSCH 2CH2SH, used for
converting C = O into thioacetal, can displace Br– (a good leaving group), hence thioacetal will not be formed.
BrCH2CH2CHO + HSCH2CH2SH ¾¾® HSCH2CH2SCH2CH2CHO + Br –
(b) Me 2C(OH) CH 2CH 2COCH 3 ¾¾® Me 2C(OH)CH2CH 2CH 2CH 3. It can be carried out by Wolf-Kishner reduction or
desulphurisation. Clemmensen method, using HCl, is not suitable because 3° alcohol is easily dehydrated in presence of acid.
(c) C6H5CH(OH)CH2COCH2CH3 ¾¾® C6H5CH(OH)CH2CH2CH2CH3.
Here again acid causes dehydration of an alcohol which is although 2° but produces quite stable alkene because its double bond
is conjugated with the benzene. Hence either of the other two methods can be used.
(d) Epoxides are very reactive, hence these are opened up by the reagents used in either of the three methods used for reducing
carbonyl group. Thus none of the three methods give good result for reducing a carbonyl group.

15. (a) [A] is ; [B] is —CHO group is reduced earlier than keto.

2 Cl , OH -
LiAlH
16. (a) C6H5CH = CHCOCH3 ¾¾¾¾¾¾¾® C 6H5CH = CHCOOH (b) C6H5CH = CHCOCH3 ¾¾®4 C 6H5CH = CHCHOHCH3
(haloform reaction)

Li, liq.NH 3 , ether NH 2 NH 2 , OH -

(c) C6H5CH = CHCOCH3 ¾¾¾¾¾¾® C 6H5CH2CH2COCH3 (d) C6H5CH = CHCOCH3 ¾¾¾¾¾® C6H5CH = CHCH2CH3
Birch reduction

(i) NH 2 NH 2 , OH -
(e) C6H5CH = CHCOCH3 ¾¾¾¾¾¾® C 6H5CH2CH2CH2CH3
(ii) H 2 /Pt
17. Aldehydes are more easily hydrated than ketones. Further, presence of electron–withdrawing group increases hydration.
(a) HCHO > CH2ClCHO > CH3CHO > CH2ClCOCH3 > CH3COCH3

(b)

18. (a) All these compounds undergo Cannizzaro reaction (a characteristic reaction of aldehydes lacking a-hydrogen atom). Note that
compounds (iv) and (v) although do not have an aldehydic group, however, in presence of OH– these are converted into aldehydes
lacking a-hydrogen atom, hence they also undergo Cannizzaro reaction.
OH - OH -
C6H5CHCl2 ¾¾® C 6H5CH(OH)2 ¾¾® C 6H5CHO; Me3CCHCl2 ¾¾® Me 3CCH(OH)2 ¾¾® Me3CCHO
Thus the products in these compunds will be

(i) and (iv) C6H5COO–Na + + C6H5CH2OH (iii)

(ii) and (v) Me3CCOO–Na + + Me3CCH2OH

(b) All these compounds have a-hydrogen, so they will undergo aldol condensation.
OH
OH - ½ –H 2O
(i) 2C 6H5CH2CHO ¾¾® C 6H5CH2 CH CHCHO ¾¾® C 6H5CH2CH = CCHO
½ ½
C6 H 5 C6H5
Highly conjugated system
(C = C is conjugated with —CHO
as well as benzene ring)
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743
(ii) In CH3CH = CHCHO, since the —CHO group is conjugated with the double bond, hydrogen atom of the methyl group (allylic
hydrogen) becomes acidic, i.e., it is the allylic carbanion that will be formed rather than vinylic, hence in such cases aldol
condensation involves allylic hydrogen atom which is, of course, not the a-hydrogen atom.
OH
½
2 CH3CH = CHCHO ¾¾® CH3CH = CH CHCH2 CH = CHCHO ¾¾® CH3CH = CHCH = CHCH = CHCHO
–H 2O

OH
½
OH - heat
(iii) C6H5CH = CHCHO + CH3CH = CHCHO ¾¾® C6H5CH = CH CHCH2 CH = CHCHO ¾¾¾®
(–H 2 O)
C6H5CH = CHCH = CHCH = CHCHO

H H
½ ½
(iv) H— C = O + HCH2CHO ¾¾® H— C ¾ CH2CHO
½
OH

Here only CH3CHO has a-hydrgoen atom so it will be forming carbanion which then adds on carbonyl carbon of formaldehyde. The
process repeats till all the three hydrogen atoms of CH 3CHO are replaced by —CH2OH group.

H CH 2 OH CH 2OH
½ CH 2O, OH - ½ CH 2O ½ CH 2 O
H— C ¾ CHO ¾¾¾¾¾¾¾¾® H— C ¾ CHO ¾¾¾¾¾¾¾¾® CH2OH — C ¾ CHO ¾¾¾¾¾¾¾®
(aldol condensation) ½ (aldol condensation) ½ (aldol condensation)
½
OH H H

CH 2OH CH2OH
½ CH 2O ½
CH 2OH — C ¾ CHO ¾¾¾¾¾® CH 2OH — C ¾ CH 2OH + HCOO –
½ (Cannizzaro
reaction) ½
CH 2OH CH OH 2

19.

[A] [B] [C] [D]

20. (a) Halogenation occurs at the a-position to the C = O group under free radical conditions, hence product will be C 6H5COCHClCH3.

(b)

21. (a) Only phenylacetaldehyde, C6H5CH2CHO responds Tollen’s reagent.

(b) Only 2-pentanone, CH3COCH2CH2CH3 responds iodoform test
(c) Only cyclohexanone gives crystals with 2, 4-dinitrophenylhydrazine
(d) Only n-valeraldehyde responds Tollen’s reagent.
(e) Diethyl acetal on treatment with acid regenerates aldehyde which responds Tollen’s reagent.
(f) Only propiophenone, C6H5CH2COCH3 responds iodoform test
(g) Only 2-pentanone responds 2, 4-dinitrophenylhydrazine, while 2-pentanol gives colour reaction with CrO 3/H2SO 4.
(h) Paraldehyde, a cyclic trimer of acetaldehyde, (CH3CHO)3, on treatment with acid gives CH3CHO which responds Tollen’s or
Schiff’s reagent.
(i) Trioxane, (CH2O) 3 on treatment with acid followed by heating gives CH2O which responds Tollen’s reagent or Schiff’s test.

Dioxane is a cyclic ether

22. First step involves the conversion of —COOH to —COCl [A]. Conversion of [A] to [B] involves loss of HCl but without any change in
carbon number, it indicates that the reaction is intramolecular Friedel Crafts acylation. Thus conversion of [A] to [C] can be repre-
sented as below.
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23. n-C 5H11C º CLi n-C 5H11C ºCCH2CH2CH2Br n-C 5H11C º CCH2CH2CH2 CHR¢
½
OH
[A] [B] [C]

[D] [E]

H+ + C6 H5 Cl
24. ¾¾® Cl 3C.C HOH ¾¾¾®
—H 2 O

25. (a) Here either of the a-carbon can act as a nucleophile to form two possible compounds by intramolecular aldol condensation.

Et CHO Et a Et
base CHO base
a carbon CHO a as nucleophile
as nucleophile
a¢
CHO
(b) Here only one product will be formed by the aldol condensation since here only one a carbon (a' carbon) can form a stable
carbanion; in the second case (a carbon) +ve and –ve charges will be present an adjacent atoms causing unstability.
a
+ CH2COC6H5 + C6H5
N base
N
N a' as nucleophile N – COC6H5
CH2COC6H5
a¢ .. . .+
O CH – .OCH
. 3 CH – OCH3
H
H 2O
Wittig
26. (a) + CH3OCH = PPh3
reaction
[A] +
OH 2 OH

CH – OCH 3 CH – OCH3 CHO

+
–H –CH 3OH

a [B]

(i) O3 O base
(b) (ii) Zn, CH3COOH
O O
(aldol cond.)
a
O
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15 .1 Reactions Involving Carbanions 15 .3 Illustrative Examples

15 .2 Reactions via Enols and Enolate Ions EXERCISES

SOLUTIONS

In the preceding chapter we found nucleophilic addition to the carbonyl group as one of the important
characteristics of aldehydes and ketones. However, another important characteristic of carbonyl compounds is the unusual
acidity of its a hydrogen atom; i.e. such hydrogens are far more acidic than a hydrogen in an alkane. The reason for the
unusual acidity of the a hydrogens of carbonyl compounds is due to stability of its corresponding enolate anion (carbanion).

– –
O H – O O O
:B . .–
–C–C– –C–C– –C=C– –C—C–

I II

Resonance-stabilized anion

Note that of the above two resonating structures, II is more stable because negative charge is present on oxygen
(an electronegative element). Since the structure II (an enolate ion) makes a greater contribution to the hybrid, such
carbanions are commonly known as enolate ions rather than carbanions.

15.1 Reactions Involving Carbanions

The carbonyl group occurs in compounds other than aldehydes and ketones and thus the a-hydrogens of such
compounds should also be acidic. Such compounds (acids) in which proton is lost from carbon are called carbon acid,
and hence the conjugate base of a carbon acid is known as carbanion. However, note that different carbon acids differ in
their acidic property, e.g. aldehydes and ketones are more acidic than esters because the lone pair of electrons of the
carbanions of an ester is not as readily delocalized as the carbanion of an aldehyde or ketone.
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.. . .–
:O : O:
.–.
R – CH – C – R R – CH = C – R
Electron pair on C is delocalised

.. – .. ..–
:O: :O : O:
.–. + .–. .. ..
R – CH – C = OR
.. R – CH – C – OR
.. R – CH = C – OR
..
Electron pair on C is localised Electron pair on C is delocalised

Note that in esters two pairs of electrons compete for delocalization onto carbonyl oxygen.
Nitroalkanes, nitriles and N,N-disubstituted amides also have relatively acidic a-hydrogens because in each
case, the electrons left after the removal of the proton can be delocalized onto an atom that is more electronegative than
carbon. Further, if the a-carbon is in between two carbonyl groups, the acidity of an a-hydrogen is even greater. Thus ethyl
acetoacetate (a b-keto ester) and acetylacetone (a b-diketone) are more acidic than the corresponding ordinary ketone.

O O O O
|| || || ||
CH 3 - C - CH2 - C - OC 2 H5 CH 3 - C - CH 2 - C - CH3
Ethyl acetoacetate Acetylacetone
(Ethyl 3 - oxobutyrate) (2, 4-Pentanedione)

Higher acidity of a-hydrogens bonded to two electronegative groups ( C = O, –NO2, –C º N) is because the
electrons left after the removal of proton can be delocalized onto two oxygen atoms.

.. ..- .. .. ..– ..
:O : O: :O :O : O: :O
|| | || .-. || | ||
CH 3 - C - CH = C - CH 3 ¬¾
® CH 3 - C - C H - C - CH 3 ¬¾
® CH 3 - C = CH - C - CH 3
Re sonance stabilization of 2,4-pentanedione anion

1. How many acidic hydrogens are present in each of the following?

(a) 3,3-Dimethyl-2-butanone (b) Benzyl methyl ketone
(c) 2,2-Dimethylpropanal (d) Cyclohexane-1,3-dione
2. Arrange the listed compounds in each of the following groups in order of decreasing acidity.

O O O
|| || ||
(a) CH 3 C CH 3 , CH 3 C OH, CH 3 C OCH 3 , CH º CH

O O O O O O
|| || || || || ||
(b) CH 3 C CH 2 C CH 3 , H 3 CO C CH 2 COCH 3 , CH3 C CH 2 C OCH 3

O O O
NCH3 O
(c) , ,
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The pKa values of some carbon acids
pKa pKa
O
||
CH 3 C NMe 2 30 N º CCH 2 CN 11.8

O O O
|| || ||
CH 3 C OCH 2 CH3 25 CH 3 C CH2 C OC2 H 5 10.7

O O
|| ||
CH 3 C º N 25 C6 H 5 - C CH2 C CH 3 9.4

O O O
|| || ||
CH 3 C CH 3 20 CH 3 C CH 2 C CH 3 8.9

O O O
|| || ||
CH 3 C H 17 CH 3 C CH 2 C H 5.9

CH 3 CH 2 NO 2 8.6 O 2 NCH 2 NO 2 3.6

15.2 Reactions via Enols and Enolate Ions

Although in majority of cases, enolates are carbanions, in some cases ordinary carbanions (not enolates) serve
as carbanions.

15.2.1 Racemization
When a solution of (+)-sec-butyl phenyl ketone in aqueous ethanol solution is treated with either acids or bases,
a racemic mixture of the ketone is formed after some time.

O
C6H5 –
C6H5 OH
OH or (±) – Butyl phenyl ketone
C – C – C6H5 + C=C
H 3C H3O H3C C6H5
H
(R) – (+) –sec-Butyl phenyl ketone Enol, E or Z
(chiral) (achiral)

In the acyclic ketone, the enol or enolate anion formed can be E or Z. Protonation on one face of the E isomer and
protonation on the same face of the Z isomer produces enantiomers.
Mechanism
Base-catalyzed enolization.

.. ..–
O: – O:
.. OH
OH H–OH –
C–C C–C C=C + OH
H Enol (achiral)
Ketone (chiral)

Acid-catalyzed enolization

.. . .+ ..
O: + O–H
H–OH2 .O. – H +
C–C C–C C=C + H3O
H H
H Enol (achiral)
Ketone (chiral)
..
H–O
..–H
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1. What do you expect when each of the following optically active ketone is treated with a base?

O O O
CH3 C2H5
H
(a) C – C – C6H5 (b) C – CH2 – C – C6H5 (c)
C2H5 CH3 CH3
C3H7 H

2. Explain with mechanism what happens when sec-butyl phenyl ketone is treated with D 3O+ in the presence of D2O.
3. Predict which form (keto or enol) will present in the larger concentration at equilibrium in each of the following. Suggest the reason
for the predominant form.
(a) 2, 4-Pentanedione (b) 2,4-Cyclohexadien-1-one

15.2.2 Formation of Lithium Enolates

The amount of carbonyl compound converted to enolate depends on the pKa of the carbonyl compound and the
base used to remove the a-hydrogen. For example, when OH– is used to remove an a-proton from acetone (pKa = 20), only
a small amount of the carbonyl group is converted into enolate because OH– is a weaker base than the base being formed.

O O- Na+
|| |
CH3 – C– CH 3 + Na+ OH – CH 3 - C = CH2 + H2 O
Weaker acid Weaker base Stronger base Stronger acid
(pK a = 20) (pKa = 16)

On the other hand, if a very strong base is used, the equilibrium lies far to the right. Lithium diisopropylamide
(LDA*) is a very strong base used for converting ketones completely to the corresponding enolate form.

O O-Li+
|| |
CH 3 - C - CH 3 + (iso - C 3 H7 )2 N - Li + ¾¾
® CH 3 - C = CH 2 + ( iso - C3 H7 )2 NH
Stronger acid Stronger base Wea ker base Weaker acid
(pK a = 20) (pK a = 38)

Regioselective formation of enolate anion : An unsymmetrical ketone can form two possible enolates. Which of the
two enolates predominates depends upon the nature of the base used and on the conditions employed.
(a) As in the formation of alkenes, the enolate with the more highly substituted double bond is the thermodynamically
more stable enolate. The thermodynamic enolate is formed predominantly under conditions that permit the
establishment of an equilibrium i.e., by using a relatively weak base in a protic solvent.
– –
O O O
H3C H3C Weak base H3C
LDA

Kinetic 2-Methylcyclohexanone Thermodynamic

(less stable) enolate (more stable) enolate

(b) The enolate with the less substituted double bond is usually formed faster because here hydrogen is removed from the
less sterically hindered and slightly more acidic position. This enolate, called the kinetic enolate is formed
predominantly when the reaction is kinetically controlled (or rate controlled), i.e. by using a very strong base like
LDA. LDA, being a strong and sterically hindered base rapidly removes proton from the less hindered a-carbon
of the ketone. The notable feature of LDA is that although it is a strong base, it is a poor nucleophile hence it does
not attack the carbonyl carbon. The poor nucleophilic character of LDA is again due to the presence of two bulky
alkyl substituents on the N which make difficult for the N to come close enough to the carbonyl carbon.

* LDA is easily prepared by adding an alkyllithium to diisopropylamine in THF at –78°C.

THF
[(CH 3 )2 CH]2 NH + C 4 H 9-Li + ¾¾¾® [(CH 3 )2 CH]2 N - Li + + C 4 H10
Stronger acid Stronger base Weaker base Wea ker acid
(pKa = 38) (pK a = 50)
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Lithium enolate in desired aldol reaction : One of the important applications of lithium enolate is to carry out (i)
aldol condensation in unsymmetrical ketone, and (ii) mixed (crossed) aldol condensation between two different aldehydes/
ketones, each capable of undergoing aldol condensation itself, in a desired direction. For example, aldol condensation
between CH3COCH3 and CH3CH2CHO gives rise to three aldol products;

OH -
CH 3 COCH 3 + CH 3 CH 2 CHO ¾¾¾® Three products
However, the desired aldol can be obtained by taking ketone in the form of lithium enolate and adding another
aldehyde or ketone to this lithium enolate.
O
||
CH 3 - C - CH 3
The ketone is added to LDA which
– +
removes an a–H from the ketone to (Me2 CH)2 N Li / THF, –78°C
produce an enolate

O- Li +
|
CH 3 - C = CH 2
The aldehyde is added when C HCH 2 CH 3
enolate reacts with the ||
aldehyde at its carbonyl carbon O

O
||
CH 3 - C - CH2 - CH - CH 2 CH 3
|
O- Li+

Acid-base reaction occurs H – OH

when water is added

O
||
CH 3 - C - CH2 - C H - CH2 CH 3
|
OH

1. Give the starting materials used for preparing following aldol products.

CH 3 OH OH
| | |
(a) CH 3 CHCOCH 2 CHCH 2 CH 3 (b) CH 3 CH = CHCOCH 2 CHCH 3

OH OH

(c) (d)
O O

15.2.3 A l k yl ati on of the a-Carbon of Carbonyl Compounds via Lithium Enolates

Alkylation of the a-carbon of carbonyl compounds (ketones*, esters and nitriles) gives us another important way
to form a new carbon-carbon bond.
O O O
LDA / THF
:
– 1° RX R

* Aldehydes are not suitable for direct alkylation because they are more reactive (strong electrophiles) than ketones, hence they will
undergo aldol condensation with enolate ion (formed from another molecule of the aldehyde) very readily.
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O R O
|| | ||
(i) LDA/THF
C 6 H 5 CH 2 C OCH 3 ¾¾¾¾¾¾® C 6 H 5 C H C OCH 3
(ii) 1° RX

R
|
(i) LDA/THF
CH 3 CH 2 CH 2 C º N ¾¾¾¾¾¾® CH 3 CH 2 C HC º N
(ii) 1° RX

Since enolate ions are strong bases, successful alkylations occur only when primary alkyl, primary benzylic, and
primary allylic halides are used; with secondary and tetiary halides, elimination becomes the main course of the reaction.
In case the ketone is unsymmetrical, two different products can be formed.

–
O O
CH3 H3C CH3
CH3I

O
CH3 Kinetic enolate
LDA (favoured at low temp.)
–
O O
CH3 CH3
CH3I
CH3

Thermodynamic enolate
(favoured at high temp.)

1. Predict the product(s) in each of the following reactions.

(i) LDA (i) LDA

(a) CH 3 COCH 3 ¾¾¾¾¾¾¾® (b) CH 3 CH 2 CN ¾¾¾¾¾¾¾®
(ii) CH 2 =CHCH 2 Br (ii) C 6H 5 CH 2 Br

O O
(i) LDA (i) LDA
(c) (d)
(ii) CH3CH2I (ii) CH3I

15.2.4 Alkylation and Acylation of the a-Carbon via Enamine

An enamine (a vinyl amine), the nitrogen analogue of an enol, is formed when an aldehyde or a ketone reacts with
a secondary amine.

O
N
+
N
H
Pyrrolidine
(a 2° amine) An enamine

The resonance of an enamine shows that it has some carbanions character. Although, an enamine is a stronger
nucleophile than an enol, it is quite selective in its alkylation reactions.
.. +
N N .–.
C=C C=C

enamine (major) iminium ion (minor)

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Like enolates, enamines react with electrophiles and thus they help in introducing an electrophile to the a-
carbon of an aldehyde or a ketone.

+
:N N O
CH3 + CH3
CH3 – Br H
+
+
N
an iminium ion H2

Since, alkylation step is an SN2 reaction, only primary alkyl halides or methyl halides should be used. Note that
the iminium ions are unreactive toward further alkylation, so only one alkyl group can be introduced via enamine route
(advantage over enolate route which may lead to monoalkylated, dialkylated and O–alkylated products).
O O O O OCH3
CH3 H3C CH3 CH3
(i) LDA
+ + CH3 +
(ii) CH3Br

Aldehydes and ketones can also be acylated via an enamine intermediate.

– O
+ O + O O
N: O N N +
C – CH3
|| C – CH3 C – CH3 H
CH3 - C- Cl + +
N
Cl H2

The enamine alkylation/acylation is sometimes called Stork reaction. Note that b-diketones are easily alkylated,
hence they serve as useful intermediates in the synthesis of more complicated molecules.

1. Give the expected product of the following acid-catalyzed reactions.

(a) Acetophenone + Dimethylamine (b) Acetophenone + Methylamine
(c) Cyclohexanone + Aniline (d) Cyclohexanone + Piperidine
2. Give steps involved in the following conversions through enamine formation.
(a) Cyclopentanone ¾¾
® 2-Allylcyclopentanone (b) 3-Pentanone ¾¾
® 2-Methyl-1-phenyl-3-pentanone

(c) Acetophenone ¾¾
® Dibenzoylmethane

15.2.5 a-Halogenation of Aldehydes and Ketones

Discussed in the chapter on 'Aldehydes and Ketones'.

1. How would you accomplish the following conversions?

(a) CH 3 CH 2 CHO ¾¾
® CH 3 C HCHO (b) CH 3 CH 2 CHO ¾¾
® CH 3 C HCHO
| |
NMe2 OH

O O O O
OCH3
(c) (d) O
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2. How will you prepare the following compounds from a carbonyl compound with no carbon-carbon double bonds?

O
O
(a) (b)

a-Brominated carbonyl compounds are useful in synthetic chemistry, because such compounds easily undergo
reactions of alkyl halides.

O O O
Br –
Nu
–
– tert–BuO : Nu –
Br + + Br

15.2.6 a-Halogenation of Carboxylic Acids (The HVZ Reaction)

Carboxylic acids do not undergo substitution reactions at the a-carbon (of course except halogenation through
the HVZ reaction) because the OH group is much more acidic than the a-carbon. However, if a carboxylic acid is treated
with PBr3 and Br2 (or red phosphorus and excess Br2), then bromination occurs at the a-carbon; the reason being the fact
that here the a-substitution occurs on an acyl bromide rather than the parent carboxylic acid. For details, consult chapter
on 'Carboxylic Acids'.

15.2.7 Nucleophilic Addition of Enolates to Carbonyl Compounds

Under this heading following reactions are covered.
(a) Aldol condensations : Discussed earlier in the chapter on 'Aldehydes and Ketones'.
(b) Reactions related to aldol condensation : There are other important reactions which involve the attack by a
carbanion (provided by compounds other than aldehydes and ketones) on a carbonyl group. These reactions are
Perkin, Knoevenagel, Claisen, Dieckmann etc. These reactions may also be grouped in nucleophilic acyl
substitution.
(i) Perkin reaction :
CH COONa
C 6 H 5 CHO + (CH 3 CO)2 O ¾¾¾¾¾¾
3 ® C 6 H 5 CH = CHCOOOH
Here the carbanion is provided by (CH3CO)2O.
(ii) Knoevenagel reaction :
piperidine
C6 H 5 CHO + H 2 C(COOC 2 H 5 )2 ¾¾¾¾¾® C6 H 5 CH = CHCOOH

Here the carbanion (nucleophile) is provided by H 2 C(COOC2 H 5 )2 .

(iii) Claisen condensation :
C H ONa
CH 3 COOC 2 H 5 + H 3 CCOOC 2 H 5 ¾¾¾¾¾
2 5 ® CH 3 COCH 2 COOC 2 H 5
Here the carbanion is provided by CH3COOC2H5.
(iv) Dieckmann condensation :

C H ONa COOC2H5
COOC2 H 5 (CH 2 )4 COOC2 H 5 ¾ ¾2 ¾5 ¾ ¾®

Here the carbanion is provided by a-carbon of the ester.

All these reactions are discussed in appropriate chapters on Aldehydes and Ketones or Functional
Derviatives of Carboxylic Acids.
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(c) Reformatsky reaction :

OZnBr
Zn
C = O + BrCH2COOR benzene
C
CH2COOR

Here the carbanion is provided by the carbon atom attached to halogen (Br).

+d -d
BrCH 2 COOR + Zn ¾¾
® BrZn CH 2 COOR

For details, consult chapter on "Aldehydes and Ketones".

(d) Addition of Grignard reagents :

+ OH
H
C = O + CH3MgX C
CH3

NMgX + O
H
- C º N + CH 3 MgX ¾ ¾
® -C –C
CH3 CH3

Here the carbanion (nucleophile) is provided by alkyl or aryl group of the Grignard reagent. For details, consult
chapter on "Organometallic Compounds".
(e) Wittig reaction :

R R + R
+ – H
C = O + Ph3P = C or Ph3P – C C=C + Ph3P = O
R' R' R'

Details are given in the chapter on "Aldehydes and Ketones".

15.2.8 Nucleophilic Acyl Substitution

Here the nucleophilic attack finally gives substituted product (the typical reaction of acyl compounds), while in
aldol condensation, the nucleophilic attack leads to addition (the typical reaction of aldehydes and ketones). Examples of this
type are Claisen condensation, Dieckmann condensation (both discussed in esters) and acylation of organocopper
compounds (discussed in the preparation of ketones in the chapter on 'Aldehydes and Ketones').

O O
|| R ||
R '- C - Cl + LiCu ¾¾
® R '- C - R + RCu + LiCl
R

Here the carbanion is provided by alkyl group.

15.2.9 Nucleophilic Aliphatic Substitution (Substitution on an sp3 Carbon by a Nucleophile)

(a) Coupling of alkyl halides with organometallic compounds : Discussed in the preparation of alkanes, in the
chapter on 'Aliphatic Hydrocarbons–I'. Here, carbanion is provided by alkyl group of the organometallic
compound.
(b) Alkylation of malonic ester, ethyl acetoacetate and related compounds.
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15.3 ILLUSTRATIVE EXAMPLES

Example 1 :
Propose a mechanism to show how acetophenone undergoes base-promoted bromination to form
tribromoacetophenone.
Solution :

O H – O O-
|| | OH - || |
C6 H 5 - C - C - H C6 H 5 - C - C
| . . H 2 ¬¾® C6 H 5 - C = CH2
H

O Cl O Cl O- Cl
|| | - || | | |
Cl–Cl OH
¾ ¾ ¾¾
® C6 H5 - C - C - H ¾ ¾ ¾® C6 H 5 - C - CH
.. ¬¾® C6 H 5 - C = CH
| –
H

O Cl O Cl O- Cl O Cl
|| | || || | | || |
Cl–Cl OH - Cl - Cl
¾¾ ¾¾
® C6 H 5 - C - C - Cl
¾ ¾ ¾¾ ® C6 H5 - C - C - Cl ¾ ¾ ¾® C6 H 5 - C - C
.. - Cl ¬¾® C6 H 5 - C = C - Cl |
| –
H Cl

Example 2 :
Propose mechanism for the following conversion.

O O
+ CH2C6H5
(i) H
+ +
(ii) C6H5CH2Br, H3O
N
H
Solution :

+ +
N N
H + H H2 O
CH2C6H5 CH2C6H5

+ +
N OH2 N OH N OH
H H + H H
H 2O H 3O
CH2C6H5 + CH2C6H5 CH2C6H5
(– H3 O )

+
OH O–H O
+ H H H
+ H 2O
N CH2C6H5 CH2C6H5 CH2C6H5
H
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Example 3 :
Give steps for preparing following compounds using malonic ester synthesis.
(a) 3-Phenylpropanoic acid (b) 2-Benzylbutanoic acid
(c) Cyclopentanecarboxylic acid (d) 2,2-Dimethylbutanoic acid
Solution :
|
In malonic ester synthesis, the –CH2COOH or - C HCOOH part of the product is coming from malonic ester itself, so
the other substituent(s) should be introduced by alkylation of malonic ester before the final steps of hydrolysis and
decarboxylation.

O O
C – OC2H5 H3O
+ C – OH heat
H2C H2C H3CCOOH + CO2
C – OC2H5 C – OH
O O

Further note that malonic ester synthesis can be applied for synthesising carboxylic acids having either one or two
|
substituents on the a-carbon (not three), i.e. either –CH2COOH or - C HCOOH type and not R3CCOOH type. For
getting the right route for synthesis of such questions, first write down the structure of the product and know the nature
of alkyl group to be introduced.

O O COOH CH3 O
|| || | ||
(a) C6 H 5 CH 2 CH 2 C OH (b) CH 3 CH2 CH C OH (c) (d) CH 3 CH 2 C — C OH
| |
CH2 C6H5 CH3

(i) C H ONa +
(i) H 3 O
(a) H2 C(COOC2 H 5 )2 ¾¾¾¾¾¾
2 5
® C6 H 5 CH 2 CH(COOC2 H 5 )2 ¾¾¾¾¾ ® C6 H 5 CH 2 COOH
(ii) C6 H 5 CH 2 Br (ii) heat

O O
(i) C H ONa (i) C H ONa
(b) ¾ ¾ ¾2 ¾5 ¾ ¾® [ ] ¾ ¾ ¾2 ¾5 ¾ ¾®
C2H5O OC2H5 (ii) CH3 CH 2 Br (ii) C6 H 5 CH2 Br

O O
O
+
(i) H3O
C2H5O OC2H5
(ii) heat OH

C6H5 C6H5

COOH
O O O O
(i) C H ONa (i) H3O+
¾ ¾ ¾2 ¾5 ¾ ¾®
(c) C2H5O OC2H5 (ii) Br(CH 2 )4 Br C2H5O OC2H5 (ii) heat

(d) 2,2-Dimethylbutanoic acid has three alkyl groups on the a-carbon atom, but malonic ester has only two
a-hydrogen atoms so only two alkyl groups (sbstituents) can be introduced in malonic ester. Thus the
compound (d) can't be prepared through malonic ester synthesis.
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Example 4 :
Give steps involved in the conversion of ethyl acetoacetate into
(a) 3-propyl-5-hexen-2-one (b) cyclopropyl methyl ketone
(c) 4-phenylbut-3-en-2-one (d) benzyl sec-2-propenylphenyl ketone
Solution :

O O
O O
–
(i) C2H5O OC2H5
(a) OC2H5 (ii) Br

O O O
O O

–
OH
(i) C2H5O OC2H5 + heat
H
(ii) Br (–CO2)

3-Propyl-5-hexen-2-one

O O
O
O O – OC2H5 (i) H3 O
+
(b) (i) C2 H5 O
(ii) Br (CH2)4 Br (ii) heat
OC2H5

CHC6H5
OC2H5 OC2H5
(c) C2H5CH = O +
(Knoevenagel
O O
reaction)
O O

C6H5 C6H5
+
H3O OH heat

O O O
4-Phenylbut-3-en-2-one

O
(d)

This compound can't be prepared from ethyl acetoacetate because here ketonic group is having substituents
on both –CH2– groups which is not possible because in acetoacetic ester only one –CH2– is activated. However,
this can be prepared from dibenzyl ketone in the following way.

O
O O Br
C6H5 C6H5
C6H5 C6H5 LDA C6H5 C6H5
– 3
1
2
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Example 5 :
Perkin condensation between benzaldehyde and ethanoic anhydride in presence of sodium ethanoate leads to the
more stable trans-cinnamic acid. Suggest a method for preparing the cis-cinnamic acid (cis-3-phenylpropenoic
acid).
Solution :
Remember that a cis-alkene can often be prepared from an alkyne by hydrogenation of a triple bond over Lindlar's
catalyst.

C6H5 H Br Br
H CH 3 COONa Br2 , CCl4 | |
C6 H 5 C = O + (CH 3 CO)2 O ¾ ¾ ¾ ¾ ¾ ¾® C=C C6 H 5 CH - CHCOOH
H COOH
trans-isomer
(more stable)

(i) alc. KOH H

C6H5 COOH
¾¾¾¾¾¾ 2
® C6 H 5 C º CCOOH ¾¾¾ ® C=C
(ii) Na, NH 3 Lindlar H H
cis - Cinnamic acid

Example 6 :
Complete the following and comment on the reaction of each step.

MgBr (i) HCHO PBr3

[A] [B] [C]
+
(ii) H

(i) Ph3P OHCCH2(CH2)7COOC2H5 H2

[D] [E] [F] + [G]
(ii) Base Lindlar

Solution :

+
MgBr HCHO / H OH
MgBr
[A] [B]

PBr3 (i) Ph3P

Br PPh3
(ii) Base
[C] [D]

OHCCH2 (CH2)7COOC2H5 (CH2)7COOC2H5

[E]

H
H
H
H2 (CH2)7COOC2H5 +
Lindlar (CH2)7COOC2H5
catalyst
H (trans) (cis)
[F]
[G]
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Example 7 :
Give steps involved in the conversion of
(a) ethyl cyanoacetate to valproic acid (2-propylpentanoic acid), an antiepileptic compound.
(b) benzaldehyde to acetophenone involving 1,3-dithiane as an intermediate.
(c) Ethyl phenyl ketone to darvone, an analgesic using (CH3CH2CO)2O, C6H5CH2MgBr, HCHO and (CH3)2NH as
reagents.
C6H5 CH3
| |
C6 H 5 CH 2 - C - CHCH 2 NMe2 (darvone)
|
OCOC2H5

COOH

(d) 2NaCH(COOC2 H5 )2 + BrCH 2 CH 2 CH2 Br ¾ ¾

® COOH

Solution :
COOH
CN COOC2H5
–
CN COOC2H5 (I) OH
base
(a) C + 2CH3CH2CH2Br (ii) heat
H2

O
+
H (i) C4H9Li
C6H5CH + S S (ii) CH3I S S
(b)
SH SH
H C6H5 CH3 C6H5

O
HgCl2,
CH3CC6H5 +
CH3OH, H2O
SH SH
CH 3
|
Mannich
(c) C6 H 5 - C - CH2 CH 3 + HCHO + HN(CH 3 )2 ¾¾¾¾¾
® C6 H 5 - C - CHCH 2 NMe2
|| reaction ||
O O

CH 2 C6 H5 CH 2C6H 5
| |
(i) C6 H 5 CH2 MgBr (CH 3 CH 2 CO)2 O
¾¾¾¾¾¾¾¾ ® C6 H 5 - C - CH - CH 2 NMe 2 ¾¾¾¾¾¾¾¾
® C6 H 5 - C - CH(CH 3 )CH 2 NMe 2
(ii) H 3 O + | | Acylation |
OH CH 3 OCOCH 2 CH 3
Darvone

COOC2H5 (i) C H ONa

(d) 2NaCH(COOC2 H5 )2 + BrCH 2 CH2 CH 2 Br ¾ ¾
® ¾¾¾¾¾¾
2 5
®
(ii) Br2
COOC2H5
H5C2OOC COOC2H5

COOC2H5 C2 H5 ONa COOC2H5

¾ ¾ ¾ ¾ ¾® (i) OH-
Br COOC2H5 ¾ ¾ ¾ ¾® COOH
COOC2H5 (ii) H 3 O+
H5C2OOC COOC2H5 (iii) heat
H5C2OOC COOC2H5 COOH
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EXERCISE 15.1 (MCQ - ONE option correct)

1. Predict the product P in the following reaction
CH 3 CH 2 CHO + D 2 O + OD - ¾¾
®P
O – (a) CH3CH2CDO (b) CD3CH2CHO
|| OD, D2O
H3 C - C - H P (c) CH3CD2CHO (d) CD3CD2CHO
7. Predict the nature of Z in the following reaction
O O
|| || 2 OH - , Br
CH 3 COCH 2 Br ¾¾¾¾¾ ®Z
(a) D3 C - C - D (b) H3 C - C - D
(a) CH2BrCOCH2Br (b) CH3COCHBr2
O OH (c) CH2BrCOCHBr2 (d) No reaction
|| |
(c) D3 C - C - H (d) H 3 C - CH - H 8. Predict the nature of [Y] and [Z] in the following reaction

2. Which of the following is true regarding conversion of a ketone

C H Li Raney Ni
into its enolic form by acids and bases? ¾ ¾4 ¾9 ¾® [X] ¾ ¾ ¾ ¾ ¾
® [Y] + [Z]
C6 H5 CH 2 Br H2
(a) In both types, the first step is the protonation of the S S
carbonyl group
(b) In both types, the first step is the removal of a-hydrogen (a) Y is C6H5CH2CH2CH2CH3 and Z is CH4
(c) The two steps i.e. protonation and removal of a-hydrogen
CH2 C6H5
are reversed in the base - and acid-catalyzed reactions |
(d) None is true (b) Y is CH 3 C HCH 3 and Z is CH4
3. Which of the following reactions of optically active sec-butyl (c) Y is C6H5CH2CH3 + CH3CH2CH3
phenyl ketone undergoes fastest? (d) Y is C6H5CH2CH2CH3 and Z is NiS
(a) Acid-catalyzed deuterium exchange 9. Which of the following order is correct regarding the percentage
(b) Base-promoted bromination of enolic form of 2,4-pentanedione in three solvents : H2O (A),
(c) Acid-catalyzed racemization CH3CN (B) and C6H14 (C)?
(d) None of these (a) A > B > C (b) B > A > C
(c) C>A>B (d) C > B > A
CH2OH
| 10. Which of the following compound does not form carbanion with
dil. Na 2 CO 3
4. 3CH 2 O + CH 3 CHO ¾¾¾¾¾¾
® HOH 2 C - C - CHO sodium ethoxide?
40° C |
CH2OH (a) CH 3 COCH 2 COOC2 H 5 (b) (CH 3 )3 C.COOC 2 H 5
The above reaction involves CN
(a) one aldol condensation and one Cannizzaro reaction (c) CH 2 (COOC2 H 5 )2 (d) CH 2
(b) two aldol condensations COOC2H 5
(c) two aldol condensation and one Cannizzaro reaction
11. Carbanion is
(d) three aldol condensations
(a) an electrophile (b) a nucleophile
5. In case, there is a competition between intramolecular aldol
(c) a Zwitter ion (d) a free radical
condensation and intermolecular aldol condensation, which factor
favours intramolecular aldol reaction over intermolecular? 12. The enol form of acetone, after treatment with D2O, gives.
(a) Using excess of base OD O
| ||
(b) Using limited amount of base (a) CH 3 – C = CH 2 (b) CD3 – C - CD 3
(c) Using high dilution technique
(d) Using large excess of the compound OH OD
| |
6. The compound P in the following reaction should be (c) CH 2 = C - CH 2 D (d) CD 2 = C - CD3

EXERCISE 15.2
(c) It can form more than two enolic forms of different stability
DIRECTIONS for Q. 1 to Q. 7 : Multiple choice questions with one (d) It can form only one enolic form
or more than one correct option(s). O O
Cl
R
2.
1. Which of the following statement is false regarding enolization of

Here the reagent R is

O
(a) Cl2 in presence of CH3COOH
(b) Cl2 in presence of NaOH
O
(c) Cl2 in presence of water
(a) It can form two enolic forms of equal stability
(d) Cl2 in presence of light
(b) It can form two enolic forms of different stability
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3. Which statement is true about acetoacetic ester?
Mechanism
(a) Its keto form boils at a higher temp. than the enolic form
Step 1.
(b) Its enolic form boils at a higher temp. than the keto form
(c) Both boil at same temperature O O
½½ ® ½½
(d) It discharges the colour of bromine dissolved in CCl 4
CH 3 ¾ C ¾ OC 2 H 5 + –OC 2H5 ¬¾¾ –CH2— C ¾ OC2 H5
Ethyl acetate
OH -
4. 2C 6 H 5 CHO ¾¾¾® C6 H 5 CH 2 OH + C6 H 5 COO -
H2O Step 2.
Which statement is correct regarding the above reduction of
benzaldehyde to benzyl alcohol? O
(a) One hydrogen is coming from H2O as H+ and another ½½ ®
from C6H5CHO as H– + –CH2— COC2 H 5 ¬¾¾
(b) One hydrogen is coming from H2O as H– and another
from C6H5CHO as H+
O O
(c) One hydrogen from H2O and another from C6H5CHO, ½½ ½½
both in the form of H– ®
¬¾¾ CH3— C ¾ CH 2 COC2 H 5 + –OC 2H5
(d) The reduction is an example of disproportionation reaction
5. A primary carbanion is
(a) more reactive than a secondary carbanion Although the products at the end of the second step are acetoacetic
(b) more stable than a secondary carbanion ester and ethoxide ion, the reaction does not stop at this step ; had it so
(c) less stable than a secondary carbanion been, the yield of the b-keto ester would have been very little because
(d) more stable than a tertiary carbanion the overall equilibrium upto this point is favourable to reactants and
not to products.
6. Which have active methylene group?
O O
|| || 8. The IUPAC name of ethylacetoacetate is
(a) CH 3 - C - CH 2 - C - CH 3 (a) acetoacetic ester (b) ethyl 3-oxobutanoate
(b) CH3 – CH2 – NO2 (c) ethyl acetic ester (d) ethylacetoacetate
9. The net reaction in the step 2 of the reaction is
O
|| (a) nucleophilic addition (b) nucleophilic substitution
(c) CH 3 - C - CH 2 - CN (c) both (a) and (b) (d) elimination
10. Which of the following statement is true ?
O
|| (a) The reaction is still not complete because acetoacetic ester is a
(d) C – CH2 – CN stronger acid than ethyl acetate
(b) The reaction is still not complete because acetoacetic ester is
7. Which have acidic H? a stronger acid than ethanol
(c) Both (a) and (b)
(a) CH3COOH (b) — OH (d) The reaction stops at the given final step giving acetoacetic
ester and ethoxide ion.
O 11. The above reaction, known as Claisen condensation involves the
|| formation of new bond between
(c) CH 3 - C - CH 2 - CN (d) NaNH2 (a) carbon and oxygen
(b) the two carbonyl carbon atoms of the two components
(c) a – carbon atoms of the two components
INSTRUCTION for Q. 8 to 11 : Read the passages given below and (d) the a-carbon of one molecule and the carbonyl carbon of
answer the questions that follow. another molecule

Instructions for Q. 12 : Following questions are Multiple Matching

PASSAGE 1 type Questions :
Due to acidic nature of a-hydrogens, esters when treated with a strong
base (generally C2H5ONa) undergo condensation of form b-keto ester. 12. Column - I Column - II
(Reaction) (Carbanion provided by)
O O
½½ ½½ ( i) C 2 H 5 ONa /C 2 H 5 OH (A) Roformatsky reaction (a) CH 3 COCH 2
CH3 COC 2 H 5 + CH3 COC 2 H 5 ¾¾¾¾¾¾¾¾® +
(ii) H 3 O
(B) Aldol condensation (b) CH 2 COOC 2 H 5
O
½½ (C) Claisen condensation (c) CH 2 CHO
CH3 CCH 2COOC 2 H5 + C2H5OH.
Ethyl acetoacetate O
(Acetoacet ic ester) ||
(D) HVZ reaction (d) RCH - C - Br
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761

EXERCISE 15.3 (Subjective Problems)

1. Give the important resonance forms for the enolate of
H3C COOH
(a) acetone (d) ethyl acetoacetate
(b) cyclohexanone (e) ethyl cyanoacetate
(c) 2,4-pentanedione (f) nitroacetone (f) CH3CHO to O
2. What happens when cyclohexanone is treated with (a) dil.
NaOH, (b) dilute HCl O
3. Give steps involved in the following conversions.

(a) ® C 6 H 5 CHO 18
C6 H 5 CHO ¾¾ (g) C6H5CHO to

(b) C6 H 5 CHO ¾¾
® C 6 H 5 CH 2 CHO O

(c) O
C6 H 5 CHO ¾¾
® C 6 H 5 CH = CH - CH = CHCHO
D D
O (h) to D
||
(d) C2 H 5 O C OC2 H 5 (ethyl carbonate) to
4. Is it possible to convert 4-hydroxy-4-methyl-2-pentanone to
Ph Ph acetone?
O OH O
O O O OH
–

O
|| 5. Give steps involved in the conversion of acetone and ethanal
(e) C2 H 5 O - C - OC 2 H 5 (ethyl oxalate) to to dehydrocitral,

+
NH3
–
O
CHO
O

O
O CH3 O CH3 O H H
|| | || | ||
1. (a) CH 3 - C - C - CH 3 (b) C6 H 5 - C - C H 3 (c) H 3 C - C - CH (d) H H
| |
CH3 CH3 O
(Three) (Three) (Zero) H H
(Six)
2. Acidity of an acid follows the stability of the corresponding conjugate base. Conjugate bases of the corresponding acids are arranged
in decreasing order.
O O O
|| || - - || . .
CH 3 - C - O - > CH 3 - C - C H 2 > C H 2 - C - O
. . CH 3 > HC º C
-
( )
(a) Equivalent resonating - ve charge is fully - ve charge is partly - ve charge not
structures delocalized onto C =O delocalized onto C =O delocalized

O O O
.. ..
– – O: – NCH3
(c) > >

I II III
–ve charge fully –ve charge partly delocalized,
delocalized O is more electronegative than N
hence II is more stable than III
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1. (a) The ketone does not have any hydrogen on its a-carbon (which is a stereocenter) and thus it will not undergo enolization.
(b) The ketone has a-hydrogen on an achiral carbon, hence it will undergo enolization but without racemization because the stereocenter
is a b-carbon which is not involved in enolization.
OH
H + CH3 +
H CH3
(c) H H
CH3 CH3 + H

(chiral) planar enol (racemic mixture)

(achiral)

+
CH3 O + CH3 OD +
| || D3O | || –H
2. C 2H5 - C - C - C6H5 C2 H5 - C - C C 6H5
| |
H H

.. +
CH3 O+ D + CH3 O
CH3 D | || –D | ||
OD
..
C=C C2 H 5 - C - C - C6 H 5 C2H 5 - C - C - C6 H 5 + Enantiomer
C2H5 C6H5 | |
D D

O O OH O
|| || | ||
3. (a) CH 3 - C - CH 2 - C - CH 3 CH 3 - C = CH - C - CH 3
Keto form (24%) 2,4-Pentanedione Enol form (76%)
The greater stability of the b-enol form is due to resonance stabilization of the conjugated double bonds and (in a cyclic form)
through hydrogen bonding.

.. H H
O
+
O: –
..

: O:
:
O
..
..

C C C C
H3C CH3 H3C CH3
C C

H H
Resonance stabilization and H-bonding in the cyclic form of enol-2,4-pentanedione

O OH
(b)

2,4-Cyclohexadien-1-one Phenol
(keto form) (enol form, »100)
The stability of the enolic form is again due to high resonance energy of the benzene ring.

CH3 O CH 3 O OH
| || | || |
(i) LDA
1. (a) CH 3 C H C CH 3 ¾¾¾¾¾¾® CH 3 C H C CH 2 CHCH 2 CH 3
(ii) OHCCH 2 CH 3

OH
|
(i) LDA
(b) CH 3 CH = CHCOCH 3 ¾¾¾¾¾® CH 3 CH = CHCOCH 2 C HCH 3
(ii) OHCCH 3

OH
OH
O
O (i) LDA
(I) LDA
(c) (d)
O O O O
(ii) (ii)
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O CN
1. (a) (b) C6H5

CH2CH3 O O
H3CH2C CH3
(c) + (d)

(Minor) (Major)

N(CH3 )2 NCH 3 NC6H5

| || N
1. (a) C6 H 5 - C = CH 2 (b) C6 H 5 - C - CH 3 (c) (d)

O NR2 O
+
H (i) Br
2. (a) + HNR2 +
(ii) H3O
(Any 2° aliphatic
amine) 2-Allylcyclopentanone

H5C2 C2H5
O N O
(C2H5)2NH (i) BrCH2C6H5 5
(b) + 3 2
(ii) H3O 4
1
C6H5

O N O O
|| HN | || ||
(i) C H COCl
(c) C6 H5 - C - CH3 ¾ ¾ ¾ ¾ ¾® C6 H5 - C = CH2 ¾ ¾ ¾6 ¾5 ¾ ¾® C 6 H5 - C - CH2 C C 6 H5
H+ (ii) H 3O +

2 H+ , H O HNMe
1. (a) CH 3 CH 2 CHO + Br2 ¾¾¾¾¾® CH 3 CHCHO ¾¾¾¾
2 ® CH C HCHO
3
| |
Br NMe2

2 H+ , H O OH -
(b) CH 3 CH 2 CHO + Br2 ¾¾¾¾¾® CH 3 C HCHO ¾¾¾® CH 3 C HCHO
| |
Br OH
O O O O O
Br OCH3 +
(c) Br2 CH3ONa (d) (i) Br2, H
OC6H5
+
H , H2O (ii) C6H5ONa

O Br O O
|| | || ||
Br2 tert - BuO -
2. (a) CH 3 CH 2 CH 2 C CH 2 CH 2 CH 3 ¾¾¾® CH 3 CH 2 CH C CH 2 CH 2 CH 3 ¾¾¾¾¾® CH 3 CH = CH C CH 2 CH 2 CH 3
+ -
H , OH

O O Br O

C CH2CH3 C CHCH3 C CH=CH2

Br2 Base
(b) + –
H OH
CH3 CH3
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EXERCISE 15.1
1 (c) 5 (c) 9 (d)
2 (c) 6 (c) 10 (b)
3 (d) 7 (b) 11 (b)
4 (d) 8 (c) 12 (b)

1. Only acidic hydrogens (a – to C = O) are replaced.

2. The steps in the base- and acid- catalyzed keto-enol interconversions are reversed. In the base-catalyzed reaction, the base removes the
a-proton in the first step and the oxygen is protonated in the second step. In the acid-catalyzed reaction, the acid protonates the oxygen
in the first step and the a-proton is removed in the second step.
3. All the three reactions proceed at about the same rate, because the rate determining step in each reaction is same (removal of a proton
from the a-carbon atom).

O O O O O O CH2OH
|| ||
|| || || || |
4. OH - HCH HCH
H C H + CH 3 C H ¾¾¾® HOCH 2 - CH 2 - C H ¾¾¾¾
® HOCH 2 - CH - C H ¾¾¾¾
® HOCH 2 - C - CHO
(aldol) (aldol) | (aldol) |
CH 2OH CH2OH

5. For getting good yield in intramolecular aldol condensation leading to cyclization, very dilute solution must be used. When very dilute
solutions are used (high dilution technique), probability for interacting one end of a molecule with the other end of the same molecule
will be more than with the other molecule.
6. Only acidic hydrogens (a-hydrogen) of an aldehyde/ketone are easily exchanged.

O
||
7. Presence of Br in CH 3 - C - CH 2 Br makes the carbon, to which it is attached, more acidic hence hydrogen attached to it will be first and
more readily replaced by Br.
8. Carbon-2 of 1,3-dithiane is more electropositive (acidic) due to the presence of electronegative sulphur on both sides. Hence it reacts
with the nucleophile (C4H9Li) easily.

C4H9Li C6H5CH2Br Raney Ni

C6H5CH2CH3 + CH3CH2CH3
(–C4H10) H2
S S S S S S
..
H CH2C6H5

9. In a polar solvent, such as water, the keto form is stabilized by solvation, hence it is more stable. When the interaction between solvent
becomes minimal, the enol form achieves stability by internal hydrogen bonding.

EXERCISE 15.2
1 (a,c,d) 2 (a,b) 3 (a,d)
>1 CORRECT OPTION 4 (a,d) 5 (b, d) 6 (a, b, c, d)
7 (a, b, c)
8 (b) 9 (b)
PASSAGE 1
10 (c) 11 (d)
MATCH THE FOLLOWING 12 (A) - b, (B) - a, c, (C) - b, (D) - d

O O O

1. or
O OH OH
More stable (conjugated system)

O O O
Cl – Cl
Cl2 / OH Cl2 / CH3COOH
2. (base-promoted (acid-catalyzed
chlorination) chlorination)
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765
d– d–
O O OH O
|| d+ ||d+ | ||
3. H3 C - C - CH2 - C - OC2 H 5 H3 C - C = CH - C - OC2 H5
ketonic form enolic form
(higher b.p. due to dipole-dipole interaction) (chelation lowers b.p.)

This form discharges colour of Br2 in CCl4.

4. The hydrogen atom that is added to the carbonyl carbon of the aldehyde in the reduction is derived directly from the other aldehyde
molecule as a hydride ion. The second hydrogen that is added to the negatively charged oxygen is coming from the solvent (consult
mechanism of Cannizzaro reaction). Oxidation of one molecule of the compound at the expense of other molecule of the same
compound is known as disproportionation.

EXERCISE 15.3
–
O O
O O-
|| . .- | :–
1. (a) CH 3 - C - C H 2 ¬¾® CH 3 - C = CH 2 (b)

– –
O O O O O O

(c)
H3C .. CH3 H3C CH3 H3C CH3
–
– –
O O O O O O

(d)
H3C .. OC2H5 H3C OC2H5 H3C OC2H5
–

O O O-
.. || - || |
(e)
N º C - CH - C - OC2 H5 ¬¾® N = C = CH - C - OC 2H5 ¬¾® N º C - CH = C - OC2H 5

O O -O O O O-
|| || | || || |
- + - + - +
(f) O - N- CH
.. - C CH 3 ¬¾® O - N = CH - C - CH3 ¬¾® O - N - CH = C - CH 3
–
(Other resonance forms of the –NO 2 group are not shown)
O O
H –
OH
2. (a) O + H (aldol cond.)
OH
as an electrophite as a nucleophile

O O O
+ +
H H
(b) O + (aldol cond.) (–H2O)
OH

H+
3. (a) C6 H 5 CHO + H 2 O 18 ¾¾¾
® C 6H 5 CHO18 + H 2 O

H H H
+ 18 | +
| H | + H2O –H
Mechanism : C6 H5 - C = O C6 H5 - C = OH C6H 5 - C - OH
|
18 O+ H
2

H H H H
+ + |
| H | –H2O | –H
C6 H5 - C - OH C6 H5 - C - + OH 2 C6 H 5 - C C6 H 5 - C = O18
| | ||
18 OH 18 OH 18 O+ H

CH3CHO + CH3 CHO

+
H
O H
O
|| ||
(b) CH 3 CH = CH - C = O
C6 H5 C H ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾
® C6 H 5 CH = CH - CH = CH C H
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Wittig H+
(c) C6 H 5 CH = O + Ph 3 P = CH - OPh ¾¾¾¾
® C6 H 5 CH = CH - OPh ¾¾¾¾¾
®
reaction Cleavage of
vinyl ether

tantomerizes
C6 H5 CH = CH - OH C6 H5 - CH2 - CH = O

O
O O
|| || OC2H5 Ph Ph Ph
OC2 H5- H3C C Ph
(d) C 2 H5 O - C - OC 2 H5 + H 3 C C Ph ¾ ¾ ¾ ¾ ¾® –
(Claisen cond.) OC2H5 (Claisen)
O O O O O

O O
+
(e)
–
OC2H5 a a' OC2H5 (i) H

OC2H5 (Crossed Claisen) (ii) heat (–CO2 from

b
+ O b-keto acids)

COOC2H5 O OC2H5

COOC2H5

O NH2
OC2H5 NH3, H2/Pd OH
(Reductive amination)
O O
(Exists as zwitterion)

(f) Proceed backward, recall that a g-lactone (a cyclic ester) can be easily obtained from a g-hydroxy acid which in turn can be
obtained from CH3CHO and succinic acid by an aldol-type condensation.

H3C COOH H3C COOH H2CCOOH

CH — CH CH3CHO +
O
H2CCOOH
OH CH2
O
A r-lactone HOOC
A r-hydroxy acid

(CH CO) O (i) H2 / Ni HF

(g) C6 H5 CHO ¾ ¾ ¾3 ¾ ¾
2 ¾
®
CH3 COONa (ii) SOCl2
HO O Cl O
O

O O OH Br
D D D D D D D D
OD
–
LiAlH4 PBr3 alc. KOH
(h) D D D D D D D
D2O
1,3,3-Trideutero cyclohexene

4. The reaction is an example of reverse of the aldol condensation commonly known as retrograde aldol or retro aldol. According to the
principle of microscopic reversibility (a reaction and its reverse follow exactly the same path but in opposite directions), all steps in the
aldol condensation take place in the reverse order.
–
O OH – O O O O O
OH H2O –
+ – + OH
H2C

H H
–
OH
5. +
O O (aldol)
O

H
–
OH
2
(aldol)
O CHO
3-methyl-2-butenal
(a, b-unsaturated aldehyde,
a-H is acidic)
 www.crackjee.xyz

16 .1 Preparation 16 .3 Illustrative Examples

16 .2 Properties EXERCISES

SOLUTIONS

a, b-Unsaturated carbonyl compounds contain both a carbon-carbon double bond and a carbon-oxygen double
bond separated by just one carbon-carbon single bond. Thus note that such compounds have a conjugated system
| |
—C = C— C = O .

16.1 Preparation

a, b - Unsaturated compounds are prepared by the following methods.

(i) Aldol condensation leads to a, b-unsaturated aldehydes and ketones.
(ii) Dehydrohalogenation of a-haloacids lead to a, b-unsaturated carboxylic acids.
(iii) Perkin reaction leads to a, b-unsaturated carboxylic acids.
(iv) Other methods specific for few compounds.

1. Give steps involved in the following preparation

O O
|| ||
(a) CH 3 CH = CH C OH from CH º CH (b) CH 2 = CH C OCH 3 from CH2=CH2
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COOH
(c) CH 2 = C COOCH 3 from CH3COCH3 (d) from adipic acid.
| COOH
CH3
O O
(e) from (f) Cinnamic acid from toluene

(g) Maleic acid from succinic acid

16.2 Properties

a, b-Unsaturated compounds possess not only the properties of the individual functional groups, i.e. C = C, and
|
- C = O , but also certain other properties, characteristic of the conjugated system.
However, here stress is given only those properties which are due to the presence of a,b-unsaturated carbonyl
moiety.

16.2.1 Electrophilic Addition

Usually, the carbon-carbon double bond is a rich source of electrons and hence undergoes electrophilic additions
easily. Further, a carbon-carbon double bond is activated by an electron-releasing substituent toward electrophilic addition
because an electron-releasing substituent stabilizes the transition state leading to carbocation by dispersing the developing
positive charge, conversely an electron-withdrawing substituent (e.g. C = O, –COOH, –COOR, –CN, etc.) on a carbon-
carbon double bond destabilizes the transition state hence it deactivates the C = C to electrophilic addition.
| | | | | |
+
C C G Y ¾¾® -C — C G ¾¾® - C - C G
G is an electron E lectrophile d+ |
releasing group Y+ Y
d
Transition state
(stable)

| | | | | |
-C= C W + Y + ¾¾® C C W ¾¾® - C - C + W
W is an electron – d+ |
withdrawing group Y+ Y
d
Transition state
(unstable)
Thus a,b-unsaturated ketones, acids, esters and nitriles are in general less reactive than simple alkenes toward
reagent like Br2 and HX. However, the groups which deactivate a C=C bond toward electrophilic reagents activate the C=C
bond toward nucleophiles. Hence, unlike ordinary alkenes, the C=C of an a,b -unsaturated ketones, acids, esters, or
nitriles are susceptible to nucleophiles. This reactivity towards nucleophiles is due to inductive effect of the substituent as
well as to its conjugation with the carbon-carbon double bond.
In the addition of an unsymmetrical reagent to the double bond of an a,b -unsaturated carbonyl compound,
hydrogen (positive end of the reagent) is attached to the a-carbon and the negative end of the reagent is attached to the b-
carbon.

CH 2 = CHCHO + HCl ¾¾
® CH 2 - CHCHO
| |
Cl H

CH 2 = CHCOOH + H 2 O ¾¾
® CH 2 - CHCHO
| |
OH H

CH 3 CH = CHCOOH + HBr ¾¾
® CH 3 CH CH - COOH
| |
Br H
H SO
(CH 3 )2 C = CHCOCH 3 + CH 3 OH ¾¾¾¾
2 4 ® (CH ) C — CHCOCH
3 2 3
| |
OCH3 H
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Such additions are again in consistent with the formation of the most stable carbocation.

| | |
—C— C — C —O —H

| | | + More stable +
H
- C = C- C = O
| | |
—C— C —C —O
|
H +
Less stable
Positive charge on the highly
electronegative oxygen

The more stable carbocation, now adds the negative ion or basic molecule in either of the two ways.

| | |
C C C O H
|
|b |a |
Br
– Br
— C— C — C — O— H Actually formed

| | |
+
C C C O H
|
Br
Not formed

Of the above two possibilities, only addition to the b-carbon yields a stable product, the enol form of a saturated carbonyl
compound.

| | | | | |
C C C O H C C C O
| | |
Br Br H
enol form Keto form

16.2.2 Nucleophilic Addition

a, b-Unsaturated carbonyl compounds contain two electrophilic sites, the carbonyl carbon and the carbon atom
that is b to carbonyl group. Thus such compounds may react with nucleophiles in two different ways.
(a) Direct or simple addition : The nucleophile preferentially adds directly to the carbonyl group forming direct
addition product, also known as 1,2-addition product (remember that the numbers 1 and 2 do not refer to IUPAC
locants but are used in a manner analogous to that employed in additions on conjugated dienes). Strong but
simple (not bulky) bases like organolithium and Grignard reagents and lithium aluminium hydride tend to react
by simple addition.

O1 OH
4 3 2|| (i) ethanol
|
CH 3 C H = C H CH + CH 3 MgBr ¾¾¾¾¾
® CH 3 CH = CH CHCH 3
(ii) H + Direct addition (1,2 -addition)
( 84%)

(b) Conjugate or 1,4-addition : When the nucleophiles are weak or bulky strong bases, they add preferentially to the
b-carbon forming conjugated or 1,4-addition product.

O O
|| ||
C6 H 5 CH = CH C OH + H 2 NOH ¾¾
® C6 H 5 CHCH2 C OH
|
NHOH
Note that in 1,4-addition, the nucleophile adds at the carbon-carbon double bond rather than at the carbon-
oxygen double bond. Here the nucleophilic portion of the reagent is attached to the b carbon quite ignoring the fact that it
has more or less number of hydrogen atoms.
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Remember that nucleophilic addition to the usual carbon-carbon double bond is very rare. However, it occurs
easily with a,b-unsaturated carbonyl compounds because here the carbanion formed is an enolate i.e. the carbanion has
a conjugated system, which is more stable and formed with a lower activation energy than a simple alkyl carbanion.
.. ..
O :O :O:– HO
C– –..
C— C— + C—
– H
Y: + C=C Y—C—C Y— C—C Y—C—C
Enolate anion

1,2- or 1,4-Nucleophilic addition to a,b-unsaturated carbonyl compounds may be governed by kinetic control or
by thermodynamic control.

O OH Y
fast
C— 1,2-addition C
C=C + HY C=C
Less stable product
slow
1,4-addition

HO O
C— C—
fast
Y—C—C Y—C—C—H

More stable product

Direct addition (1,2-) occurs faster than conjugate addition (1,4-) but gives a less stable product. This kinetic control
addition operates with strongly basic nucleophiles. The conjugate (1, 4-) addition gives the more stable product; recall that
the carbon-oxygen double bond, in general, is a more stable structural unit than the carbon-carbon double bond. This
thermodynamic control addition occurs in presence of a weakly basic nucleophile.

1. Write down the products in each of the following reactions :

heat
(a) C6 H 5 CH = CHCOOC 2 H 5 + OH - ¾¾¾
® (b) CH3 CH = CHCOCH 3 + I 2 + NaOH ¾¾
®

Zn
(c) CH 3 CH = CHCOC6 H 5 + O 3 ¾¾
® [ ] ¾¾¾
® (d) Maleic acid + Br2 (CCl 4 ) ¾¾
®
H 2O

(e) Fumaric acid + Cold alkaline KMnO4 ¾¾® (f) Ni, low temp.
C6 H 5 CH = CHCOOH + H 2 ¾¾¾¾¾¾®
pressure

Ni, high temp.

(g) C6 H 5 CH = CHCOOH + H 2 ¾¾¾¾¾¾¾
®
pressure

HOCH CH NH
(h) C6 H 5 CH = CHCOOH + 9 - BBN ¾¾
®[ ] ¾¾¾¾¾¾¾¾
2 2 2®

OC H -
(i) 2 5
CH 3 CH = CHCOOC2 H 5 + (COOC 2 H 5 )2 ¾¾¾¾ ®

2. Compare the reaction of sodium azide in aqueous acetic acid with acrolein and propanal.
3. Give the product in each case.

(a) CH3 CH = CHCHO + CH º CMgBr ¾¾

® (b) C6 H 5 CH = CHCOC6 H 5 + HCN ¾¾
®

4. Predict the nature of products in the following reactions.

NH CH NH CH = CHCOOCH
(a) 3
CH 2 = CHCN ¾¾¾ ®X + Y (b) 3 2
CH2 = CHCOOCH 3 ¾¾¾¾¾ 2 3
® [A] ¾¾¾¾¾¾¾¾ ® [B]
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Michael reaction.
In the nucleophilic addition to a, b-unsaturated carbonyl compounds, when the nucleophile is a carbanion, the
reaction is known as Michael addition or Michael reaction. The most common types of carbanions used are enolate ions
derived from b-diketones, b-diketo esters, b-keto esters, and b-keto nitriles. Since these enolates are weak bases and quite
bulky, addition occurs at the b-carbon to form 1,4-addition product.
O O O O
|| || || ||
OH -
(a) CH 2 = CH C H + CH 3 C CH 2 C CH3 ¾¾¾® C H 2 CH 2 C H
|
a ,b- unsaturated A b- diketone
aldehyde CH3 CCH CCH3
|| ||
O O

O O O O
|| || || C2 H 5 O - ||
(b) CH 3 CH = CH C CH 3 + C 2 H5 O C CH 2 C OC 2 H 5 ¾¾¾¾¾
® CH 3 C HCH 2 C CH 3
a ,b- unsaturated ketone A b- diketo ester |
CH(COOC2H5 )2

CH O -
(c) CH 3 CH = CHCONH 2 + C2 H 5 COCH 2 COOCH 3 ¾¾¾¾
3
® CH 3 C HCH 2 CONH 2
a ,b- unsaturated amide a b- keto ester |
C2H5COCHCOOCH3

O
|| -
OCH
(d) C 2 H 5 CH = CHCOOCH 3 + CH 3 C CH 2 C º N ¾¾¾¾
3® C 2 H 5 C HCH 2 COOCH 3
a ,b- unsaturated ester a b-keto nitrile |
CH 3 COCHCN

O O
CH3 –
CH3
OCH3
(e) CH2 = CHCOCH3 + CH2CH2COCH3
a,b-unsaturated O O
ketone a b-diketone

Thus, Michael reaction involves addition of a stabilized enolate ion to the double bond of an a,b-unsaturated carbonyl
compound. The electrophile (the a,b-unsaturated carbonyl compounds) accepts a pair of electrons, and thus called the
Michael acceptor; while the attacking nucleophile donates a pair of electrons, hence called the Michael donor. A wide
variety of compounds can serve as Michael acceptors and donors (Table below). Common acceptors contain a double
bond conjugated with a carbonyl group, a cyano group, or a nitro group. Common donors are enolates that are stabilized
by two strong electron-withdrawing groups such as carbonyl groups, cyano groups, or nitro groups.
Table : Some common Michael donors and Michael acceptors
Michael donors (Nucleophiles) Michael acceptors (Electrophile)
O - O O
|| .. || b-Diketones ||
Conjugated aldehydes
R - C - CH - C - R' CH 2 = CH - C - H

O - O O
|| .. || b-Keto esters ||
Conjugated ketones
R - C - CH - C - OR ' CH 2 = CH - C - R

O
||
R2Cu Li Dialkyl cuprates Conjugated esters
CH 2 = CH - C - OR

.. O
||
N–C=C Enamines CH 2 = CH - C - NH 2 Conjugated amides

O -
|| .. b-Keto nitriles CH 2 = CH - C º N Conjugated nitriles
R - C - CH - C º N
O -
|| ..
a-Nitro ketones CH 2 = CH - NO 2 Nitroethylene
R - C - CH - NO 2
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Mechanism. The base removes a proton from a-carbon of the compound having active methylene group to form a
carbanion which acts as a nucleophile. The nucleophile adds to the b -carbon of the conjugated system in the usual
manner.

O O O O
|| || -
.. || ||
® R - C - CH - C - R + H : Base +
R - C - CH 2 - C - R + : Base ¾¾
Nucleophile

O O O O
|| || .. || |
R CH CH C R R C C H C R ¾¾® R C H CH C R
|
RCOCHCOR
OH O
| ||
H : Base +
¾¾ ¾¾¾® R C H CH C R R C H CH 2 C R
( : Base ) | |
RCOCHCOR RCOCHCOR
E nol form Keto form

Note that if either of the reactant in a Michael reaction has an ester group, the base used to remove the a-proton
must be the same as the leaving group of the ester. This is because the base can also act as a nucleophile and attack the
carbonyl group of the ester. In case the nucleophile is different to the –OR group of the ester, the nucleophilic attack on the
carbonyl group will change the reactant.
–
O O O
|| | ||
CH 3 C OCH3 OC 2 H 5 ¾¾® CH 3 C OCH3 ¾¾® CH 3 C
Original reactant (nucleophile) | |
OC2 H5 OC2 H5
New reactant

Ammonia, primary and secondary amines are especially powerful catalysts for the Michael addition. They
function not merely as a base to regenerate a carbanion but also reacts with the carbonyl groups of the substrate to form an
intermedciate imine or iminium ion which is highly reactive toward nucleophilic addition. When enamines (tautomer of
imines) are used in place of enolates, the reaction is called Stork enamine reaction. Thus reaction between cyclohexanone
and acrolein in presence of pyrrolidine takes place as below.

+ –
N: N O
O O
CH2–CH=CH
CH2=CH– CH
+
N
H

+ O O
N O
CH2CH2CH + CH2CH2CH
H2O H , H2 O
– + +
(–OH ) N
H2

1. Write down the product obtained in the following reactions :

-
OC H
(a) Ethyl crotonate + Ethyl methylmalonate ¾¾¾¾¾
2 5®

-
OC H
(b) Ethyl a-methylacrylate + Ethyl cyanoacetate ¾¾¾¾¾
2 5®
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-
OC H
(c) Benzalacetophenone + Acetophenone ¾¾¾¾¾
2 5®

-
OCH
(d) Acrylonitrile + Allyl cyanide ¾¾¾¾
3®

-
OC H
(e) 2 5
C2H 5 O 2 CC º CCO2 C2 H 5 (1 mol.) + Acetoacetic ester (2 mol.) ¾¾¾¾¾ ®

-
2 5 OC H heat(i) OH -
(f) Ethyl crotonate + Malonic ester ¾¾¾¾¾ ® [X] ¾¾¾¾® [Y] ¾¾¾ ® [Z]
(ii) H +

2. What reagent would you use to prepare the following compounds?

(a) CH 3 COCH 2 CH 2 CH(COOCH 2 CH 3 )2 (b) COCH3

CH
COOCH3

3. (a) Write structural formulas corresponding to the intermediates formed in the following reaction.

C6H5
O
CH 3 ONa
C6 H5 CH2 COCH2 C6 H5 CH2 CHCOCH3 ¾ ¾ ¾ ¾¾®
CH 3OH
C6H5

(b) Write down the structure of the resonance hybrid obtained by the attack of (i) an electrophile (H +), (ii) a nucleophile on a
| | |
typical a,b-unsaturated carbonyl compound, - C = C - C = O

16.2.3 Diels-Alder Reaction

a,b-Unsaturated carbonyl compounds undergo addition reaction with conjugated dienes in which C-1 and C-4
of the conjugated diene is attached to the doubly bonded carbons of the a,b-unsaturated carbonyl compound to form a 6-
membered ring. The reaction, known as Diels-Alder reaction, is the example of cycloaddition.

CH2 O CH2 CH
CHO
CH CH HC CH
| + |
CH CH HC CH2
|| C
CH2 CH2 H2
1,3-Butadiene Acrolein 1,2,3,6-Tetrahydrobenzaldehyde
(Diene) (Dienophile)
(Greek : diene-loving)

Diels-Alder reaction, is although favoured by the presence of electron-withdrawing group in dienophile as in

the case of a,b-unsaturated carbonyl compounds, it also takes place when the dienophile is a simple alkene.

CH2

CH CH2
| + ||
CH CH2

CH2
(Diene) (Dienophile) Cyclohexene

Since Diels-Alder reaction involves a system of four p electrons (the diene) and a system of two p electrons (the
dienophile), it is also known as [4+2] cycloaddition.
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1. Predict the product in each of the following reactions :

O O

(a) + O (b) (c) +

+

O
2. Write down the diene and dienophile from which following products can be obtained
CH3 O O
CH3
C2H5O
(a) (b)

CH3O
O O

16.3 ILLUSTRATIVE EXAMPLES

Example 1 :
Give steps involved in the following conversion.
O HN NC6H5
C6H5NHNH2
OH O
Solution :
C6H5
N
OH H
1,4-addition
HN OH HN NC6H5
+ C6H5NHNH2 –H2 O
O
O O
Crotonic acid Phenylhydrazine
(a,b -unsaturated carboxylic acid) (a weak nucleophile)

Example 2 :
Steps for converting cyclohexanone to each of the following

O O
CN
(a) (b)
CN
Solution :
O O O
Br CN
Br 2 NaCN
(a)
+
H , H2O

O O O
Br
base HCN
(b)
Michael (1,4-addition)
CN
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Example 3 :
Predict the final product in the following reaction and comment on the main concepts involved.

O
CH3
(i) KOH / CH3OH
+ (ii) Al [OC(CH3 )3 ]3
O O

Solution :

O O
CH3
KOH / CH3OH
+ (Michael reaction)
O O O O

O O

Al tert-butoxide –H2O
(intramolecular
aldol condensation) O O
OH

First step of the reaction involves Michael reaction. The product of Michael addition has necessary functional
groups to undergo intramolecular aldol condensation to form cyclic product which undergoes dehydration to form
stable a,b -unsaturated ketone. The synthesis of cyclohexanone derivatives by Michael addition followed by
intramolecular aldol condensation is called Robinson annulation. The term annulation or annelation means building
of a ring onto some starting molecule.

Example 4 :
Give steps involved in the following conversion.

HCHO (1 mol.) + CH 2 (COOC 2 H 5 )2 (2 mol.) ¾¾

® HOOC(CH 2 )3 COOH

Solution :
The reaction involves aldol condensation followed by Michael additions.

H
|
base
H C = O + H 2 C(COOC2H 5 )2 ¾¾¾¾¾¾ ® H2 C - CH(COOC2H 5 )2
(aldol conden.) |
OH

-H O CH (COOC H )
¾¾¾¾
2
® H 2 C = C(COOC 2H 5 )2 ¾¾¾¾¾¾¾¾
2 2 5 2
® C H 2 CH(COOC 2H 5 )2
Michael addition |
CH(COOC2H5 )2

(i) OH - (i) OH - heat

¾¾¾¾® ¾¾¾¾® C H 2 CH(COOH)2 ¾¾¾® C H 2 CH 2 COOH
+ + | ( -2CO 2 ) |
(ii) H (ii) H
CH(COOH)2 CH 2COOH
Glutaric acid
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Example 5 :
5,5-Dimethylcyclohexa-1,3-dione can be prepared from mesityl oxide, (CH3)2C=CHCOCH3 and malonic ester using
Michael reaction as the main rection. Give necessary steps involved in the conversion.
Solution : O O
– –
OC2H5 OC2H5
+ CH2(COOC2H5)2 COOC2H5 Claisen
condensation
Mesityl oxide
O O COOC2H5 O
–
(i) OH heat
+ (–CO2 )
(ii) H
O O O
COOC2H5 COOH

Example 6 :
Write steps involved in the following conversion using Diels-Alder reaction.
O O

benzene

O O
Solution :
The conversion involves the Diels-Alder reaction between one molecule of p-benzoquinone and two molecules of
1,3-butadiene.
O O O
8 1
13 9 12 2
7
+
(Diels-Alder 6 3
14 11
reaction) 5 10 4
O O O
1,3-Butadiene 1,4-Benzo- 5,8,9,10-Tetrahydro- 1,4,5,8,11,12,13,14-Octahydro-
quinone 1,4-naphthaquinone 9,10-anthraquinone

Example 6 :
Dibenzalacetone, C 6H5CH=CHCOCH=CHC 6H5, and ethyl malonate are treated in equimolar amounts to give a
product (X) which does not respond to olefinic reagent. Suggest the structure for (X) and explain its formation.

Solution :
O O
|| a b b a ||
Michael
C6 H5 CH = CH C C H = C HC6 H5 + H 2 C(COOC2 H5 )2 ¾¾¾¾® C 6 H 5 C H = C H C CH2 C HC 6 H 5
addition |
CH(COOC 2 H 5 )2
O (X )

C
O
internal
|| H2C CH2
¾¾¾ ¾¾¾ ¾ ® C6 H 5 CH CH2 C CH2 C HC6 H 5
Michael reaction |
C6H5CH CHC6H5
C(COOC2H 5 )2
C
C2H5OOC COOC2H5

Note that the compound (X) still has a,b -unsaturated carbonyl group and also a structural moiety capable of
forming stable carbanion (marked by bold type), so it can undergo internal Michael reaction to form cyclic product
having no carbon-carbon double bond.
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EXERCISE 16.1 (MCQ - ONE option correct)

1. Which of the following is not an example of a,b-unsaturated

CH3
carbonyl compound? +
H3O /H2O
(a) Fumaric acid (b) p-Benzoquinone 7. H3 CO C = CHOCH3 P . Here P
(c) Mesityl oxide (d) None of these
2. Which of the following is not formed during dehydration of is
glycerol to prop-2-enal?
CH3
KHSO 4
C H 2 - CH - CH 2 ¾¾¾¾
® CH 2 = CHCHO (a)
| | | H3CO C=O
OH OH OH

CH 2 - CH = CH CH 2 = C - CH 2 CH3
(a) | | (b) | |
OH OH OH OH (b) H3CO CHCHO
CH 2 CH 2 CHO
(c) | (d) None of these
OH CH3
3. The reactions 1 and 2 used in the preparation of the following (c) H3 CO C – CH2OCH3
unsaturated carbonyl compounds are
OH
1
2
CHO (d) None of these
8. Predict the nature of the product in the reaction
(a) Oxidation by conc. HNO 3 and intramolecular aldol
condensation O
||
(b) Oxidation by alkaline KMnO4 and Michael reaction
C 6 H 5 CH = CH C C 6 H 5 + NaCN (aq.) ¾¾®
(c) Ozonolysis and aldol condensation
(d) Ozonolysis and Michael addition
OH
4. Which of the following carbocation is most likely to be formed |
during following reaction? (a) C 6 H 5 CH = CH C C 6 H 5
|
CN
CH 2 = CHCOOH + HBr ¾¾
® CH 2 BrCH 2 COOH
+ + O
(a) C H 2 CH 2 COOH (b) CH 3 C HCOOH ||
(b) C 6 H 5 CHCH 2 C C 6 H 5
OH |
| CN
(c) CH 2 = CH - C - OH (d) None of these
+
O
||
5. (i) CH 2 = CHCOCH 3 + HBr ¾¾
® P1 (c) C 6 H 5 CH2 C H C C 6 H 5
|
(ii) CN
CH 2 = CH - CH 2 CHO + HBr ¾¾
® P2
Here P1 and P2 respectively are (d) None of these
9. Predict the major product in the following reaction
(a) CH 3 CH(Br)COCH 3 , CH 3 CH(Br)CH 2 CHO
(b) CH 2 (Br)CH 2 COCH 3 , CH 2 BrCH 2 CH 2 CHO O
–
OH
(c) CH 2 (Br)CH 2 COCH 3 , CH 3 CH(Br)CH 2 CHO + CH3CH2SH
(d) P1 and P2 are same CH3
2 5 2 (i) (C H ) O
6. CH 3 CH = CHCOCH 3 + CH 3 MgBr ¾¾¾¾¾¾ ® P . Here
(ii) H3 O + HO SCH2 CH3 O
P may be
(a) (b) SCH2CH3
OH
| CH3 CH3
(a) CH 3 CH = CH C(CH 3 )2
HO SCH2CH3
CH3
|
(b) CH 3 CH - CH 2 COCH 3 (c) SCH2CH3 (d) None of these
(c) Both CH3
(d) None
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10. Predict the possible product in the following reaction :
C H 2 CH 2 CHO
|
piperidine CH3 COCHCOOC3H7 -n
+ Br COCH = CH
the best yield is obtained, when the base is
(a) OCH -3 (b) OC2 H -5
(a) CH – CH2 – C Br
(c) - (d) Equal
C 3 H7 - n
O
13. How many different products are possible by the Michael
addition between following two compounds?

2 5 OC H -
(b) Br CH 3 CH = CHCOCH = CHCH 3 + CH 2 (COOC2 H 5 )2 ¾¾¾¾ ®
COCHCH2
(a) One (b) Two
(c) Three (d) Four
14. Benzyl and dibenzyl ketone when treated in presence of a base
(c) Both (a) and (b) leads to the formation of a cyclic compound, tetracyclone
(d) No reaction
C6H5 C6H5
11. D1, 9 - Octalone is prepared according to the following series of
C6H5 C6H5
reactions
O O base
O O – O
OC2 H5
[ ] +
+ (1) (2) C6H5 C6H5
1,9
C6 H5 C6H5 O
D -Octalone
O Tetracyclone
The reactions involved at (1) and (2) steps are
(a) conjugate addition, 1,2-addition The reaction involved in the conversion is
(b) 1,2-addition, aldol condensation (a) Michael addition (b) Knoevenagel reaction
(c) 1,4-addition, aldol condensation (c) aldol condensation (d) Both (a) and (c)
(d) 1,2-addition and 1,4-addition 15. In Diels-Alder reaction, 1,3-butadiene can function as a
12. In the following Michael reaction (a) diene (b) dienophile
base (c) both (d) none
CH 2 = CHCHO + CH 3 COCH 2 COOC 3 H7 - n ¾¾¾
®

EXERCISE 16.2

DIRECTIONS for Q. 1 to 2 : Multiple choice questions with one or INSTRUCTION for Q. 3 to 11 : Read the passages given below and
more than one correct option(s). answer the questions that follow.

1. Which of the following does not undergo Michael addition? PASSAGE 1

The following questions relate to the reaction sequence outlined below
(a) C6 H 5 CH = CHCOCH 3 + C6 H 5 COCH 3
O C2H5 O C2H5
(b) C6 H 5 CH = CHCH 2 COC6 H 5 + CH 2 (COOC 2 H 5 )2 –
O O O O
–
EtO /EtOH CH3Cl

(c) + Br COCH = CH H3 C H3C

(d) CH 2 = CHCOCH 3 + CH 3 COCH 3 O C2H5

O O O 4
2. In the absence of peroxide addition of HBr is by anti-Markownikoff +CO2
+
rule : H 3O /heat
H3 C CH3 H3C CH3
(a) CH2 = CH – COOH
(b) CH2 = CH – CHO 3. Compound 1 is a/an
(a) a-keto carboxylic acid
(c) CH2 = CH – CH2OH
(b) b-keto carboxylic acid
(d) CH2 = CH – CN (c) a-keto ester
(d) b-keto ester
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4. The first step in the sequence could be enhanced by 10. CH 2 = CHCHO + HCl ¾¾
® P, here P should be
(a) replacing the hydrogens at the alpha position by two alkyl
Cl
groups |
(b) replacing one of the hydrogens at the alpha position by a (a) CH 3 CHCHO (b) ClCH2CH2CHO
chlorine atom (c) both (d) other product
(c) replacing one of the carbonyl groups with iodine atoms
11. ® P, here P should be
CH 2 = CHCH 3 + HCl ¾¾
(d) using ethanoate/ethanoic acid instead of ethoxide/ethanol
5. Although sodium methoxide is readily available, it was not used Cl
in the first step because |
(a) CH 3CHCH3 (b) ClCH2CH2CH3
(a) it is not as strong base as ethoxide
(b) it would cause an undesired transesterification (c) both (d) other product

(c) it would be more difficult to hydrolyze a methyl ester than

an ethyl ester
Instructions for Q. 12 to 13 : Following questions are Multiple
(d) a hindered base is needed to protect the carbonyl group
Matching type Questions :
6. The second step is a type of reaction known as
(a) SN 1 12. Column - I Column - II
(b) SN 2 (Carbon Acid) (pKa )
(c) electrophilic addition. (A) CH 3 COCH 2 COOC2 H 5 (a) 3.6
(d) free radical substitution
(B) CH 3 COOC 2 H 5 (b) 10.7
7. The third step involves
I. protonation of O in the C=O of the ester group (C) CH 3 CON(CH 3 )2 (c) 25
II. SN2 substitution of OC2H5 by OH (D) O2 NCH 2 NO2 (d) 30
III. heat-induced decarboxylation
(a) I and II (b) I and III 13. Column - I Column - II
(c) II and III (d) I, II, and III Minimum no. of Reaction
8. What type of reaction does not occur in the sequence? steps required
(a) Hydrolysis (b) Acid-base (A) One (a) Aniline to
p-bromoaniline
(c) Reduction (d) Decarboxylation
O O
|| ||
CN
(B) Two (b)
PASSAGE 2
A carbon-carbon double bond is a rich source of electrons and hence
(C) Three (c)
undergoes electrophilic additions easily. Further, a carbon-carbon
double bond having an electropositive group undergoes such reactions OH OH
very easily as compared to those having electronegative group. | |
COOH COOH

| | |d+ | |+ |
+
– C = C – CH3 + Y –C C – CH3 – C – C – CH3 Br
+ |
d (d)
Y Y
OH OH
I | |
COOH Br Br
| +
| | | |+
– C = C – NO2 + Y –C C+– NO2 – C – C – NO2 |
+ d | Br
d
Y Y
II Instructions for Q. 14 : Following questions are Integer Type
Questions :
9. Which of the following transition state is more stable?
14. In the scheme given below, the total number of intramolecular
(a) I (b) II
aldol condensation products formed from ‘Y’ is
(c) I = II (d) It can’t be predicted
1. O3 1. NaOH (aq)
2. Zn, H 2O
Y 2. heat
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EXERCISE 16.3 (Subjective Problems)

1. Give the structures of the products obtained when benzalacetone, (b) Give mechanism for the following reaction
C6H5CH=CHCOCH3 reacts with each of the following. Name
base
the main reaction involved in each of the following Crotonaldehyde + Cinnamaldehyde ¾¾¾
®
C 2H 5 OH
(a) HCl
(b) H2O, H+ CHO
Ph
(c) 1,3-butadiene
7. Propose a mechanism for the conjugate addition of a
(d) Benzaldehyde in presence of a base nucleophile to (a) acrylonitrile (CH 2 = CHCN) and to (b)
(e) NH2OH nitroethylene (CH2 = CHNO2).
(f) Malonic ester 8. Give the suitable Michael donors and acceptors for synthesizing
2. Give reactions involved in the conversion of ethyl 3-methylbut- the following compounds by Michael reaction.
2-enolate to 3,3-dimethylpentane-1,5-dioic acid using Michael
addition. C6 H 5 CHCH 2 COC6 H 5
(a) | (b) HOOCCH2 CH 2 CH 2 CN
3. Suggest a mechanism for the reaction between acrolein and C6H5 COCH 3
hydrazine to form dihydropyrazole
O O
O
CH2CH2CN CH3
(c) (d)
H + H N – NH
2 2 CH2 CH2COC6H5
N
N
H 9. The ketone X can't be prepared in good yield by the following
Michael addition between
4. Write down the final stable product obtained by the reaction of
HCl on p-benzoquinone. O
O O
5. Give steps involved in the following conversions
–
OH
CH2COOH + CH2 = CHCOCH3
(a) (CH 3 )2 C = CHCOCH 3 to (CH3)2C
CH2COOH X

Suggest a method for getting X in good yield from cyclohexanone

NH2
(b) H 2N to and methyl vinyl ketone.
10. How the following can be prepared by using Robinson
annulations?
H
N NH2 O
H2 N N
H (a) (b)
6. (a) Which hydrogen of crotonaldehyde, CH3CH=CHCHO, is O O
acidic? Write the resonating structures of the corresponding CH3
carbanion; which resonating structure is more stable?

HO
(c)

CH3
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1. To achieve the best result and in a minimum time, carry out the conversion backwards.
OH
Ag( NH 3 )2+ |
H+
(a) CH 3 CH = CHCOOH ¬¾¾¾ ¾ ¾ CH 3CH = CHCHO ¬¾
¾¾ CH3 C HCH2 CHO
( - H 2O)
–
OH
(aldol cond.)
H + , Hg 2+
CH º CH ¾¾ ¾¾ ¾® CH 3CHO

(b) H+ 3 ¾ ¾ C H CH COOH CH OH
CH 2 = CHCOOCH 3 ¬¾
¾¾ C H2 CH2 COOCH 3 ¬¾¾ 2 2
( - H2 O ) | |
OH OH
+
H
( i) HOCl
CH 2 = CH 2 ¾¾¾ ¾
¾® CH2CH2 CN
( ii) CN - |
OH

CH3 CH3
| |
H+ CH 3OH
(c) CH 2 = C COOCH 3 ¬¾
¾¾ CH3 - C - COOCH 3 ¬¾¾ ¾ ¾ CH 3 - C - COOH
| ( -H 2O) | |
CH3 OH OH

O CH3
|| |
CH 3 - C - CH 3 ¾¾® CH3 - C - CN
|
OH
O Br O O
(d) HO KOH (alco.) OH P, Br 2 HO
OH (–HBr) OH OH
O O Br O
Adipic acid
O +
O –
O
(e) H CH 2O, OH
(–H2O) OH (aldol cond.)
(CH CO ) O (i ) CrO , Ac O
(f) C6 H 5 CH = CHCOOH ¬¾¾ ¾3¾ ¾
2¾¾¾ C 6 H 5 CHO ¬¾ ¾¾3¾¾2¾¾ C6 H 5 CH 3
CH 3COO - (ii ) H2O
( Perkin reaction )

H 2O heat
HOOCCH = CHCOOH
(g) COOH COOH O O O cis- and trans-

KOH
(alc.)
P, Br 2
HOOCCH2CH2COOH HOOCCH2CHCOOH

Br

1. (a) C6 H 5 CH = CHCOO - (b) CH 3 CH = CHCOO - + CHI3

(c) CH 3 CHO + OHCCOC6 H 5 (d) rac - HOOCCH(Br)CH(Br)COOH
(e) rac - HOOCCH(OH)CH(OH)COOH (f) C6 H 5 CH 2 CH 2 CHO
(g) C6 H 5 CH 2 CH 2 CH 2 OH (h) C6 H 5 CH = CHCH 2 OH
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(i) The reaction is an example of crossed Claisen condensation. Here the carbanion is provided by g-hydrogen due to conjugated
system.

O O
|| ||
OC2H 5- - (COOC H )
CH 3 CH = CH C - OC2 H 5 ¾¾¾¾® CH 2 CH = CH - C - OC2 H 5 ¾¾¾¾¾¾
2 5 2 ® CH CH = CHCOOC H
2 2 5
OC2 H 5- |
COCOOC2H5
2. Acrolein (CH2=CHCHO) is an a,b-unsaturated aldehyde, hence it undergoes 1,4-addition reaction with sodium azide, a weak nucleophile.
NaN
CH 2 = CHCHO ¾¾¾¾
3 ® N CH CH CHO
3 2 2

Propanal (CH3CH2CHO) does not contain any a,b-unsaturation, hence it does not undergo addition reaction with sodium azide.
3. (a) Acetylide ion is a strong base, hence it adds on a,b-unsaturated carbonyl compounds by 1,2-addition.

OMgBr
|
CH 3 CH = CHCHO + CH º CMgBr ¾¾
® CH 3 CH = CH CHC º CH

(b) CN– is a weak base, hence it gives conjugate (1,4-)addition product.

C6 H 5 CH = CHCOC6 H 5 + HCN ¾¾
® C6 H 5 CHCH 2 COC6 H 5
|
CN

1,4 - CH = CHCN
4. (a) CH 2 = CHC º N + NH 3 ¾¾¾ ® CH 2 CH 2 CN ¾¾¾¾¾¾ 2 ® C H 2 CH 2 CN
a , b- unsaturated addition | 1,4 - addition |
nitrile NH2 NH
[X] |
(a weak nucleophile) CH 2CH2 CN
[Y]

CH NH CH = CHCOOCH
(b) CH 2 = CHCOOCH3 ¾¾¾¾¾
3 2 ® CH CH COOCH
2 2 3 ¾¾¾¾¾¾¾¾®
2 3 C H 2CH2 COOCH3
(conjugate | conjugate addition |
addition) NHCH3 NCH 3
[A], a weak nucleophile |
CH2 CH2COOCH3
[B]

-
OC H
1. (a) CH3 CH = CHCOOC 2 H5 + CH3 CH(COOC2 H 5 )2 ¾¾¾¾¾
2 5 ® CH C HCH COOC H
3 2 2 5
Ethyl crotonate Ethyl methylmalonate |
CH3C(COOC2H5 )2

CH3 CH3
| - OC H |
(b) CH2 = CCOOC2 H 5 + CNCH 2 COOC 2 H5 ¾¾¾¾¾2 5® C H 2CHCOOC2 H 5
Ethyl a- methylacrylate Ethyl cyanoacetate |
CNCHCOOC2H5

-
OC H
(c) C6 H 5 CH = CHCOC 6 H 5 + C6 H 5 COCH 3 ¾¾¾¾¾
2 5 ® C H C HCH COC H
6 5 2 6 5
Acetophenone |
CH2COC6H 5

Acetophenone forms a stable carbanion (C6H5CO CH -2 ) which, being a weak base, adds to form conjugate addition.

-
2 5 OC H
(d) CH 2 = CHCN + CH 2 = CHCH 2 CN ¾¾¾¾¾ ® CH 2 CH 2 CN
Acrylonitrile Allyl cyanide |
CH2 = CHCHCN

-
Allyl cyanide in presence of base forms a stable carbanion CH2 = CH C HCN which undergoes Michael addition.
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783
- OC H
2 5
(e) EtOOCC º CCOOEt + CH 3 COCH 2 COOC 2 H 5 ¾¾¾¾¾ ®

3 2 2 5 CH COCH COOC H
Et OOC C = CHCOO Et ¾¾¾¾¾¾¾¾¾ ¾® CH 3 COCHCOOC 2 H 5
| |
CH3COCHCOOC2H5 EtOOCCCH2 COO Et
|
CH3COCHCOOC2H5

(f) CH 3 CH = CHCOOC2 H 5 + CH 2 (COOC 2 H 5 )2 ¾¾

® CH 3 C HCH 2 COOC2 H 5
|
CH(COOC2H5 )2
[X]

(i) OH - heat
¾¾¾¾® CH 3 CHCH 2 COOH ¾¾¾
® CH 3 C HCH 2 COOH
+ (ii) H | |
CH(COOH)2 CH2COOH
[Y]

O
O O O O
|| || || ||
2. (a) CH 2 = CH C CH 3 + CH 3 CH 2 O C CH 2 C OCH 2 CH 3 (b) + CH3COCH2 C OCH3

C6H5
O
CH3ONa, CH3OH
O
3. (a) + C6H5 (Michael addition)
C6H5 O C6H5
O

C6H5 C6H5
CH 3ONa
O –H 2O
O
(intramolecular
C6H5 C6H5
aldol condensation)
OH

(b) (i) — C — C — C — OH (ii) —C—C—C—O

+ –
Z

O O

1. (a) O (b) (c)

CH3 O CH3 O
C2 H5O C2H5O
2. (a) +

O O

O O
CH3 CH3
Diels-Alder +
(b)
reaction
CH3O CH3O
O O
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EXERCISE 16.1
1 (d) 6 (c) 11 (c)
2 (b) 7 (b) 12 (c)
3 (c) 8 (b) 13 (c)
4 (c) 9 (b) 14 (c)
5 (b) 10 (a) 15 (c)

1. All have unsaturation between a and b carbon atoms with respect to C=O linkage.

O
|| O
H - C - C - COOH O
||
(a) HO - C - C - H (b) (c) (CH 3 )2 C = CH - C - CH 3
||
O
O
2. 2° Alcohol is more reactive than 1°, hence former is preferentially formed.
tantomerises
-H O -H O
2¾® C H - CH = CH
CH2 - CH - CH 2 ¾¾ ¾ 2 C H 2 - CH 2 - CHO ¾¾¾
2¾® CH = CH - CHO
2
| | | | | |
OH OH OH OH OH OH

O H
(i) O3 CHO base CHO
3. (ii) Zn, CH3COOH (aldol cond.)
a

O O OH
+ || + || |
4. C H 2 - CH 2 - C - OH ; CH3 - C H – C - OH CH2 = CH - C+- OH
+ ve ch arg e localised + ve charge delocalised in both cases

5. In reaction (i), HBr undergoes conjugate addition because the compound is a,b-unsaturated ketone. In reaction (ii), HBr adds
according to Markownikov's way because a,b-unsaturation is not present.
6. Grignard reagent adds on a,b-unsaturated carbonyl compounds in a simple way as well as in conjugate way. However, simple addition
product dominates because CH3MgBr is a strong nucleophile.

CH3 CH3
+
.. H +
7. H3CO C = CH–OCH
.. 3 H3CO C – CH = OCH
.. 3
H

CH3 CH3
+
H2O .. –H
H3CO C – CH–OCH H3 CO CH–CHOCH3
.. 3

H OH2
+ OH

CH3
–CH 3OH
H3 CO CH–CHO

8. CN–, being a weak nucleophile, adds on b-carbon w.r.t. the carbonyl group to form conjugate addition product (Michael reaction).
9. CH3CH2S– is a weak nucleophile, hence it adds in 1,4-addition way.
10. This is an example of Michael reaction in which nucleophile adds on b-carbon w.r.t. to carbonyl group.

OH
O O – O O O
OC 2H5 O intramolecular –H 2O
11. + 1,4-addition aldol condensation
(Michael addition) 1,9
D -Octalone
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785
12. The base used in Michael reaction may also act as a nucleophile, so it will add to the carbonyl carbon of the ester group and change the
reactant leading to low yield of the desired product.

O O
b a || a b Michael addition
||
13. (i) 2H 2 C(COOC 2 H 5 )2 + CH 3 C H = C H C C H = C HCH 3 ¾¾¾¾¾¾¾® CH 3 - C H - CH 2 - C - CH 2 - C H - CH 3
at both C = C | |
CH(COOC2H 5 )2 CH(COOC2H5 )2

O O
|| ||
Michael addition
(ii) CH 3 CH = CH - C - CH = CHCH 3 + H 2 C(COOC 2 H 5 )2 ¾¾¾¾¾¾¾® CH 3 - CH - CH 2 - C - CH = CHCH 3
only at one C = C |
CH(COOC2H 5 )2
(A)

O
C O
CH CH2 internal

(iii) Michael addition

CH3CH CHCH3 H3C CH3
H5C2OOC COOC2H5
CH
H5C2OOC COOC2H5
(A) from (ii)

14. The reaction involves double aldol condensation.

C6H5 C6H5
C6H5 C6H5 C6H5 C6H5
O O HO OH
base
+ (double aldol (–2H 2O)
condensation) C6H5 C6H5 C6H5 C6H5
C6 H5 C6H5 O O
O

15. 1,3-Butadiene can function both as a diene as well as dienophile.

1,3-Butadiene 1,3-Butadiene
(diene) (dienophile)

EXERCISE 16.2
>1 CORRECT OPTION 1 (b,d) 2 (a, d)
3 (d) 4 (b) 5 (b)
PASSAGE 1
6 (b) 7 (b) 8 (c)
PASSAGE 2 9 (a) 10 (b) 11 (a)
MATCH THE 12 (A) - b, (B) - c, (C) - d, (D) - a
FOLLOWING 13 (A) – c,d; (B) – b; (C) – a
INTEGER 14 1

1. (b) does not have a,b-unsaturated carbonyl group, while (d) can't form stable carbanion (from acetone). Remember that cyclopentadiene
is quite acidic in nature, because its carbanion is stable due to presence of conjugated system; hence it functions as the nucleophile
required in Michael reaction.

14. 1

O O OH
1. O 3 NaOH(aq) heat
2. Zn, H 2O –H 2O

O (–) O O O
The number of intra molecular aldol condensation products ( a, b –unsaturated carbonyl compound formed from Y is 1.
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EXERCISE 16.3
Cl
|
1. (a) C6 H 5 CHCH 2 COCH 3 (b) C6 H 5 CHCH 2 COCH 3
|
Obtained by 1,4-electrophilic addition OH
C6H5
C6H5
CH Diels
(c) + Alder (d) C6 H 5 CH = CHCOCH = CHC6 H 5
CH formed by crossed aldol condensation
COCH3
COCH3
1,3-Butadiene Benzalacetone
(a diene) (a dienophile)

(e) C6 H 5 CHCH 2 COCH 3 (f) C6 H 5 C HCH 2 COCH 3

| |
NHOH CH(COOC2H 5 )2
formed by 1,4 - nucleophilic addition formed by 1,4 - nucleophilic addition

CH3 O CH 3 O
| || - | ||
OC2 H 5
2. CH 3 - C = CH - C - OC2 H 5 + CH 2 (COOC 2 H 5 )2 ¾¾¾¾¾¾® CH 3 - C - CH 2 - C - OC 2 H 5
Ethyl malonate (Michael addition) |
Ethyl 3 - methylbut - 2 - enoate
CH(COOC2H5 )2

CH 3 CH3 CH 3
| | |
(i) OH - heat
¾¾¾¾® CH 3 - C - CH 2 COOH ¾¾¾
® CH 3 - C - CH 2 COOH º HOOCCH 2 C CH 2 COOH
+ | (– CO2 ) | |
(ii) H
CH(COOH)2 CH 2COOH CH 3
3,3 - Dimethylpentane -1,5 -dioic acid

1 –
O O O OH
2 –H2O
3
H Conjugate H +
3. + H2N–NH2 .. NH2 NH N
4 addition NH2 N N N
N H H H
Acrolein Hydrazine
H
(a,b -unsaturated (a weak base)
ketone)

O O OH
1,4-addition tauto-
+ HCl merization
4. Cl Cl
H
O O OH
p-Benzoquinone 2-Chlorohydro-quinone
(a ,b -unsaturated ketone)

CH(COOEt)2
|
H 2 C(COO Et)2 (i) NaOI
5. (a) (CH 3 )2 C = CHCOCH 3 ¾¾¾¾¾¾¾
® (CH 3 )2 C CH 2 COCH 3 ¾¾¾¾®
(Michael addition) (ii) OH -

CH(COO - )2 CH2 COOH

| |
- (i) H +
(CH 3 )2 C CH 2 COO ¾¾¾¾
® (CH 3 )2 C CH 2 COOH
(ii) heat

(b) The required compound, spermine (a compound found in seminal fluid) can be prepared by the double nucleophilic addition of
1,4-diaminobutane (putrescine) on acrylonitrile.
NH2 1,4-nucleo- N
CN + H2 N philic addition H2N H CN

CN N CN
NC N
(nucleo addn.) H
H
H2 / Ni N NH2
H2N N
H
H
Spermine
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6. (a) Crotonaldehydeis an a,b-unsaturated aldehyde so here g-hydrogens are acidic.

O O O O-
g b a || - || || |
Base
H 3 C- C H = C H - C H ¾¾¾® H 2 C - CH = CH - CH ¬¾® CH2 = CH - CH - C H ¬¾® CH2 = CH - CH = CH
I II III
This structure is more stable
because – ve charge in on the O atom

O O- +
|| | H
- C6 H5 CH = CH CHCH2 CH = CHCHO
(b) C6 H5 CH = CH C H + CH 2 CH = CHCHO

OH
|
-H O
C 6 H 5 CH = CH C HCH 2CH = CH CHO ¾¾¾
2¾® C H (CH = CH) CHO
6 5 3

é + .. + .. ù
êCH 2 = CH - C º N : ¬¾® CH 2 = CH - C = N –: ¬¾® C H 2 - CH = C = N –: ú
7. (a) ê ú
Acrylonitrile
ë û

é ù
.. .–. ..
:Nuê ú Nu : H
¾¾¾® ê CH 2 - CH = C = N :- ¬¾® C H 2 - C H - C º N ú ¾¾¾ ¾® CH 2 - CH 2 - CN
| | |
ê Nu Nu ú Nu
ë û

é .. ù
ê :O : :O:- ú
ê || .. + | . . -ú
+ - :Nu
êCH 2 = CH - N - O. . : ¬¾® CH 2 - CH = N - .O. : ú ¾¾¾®
(b) ê + ú
ê ú
êë úû

é .. ù
ê :O:- :O : ú :O :
ê | .. - . -. || .. ú || .-.
Nu : H
ê CH 2 - CH = N + - O : ¬¾® +
CH 2 - C H - N - O -
: ú ¾¾ ¾ ¾® C H 2 - CH 2 - N - O :
ê | .. | . . ú | + ..
ê Nu Nu ú Nu
êë úû

O O O
|| .-. || ||
8. (a) C6 H 5 CH = CH C - C6 H 5 , C 6 H 5 C H - C - CH 3 supplied as C6 H 5 - C H - C - CH 3
acceptor donor |
COOC2H5

.-.
(b) CH 2 = CH - C º N, C HCOOH supplied as C H 2COOC2 H 5
| |
acceptor
COOC2H5

O
(c) CH 2 = CH - C º N ;
acceptor COOC2H5

donor

N(CH3)2
O
||
(d) CH 2 = CH - C C6 H 5 ; CH3
acceptor
donor
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9. Although theoretically following reaction should take place

O
O O O O
–
OH
CH3
(Michael addition)

Enolate, I

However, in such reaction, yield of the final product is very low due to following competitive reactions.
(i) The ketone enolate I can undergo self aldol condensation.
(ii) The ketone enolate I can condense with methyl vinyl ketone in aldol condensation manner.
(iii) The ketone enolate I can deprotonate the methyl vinyl ketone to form a new nucleophile.
Thus the ketone cyclohexanone must be converted into other resonance stabilized enolate, enamine which does not undergo any
side reaction and also undergoes Michael addition smoothly.

O
O O O
NH
(i)
N
+
(ii) H3 O

10. Always remember that the Robinson annulation consists of a Michael addition followed by aldol cyclizaton with dehydration. In the
retrosynthetic direction, perform following two disconnections.
(i) Disconnect the alkene formed in the aldol/dehydration. Since aldol condensation with dehydration forms a,b-unsaturated double
bond, disconnect this double bond.
(ii) Disconnect the Michael addition to get the reactants. Since Michael addition forms a bond to the b' carbon atom, disconnect this
particular b' bond.

b'
a'
(a) b +
O O O O O
a
CH3 CH3

O O O
CH3 CH3 b'
a'
(b) +
b
a O O O O O

HO O O
(c) + O

CH3 CH3
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17 .1 Nomenclature 17 .7 Distinction Between a-, b-, and g-Substituted Carboxylic

17 .2 Preparation of Carboxylic Acids Acids
17 .3 Physical Properties 17 .8 Additional Chemistry of Aromatic Carboxylic Acids
17 .4 Chemical Properties 17 .9 Analysis of Carboxylic Acids
17 .5 Special Properties of Formic Acid 17.10 Illustrative Examples
17 .6 Dicarboxylic Acids EXERCISES
SOLUTIONS

17.1 Nomenclature
O
Carboxylic acids are the organic compounds having the carboxyl group, ¾ C ¾OH (abbreviated as —COOH or
—CO2 H ). Many of the carboxylic acids are better known by common names than by their systematic names. For example,
formic acid (Latin : formica, ant), acetic acid (Latin : acetum, vinegar), butyric acid (Latin : butyrum, butter), and caproic,
caprylic and capric acids (Latin : caper, goat) are named on their natural sources. The positions of the substituent groups
are shown by Greek letters a, b, g, d, etc. Names of some acids are derived from acetic acid, e.g.

(CH 3 )3 CCOOH C 6 H 5 CH 2 COOH

Trimethylacetic acid Phenylacetic acid

Occasionally, they are named as carboxylic acids, e.g. cyclohexane carboxylic acid.
In IUPAC system, names of carboxylic acids are obtained by replacing the -e of the corresponding alkane with -
oic acid. The carboxyl carbon atom is always assigned number 1.

HCOOH CH 3 CH 2 CH 2 CH 2 COOH CH 3 CH = CHCOOH CH 3 (CH 2 )4 COOH

Methanoic acid
(Formic acid) Pentanoic acid 2-Butenoic acid Hexanoic acid
(Valeric acid) (Caproic acid)

CH 3 H3C H
|
CH 3 (CH 2 )6 COOH CH 3 (CH 2 )8 COOH CH2 = CCOOH C=C
Octanoic acid Decanoic acid 2-Methyl-2-propenoic acid H COOH
(Caprylic acid) (Capric acid) or 2-Methylpropenoic acid
(Methacrylic acid) trans-2-Butenoic acid
(Crotonic acid)
Common name, if any, is given in bracket.
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When a carboxyl group is attached to a ring, the parent ring is named (retaining the final -e) and the suffix
-carboxylic acid is added. For example,

COOH COOH

Benzene carboxylic acid

CH3
Benzoic acid m-Methylbenzene carboxylic acid
m -Toluic acid

In case, carboxylic is present on the side chain, compound is named as a derivative of the corresponding alkane.

CH2CH2COOH CHOHCOOH CH(CH3)CH2COOH

Cl
3-Phenylpropanoic acid 2-Hydroxy-2-phenylethanoic acid 3-(p-Chlorophenyl)butanoic acid
(Mandelic acid)

Compounds with two carboxyl groups are designated by the suffix -dioic acid or dicarboxylic acid. The final -e in
the base name of the alkane is retained.

COOH
COOH
COOH CH 2 COOH
½ CH 2 ½
COOH COOH CH 2 COOH
COOH
Ethanedioic acid Propanedioic acid Butanedioic acid 1, 2-Benzene dicarboxylic
(Oxalic acid) (Malonic acid) (Succinic acid) (Phthalic acid)

1. Give IUPAC name of the following compunds.

O COOH
(a) (b) COOH (c)
COOH
H

F
OH
(d) OH COOH (e) (f) CH2 = CHCOOH
O O
O
(g) (h) CH3(CH2)7CH = CH(CH2)7COOH
CHO OH

CH3CH 2 CH2 CH2 (CH 2)7COOH

(i) C=C C=C C=C (j) HOOC COOH
H HH HH H

Carboxylic acids exhibit chain, position and functional isomerism. Its functional isomers are esters,
hydroxyaldehydes, hydroxyketones and hydroxyoxirane. Thus functional isomers of ethanoic acid are

CH 2 OH O
HCOOCH 3 ½
Methyl formate
CHO OH
Glycolaldehyde Hydroxyoxirane
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Similarly, functional isomers of propanoic acid (CH3CH2COOH) are

CHO COCH 3 O
| |
HCOOCH2CH3, CH3COOCH3, CH2 CH2 OH , CH 2 OH , CH2OH

17.2 Preparation of Carboxylic Acids

Many carboxylic acids were first isolated from natural sources, viz. formic acid was obtained by distilling ants,
lactic acid from sour milk, etc. However, such methods are now only of historical importance.
1. By oxidation of 1° alcohols and aldehydes. Potassium permanganate (acidic or alkaline) and chromic acid
convert primary alcohols to carboxylic acids through the formation of corresponding aldehydes.
KMnO4
RCH2OH ¾¾¾¾¾® [RCHO] ¾¾¾® RCOOH
K 2 Cr2 O7 , H 2 SO 4

OH KMnO4
¾¾¾¾®
H2SO4 COOH
Isobutyl alcohol Isobutyric acid

1
CH2OH 2 COOH
H2CrO4
H2O, H2SO4 3
4

2-tert-Butyl-3, 3-dimethylbutanol 2-tert-Butyl-3, 3-dimethylbutanoic acid

Aldehydes are very sensitive to oxidation and oxidised easily even with mild oxidising agents like Tollen’s
reagent, [Ag(NH3)2]+.
Ag 2 O or Ag (NH 3 )2 +
RCHO ¾¾¾¾¾¾¾¾¾¾® RCOOH
or KMnO 4/H+ or K 2 Cr2 O 7/H +

Ketones, although are also oxidised by strong oxidising reagents to carboxylic acids having lesser number of
carbon atoms, these give poor yields. However, methyl ketones are good sources for carboxylic acids as these are
quantitatively oxidised to carboxylic acids by hypohalites (haloform reaction).
heat
RCOCH3 + 3I2 + 4NaOH ¾® RCOONa + 3NaI + CHI3 + 3H2O

[O]
Oxidation
HCOOH + HOOC14CH2CH3 ¬¾ CH3C14OCH2CH3 ¾¾¾¾¾ ® CH3C14OOH + CH3COOH.
However, remember that in mixed ketones, major oxidation product is that in which carbonyl carbon (C 14)
remains with smaller alkyl group.
2. By oxidation of alkenes, alkynes and cycloalkenes. These compounds can be oxidised to carboxylic acids by
hot alkaline KMnO4 or by ozonolysis followed by reaction with H2O2.
(i) KMnO 4 , OH – , heat
RCH = CHR¢ ¾¾¾¾¾¾¾¾® RCOOH + R¢COOH
(ii) H 3 O +

(i) O 3
RCH = CHR¢ ¾¾¾® RCOOH + R¢COOH
(ii) H 2 O 2

(i) KMnO 4 or O 3
RC º CR¢ ¾¾¾¾¾¾® RCOOH + R¢COOH
(ii) H 2 O

+ COOH
KMnO4 , H COOH
¾¾¾¾¾¾®
heat
Cyclopentene Glutaric acid
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1. From the knowledge of the chemistry so far studied, try to give steps for converting.
(a) CH3CH = CH2 to CH3CH2COOH
(b) Me 3CCH = CH2 to Me3CCOOH by four different methods.

(c) CH2OH ¾¾¾® COOH (Two methods)

2. (a) Formulate the compounds from which Me2CHCOOH can be prepared by oxidation in good yield.
(b) Give the structure of a compound that gives an equimolar amount of succinic acid on oxidative cleavage.

3. By the carbonation of Grignard reagents. (For details, consult chapter on “Organometallic Compounds’’).

O O
ether || H 3 O+
CO 2 ||
RX + Mg ¾¾® RMgX ¾¾® R— C —O – (MgX + ) ¾¾® R— C —OH
This synthesis of carboxylic acids is applicable to 1°, 2°, 3°, allyl, benzyl and aryl halides, provided they have no
groups incompatible with a Grignard reaction, such as OH, SH, NH or C = O.
Mg (i) CO 2
(CH 3 )3 CCl ¾¾® (CH3)3 CMgCl ¾¾¾® (CH 3 )3 CCOOH
ether +
tert -Butyl chloride (ii) H 3 O 2, 2-Dimethylpropanoic acid

Mg (i) CO2
Br ¾¾® MgBr ¾¾¾¾® + COOH
(ii) H3 O

Br COOH
CH3 CH3 Br 2 CH3 CH3 (i) Mg CH3 CH3
¾¾® ¾¾¾¾¾® +
(ii ) CO2 ,H
CH3 CH3 CH3
Mesitylene 2, 4, 6-Trimethylbenzoic acid
(Mesitoic acid)

4. By hydrolysis of nitriles. Aliphatic nitriles, obtained by the reaction of an alkyl halide with sodium cyanide in
dimethyl sulphoxide (DMSO) as solvent, are easily hydrolysed by boiling aqueous alkali or acid to corresponding
carboxylic acids.

OH – H+
RCOO– + NH3 ¬¾¾¾ RC º N ¾¾¾® RCOOH + NH4+
heat Alkyl nitrile heat

The fact that HCN is a very weak acid tells us that CN– ion is a strong base and hence can cause elimination as
well as substitution. Indeed, with tert-halides elimination is the principal reaction ; even secondary halides
undergo elimination reaction to some extent. Hence this synthetic method of carboxylic acids from alkyl halides
is limited to the use of primary alkyl halides. Aryl halides (except for those with o- and p-nitro groups) do not
react with sodium cyanide ; hence aryl nitriles are obtained from diazonium salts.

NaCN (i) aq. alc. OH - , reflux

n-C4H9Br ¾¾¾® n-C 4 H 9 CN ¾¾¾¾¾¾¾¾® n-C 4 H9 COOH
Pentanenitrile (ii) H3 O + n -Valeric acid
(n -Valeronitrile)

NaCN (i) aq. OH –

HOCH2CH2Cl ¾¾¾® HOCH 2 CH 2 CN ¾¾¾¾® HOCH 2 CH 2 COOH
3-Hydroxypropanenitrile (ii) H 3 O + 3-Hydroxypropanoic acid

NaCN H 3O +
BrCH2CH2CH2Br ¾¾¾® NCCH 2 CH 2 CH 2 CN ¾¾¾® HOOCCH2 CH 2 CH 2 COOH
1, 5-Pentanedinitrile 1, 5-Pentanedioic acid
(Glutaric acid)
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Nitrile groups in cyanohydrins (aldehyde or ketone + CN– ® cyanohydrin) are hydrolyzed to corresponding
a-hydroxy carboxylic acids.

O OH OH
(i) NaCN H2O, HCl
¾¾¾® + ¾¾¾¾®
(ii) H heat
CN COOH
2-Pentanone 2-Pentanonecyanohydrin 2-Hydroxy-2-methylpentanoic acid

Grignard synthesis and the nitrile synthesis for carboxylic acids have the advantage of increasing the length of
a carbon chain by one carbon atom. Moreover, in both methods parent compounds are halides which in turn are
usually prepared from alcohols, so the net result involves the conversion of an alcohol to a carboxylic acid with
one more carbon atom.
5. Malonic ester synthesis. This is one of the most valuable methods for preparing carboxylic acids. The synthesis
is based upon following two important properties of ethyl malonate (malonic ester), CH2 (COOC2H5)2.
(i) High acidity of the a-hydrogens of malonic ester.
(ii) Extreme ease of decarboxylabion of malonic acid and substituted malonic acids.
+ +-
HCH(COOC2H5)2 + C2H5O–N a ¾¾¾®
¬ Na CH (COOC2H5)2 + HOC2H5
Malonic ester Sodiomalonic ester Weaker acid
(stronger acid)

- RX R¢ X
Na+ CH (COOC2H5)2 ¾® R—CH(COOC2 H 5 )2 ¾® R ¾ C(COOC2 H 5 )2 + NaX
Ethyl alkylmalonate
(An alkylmalonic ester) ½
R¢
A dialkylmalonic ester

The monoalkylmalonic and dialkylmalonic esters, so prepared are readily converted into monocarboxylic acids
by hydrolysis, acidification, and heat

- H+ heat
H2 O, OH
RCH(COOC2H5)2 ¾¾¾¾¾® RCH(COO–)2 ¾¾® RCH(COOH)2 ¾¾® RCH2COOH
heat 140° C

H+ heat
R2C(COOC2H5)2 ¾¾® R2C(COO–)2 ¾¾® R2C(COOH)2 ¾¾® R2CHCOOH
140° C

Thus malonic ester provides an important method for synthesising RCH2COOH, R2CHCOOH and RR¢CHCOOH.
6. Favorskii rearrangement. a-Haloketones, when treated with base, are converted into carboxylic acids.

O
Br –
COOH
OH
¾¾¾®

–
O O O O
OH
Br – Br Br –
Mechanism. OH OH
¾¾¾® ¾¾¾®
– ¾¾¾®
(–H2O) (–Br )

O
–
C—O + COOH
H
¾¾® ¾¾®
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Industrial sources. Acetic acid is considered to be the most important carboxylic acid. Industrially, it is prepared
(a) By catalytic air oxidation of acetaldehyde or of various hydrocarbons.
O2
CH3CHO ¾¾¾® CH3COOH ¬¾¾ Hydrocarbons
Catalyst

(b) From the reaction of methanol with carbon monoxide in the presence of iodine-rhodium catalyst (Modern
method).
Rh/I 2
CH3OH + CO ¾¾¾® CH3COOH
(c) Dilute aqueous solution of acetic acid, known as vinegar, is prepared by air oxidation of ethyl alcohol in the
presence of bacterial enzymes (acetobacter).
Formic acid is prepared by the reaction of carbon monoxide with sodium hydroxide followed by acidification
with sulphuric acid.
H 2 SO 4
CO + NaOH ¾¾® HCOO– Na+ ¾¾¾® HCOOH
The important source of aliphatic carboxylic acids are the animal and vegetable fats from which straight chain
carboxylic acids of even number of carbon atoms ranging from 6 to 18 are obtained in purity of over 90%. It is important to note
that naturally occurring fatty acids (acids obtained from fats) always contains even number of carbon atoms because plants and
animals biosynthesize fatty acids by building up CH3COOH (a C2 compound) units.

1. Which of the two methods : Grignard synthesis and nitrile synthesis ; is suitable for converting each of the halide to the corresponding
carboxylic acid. Also write down the steps involved during the reaction.
(a) 2-Chloroethanol to 3-hydroxypropanoic acid. (b) 2-Chloro-2-methylpropane to 2, 2-dimethylpropanoic acid.
(c) Chlorobenzene to benzoic acid. (d) 1, 2-Dibromoethane to succinic acid
(e) Vinyl bromide to propenoic acid.
2. (a) Show how you would prepare each of the following carboxylic acid through a Grignard synthesis ?
(i) 2, 2-Dimethylpentanoic acid (ii) 3-Butenoic acid (iii) 4-Methylbenzoic acid.
(b) Which of the above carboxylic acids can be prepared by a nitrile synthesis as well ?
3. Give the structure and name of the acids formed by a step-up reaction of the following halides.
(a) C6H5Cl (b) CH3CHClCH2CH2CH3 (c) C6H11CMe2Cl (d) Z-MeCH = CHBr.
4. Synthesize succinic acid from CH2 = CH2.
5. Use malonic ester to prepare
(a) 2-ethylbutanoic acid (b) 3-methylbutanoic acid
(c) 2-methylbutanoic acid (d) trimethylacetic acid.
6. A sulphuric acid solution of each of the following compounds, when treated with carbon monoxide, gives the same acid, 2, 2-
dimethylbutanoic acid. Explain.
2-Methyl-2-butene, Neopentyl alcohol, tert-Pentyl alcohol

17.3 Physical Properties

(i) Carboxylic acids are rolar substances. Like alcohol molecules, their molecules O---H—O
can form hydrogen bonds with each other and also with water. As a result, low
molecular weight carboxylic acids (the first four members) are miscible with water R—C C—R
in all proportions ; water solubility decreases with increase in the length of the O—H---O
carbon chain.
(ii) Carboxylic acids have higher boiling points than the corresponding alcohols. This is due to a unique hydrogen
bonding arrangement in carboxylic acids ; carboxylic groups of two molecules are held together not by one but
by two hydrogen bonds. This hydrogen bonding is so efficient that some carboxylic acids exist as hydrogen-
bonded dimers even in the gas phase. In the pure liquid state, a mixture of hydrogen-bonded dimers and higher
aggregates is present.
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(iii) First two carboxylic acids have a sharp and acrid odour, while the acids with four to eight carbon atoms have
unpleasant odours. These acids, formed by bacterial action, are present in trace amounts in the skin secretions
of most mammals. Since metabolic processes of different persons are not exactly identical, these acids are present
in different compositions on the skin of different persons which give a characteristic smell different from person
to person ; this is the reason why dogs (having highly developed sense of smell) are able to differentiate one
person from another.

1. Arrange the following compounds in order of decreasing boiling points :

O O

(a) , , , , ,
OH OH OH HO
(i) (ii) (iii) (iv) (v) (vi)
(b) C3H8 (A), CH3CH2CH2OH (B), CH3CHOHCH2OH (C), CH3OCH2CH3 (D), CH3CH2COOH (E).
2. The true value of molecular weight of acetic acid is found to be 60, however, just above its boiling point, it is found to be 120. Explain.
3. What is glacial acetic acid and why it is so called ? What is vinegar and how is it made ?

17.4 Chemical Properties

17.4.1 Acidity of Carboxylic Acids

Carboxylic acids are the most acidic compounds that contain C, H and O. Ionization constants (K a) of the
caboxylic acid, is of the order of 10–5 (pKa ~ 5), they are much stronger acids than water and alcohols.
–
The acidic character of carboxylic acids is due to resonance* O:
:
:O:

:
in the acidic group which imparts electron deficiency (positive charge) ½½ ½ +: :
R—C—O—H ¬¾® R—C = O—H
on the oxygen atom of the hydroxyl group.

:
Non-equivalent structures (Resonance less important)

The positive charge (electron deficiency) on oxygen atom causes a displacement of electron pair of the O—H
bond towards the oxygen atom with the result the hydrogen atom of the O—H group is eliminated as proton and a
carboxylate ion is formed. Once the carboxylate ion is formed, it is stabilised by means of resonance.
–
O: O: O –
:

: :

R—C ¬¾® R—C R—C

O
O :– O:
: :

Resonating forms of carboxylate ion (Equivalent structures), Resonance hybrid of carboxylate ion
hence resonance more important.
Due to equivalent resonating structures, resonance in carboxylate anion is more important than in the parent
carboxylic acid. Hence carboxylate anion is more stabilised than the acid itself and hence the equilibrium of the ionisation
of acids shifts to the right hand side.
RCOOH RCOO– + H+
The existence of resonance in carboxylate ion is supported by bond lengths. For example, in formic acid, there is
one C = O double bond (121 pm) and one C—O single bond. (136 pm), while in sodium formate both of the carbon-oxygen
bond lengths are identical (125 pm) which is nearly intermediate between C = O and C—O bond length values. This proves
resonance in carboxylate anion.
–
121 pm O 125 pm O
+
H—C H—C Na
136 pm 125 pm
OH O
Formic acid Sodium formate

* Note that in resonance of carboxylic acids, —CO part of the acidic group enters into resonance with the lone pair of the —OH group and
hence —COOH does not give reactions of the carbonyl group.
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It is important to note that although carboxylic acids and alcohols both
contain —OH group, the latter are not acidic in nature. It is due to the absence of R—O—H R—O – +H +
Alcohol Alkoxide ion
resonance (factor responsible for acidic character of —COOH) in both the alcohols (No resonance) (No resonance)
as well as in their corresponding ions (alkoxide ions).
Alkoxide ions are stabilized by solvation forces, while carboxylate ions are stabilized by solvation as well as
resonance and inductive effect of the carbonyl group.
Role of inductive effect of the carbonyl group. The carbonyl group is electron-withdrawing, and by attracting
electrons away from the negatively charged oxygen, carboxylate anion is stabilized.
Relative acidic character of carboxylic acids with common species not having —COOH group.
RCOOH > HOH > ROH > HC º CH > NH3 > RH
Effect of substituents on acidity. We know that the carboxylic acids are acidic in nature because of stabilisation
(i.e., dispersal of negative charge) of carboxylate ion. So any factor which can enhance the dispersal of negative charge of
the carboxylate ion will increase the acidity and vice versa. Thus electron-withdrawing substituents (like halogens,
—NO2, —C 6H5 etc.) would disperse the negative charge and hence stabilise the carboxylate ion and thus increase acidity
of the parent acid. On the other hand, electron-releasing substituents would intensify the negative charge, destabilise the
carboxylate ion and thus decrease acidity of the parent acid.
– –
O O
G—¬C G®—C
O O
The substituent G withdraws electrons, stabilises The substituent G releases electrons, destabilises
anion and hence increases acidity anion and hence decreases acidity

Now since alkyl groups are electron-releasing, their presence in the molecule will decrease the acidity. In general,
greater the length of the alkyl chain, lower shall be the acidity of the acid. Thus formic acid (HCOOH), having no alkyl
group, is about 10 times stronger than acetic acid (CH 3 COOH) which in turn is stronger than propanoic acid
(CH3CH2COOH) and so on. Similarly, following order is observed in chloro acids.
Cl 3 CCOOH Cl 2 CHCOOH ClCH 2 COOH CH 3 COOH
Trichloroacetic acid
> Dichloroacetic acid
> Monochloroacetic acid > Acetic acid

Trichloroacetic acid is more than 10,000 times more stronger than acetic acid, actually it is almost as strong acid as a
mineral acid. For further details of the relative acidities of the carboxylic acids, consult inductive effect in Chapter on
“General Organic Chemistry”.

Decreasing order of aliphatic acids

(i) O2NCH2COOH > FCH2COOH > ClCH2COOH > BrCH2COOH
(ii) HCOOH > CH3COOH > (CH3)2CHCOOH > (CH3)3 CCOOH
(iii) CH3CH2CCl2COOH > CH3CHCl.CHCl.COOH > ClCH2CHClCH2COOH
(iv) F3CCOOH > Cl3CCOOH > Br3CCOOH
Benzoic acid is somewhat stronger than simple aliphatic acids. Here the carboxylate group is attached to a more
electronegative carbon (sp2 hybridised) than in aliphatic acids (sp3 hybridised). Remember that carbon becomes more
electron-withdrawing as its s character increases.

Acidity of dicarboxylic acids

Here two ionization constants (K1 and K2) characterise the two successive ionization steps of a dicaboxylic acid.

O O O O
|| || K1 || ||
HO— C— C—OH HO— C— C—O – , K1 = 6.5 × 10–2 ; pK1 = 1.2
Hydrogen oxalate
(monoanion)

O O O O
|| || K2 || ||
HO— C— C—O – –O— C— C— O– , K2 = 5.3 × 10–5 ; pK2 = 4.3
Oxalate (dianion)
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The first ionization constant of dicarboxylic acids is larger than Ka for monocarboxylic analogs. There are two
reasons for this.
(a) Presence of two potential sites for ionization rather than one.
(b) One carboxyl group acts as an electron-withdrawing group to facilitate dissociation of the other. This factor is
significant when two carboxyl groups are separated by only a few bonds. Thus oxalic and malonic acids are
highly acidic than the corresponding monocarboxylic acids while heptanedioic acid is only slightly stronger
than acetic acid.

HOOCCOOH HOOCCH 2 COOH HOOC(CH 2 )5 COOH

Oxalic acid Malonic acid Heptanedioic acid

K1 6.5 × 10–2 1.4 × 10–3 3.1 × 10–5

pK1 1.2 2.8 4.3

1. (a) Compare the carbon-oxygen bond length in sodium formate and sodium carbonate.
(b) Compare the carbon-oxygen single bond in carboxylic acids with that in alcohols.
2. Which is the stronger acid in each of the following pairs.
+
(i) Me 3CCH2COOH or Me3 N CH2COOH (ii) CH3CH2COOH or CH3CHOHCOOH

(iii) CH3COCOOH or CH2 = CHCOOH (iv) CH3CH2CH2COOH or CH3SO 2CH2COOH

(v) Me 3CCH2COOH or Me3SiCH2COOH (vi) 3-Butenoic acid or 3-Butynoic acid
3. Arrange the following in decreasing order of acidity.
(i) C2H5OH, HCOOH, CH3COOH, C6H5OH
(ii) HCOOH, C2H5COOH, CH3COOH, CH2ClCOOH, C6H5COOH
(iii) CH3CH2CH2COOH, CH3CHClCH2COOH, CH3CH2CHClCOOH, ClCH2CH2CH2COOH
(iv) CH3COOH, CH2ClCOOH, CHCl2COOH, CCl3COOH
(v) CH2BrCOOH, CH2ClCOOH, CH2ICOOH, CH2FCOOH
(vi) ClCH2COOH, CH3CH2COOH, ClCH2CH2COOH, Me2CHCOOH,CH3COOH
(vii) HCOOH, C6H5COOH, C6H5OH, HCl
(viii) Acetic acid, acetylene, ammonia, ethane, ethanol, sulphuric acid, water.
(ix) Acetic acid, malonic acid, succinic acid.
(x) a-Chlorophenylacetic acid, p-chlorophenylacetic acid, phenylacetic acid, a-phenylpropanoic acid.
4. Explain the following :
(a) Peroxy acids are much weaker acids than carboxylic acids.
(b) Highly branched acids are less acidic than unbranched acids.
(c) The K2 for fumaric acid (trans-butenedioic acid) is greater than for maleic acid, the cis isomer.

Although much weaker than the strong mineral acids ( H2SO4, HCl, HNO3), carboxylic acids are most acidic
among organic compounds containing C, H and O. They are neutralized rapidly and quantitatively in presence of strong
bases like sodium hydroxide. Aqueous mineral acids readily convert the salts back into the carboxylic acids.
RCOOH + OH – + RCOO– + H2O
H
Carboxylic acid Hydroxide ion Carboxylate ion Water
(stronger acid) (stronger base) (weaker base) (weaker acid)
Salts of carboxylic acids are crystalline, non-volatile solids. The strong electrostatic forces holding the ions in
the crystal lattice can be overcome only by heating to a high temperature, or by a very strong polar solvent. The mp of the
salts are so high that before it can reach, carbon-carbon bonds break and the molecule decomposes (300° – 400°C). The
alkali metal salts of carboxylic acids (sodium, potassium, ammonium) are soluble in water but insoluble in non-polar
solvents ; however most of the heavy metal salts (iron, silver, copper etc.) are insoluble in water.
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Except for the first four carboxylic acids, which are soluble both in water and organic solvents, carboxylic acids
and their alkali metal salts show exactly opposite solubility behaviour. This solubility difference along with the fact that
acids and their salts are readily interconvertible has been used for identifying and separation of carboxylic acids from
compounds having other functional group.
(i) In case an organic compound is insoluble in water but soluble in cold dilute aqueous sodium hydroxide or aq.
NaHCO3, it must be an organic compound which is more acidic than water, i.e., generally a carboxylic acid.

RCOOH + NaOH ¾¾¾® RCOONa + H2O

Stronger acid Weaker base
Weaker acid
(insoluble in H 2 O) (soluble in H 2 O)

RCOOH
Insoluble in water + NaHCO3 ¾¾¾® RCOONa + H2O + CO2­
Soluble in H 2 O

(ii) A carboxylic acid can be saparated from non-acidic compounds by taking advantage of its solubility in aqueous
base. The acid can be easily regenerated by acidifying the aqueous solution containing salt.
Scheme for separation of carboxylic acid from non-acidic compounds.

Insoluble
filter
For solids : Mixture + aq. base
+
H
Soluble ¾® RCOOH
Ether layer
(Non acidic component)
For liquids : Mixture + aq. base
+
In a separatory funnel H
Aq. layer ¾® RCOOH
(—COONa component)

For complete separation, generally a water-insoluble solvent like ether is added to the acidified mixture. Since
carboxylic acids are soluble in ether, ether layer containing carboxylic acid is separated, ether evaporated
leaving carboxylic acids.
(iii) Salts of higher fatty acids such as palmitic acid, C 15H 31 COOH, stearic acid, C 17 H35 COOH, oleic acid
[C17H33COOH] are known as soaps ; potassium salts are soft soaps while sodium salts are hard sops.

1. Write an ionic equation for the reaction of acetic acid with each of the following, and specify whether the equilibrium favours
starting materials or products.
(a) Sodium ethoxide (b) Potassium tert-butoxide (c) Sodium bromide
(d) Sodium acetylide (e) Potassium nitrate (f) Lithium amide.

17.4.2 Reactions in which ¾OH of ¾COOH Group is Replaced (Conversion into functional derivatives)
O O
|| ||
R ¾ C ¾ OH ¾¾® R ¾ C ¾ Z (Where, Z = —Cl,—OR¢, —NH2)

1. Conversion into acid chlorides. Three reagents are commonly used for this purpose, namely thionyl chloride,
phosphorus trichloride and phosphorus pentachloride.
RCOOH + SOCl2 ¾¾¾® RCOCl + HCl­ + SO2­
3RCOOH + PCl3 ¾¾¾® 3RCOCl + H3PO3
RCOOH + PCl5 ¾¾¾® RCOCl + HCl­ + POCl3
However, thionyl chloride is particularly convenient since the two gaseous products (SO2 and HCl) are readily
removed from RCOCl, any excess of the low-boiling thionyl choride (79°C) is easily removed by distillation.
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2. Conversion into esters. A carboxylic acid may be converted into esters in two ways ; (i) direct esterification with
an alcohol, (ii) esterification through acid chlorides
+
H
RCOOH + R¢OH RCOOR¢ + H2O
Acid Alcohol Ester

SOCl2 R ¢OH
RCOOH ¾¾® RCOCl ¾¾® RCOOR¢
(i) Direct esterification. A carboxyl group is converted directly into an ester when heated with an alcohol in
the presence of a little mineral acid, usually conc. H2SO4 or dry hydrogen chloride.
O + O
H
R—C + R'—OH R—C + H2O
OH OR'
Acid Alcohol Ester

This reaction is reversible and generally reaches equilibrium when appreciable quantities of both reactants
and products are present. Although reversibility is a disadvantage in the direct esterification, the process
has the advantage of being a single-step process and can often be made useful by application of our
knowledge of equilibria. Since the position of equilibrium controls the amount of the ester formed, the use
of an excess of either the carboxylic acid or the alcohol increases the yield. Just which component is used in
excess depends on its availability and cost ; e.g.
H 2 SO 4 , reflux
C6 H 5 CH2 CH 2 CH2 COOH + C2 H 5 OH ¾¾¾¾® C 6 H 5 CH 2 CH 2 CH 2 COOC 2 H 5 + H2O
¬¾¾
g -Phenylbutyric acid Ethanol Ethyl-g -phenylbutyrate
valuable, 1 mole cheap, 8 mole

The yield of esterification can also be increased by removing water (one of the products) from the reaction
mixture as soon as it is formed. For example, in the preparatioon of ethyl adipate, water is removed as lowest
boiling point component (75°C) of the mixture in the form of azeotrope of water, ethyl alcohol, and toluene.
Hence the reaction should be carried out in presence of excess of ethanol and in presence of toluene.
toluene,
H 2 SO 4
HOOC(CH 2 )4 COOH + 2C 2 H 5 OH ¾¾¾¾® C 2 H 5 OOC(CH 2 )4 COOC 2 H 5 + 2H 2 O
Adipic acid (non-volatile) ( b.p.78 °C) Ethyl adipate (boiling point 245 °C) Removed as
azeotrope,
boiling point 75° C
Note that it is the C—OH bond of the carboxylic acid that breaks up during esterification.
O O
½½ 18 H
+ ½½ 18
C6H5—C——OH + CH3O ——H C6H5—C—O CH3 + H2O

Mechanism of esterification is necessarily the exact reverse of the mechanism of acidic ester hydrolysis that
will be discussed in the chemisty of esters.
(ii) The presence of bulky groups near the site of reaction, whether in alcohol or in the acid, slows down
esterification (as well as its reverse, hydrolysis).
Reactivity in CH3OH > 1° > 2° (>3°)
esterification HCOOH > CH3COOH > RCH2COOH > R2CHCOOH
In some cases steric hindrance is so marked that special methods are required to prepare esters of tertiary
alcohols or esters of acids like 2, 4, 6-trimethylbenzoic acid (mesitoic acid).
(iii) Esterification through acid chlorides. Since acyl chlorides are much more reactive toward nucleophilic
addition-elimination than carboxylic acids, reaction of an acyl chloride and an alcohol occurs rapidly and
does not require an acid catalyst. Pyridine is generally added to remove the HCl formed during reaction.
Moreover, pyridine may also react with the acyl chloride to form an acylpyridinium ion, an intermediate
that is even more reactive toward the nucleophile than the acyl chloride itself.

C6H5COCl + C2H5OH + ¾¾® C6H5COOCH2CH3 +

N Ethyl benzoate +N –
HCl
Esterification through acid chloride gives better results when tert-alcohols are used as one of the components
because in the direct esterification, the acid used may cause dehydration by elimination reaction.
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Intramolecular esterification. Hydroxy acids (compounds containing a hydroxyl and a carboxyl group in the
same molecule) have the capacity to form cyclic esters called lactones. This intramolecular esterification takes
place spontaneously and is especially favourable when the ring formed is either 5-membered or 6-membered.
Lactones having a five membered ring are known as g-lactones since they are formed from g-hydroxy acids. The
six-membered analogs are known as d-lactones.

OH OH OH
O
g O ¾¾® O
HO
O b a
4-Hydroxybutanoic acid 4-Butanolide (g-Butyrolactone)

H
OH OH d O OH O
g ¾¾® O
O
O b a
d-Hydroxypentanoic acid 5-Pentanolide (d -Valerolactone)

Like other esters, lactones are hydrolyzed by aqueous base.

3. Conversion into amides. Acids are converted into amides by treating acid chlorides with ammonia, primary
amines, and secondary amines.
SOCl 2 NH 3
RCOOH ¾¾¾® RCOCl ¾¾® RCONH2
NH 3
C 6 H 5 CH 2 COOH ¾¾® C6 H 5 CH 2 COCl ¾¾® C 6 H 5 CH 2 CONH 2
Phenylacetic acid Phenylacetyl chloride Phenylacetamide
(Phenacyl chloride)

1. (a) Which bond of carboxylic acid is broken in the formation of acid chloride, i.e. whether C—OH or CO—H ?
(b) When benzoic acid is allowed to stand in water enriched in O 18 in presence of acids, heavier oxygen becomes incorporated
into the benzoic acid. Explain.
(c) When reactive alcohols like CH2 = CHCH2O18H are esterified in acid, some H2O18 is found in the product.
2. Discuss in three lines, how will you prepare ethyl acetate (an important commercial solvent) from ethanol.

4. Formation of anhydrides. Only one monocarboxylic acid anhydride (acetic anhydride) is important. It is prepared
by the reaction of acetic acid with ketene (CH2 = C = O), which in turn is prepared by high temperature dehydration
of acetic acid.
AlPO , 700°C
CH 3COOH
CH3COOH ¾¾¾¾¾¾®
4
CH2 = C = O ¾¾¾¾¾ ¾® (CH3CO)2O
-H 2 O

Acid anhydrides, in general, can be prepared by treating acyl chloride with —COOH in the presence of pyridine
or by treating sodium salts of carboxylic acids with acyl chlorides.
RCOCl + R¢COOH (or R¢COONa) ¾¾¾® RCO.O.COR¢ + HCl (or NaCl)

17.4.3 Reduction of >C = O of –COOH to –CH2OH

For details, consult preparation of alcohols.
(i) LiAlH , ether
RCOOH ¾¾¾¾¾¾¾
4
® RCH2OH
(ii) H 2 O

An alternate way of reducing carboxylic acid is via esters.

H , Copper chromite
RCOOH ¾¾¾® RCOOR¢ ¾¾¾¾¾¾¾¾¾
2
® RCH2OH + R¢OH
150°C pressure
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17.4.4 Halogenation of a-Hydrogens

Aliphatic carboxylic acids react with bromine or chlorine in the persence of phosphorus (or a phosphorus
halide) to give a-halo acids, the reaction as known as Hell-Volhard-Zelinski (or HVZ) reaction.

Cl
Cl2 , P | Cl2 , P
RCH2COOH ¾¾¾® RCHCOOH ¾¾¾® R C COOH
|
½ Cl
Cl

Halogenation occurs specifically at the a-carbon ; because of this regioselectivity and the ease with which it
takes place, HVZ reaction is of considerable importance in synthesis.
The function of phosphorus is to convert a little of the acid into acid halide which is the actual molecule on
which halogenation takes place and not on acid itself. Specific halogenation at a-position is due to formation of enols
which are readily formed by acyl halides than from carboxylic acids itself.

: :
O O OH
P + Br2
RCH2—C ¾¾¾¾® RCH2—C ¾¾®
¾
¾ ® RCH = C
(PBr3)
OH Br Br
Acyl bromide Enol form

Br—Br

O O
H2O
RCH—C ¾¾¾¾® RCH—C + HBr
Br OH Br Br

Harpp reaction is the modification of HVZ reaction. This reaction involves a-halogenation of carboxylic acid
with N-halosuccinimide in presence of HCl or HBr and SOCl2.

O O

SOCl 2 HX
RCH 2 COOH ¾¾¾¾ ® RCH2COCl + N—X ¾¾® RCHCOCl + NH
|
O X O
(X = Cl or Br)

Like alkyl halides, the halogen of these halogenated acids undergoes nucleophilic displacement and elimination,
hence a-halo acids are important synthetic intermediates.
(i) K 2 CO3 , H 2O,100° C
(i) CH 3 CH 2 CHCOOH ¾¾¾¾¾¾¾® CH 3 CH 2 CHCOOH
(ii) H 3 O +
½ ½
Br OH

2-Bromobutanoic acid 2-Hydroxybutanoic acid

CH 2 COO –
(ii) CH 2 COOH + 2NH 3 ¾¾¾® ½ + NH 4 Br
+
½ NH 3
Br

Aminoacetic acid (glycine)

+
alc. KOH H
(iii) CH3 CHCOOH ¾¾¾¾¾® CH2 = CHCOO– ¾¾¾® CH 2 = CHCOOH
½ Propenoic acid

Br
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1. Give the reagent(s) required to convert the keto acid,

O

OH
O
into each of the following compunds. In case two steps are required, give the proper order.
O O O

(a) H (b) (c) OH (d) OH

H
O OH OH
2. a-Iodo acids are not normally prepared by direct HVZ reaction. Show how you could convert octadecanoic acid to its 2-iodo
derivative by efficient sequence of reactions.
3. Predict the product of each of the following reactions :

H + , heat H + , heat
(a) C6H5CH(OH)CH2COOH ¾¾¾® (b) o-HOOCC6H4CH2OH ¾¾¾®
(- H 2 O) (- H 2 O)

COOH aq, NaOH Br

¾¾¾¾® COOH aq, NaOH
(c) (d) ¾¾¾¾®
Br
4. (a) Convert ethanoic acid into propanedioic acid.
(b) One of the steps in the above sequence involves conversion of chloroacetic acid to cyanoacetic acid ; for this step chloroacetic
acid is first converted into its salt before treatment with cyanide ion. Explain.

17.4.5 Decarboxylation of Carboxylic Acids

The loss of a molecule of carbon dioxide from a carboxylic acid is known as decarboxylation.
RCOOH ¾¾¾® RH + CO2
Decarboxylation of simple carboxylic acids takes place with great difficulty and is rarely encountered. However,
there are certain groups which if present in b-position of a carboxylic acid, decarboxylation takes place readily. Thus b-
keto and b, g-unsaturated carboxylic acids decarboxylate readily when they are heated to 100–150°C (some b-keto acids
decarboxylate although slowly even at room temperature).

O O O
||b a || 100–150° C ||
R — C — C H 2 — C—OH ¾¾¾¾® R— C— CH3 + CO2

g b a heat
C H 2 = C H CH 2 COOH ¾¾¾® CH 2 = CH CH 3 + CO 2
Decarboxylation of b-keto acids takes place in the form of free acid or in the form of carboxylate ion.
(a) When the carboxylate anion decarboxylates, it forms a resonance stabilized enolate anion ; I.

O – O
–
O O
O:
: :

+
½½ ½ ½½ – ½ Q H
R—C—CH2—C ¾¾¾® R—C = CH2 ¬® R—C—CH2 R—C—CH2 ¾¾®
—CO2
O Resonance stabilized anion, I
b-Keto acid or Malonic acid, when R = OH Ia Ib

OH O
½ ½½
R—C = CH2 ¾¾® R—C—CH3
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–
This carbanion is formed faster than the simple carbanion (R: ) from a simple carboxylate ion (RCOO–) because
it is more stable. Recall that of the two contributing structures (Ia and Ib), Ia is more stable because here the
negative charge is accommodated by oxygen (every atom has eight electrons, except hydrogen).
(b) Decarboxylation of the acid itself involves transfer of the carboxylic acidic hydrogen to the keto group, either
prior to loss of carbon dioxide, or simultaneously with loss of carbon dioxide.
+
O O OH O OH O
½½ ½½ ½½ ½½ –
½ tautomerizes ½½
(i) R—C—CH2—C—OH ¾¾® R—C—CH2—C—O ¾¾¾® R—C = CH2 ¾¾¾¾¾® R—C—CH3
¾¾® —CO2
b-Keto acid or Malonic
acid, when R = OH

H H
O O H
O O O O
(ii) C C ¾¾®
C C ¾¾® ¾¾® C
R C O —CO2 C
R C O H2 R CH2
H2 R CH3

b-Keto acid or Transition state Enol Keto

(Malonic acid, when R = OH)

Malonic acid and its monoanion undergo decarboxylation exactly in the same ways. Replace R— by —OH.
b, g-Unsaturated carboxylic acids also undergo decarboxylation in the same ways.
O
+
– – H
CH2 = CH—CH2—C ¾¾® [ CH2—CH = CH2¬® CH2 = CH—CH2 ] ¾® CH 3 —CH = CH 2
—CO2
–O

1. (a) It is difficult to decarboxylate C6H5CH2CH2COOH, while the corresponding phenylpropiolic acid, C6H5C º CCOOH
undergoes decarboxylation in alkaline solution. Explain.
(b) It is difficult to decarboxylate benzoic acid and phenylacetic acid, while 2, 4, 6-trinitrobenzoic acid can be decarboxylated
easily by heating.
2. Give the product isolated after thermal decarboxylation of each of the following :
(a) 1, 1-Cyclobutane dicarboxylic acid. (b) 2-Cyclopentenylmalonic acid. (c) Phenylmethylmalonic acid.
3. Give the products obtained on heating each of the following compounds.
COOH COOH
COOH
(a) (b) COOH
COOH
COOH

17.4.6 Reactions of Salts of Carboxylic Acids

(i) Heating of sodium salts with soda lime (NaOH + CaO) to form alkanes.
heat
CH 3 COONa + NaOH ¾¾® CH 4 ­ + Na2CO3
Sod. acetate Methane
However, sodium formate on decarboxylation with soda lime gives hydrogen.
NaOH
HCOONa ¾¾® H2 + Na2CO3
(ii) Sodium formate on heating gives sodium oxalate and hydrogen.

300°C COONa
2HCOONa ¾¾® | + H2
COONa
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(iii) Heating of sod. formate with conc. H2SO4.
2HCOONa + H2SO4 ¾¾¾® Na2SO4 + 2H2O + 2CO

(iv) Electrolysis of conc. aq. solution of sod. or pot. salts gives alkanes (reaction is not given by sod. or pot. formate).
electrolysis
2CH 3 COONa + 2H 2 O ¾¾¾¾® CH 3 - CH3 + 2CO 2 + 2NaOH + H 2
Sod. acetate
1444 424444 3 144244 3
at anode at cathode

(v) Heating of ammonium salts (Formation of amides).

heat
CH 3 COONH 4 ¾¾® CH 3 CONH2 + H2O
Ammo. acetate Acetamide

(vi) Dry distillation of calcium salts (Formation of aldehydes and ketones).

heat
(a) (HCOO)2 Ca ¾¾® HCHO + CaCO3
Cal. formate Formaldehyde

heat
(b) (CH 3 COO)2 Ca ¾¾® CH COCH + CaCO
3 3 3
Cal. acetate Acetone

heat
(c) (CH 3 COO)2 Ca + (HCOO)2 Ca ¾¾® 2CH 3 CHO + 2CaCO3
Cal . accetate Cal . formate Acetaldehyde

CH2CH2COO heat
(d) ½ Ca ¾¾® O + CaCO3
CH2CH2COO
Calcium adipate Cyclopentanone

(vii) Silver salt of a carboxylic acid on heating with bromine gives alkyl halide (Hunsdiecker reaction).

4 CCl , heat
RCOOAg + Br2 ¾¾¾¾® R–Br + CO2 + AgBr

17.5 Special Properties of Formic Acid

In addition to properties discussed earlier, formic acid gives the following reactions.
H 2 SO 4 , heat
1. Action of conc. H2SO4 (Dehydration). HCOOH ¾¾¾¾® H2O + CO
160°C
2. Action of heat. HCOOH ¾¾¾® H2 + CO2
3. Reducing agent. (Reactions due to —CHO group). Like aldehydes, but unlike other acids, formic acid reduces
Tollen’s reagent, Fehling solution, mercuric chloride and potassium permanganate.

(i) HCOOH + Ag 2 O ¾¾¾® CO2 + H2O + 2Ag ¯

Tollen’s reagent Silver mirror

(ii) HCOOH + 2CuO ¾¾¾® CO2 + H2O + Cu 2 O ¯

Fehling solution Cuprous oxide
(reddish brown)

(iii) HCOOH + 2HgCl2 ¾¾¾® CO2 + 2HCl + Hg 2 Cl 2 ¯

Mercurous chloride (white)

HCOOH + Hg2Cl2 ¾¾¾® CO2 + 2HCl + 2Hg ¯

Mercury (black)

or 2HCOOH + 2HgCl2 ¾¾¾® 2CO2 + 4HCl + 2Hg¯

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(iv) 2KMnO4 + 3H2SO4 ¾¾¾® K2SO4 + 2MnSO4 3H2O + 5O
5HCOOH + 5O ¾¾¾® 5CO2 + 5H2O

2KMnO4 + 3H2SO4 + 5HCOOH ¾¾¾® K2SO4 + 2MnSO4 + 5CO2 + 8H2O

However, remember that formic acid does not react with NH2OH, semicarbazide, phenylhydrazine, etc.

17.6 Dicarboxylic Acids

Important dicarboxylic acids along with their IUPAC and common names are given below.
HOOC.COOH HOOCCH 2 COOH HOOCCH2 CH 2 COOH
Ethanedioic acid Propanedioic acid 1, 4-Butanedioic acid
(Oxalic acid) (Malonic acid) (Succinic acid)

CH2COOH CH2CH2COOH CH2CH2COOH

CH2 ½ CH2
CH2COOH CH2CH2COOH CH2CH2COOH
1, 5-Pentanedioic acid 1, 6-Hexanedioic acid 1, 7-Heptanedioic acid
(Glutaric acid) (Adipic acid) (Pimelic acid)

Dicarboxylic acids exhibit position isomerism among themselves, e.g.

CH2COOH COOH
½ CH3CH
CH2COOH COOH
Succinic acid Methylmalonic acid

Methods of preparation and chemical properties are similar to that of monocarboxylic acids. Two properties
deserve special attention.
1. Acidity. Like inorganic acids containing two or more ionizable hydrogen (H2SO4, H2CO3, H3PO4 etc.), ionization
of the second carboxyl group occurs less readily than ionization of the first, i.e. K1 > K2. This is because, more
energy is required to separate a positive hydrogen ion from the charged anion than from the uncharged species.
Dicarboxylic acids are stronger than monocarboxylic acids because one —COOH group (electron-withdrawing
group) enhances the acidity of the other. This also explains that the K1 value of dicarboxylic acids decreases
with the increase in number of intervening CH2 group(s). Thus the acidic order is

HOOCCOOH > HOOCCH 2 COOH > HOOCCH 2 CH 2 COOH

Oxalic acid Malonic acid Succinic acid

2. Effect of heating. Different dicarboxylic acids on heating give different products depending upon the relative
position of the two carboxyl groups.
(i) Dicarboxylic acids having two carboxyl groups on the same carbon atom eliminate a molecule of carbon dioxide
(decarboxylation) on heating to form monocarboxylic acids.

COOH heat heat

| ¾¾® HCOOH + CO2 ; HOOCCH 2 COOH ¾¾® CH COOH + CO2
Formic acid 3
COOH Malonic acid Acetic acid
Oxalic acid

(ii) Dicarboxylic acids in which the two carboxylic groups are separated by two or three carbon atoms, i.e., 1, 4- and
1, 5-dicarboxylic acids lose a molecule of water on heating or on distillation with acetic anhydride to form cyclic
anhydrides. The reaction is known as cyclodehydration. For example,

CH2COOH heat
CH2—CO CH2—COOH heat CH2—CO
½ ¾¾¾® ½ O ; CH2 ¾¾¾® CH2 O
CH2COOH (—H2O) CH2—CO CH2—COOH (—H2O) CH2—CO
Succinic acid Succinic anhydride Glutaric acid Glutaric anhydride
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(iii) Dicarboxylic acids in which the two carboxyl groups are separated by four or more carbon atoms (i.e. 1, 6- and
1, 7-dicarboxylic acids) when distilled with acetic anhydride form cyclic ketones. For example,

CH 2 —CH 2 —COOH CH2—CH2

300°C
½ ¾¾¾® ½ CO + CO2 + H2O
(CH3 CO)2 O CH2—CH2
CH 2 —CH 2 —COOH
Cyclopentanone

CH2—CH2—COOH CH2—CH2
300°C
H2C ¾¾¾® H2C CO
CH2—CH2—COOH (CH3CO)2O CH2—CH2
Pimelic acid Cyclohexanone

The effect of heating on various dicarboxylic acids can be summarised in the form of Blanc rule according to
which dicarboxylic acids having two carboxylic groups on the same carbon atom when heated form monocarboxylic acids
; 1, 4- and 1, 5-dicarboxylic acids, on heating or on distillation with acetic anhydride form cyclic anhydrides while 1, 6- and
1, 7-dicarboxylic acids on distillation with acetic anhydride form cyclic ketones.

1. Give the structure of the compound formed in each of the following reaction :

O
O OH
OH OH
(a) + ¾¾¾® A (b) heat
HO ¾¾® B
O OH
OH
O

2. (a) Give the products obtained on heating the following with conc. H2SO 4.
(i) CH3COOH (ii) HCOOH (iii) Ph3CCOOH (iv) C6H5COCOOH
(b) Compare the reactivities of CH3COOH and Cl3CCOOH on heating with a base like soda lime, a mixture of NaOH and CaO.
(c) Give the product obtained by the oxidative cleavage of the following compounds with conc. KMnO 4.

(i) (ii)

17.7 Distinction Between a-, b-, and g-Substituted Carboxylic Acids

1. The three halogen substituted acids (a-, b- and g-) give different compounds with aqueous base (NaOH).

Br OH
–
(i) OH
OH ¾¾® OH
+
(ii ) H
O O
2-Bromopentanoic acid 2-Hydroxypentanoic acid

–
OH (i) OH OH
¾¾®
+
(ii ) H
Br O O
3-Bromopentanoic acid 2-Pentenoic acid
(conjugated system)
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– +
Br OH Br O Na O
NaOH
O ¾¾® O ¾¾® O

4-Bromopentanoic acid 3-Methyl-g- butyrolactone

– +
Br OH Br O NaO
O NaOH ¾¾® O O
¾¾®

5-Bromopentanoic acid d-Valerolactone

2. The three (a-, b-, and g-) hydroxy and amino acids behave differently, on heating. Hydroxy and amino acids
behave in similar ways.

OH HO O O
O
(a) heat
+ ¾¾®
O OH OH O O
(Two molecules of a-hydroxy acids) Glycollide

H
NH2 HO O O
N
+ heat
¾¾®
O OH H2N O N
H
(Two molecules of a-amino acids) Diketopiperazine

G O O
heat
(b) ¾¾®
OH OH + H2O or NH3
Two molecules of b-hydroxy acids
or b-amino acids
(G = OH or NH2)

OH OH O
heat
(c) O ¾¾® O

g-Hydroxy acid A g-lactone

H2
N OH NH
heat
O ¾¾® O

g-Amino acid A g-lactam

OH OH O O
d O heat
(d) ¾¾®
g a
b
d-Hydroxy acid A d-lactone
H2 H
N OH N O
heat
O ¾¾®

d-Amino acid A d -lactam

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17.8 Additional Chemistry of Aromatic Carboxylic Acids

Preparation. Although the methods used for aliphatic carboxylic acis can be applied for preparing aromatic
carboxylic acids, the most important one is due to oxidation of side chain.
Oxidation of the side chain. Generally, benzene ring is very resistant to oxidation and hence benzene homologues
are oxidised in the side chain to form a carboxylic acid, the side chain is always oxidised to —COOH group, ignoring its
length.

R COOH
COOH
KMnO4
¾¾¾® ; KMnO4 K2Cr2O7
hot ¾¾¾® ¾¾¾¾®
+
hot H

(R = —CH3, —CH2CH3, -n-C3H7) Cyclopropylbenzene

COOH
+ CH3COOH

COOH

(i) If the side chain is a tert-alkyl group, oxidation is difficult, but on vigorous oxidaton benzene ring in oxidised.

alk. KMnO
4
¾¾¾¾¾® (CH3)3CCOOH
heat

(ii) Side chain, like —CH2Cl, —CH2OH, and —CH2NH2, attached to benzene ring is also oxidised to —COOH
group.

CH2X COOH

KMnO4
¾¾¾¾®

(X = —Cl, —OH, —NH2)

(iii) Presence of electron withdrawing group like —NO2 makes the ring resistant to oxidation, while presence of
electron-repelling group lik —NH2 makes the benzene ring susceptible to oxidation.

NO2 NO2
HOOC
Ring B containing —NO 2
A B oxidaton B
¾¾¾¾® group is retained
HOOC

NH2
COOH
Ring B containing —NH 2
A B oxidaton A
¾¾¾¾® group is oxidised
COOH

However, oxidation of alkyl group to —COOH group in OH OH

compounds containing alkyl group as well as electron-repelling PbO2
group can be achieved either by carrying oxidation with a mild ¾¾¾®
oxidising agent (like PbO2) or by protecting the electron-releasing CH3 COOH
group first with tosyl chloride followed by oxidation.

OH OTs OTs OH
KMnO4 H2O
TsCl ¾¾¾®
¾¾¾® ¾¾®
CH3 CH3 COOH COOH
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Acidity of aromatic acids. Benzoic acid itself is somewhat stronger acid than acetic acid. Its carboxyl group is
attached to an sp2 hybridized carbon and ionizes to a greater extent than one that is attached to an sp3 hybridized carbon
(recall that carbon becomes more electron-withdrawing as its s character increases).

CH3COOH CH2 = CHCOOH COOH

Acetic acid Acrylic acid Benzoic acid

Ka 1.8 × 10–5 5.5 × 10–5 6.3 × 10–5
pK a 4.8 4.3 4.2

O O
C C
OH O–
2
sp
sp
3
O O
¾¾® ; H3C—C ¾¾® H3C®¾ C –
OH O
—COOH group attached –ve charge on O —COOH group on –ve charge on O
2 dispersesed 3 intensified
on sp C, hence more sp C, hence less
electronegative (hence more stable) electronegative (hence less stable)

Moreover, benzoate anion is more stable, due to presence of benzene ring, than acetate ion.
– – – – – – –
O = C—O O—C—O O—C—O O—C—O

+ +
¬¾® ¬¾® ¬¾®

+
Resonance in benzoate anion due to benzene ring
Like aliphatic acids, acidity of aromatic acids is affected by substituents : electron-releasing groups like —CH3,
—OH and —NH2 make benzoic acid weaker, while electron-withdrawing groups like —Cl, —NO2, —CN, etc. make
benzoic acid stronger.
– –
O O
C C
O O

G G
G (—NO2, —Cl, —CN) G (—CH3, —OH, —NH2 , —OCH3)
withdraws electrons, disperses releases electrons, intensifies –ve
–ve charge on O, stabilises the charge on O, destabilises the anion,
anion, hence strengthens acidity hence weakens acidity

Following table lists the ionization constants (acidity) of some substituted benzoic acids,
Acidity of some substituted benzoic acids, XC6H4COOH
Ka(pKa) for different positions of the substituent X
Value of X ortho meta para
H 6.3 × 10–5 (4.2) 6.3 × 10–5 (4.2) 6.3 × 10–5 (4.2)
CH3 1.2 × 10–4 (3.9) 5.3 × 10–5 (4.3) 4.2 × 10–5 (4.4)
F 5.4 × 10–4 (3.3) 1.4 × 10–4 (3.9) 7.2 × 10–5 (4.1)
Cl 1.2 × 10–3 (2.9) 1.5 × 10–4 (3.8) 1.0 × 10–4 (4.0)
Br 1.4 × 10–3 (2.8) 1.5 × 10–4 (3.8) 1.1 × 10–4 (4.0)
I 1.4 × 10–3 (2.9) 1.4 × 10–4 (3.9) 9.2 × 10–5 (4.0)
CH3O 8.1 × 10–5 (4.1) 8.2 × 10–5 (4.1) 3.4 × 10–5 (4.5)
O2N 6.7 × 10–3 (2.2) 3.2 × 10–4 (3.5) 3.8 × 10–4 (3.4)
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(a) Nearly all ortho substituents, whether electron-withdrawing or electron-releasing, exert an acid-strengthening
effect, and the effect is unsually large. This ortho effect is partly due to closeness of the groups involved. Sometimes
H—bonding also plays a role, e.g., o-hydroxybenzoic acid (salicylic acid) is far stronger than the corresponding
m- and p- isomers. The carboxylate ion of the o-isomer is stabilised by intramolecular H-bonding.

– – –
O O O O O O
C C H H C H

O O O

OH
p-Hydroxybenzoate o-Hydroxybenzoate ion, II 2, 6-Dihydroxybenzoate ion, III
ion, I (more stable than I) (more stable than II)

(b) The —OH and —OCH3 groups display both kinds of effect. When present in meta position, these groups produce
electron-withdrawing acid-strengthening effect. When present in para position, these groups produce electron-
releasing acid-weakneing resonance effect.

1. Discuss the resonance of the p-NO2 group in p-NO2C6H4COO–.

2. Account for the following
(a) p-Nitrobenzoic acid is more acidic than its meta isomer, while p-chlorobenzoic acid is less acidic than its meta isomer
(b) p-Toluic acid is weaker than m-toluic acid.
(c) p-Hydroxybenzoic acid is weaker than benzoic acid while the corresponding m —OH acid is stronger than benzoic acid.
3. Which of the two carboxylic acids is more stronger ?

COOH COOH COOH COOH COOH COOH

(a) (b) (c)

or or or

CH3 OCH3 NO2 COCH3 F Cl

4. Arrange the following carboxylic acids in decreasing order of acidity.

(a) Benzoic acid, p-chlorobenzoic acid, 2, 4-dichlorobenzoic acid
(b) Benzoic acid, p-toluic acid, p-nitrobenzoic acid
(c) p-Nitrobenzoic acid, p-nitrophenylacetic acid, b– (p-nitrophenyl)propanoic acid

Substitution in benzene nucleus. As described earlier, —COOH group is m-directing and deactivating group,
so substitution takes palce in meta- position and require stronger conditions.

COOH COOH COOH COOH

Br2, Fe Conc. HNO3,

¾¾¾¾® ; ¾¾¾¾¾¾¾®
heat Conc. H2 SO4 , heat
Br NO2

COOH COOH

Conc. H2 SO4 ,
¾¾¾¾¾¾¾®
heat
SO3H
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When some activating group e.g., —OH is present along with —COOH, substitution occurs w.r.t. —OH and —
COOH group is replaced by the new group. For example,
OH OH OH OH
COOH Br COOH
Br COOH
Br2, water Br2
¾¾¾¾¾® ¾¾¾¾®
CH3COOH

Br Br
In the second example, brominating agent is mild, hence only monobromo product will be formed. Further,
bromination will be favoured at para position because of steric factors.
OH OH
O2N NO2
fuming
¾¾¾¾®
HNO3

COOH NO2

1. Identify the bracketed compounds in the following reactions.

COOH COOH
(i) PCl 5 (i) CH 3Li
(a) ¾¾¾¾¾¾¾® [A] (b) ¾¾¾¾® [B]
(ii) H 2 , Pd/BaSO 4
(ii) H 3 O+

COOH
CH2COOH
(CH 3 CO)2 O (i) B 2H 6 , THF
(c) ¾¾¾¾® [C] (d) ¾¾¾¾¾® [D]
heat (ii) H 2O
COOH
NO2

O OH
COOH
NaBH 4 O LiAlH 4 ICl
(e) [F] ¬¾¾¾ ¾¾¾® [E] (f) ¾¾® [G]

OH COOH
NO2
(i) NaOH Br2 H2O C 2H 5 OH (i) excess of C 6H 5 MgBr
(g) ¾¾¾¾¾® [H] ¾¾¾¾® [I] ¾¾® [J] (h) ¾¾¾¾® [K] ¾¾¾¾¾¾¾¾® [L]
(ii) CO 2 , heat CH 3 COOH boil H+ (ii) H 3O +
OH (iii) H+

17.9 Analysis of Carboxylic Acids

(i) Carboxylic acids are recognized through their acidity. They dissolve in aqueous NaOH and in aqueous NaHCO3;
in the latter case bubbles (effervescences) of CO2 are evolved.
NOTE.
(a) Phenols, with certain exceptions, are considerably weaker than carboxylic acids. Thus although they
dissolve in aq. NaOH (a strong base), but not in aq. sodium bicarbonate (a weak base).
(b) Sulphonic acids are even more acidic than carboxylic acids, but they can be differentiated by presence of
sulphur.
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(ii) Determination of neutralization equivalent (NE), the equivalent weight of the acid as determined by titration with
standard base, is one of the characteristics of a carboxylic acid. For this, a known weight of the acid is dissolved
in water or aqueous alcohol. The volume of a standard base required to neutralize the solution is measured by
titration using phenolphthalein as an indicator. Suppose x g of an unknown acid requires V mL. of 1M NaOH
for neutralisation. It means
Since 1000 mL of the base contains 1 equivalent of the base

1M
V mL of the base contains × V equivalent of base.
1000

1M´V
Since No. of eq. of base required = No. of eq. of acid present =
1000

1M´V
eq. of acid = x g (Wt. of acid present)
1000

x ´ 1000
\ 1 eq. of acid = g of acid
1M´ V

Thus by knowing the wt. of acid, and volume of standard base (known molarity), neturalization equivalent of
the acid can be ascertained.

Detection of a metal salt of a carboxylic acid

(i) On strongly heating, it leaves a residue;
(ii) it decomposes at a high temperature instead of melting, and
(iii) it is converted into a carboxylic acid upon acidification.

1. (a) What is the relation between NE and the number of acidic hydrogens per molecule of acid?
(b) Wha t is the neutra liz ation eq uivalent of ter ephthalic acid, p -HOOCC 6 H 4 COOH, and melittic a cid,
C 6(COOH) 6 ? How many moles of a base (NaOH) are needed to neutralize one mole of each of the two acids ?
2. Differentiate among 2-chloropropanoic acid (CH3CHClCOOH), pyruvic acid (CH3COCOOH), acrylic acid (CH2 = CHCOOH)
and propanoic acid (CH3CH2COOH).
3. Give a chemical reaction with the help of which we can distinguish among following three carboxylic acids.
n-Pentanoic acid, 2-methylbutanoic acid, and 2, 2-dimethylpropanoic acid.

17.10 ILLUSTRATIVE EXAMPLES

Example 1 :
Identify the bracketed compounds in each of the following reactions.

1 mole HBr (i) Mg heat

(i) ¾¾¾¾® [A] ¾¾¾¾® [B] ¾¾® [C]
+
(ii) CO 2 , H 3 O

Zn
(i) acetone (i) H O +
(ii) CH2BrCOOC2H5 ¾¾® [A] ¾¾¾¾¾® [B] ¾¾¾¾¾
3 ® [C]
(ii) H 2 O (ii) heat
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OH

K 2 Cr2 O7 C 6 H 5 MgBr CrO 3 , CH 3 COOH

(iii) ¾¾¾¾¾ +
® [A] ¾¾¾¾¾¾ ® [B] ¾¾¾¾¾¾¾¾ ® [C]
H heat

HNO 3 HCN/CN -
H3O conc. +
LiAlH 4
(iv) Cyclopentanol ¾¾¾¾ ® [A] ¾¾¾® [B] ¾¾¾® [C] ¾¾¾¾ ® [D] ¾¾¾¾ ® [E]
H2 SO 4

S, heat
(i) C 6 H 5 MgBr
(v) ¾¾¾¾¾¾® [A] ¾¾¾¾® [B]
+
(ii) H

[B] dil. NaOH

(i) NaOH P, Br 2 SOCl 2
(vi) [E] ¬¾¾¾¾ +
¾ [D] ¬¾¾¾
excess
¾ CH3COOH ¾¾¾¾ ® [A] ¾¾® CH3CHO ¾¾¾® [C]
(ii) H D

NBS KCN +
conc. H3O
(vii) Benzyl alchol ¾¾¾® A ¾¾® B ¾¾® C ¾¾¾¾ ® D
H2 SO 4

CH3 (i) HCN heat

O /H O
(viii) ¾¾¾¾¾
3 2 ®
A ¾¾¾® B ¾¾® C
+
(ii) H

Solution :

(i)
Br COOH
[A] obtained by 1, 4- addition [B] [C]

(ii) CH 2 COOC2 H5 (CH 3 )2 CCH 2 COOC2 H 5 (CH3)2C = CHCOOH

| ½
ZnBr OH

[A] [B] [C]

O HO C6H5 C6H5 C6H5

CrO3 O
(iii) ¾¾® ¾¾® COOH
heat

[A] A cyclanol [B]

6-Oxo-6-phenylhexanoic acid [C]

Cyclanols undergo acid catalyzed oxidative cleavage, probably via the alkene.

(iv)

O HO CN CN COOH CH2OH
[A] [B] [C] [D] [E]

C6H5 C6H5
C6H5 OH

(v) is formed via

[A] [B]
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(vi) CH3COCl, H2/Pd/BaSO4, CH3CH = CHCHO, Br3CCOOH, HOOC.COOH
A B C D E

+
CH2OH CH2 CH3 CH3
+ +
H —H NBS
(vii) ¾¾® ¾¾® ¾¾® ¾¾®

1° Carbocation 3°Carbocation A

CH3 CH3 CH3

Br CN +
COOH
KCN H3O
¾¾® ¾¾®

B C D

COOH COOH
CH3 CH3 CH3
O3/H2O (i) HCN heat
(viii) ¾¾¾® ¾¾¾®
+ ¾¾® O
O (ii) H OH
O
COOH COOH
(A) (B) (C)

Example 2 :
Establish the structure of [X] on the basis of following reactions/facts.
HBr KOH alc. H 2/Ni
[X] ¾¾¾® C9H9O2Br ¾¾¾® [Y] ¾¾¾® [Z]
(i) Compound X gives a positive test with CrO3 in acid.
(ii) Compound Z can be obtained by the carbonation reaction of C6H5CH(CH3) MgBr. Is there any isomer of X ?
Solution :
Structure of Z can be ascertained by its synthesis from carbonation reaction.

(i) CO 2
C6H5CH(CH3) MgBr ¾¾¾® C 6 H 5 CH(CH 3 )COOH
(ii) H 3O + [Z]

Thus going backward from Z, structure of X can be ascertained

CH 3 CH 2 CH2 Br CH2 OH
½ H 2/Ni ½½ alc.KOH ½ HBr ½
C6 H 5 CHCOOH ¬¾¾¾ C6 H5 CCOOH ¬¾¾¾ C6 H 5 CHCOOH ¬¾¾¾ C6 H 5 CHCOOH
Z Y (C9 H9 O 2 Br) X

Structure of X is confirmed by positive response with CrO3 in acid.

OH
½
Isomer of X is C6 H 5 C(CH 3 )COOH ; but it, being a 3°alcohol, is inert to CrO3.
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Example 3 :
Give stereochemical formulas of compounds A to G.
1 mole P, Br2
(a) rac-b-Bromobutyric acid ¾¾¾¾¾® A + B
(b) Maleic acid + Performic acid ¾¾® C + D
CHBr3 KMnO 4 H 2 /Ni
(c) ¾¾¾¾® E ¾¾¾¾® F ¾¾¾¾® G.
tert - BuOK

Solution :

COOH
COOH COOH
CH2
P, Br2 H Br Br H
+
¾¾¾® H Br H Br
(a) H C Br
CH3 CH3
CH3
I II

Or

COOH
COOH COOH
CH2
P, Br 2 Br H H Br
+
¾¾¾® Br H Br H
Br C H
CH3 CH3
CH3
III IV
Note that I and III are enantiomers, hence they represent one racemic mixture ; similarly II and IV are enantiomers;
and respresent a different racemic mixture. The two racemic mixtures are thus A and B.

OH COOH
H H OH
H COOH º HO H
H
COOH
H COOH OH COOH
(b) anti-
hydroxylation
[C]
COOH H COOH
Maleic acid HO COOH
H
º HO
H OH H OH
COOH
COOH
[D]
rac-Tartaric acid

tert -BuOK
(c) CHBr3 ¾¾¾® : CBr2 + HBr

H H H
: CBr2 Br KMnO4 HOOC Br H2/Ni HOOC
¾¾¾¾¾® ¾¾¾® ¾¾¾®
syn-addition Br HOOC Br HOOC

H H H
[E] [F] meso- [G] meso-
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Example 4 :
Give essential steps involved in the following conversions :
(i) Ethanol to glycine (ii) 2-Butanol to 2-methylbutanoic acid.
(iii) 2-Chlorobutanoic acid to 3-chlorobutanoic acid. (iv) 2-Propanol, (CH3)2CHOH to 3-hydroxybutyric acid.
(v) Benzene to adipic acid, HOOC.(CH2)4 . COOH. (vi) Toluene to 2-methyl-5-chlorobenzoic acid.
(vii) Tetrahydrofuran to adipic acid. (viii) Tetrahydrofuran to succinic acid.
(ix) Cyclopentanol to 2-oxocyclopentanecarboxylic acid. (x) Benzene to 6-oxo-6-phenylhexanoic acid.
Solution :

MnO 4 - , H + Cl 2/P NH 3
(i) CH3CH2OH ¾¾¾¾® CH3COOH ¾¾® ClCH2COOH ¾® H2NCH2COOH
(ii) The conversion involves the conversion of —OH to —COOH, which can be easily accomplished through Grignard
reagent.

H H H H
½ ½ ½ ½
SOCl 2 Mg (i) CO2
CH 3 CH 2 CCH 3 ¾¾® CH CH CCH CCH 3
, CH 3 CH 2 CCH 3 ¾¾® 3 2 3 ¾¾¾¾® CH3CH2
½ ether
½ (ii) H3O +
½ ½
OH MgCl COOH
Cl
2-Butanol

Nitrile route should not be used because a 2° halide may undergo extensive dehydrohalogenation.

Cl
½ alc.KOH
(iii) CH 3 CH 2 CHCOOH ¾¾¾¾® CH3CH = CHCOOH
2-Chlorobutanoic acid

+
H

Od -
Cl -
d+ |
+ | +
CH 3 CH2 CH - C - OH or CH 3 C HCH 2 COOH ¾¾® CH 3 CHCH 2 COOH
An a- carbocation A b- carbocation |
(unstable, + ve ch arg e on adjacent C' s) (more stable) Cl
3 - Chlorobutanoic acid

OH OH
½ H2 SO 4 HOCl ½ CN - , H +
(iv) CH 3 CH CH 3 ¾¾¾® CH3CH = CH2 ¾¾¾® CH3 CHCH2 Cl ¾¾¾®
2-Propanol

OH OH
½ H 3O + ½
CH3 CHCH2 CN ¾¾¾® CH3 CHCH2 COOH

3-Hydroxybutanoic acid

Cl
H2/Pd Cl2 alc. KMnO COOH
(v) ¾¾® ¾¾® ¾¾® ¾¾¾®
+
4

KOH H COOH
Adipic acid
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CH3 CH3 CH3 CH3

Br COOH
Cl2 /Fe Br 2/Fe (i) Mg/ether
(vi) ¾¾® ¾¾® ¾¾¾¾®
+
(iii) H
Cl Cl Cl
Here it is advisable to introduce —COOH grop through carbonation route, because route involving the oxida-
tion of the alkyl group gives poor yields, until a strong electron-withdrawing group like —NO2 is present.

(vii) Conc. HI dicarbonation COOH

¾¾¾¾® ¾¾¾¾¾®
O I I COOH
THF Adipic acid

–
(viii) Conc. HI OH KMnO4
OH ¾¾¾®
¾¾¾® ¾¾® HOOC COOH
O I I OH
Succinic acid
THF
(ix) The required product has a keto and a carboxylic group for which CHOH and CN should be the respective precursor.
OH OH O
–
H2SO4 HOCl (i) CN K2Cr2O7
¾¾¾®
+
¾¾¾®
+
OH Cl (ii) H3O COOH H COOH
2-Oxocyclopentane
carboxylic acid

(x) First write down the structure of the product and then think of its precursor, i.e. proceed backward. It will be very
easy to write reactions.
HNO3 C6 H5MgBr KMnO4
¬¾¾¾ ¬¾¾¾¾ ¬¾¾¾
COC6H5
COOH
HO C6H5 O OH
­
½(aq.)
½
H /Pd Cl , hv
¾¾¾®
2
¾¾¾®
2
heat,
high P
Benzene
Cl

Example 5 :
Give necessary steps (reagents) to explain the following reactions :

H+
(a) C6H5CH = CHCH2COOH ¾¾¾® O
C6H5 O

O
(i) Tollen’s reagent O
CH 2 CH 2 CH 2 CH 2 OH
(b) ¾¾¾¾¾¾¾® O (c) CH3CH(OH)CH2C º CCOOH ¾¾¾®
½ (ii) H+ O
CHO
CH3
MeO OMe

refluxed A keto acid

¾¾¾¾®
(d) with HCl

Me2HCOOC COOCHMe2
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Solution :

H+
+
+ + –H
(a) C6H5CH=CHCH2COOH ¾¾® C6 H 5 C HCH 2 CH2 COOH º C H O C6H5 O
Benzyl carbocation 6 5
O O

O O O
– +
H Tollen’s O H O
(b) ¾¾¾® ¾¾¾¾¾¾®
reagent (Intramolecular
OH OH esterification)

O O O
+
(c) H2 , Lindlar catalyst H
OH ¾¾¾¾¾¾¾¾® OH ¾¾¾¾¾¾¾¾® O
OH OH (intramolecular
esterification)
CH3 CH3 CH3
cis-isomer

(d) The given compound has two types of functional groups (acetal and ester) both of which are hydrolysed by HCl.

MeO OMe HO OH

HCl
¾¾® + 2 MeOH + 2 Me2CHOH

Me2HCOOC COOCHMe2 HOOC COOH

HO OH O O

—H O —CO
¾¾¾®
2
¾¾¾®
2

HOOC COOH HOOC COOH

COOH
A g -keto acid

Example 6 :
A sulphuric acid solution of each of the compounds namely tert -pentyl alcohol, neopentyl alcohol and 2-methyl-2-
butene when treated with carbon monoxide gives 2, 2-dimethylbutanoic acid. Explain with mechanism.
Solution :
Each of the three compound gives tert-pentyl cation in presence of sulphuric acid.

CH3
½
CH3CH2— C—OH
½
CH3
tert-Pentyl alcohol
+
H , (–H2O)
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CH 3 CH 3
CH3
| H + ½ CO ½
CH3CH = C – CH 3 ¾¾® CH 3 CH 2 ¾ CÅ ¾¾¾® CH 3 CH 2 ¾ C ¾ COOH
H 2O
½ ½
CH 3 CH 3
2-Methyl-2-butene tert-Pentyl cation 2, 2-Dimethylbutanoic acid

rearrangement

CH 3 CH3
½ ½ Å
CH 3 ¾ C ¾ CH 2 OH ¾¾¾® CH 3 ¾ C ¾ CH 2
½ ½
CH 3 CH3
Neopentyl alcohol 1° Carbocation
Mechanism of conversion of R+ to RCOOH by means of CO

– + + H 2O
R+ + : C º O : ¾¾¾® R -CºO: ¾¾¾® R— C =O
Acylium ion - H+
(every atom has octet)
½
OH
Carboxylic acid

Example 7 :
Outline a typical method for resolving rac-(R,S)—RCOOH.
Solution :
Racemic mixture of carboxylic acids are best separated by using optically active (R)- or (S)- naturally occurring base
like quinine.
(R, S)-RCOOH + (R)-base ¾¾® [(R)-RCOO– (R)-base H+] + [(S)-RCOO–(R)-base H+]
[A] [B]
Insoluble Diastereomeric salts

Due to difference in solubilities, [A] and [B] are separated by fractional crystallization and then hydrolysed to give
back the corresponding acid and the (R)-base.
HX HX
A ¾¾® (R)-RCOOH + (R)-base H+ X– B ¾¾® (S)-RCOOH + (R)-base H+ X–

Example 8 :
Write down the structures of the various isomers of the formula C4H4O4, corresponding to following reaction.
(a) A dibasic acid which on heating gives propenoic acid.
(b) An unsaturated dibasic acid which gives a meso compound on reaction with alkaline KMnO4.
(c) An unsaturated dibasic acid which gives a racemic mixture on reaction with alkaline KMnO4.
(d) A cyclic ester that on hydrolysis gives glycol and oxalic acid.
Solution :
Write down the structure of the product and proceed backward keeping in mind the type of reaction that can give the
desired product.
- CO 2
(a) CH2 = CHCOOH ¬¾¾¾ CH2 = C(COOH)2
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(b) Recall that alk. KMnO4 is a hydroxylating reagent and causes hydroxylation in syn- manner. Thus meso product
is obtained from cis-isomer, while rac-from trans-.

COOH
½ COOH
H— C—OH ½
(b) ½ ¬¾¾ H— C
H— C—OH ||
H— C
½
COOH ½
COOH
meso- Maleic acid (cis)

COOH COOH
½ ½ COOH
HO — C—H H— C—OH ½
(c) ½ + ½ ¬¾¾ H— C
H— C—OH OH— C—H ||
C—H
½ ½
COOH COOH ½
COOH
rac- Fumaric acid (trans)
OH HO O O O
hydrolysis
(d) + ¬¾¾¾¾
OH HO O O O
Glycol Oxalic acid Glycol oxalate

Example 9 :
There are four isomeric hydrocarbons corresponding to molecular formula C8H14. On ozonolysis, different isomers
give different products, assign the structure to each.
(a) Isomer A gives isobutyric acid.
(b) Isomer B gives a, a¢- dimethyladipic acid.
(c) Isomer C gives b , b - dimethyladipic acid.
(d) Isomer D gives diketone giving iodoform test at both ends of the molecule.
Assign structure to A, B, C and D.
Solution :
Molecular formula C8H14 suggests that the compounds have 2° of unsaturation ; which means they may contain (i) a
triple bond, or (ii) two double bonds, or (iii) a double bond and a ring. Nature of unsaturation and structure of various
isomers can be ascertained by their ozonolysis products :
Ozonolysis
(a) (CH3)2CHCOOH ¬¾¾¾ (CH3)2CHC º CCH(CH3)2
Isobutyric acid [A]

COOH Ozonolysis
¬¾¾¾¾ COOH ¬¾¾¾
(b) COOH (c)
COOH
b, b-Dimethyladipic acid [C]
a, a¢-Dimethyladipic acid [B]
O O O O
|| || || ||
(d) CH 3 ¾ C ........ C ¾ CH 3 or CH 3 C (CH 2 )4 C CH 3 .¬¾¾

[D]
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Example 10 :
Assign structure to each isomer of the formula C4H8O2 corresponding to the following reaction.
(a) The isomer (A) that can be hydrolysed to form ethanoic acid and alcohol.
(b) The isomer (B) that can reduce Tollen’s reagent due to —CHO group and also responds haloform test.
(c) The isomer (C) that can reduce Tollen’s reagent but does not respond haloform best.
(d) The isomer (D) that gives haloform test due to —COCH3 group and also reduces Tollen’s reagent
(e) The isomer (E) that gives haloform test due to —COCH3 group and also gives turbidity with Lucas reagent.

Solution :
hydrolysis
(a) CH3COOH + C2H5OH ¬¾¾¾ CH3COOC2H5 (A)
(b) Molecular formula C4H8O2 indicates that all isomers, including (B) has 1° of unsaturation which is present
in the form of —CHO group. Hence the positive haloform reaction must be due to CH3CHOH– grouping
(presence of CH3CO— grouping is discarded due to fact that the compound has only 1° of unsaturation
which is in the form of —CHO group). Thus the isomer B should be CH3CH(OH)CH2CHO.
(c) HOCH2CH2CH2CHO (C)
(d) Since the compound D has —COCH3, it can’t have —CHO group (note that 1° of unsaturation is present in
C4H8O2). Hence the positive reaction with Tollen’s reagent is due to a-hydroxy ketone. Thus D should be as
shown below.
(e) Since the compound gives turbidity with Lucas reagent, it must have 1° aloholic group.
O OH O
½½ ½ ½½
CH 3 ¾ C ¾ CH ¾ CH 3 CH 3 ¾ C ¾ CH 2 ¾ CH 2 OH
(D) (E)

Example 11 :
Sodium salt of a carboxylic acid on ignition gives a white residue. The residue is soluble in water, reacts with
hydrochloric acid with the evolution of bubbles, and turns moist litmus blue. Give the probable chemical structure
of the residue and explain its formation.
Solution :
The residue should be Na2CO3
O
½½
2H ¾ C ¾ ONa ¾¾® HCHO + Na2CO3

Example 12 :
A hydrocarbon of the molecular formula C6H10 has two isomers ; X and Y. On oxidation X gives butanoic acid and
ethanoic acid, while Y gives 1, 6-hexanedioic acid Assign structure to X and Y.
Solution :
Molecular formula C6H10 indicates that it has two degree of unsaturation which may be in the form of a triple bond
or one double bond and one ring. Proceed backward from the oxidation product(s) in each case.
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oxidation
n-C3H7COOH + CH3COOH ¬¾¾¾ n-C3 H 7 C º CCH 3
[X]

COOH ¬¾¾¾
COOH
1, 6-Hexanedioic acid Cyclohexene
[Y]

Example 13 :

(i) An alkyl halide A of the formula C3H5Br reacts with Mg in presence of ether of form Grignard reagent which,
on reaction with dry ice followed by acidification, is converted into a carboxylic acid B.

(ii) Two molecules of B are also formed by the ozonolysis of a compound C, C8H10.

Assign structures to A, B and C. Is there any isomer of A, if yes give its structure and ozonolysis.

Solution :

Alkyl halide has one degree of unsaturation ; which may be in the form of ring or a double bond. So three possible
structures for A are

CH2 = CHCH2Br, CH 3 CH = CHBr Br

[Not possible]

However, CH3CH = CHBr, being vinylic halide does not form Grignard reagent under given conditions. So the two

possible carboxylic acids (B) from the remaining alkyl halides will be CH2 = CHCH2COOH and COOH .

Two molecules of B are formed from C (C8H10) by ozonolysis, so corresponding C should be either

CH2 = CHCH2—C º C—CH2CH = CH2 or CºC

ozonolysis ozonolysis

2CH2O + 2OHCCH2COOH 2 COOH

It is not [B] [B]

So, compounds A, B, C and isomer of A are

Br ; COOH ; CºC ; CH2 = CHCH2C º C CH2CH = CH2

[A] [B] [C] Isomer of [A]

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Example 14 :
Give structures of the four optically acitve structural isomers A to D for C 4H8O3 that evolve CO2 with aqueous
NaHCO3.
One of the isomers (say A) reacts with LiAlH4 to give an achiral product. Assign the structure to A, B, C and D. Give
chemical reactions to distinguish among B, C and D.
Solution :
(i) The molecular formula C4H8O3 suggests that the isomers have 1° of unsaturation that must be due to —COOH,
indicated by their reaction with aq. NaHCO3. Hence the third oxygen may be present either as —OH or —OR.
(ii) Since A on reduction with LiAlH4 (—COOH ¾¾® —CH2OH) gives an achiral product, a —CH2OH group
should already be is present in A . Hence the structure of A is

CH 3 CH 3
½ LiAlH 4 ½
H ¾ C ¾ COOH ¾¾¾® H ¾ C ¾ CH 2 OH
½ ½
CH 2 OH CH 2 OH
[A], Chiral Achiral

Thus the three other isomers may be written as below.

CH3 CH CH2COOH CH3CH2 CH COOH CH3 CHCOOH

½ ½ ½
OH OH OCH 3

[B] [C] [D]

Differentiation between B, C and D. B and C are oxidisable by KMnO4 or CrO3, while D (an ether) is inert.
Further, B gives a positive haloform test, while C does not respond to it.

Example 15 :
Two isomeric carboxylic acids (A and B ) of the formula C9H8O2, on oxidation, give benzoic acid. Acid A takes up one
mole of hydrogen to form resolvable carboxylic acid, while acid B on similar treatment gives non-resolvable carboxylic
acid. Assign structures to A and B and their corresponding hydrogenated products.
Solution :
The given statements indicate tht A and B have a C = C linkage and a phenyl group. Since the hydrogenated product
from A is resolvable, it must have four different groups to the central carbon atom, two of which are —COOH and —
C6H5. The remaining fragment (CH4) can be present only as H and CH3. Hence the complete structure of the resolvable
product and its precursor, A can be drawn as below.

CH 3 CH 2
½ H2 ½½
C6 H 5 ¾ C ¾ COOH ¬¾¾¾ C 6 H 5 ¾ C ¾ COOH
Pd [A] (C9H 8 O 2 )
½
H

Thus the isomeric carboxylic acid B and its hydrogenated product (non-resolvable) should have following structure.
H 2/Pd
C6 H 5 CH = CHCOOH ¾¾¾® C6 H 5 CH 2 CH 2 COOH
B (C9H 8 O 2 ) Non-resolvable
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Example 16 :
Write the structural formula for a chiral hydrocarbon, C11H16, which on oxidaton affords terephthalic acid.
Solution :
Oxidaton of the hydrocarbon (C11H16) to terephthalic acid indicates that the hydrocarbon is 1, 4-dialkylsubstituted
benzene.
oxidation
R R ¾¾¾¾® HOOC COOH

tere-Phthalic acid
Thus the two alkyl groups of the hydrocarbon should have five carbon atoms. The smallest alkyl group with a chiral
carbon is sec-butyl, hence the other alkyl group should be methyl.
* oxidation
H3C CHC2H5 ¾¾¾¾® HOOC COOH
½
CH3

Example 17 :
Assign structure to the compound A, C8H9Br which responds following series of reactions.

(i) Mg, ether KMnO 4 , OH-

[A] ¾¾¾¾¾¾¾® [B] ¾¾¾¾¾® Phthalic acid
(ii) CO2 , (iii) H 3O +

Solution :
Reaction of compound A with Mg in ether followed by CO2 points out the conversion of Br to MgBr which reacts
with CO2 to form —COOH.
Mg, ether (i) CO 2
C8H9—Br ¾¾¾¾® —MgBr ¾¾¾® —COOH
(ii) H 3O +
Since the final product has two —COOH groups, the second must have been introduced through the oxidation of
the side chain, which should be —CH2CH3. Hence A is o-bromoethylbenzene.
Br COOH –
COOH
(i) Mg, ether KMnO , OH
¾¾¾¾® ¾¾¾¾®
4
(ii) CO2
CH2CH3 (ii)H3 O
+ CH2CH3 COOH

Example 18 :
Give structure of a hydrocarbon (C12H20 ) which gives two diastereomeric aliphatic dicarboxylic acids on oxidation.
Solution :
(i) Molecular formula of the hydrocarbon indicates that it has 3° of unsaturation ; two of which must be present
in the form of double bonds (indicated by the formation of two dicarboxylic acids) ; the third degree of
unsaturation should be present in the form of ring.
(ii) The two diastereomeric dicarboxylic acids must be meso and recemic which is possible for the following
cyclo-octadiene derivative.
CH3 CH3
H H
H3 C H
H CH3
One half of the molecule with the cis Me’s gives the meso diacid and the other half with the trans Me’s gives the
racemic diacid.
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EXERCISE 17.1 (MCQ - ONE option correct)

1. The systematic name of CH2 = C(CH3) COOH is 8. Which of the following carboxylic acids is decarboxylated easily?
(a) 2-methyl-2-propenoic acid
(b) 2-methylpropenoic acid
(c) both (a) and (b)
(d) Methacrylic acid. (a) (b)

2.

Above reaction can be achieved satisfactorily by which set of

reagents ?
(c) (d) n-C 4H9COOH.
(a) NaCN, H+, heat (b) Mg + ether, CO2, H3O+
(c) Both (a) and (b) (d) Oxidation.
3. Which method is expected to give good result for following
reaction ?
9. 0.187 g of an acid required 18.7 mL of 0.0972 M NaOH for
HOCH2CH2CMe2Cl ¾¾® HOCH2CH2C(Me2)COOH
neutralisation. The acid should be
(a) Grignard synthesis (b) Nitrile synthesis
(c) Either of the two (d) None of the two. (a) methoxyacetic acid
(b) ethoxyacetic acid
(i) Mg / ether
4. [A] ¾ ¾¾¾¾¾
+
® [B]. Here [B] is (c) caproic acid, C5H11COOH
(ii) CO2 , H 3 O
(d) datas are insufficient.
10. Which type of halogen containing compound could react with
(a) (b) OH– to give a carboxylic acid ?
(a) RCH2 X (b) RCHX2
(c) RCX3 (d) None.
(c) (d) 11. Identify the nature of reducing agent in the following reaction.
?
CO, H 2 SO 4
BrCH2CH2COOH ¾¾¾® Br CH2CH2CH2OH
5. CH 3CH 2CH 2CH 2OH ¾¾¾¾® A ; CH3CH 2CH(OH) CH 3
(a) LiAlH4 (b) BH3/THF followed by H3O+
CO
¾¾¾¾® B. Predict the nature of A and B. (c) Both (d) None.
H 2SO 4

(a) A is CH 3 CH 2 CH 2 CH 2 COOH and B is 12. Identify the respective final products in the following two
CH3CH2CH(CH3)COOH reactions.
(b) A and B both are CH3CH2CH(CH3)COOH Br2 / PCl 3 Br2 H2O
(i) CH3CH2COOH ¾¾¾® [A] ¾¾¾® [B] ¾¾¾® [C]
(c) A is CH3CH2CH = CH2 and B is CH3CH = CHCH3
Cl 2 / PBr3
(d) Reaction is not possible. ¾¾¾®
Cl 2 H2O
(ii) CH3CH2COOH [D] ¾¾¾® [E] ¾¾¾® [F]
6. Sodium malonate having one labelled oxygen is decarboxylated
(a) CH3CHOHCOOH and CH3CHOHCOOH
to form monocarboxylic acid. Predict the final products.
(b) CH3CHOHCOCl and CH3CHOHCOBr
1.NaOH 18
HOOC—CH2—COO18H ¾¾¾® HOOC—CH2— COO- Na+ (c) CH3CHBrCOOH and CH3CHClCOOH
heat
¾¾¾® (d) CH3CHClCOOH and CH3CHBrCOOH.
(a) CH3COOH + O = C = O18 13. Both propa noic a cid, CH 3 CH 2 COOH as well as 2-
(b) CH3COOH + O18 = C = O18 chloropropanoic acid give precipitate with aq. AgNO 3. How
(c) CH3COO18H + O = C = O18 you distinguish the precepitates in the two ?
(d) CH3COO18H + O = C = O (a) By aq. NH4OH (b) By aq. HNO3
7. Which of the following is most difficult to decarboxylate ? (c) By either of the two (d) By none of the two.
14. Identify the product A
(a) (b) (i) 2Na
Na / C 2 H 5OH
HC º CH ¾¾¾®
( ii) 2CO
[Intermediate] ¾¾¾¾® [A]
2

(a) Maleic acid (b) Fumaric acid

(c) (d) (c) Both (a) and (b) (d) Succinic acid.
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(i) BH / THF
3 22.
15. ¾ ¾¾¾¾¾® P. Here product P is
( ii) H 2 O

(a) (b)

(c) (d) The product A will be

16. Predict the nature of P

H 2SO 4
CH3CH2CH2CH2OH + CO ¾¾¾¾® P
(a) CH3CH2CH = CH2 (a)
(b) CH3CH = CHCH3
(c) CH3CH2CH2CH2COOH
(d) CH3CH2CH(CH3)COOH.

17. On vigorous oxidation by permanganate solution,

gives

(a)

(b)

(b)

(c)

(d)

18. Identify the correct order of boiling points of the following

compounds.
CH3CH2CH2CH2OH (1) ; CH3CH2CH2CHO (2) ;
CH3CH2CH2COOH (3) (c)
(a) 1>2>3 (b) 3>1>2
(c) 1>3>2 (d) 3 > 2 > 1.
19. Which of the following acids has smallest dissociation constant?
(a) CH3CHFCOOH (b) FCH2CH2COOH
(c) BrCH2CH2COOH (d) CH3CHBrCOOH.
20. Dimerisation of carboxylic acids is due to
(a) ionic bond
(b) covalent bond
(c) coordinate bond
(d) intermolecular hydrogen bond.
(d)
21. When propionic acid is treated with aqueous sodium bicarbonate,
CO 2 is liberated. The carbon of CO2 comes from
(a) methyl group (b) carboxyl group
(c) methylene group (d) bicarbonate.
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23. Two moles of acetic acid are heated with P2O5. The product 33. Which of the following acids has the least pKa value ?
formed is (a) CH3COOH (b) C6H5COOH
(a) 2 moles of ethyl alcohol (c) CH2 = CHOOH (d) All have same pKa
(b) formic anhydride 34. Arrange the following in increasing order of their pKa values.
(c) ethanoic anhydride CH3COOH (1) ; Me3CCH2COOH (2) ; Me3N+ CH2COOH (3)
(d) 2 moles of methyl cyanide. (a) 1<2<3 (b) 2<1<3
Cl 2 ,red P alc. KOH (c) 3<2<1 (d) 3 < 1 < 2.
24. CH3CH2COOH ¾¾¾¾® A ¾¾¾¾® B ; B is
35. Acetic acid reacts with ketene to form
(a) CH3CH2COCl (b) CH3CH2CHO
(a) ethyl acetate (b) propanoic acid
(c) CH2 = CHCOOH (d) ClCH2CH2COOH.
(c) acetic anhydride (d) methyl acetate
25. Lactic acid, CH3CHOHCOOH, on oxidation by alkaline KMnO4
36. Predict the structure of the product in the following reaction.
gives.
(a) tartaric acid (b) pyruvic acid
(c) cinnamic acid (d) propionic acid.
26. An enantiomerically pure acid is treated with racemic mixture
of an alcohol having one chiral carbon. The ester formed will be
(a) optically active mixture (a) (b)
(b) pure enantiomer
(c) meso compound
(d) racemic mixture.
27. Arrange the following alcohols in increasing order of acid- (c) (d)
catalyzed esterification by ethanol.

37. Identify Z in the reaction

(a) A<B<C (b) C<B<A
(c) B<C<A (d) C < A < B.
28. Identify the final porduct, P.

(a) (b)
(a) CH3CH2CHO (b) CH3CH2CH2CHO
(c) CH3CH2COOH (d) CH3CH2CH2COOH.
( i) 2NaNH 2 H 2SO 4 /Hg 2 + OH - / Br2
29. HC º CH ¾¾¾¾® [X] ¾¾¾¾® [Y] ¾¾¾¾® [Z] (c) (d)
(ii) CH 3 I

Here Z is
(a) CH3CH2COOH (b) CH3CHBrCOOH
(c) CH3COOH (d) CH2BrCOOH. 38. The possible structure for Z in the following reaction is
30. Which of the following reactions yields acetic acid as the final (i) BH / THF Cl 2 / NaOH
3 heat
product ? ¾ ¾¾¾¾¾® [X] ¾ ¾¾¾¾® [Y] ¾® [Z]
(ii) H 2 O2 , OH - H+
OH -
(i) CH3CCl3 ¾¾¾¾®
OH -
(ii) CH3COOC2H5 ¾¾¾¾®
(a) (b)
(i ) Tollen’s regent 
(iii) CH3CHO ¾¾¾¾¾®
+
( ii) H

(a) Only (i) (b) Only (ii)

(c) (d)
(c) Only (iii) (d) All the three.
31. Identify the main product in the following reaction.
P2O5 , heat
39. Which of the following set of reactants does not form phthalic
CH2 (COOH)2 ¾¾¾¾® X acid on oxidation ?
(a) CH3COOH (b) CO 2 + H2O
(c) C3 O 2 (d) COOH.COOH.
32. Identify the product Z in the following series of reactions.
(a) (b)
CH2COOH P / Br2 alc. KOH CF3COOH
½ ¾¾¾¾¾® X ¾¾¾¾¾® Y ¾¾¾¾¾® Z
CH2COOH

(a) Maleic anhydride (b) Maleic acid

(c) (d)
(c) meso-Tartaric acid (d) rac-Tartaric acid.
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40. Which of the following has minimum pKa value ?
(a) FCH2COOH (b) Cl3CCOOH (i) Mg, THF, ( ii) H 2 O
47. ¾¾¾¾¾¾¾¾¾® X. Here X is
( iii) KMnO 4 , OH - , (iv) H +

(c) (d)
(a) (b)

41. The correct decreasing order of pKa values of the o-, m-, and p-
nitrobenzoic acids is
(c) (d)
(a) o > m > p (b) m > p > o
(c) p > m > o (d) o > p > m
42. The correct order of decreasing acidity of the three acids is 48. Predict the nature of the final product Z in the following series
of reactions.
PCl 5 C 6H6 C 6 H 5 CO 3 H
C6H5COOH ¾¾¾® [X] ¾¾¾® [Y] ¾¾¾¾¾® [Z]
AlCl 3

(a) III > II > I (b) II > I > III (a) C6H5COOC2H5 (b) C6H5COOH
(c) II > III > I (d) I > II > III (c) C6H5COOC6H5 (d) C6H5OH
43. Which of the following car boxylic a cids undergoes
49. Pick up the major product in the following reaction.
decarboxylation easily ?
(a) C6H5CHOHCOOH (b) C6H5COCOOH
(c) C6H5COCH2COOH (d) C6H5COCH2CH2COOH
44. Predict the nature of P in the following reaction. + Br2 (in CH3COOH) ¾¾®
heat
C6H5COCH(CH3)COOH ¾¾® P
(a) C6H5COCH3 (b) C6H5COCH2CH3
(c) C6H5COOH (d) No action

(a) (b)
conc. HNO 3 Br2
45. B ¬¾¾¾¾ ¾¾¾® A
water

Here A and B are ... and ... respectively

(a) o-bromophenol, o-nitrophenol
(b) 3-bromosalicylic acid, 3-nitrosalicylic acid (c) both (a) and (b) (d)
(c) 2, 4, 6-tribromophenol, picric acid
(d) 4-bromosalicylic acid, 4-nitrosalicylic acid
50. The organic product(s) formed in the reaction
pH = 7
I LiAlH
46. + H2O ¾¾¾® A. Here A should be C6H5COOH ¾¾¾¾
4
+
®
II H 2 O

(a) C6H5CH2OH (b) C6H5COOH

(c) C6H5CH3 (d) CH4
(a)
51. Which of the following gives effervescences of CO 2 with
NaHCO3 solution ?
(a) HCOOH (b) 2, 4, 6-Trinitrophenol
(c) Both (d) None
(b) 52. H. V. Z reaction involves the use of P and Cl2

2 P, Cl
CH3 CH 2COOH ¾¾¾¾ ® CH 3CHClCOOH

The function of phosphorus is

(c) (a) as a catalyst.
(b) in the formation of PCl3 which carries out halogenation at
the a-carbon atom.
(c) in the formation of PCl3 which converts –COOH into
(d) –COCl.
(d) none of the three.
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COOH is COOH COOH

53. What is the main product when HOOC
COOH HO
OCH3 OH
heated ?

V
COOH O IV
(a) COOH (b)
(a) IV > I > II > III > V (b) V > II > III > I > IV
O (c) V > II > IV > III > I (d) V > II > IV > I > III
58. Salicylic acid is treated with bromine under two different
(c) HOOC O (d) C conditions.
C O
OH
54. The correct order of decarboxylation of the three acids is
Br2 COOH Br 2 in
OH OH O O [Y] [X]
Water CH 3COOH
O O OH
I II III Predict the nature of [X] and [Y] in the above reactions

(a) III > II > I (b) III = II > I

OH OH
(c) III > II = I (d) III = II = I
55. Which statement is true regarding oxidation of the following Br COOH COOH
two compounds (a) ;

Br

[X] [Y]

I II OH
OH
(a) Both are oxidisable to benzoic acid under similar COOH Br Br
conditions (b) ;
(b) It is very difficult to oxidise either of the two
(c) Compound I is oxidisable to benzoic acid easily while Br Br
compound II is oxidisable only under vigorous conditions
[X] [Y]
to benzoic acid
(d) Compound I is oxidisable to benzoic acid, while II is OH
oxidisable only under vigorous conditions to OH
2, 2-dimethylpropanoic acid. COOH COOH
56. Predict the nature of end product in the following reaction. (c) ;

O O Br
(i) NaBH4 Br
Product
(ii) H 3O + [X] [Y]
OH
OH OH
O O Br COOH Br Br
(a) (b)
O (d) ;

OH Br Br
O
(c) (d) [X] [Y]
OH O
59. Choose the correct statement regarding acidic character of acetic
57. The correct order for the acidic character of the following acid, CH3COOH and peroxyacetic acid, CH3COOOH.
carboxylic acids is (a) Peroxyacetic acid is stronger acid than acetic acid since
the former has one extra oxygen, an electronegative element
COOH COOH COOH (b) Peroxyacetic acid is stronger than acetic acid because its
OH conjugate base is a weaker base than acetate
(c) Peroxyacetic acid is weaker than acetic acid because its
conjugate base is less stable than that of acetate ion.
I II OH
III (d) Both are equally strong
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60. b-Keto acids on heating easily undergo decarboxylation because 63. Which of the following is least acidic in nature ?

(a) it is a very storng acid COOH

(a) CH3COOH (b) CH2
(b) it is a very weak acid COOH
(c) CH3CH2COOH
(c) its carboxylate ion is highly stable.
(d) Me3N+CH2CH2CH2COOH
(d) it involves the formation of a cyclic six-membered transition 64. Arrange the following four acids in their decreasing order of
state. acidity
61. The products X and Y are respectively COOH COOH
CH3
O O
+ +
NaBH 4, H 3O LAH, H3O
Y heat
X
heat OH
I II
COOH COOH
CMe3 H3C CH3
(a) O and O
O O

III IV
(a) I > II > III > IV (b) IV > III > II > I
(b) and (c) II > IV > III > I (d) III > IV > II > I
O 65. Which of the following is the correct order of decarboxylation of
O
b-keto carboxylate anion ?
O O O O

(c) O and R O R O–
O O F NO2
I II
O O O O
(d) and O
O O R O– R O–
CN Cl
III IV
CHO CN (a) I > II > III > IV (b) II > I > III > IV
(i) Pyridine
62. + CH2 ¾¾¾¾¾¾
+ ® Z, Z is (c) II > III > IV > I (d) I > IV > II > III
CN (ii) H 3 O
(iii) heat
O
(i) NaIO
66. + P. The product P should be
(ii) H
CH CH COOH ]
(iii) heat
(a)
O

O O
OH
CH CH2 COOH (a) (b)
(b) COOH

COOH
(c) (d) A mixture of (a), (b) and
CHO COOH
(c) (c)
CH 2COOH 67. Among the following compounds, the most acidic is
(a) p-nitrophenol (b) p-hydroxybenzoic acid
(c) o-hydroxybenzoic acid (d) p-toluic acid
CHO
COOH COOH COOH OH
OH
(d)
> > >

CH2 COOH
CH3 OH NO2
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EXERCISE 17.2
7. Anthranilic acid can exist in the form of following structures?
DIRECTIONS for Q. 1 to Q. 22 : Multiple choice questions with
one or more than one correct option(s).

O
|| H+
1. C6 H 5 - C - OH + H2O18 ¾¾¾® Product Which of the following statement is not correct regarding an-
thranilic acid structure ?
Here the product may be (a) Structure I exists in neutral solution (pH = 7), structure II
in acidic solution (pH < 7) and structure III exists in alka-
(a) C6H5CO 18OH (b) C6H5COO18H
line solution (pH > 7).
(c) C6H5COOO18H (d) C6H5C18OOOH.
(b) Structure II exists when pH > 7 and structure III exists
2. RCOOH can be reduced to RCH2OH by when pH < 7.
(a) NaBH4 (b) LiAlH4 (c) Structures I and II exist when pH > 7 and structures I and
(c) Na/C2H5OH (d) H2/Catalyst III exist when pH < 7.
(d) All the thre structures exist in all the three mediums.
3. Which of the following statement is true for the following reac-
tion ? 8. Which of the following exhibit hydrogen bonding?
(a) Chloroform (b) Ethyl alcohol
RCOOH + LiAlH4 ¾¾¾® RCH2OH
(c) Acetic acid (d) Dimethyl ether
(a) The first step of the reaction is the formation of AlH 3 and
9. Which of the following statements are correct?
H2.
(a) Carboxylic acids have higher boiling points than those of
(b) A hydride ion is transferred from AlH3 to the carboxy-
alcohols of similar molecular weight
late carbon.
(b) Carboxylic acids have lower boiling points than those of
(c) An aldehyde is formed as an intermediate. alcohols of similar molecular weight
(d) Aldehyde is not the intermediate in this reaction (c) Carboxylic acids (C1 to C4) are soluble in water
4. Which of the following statement is not true ? (d) The melting points of carboxylic acids increase or decrease
(a) Maleic acid and fumaric acid are similar in their acidic in irregular manner
strength, same is true for their corresponding monoanions. 10. Which of the following statements are correct?
(b) Maleic acid is a stronger acid than fumaric acid, similarly (a) The two carbon-oxygen bond lengths in formic acid are
maleate monoanion is a stronger acid than fumarate different
monoanion. (b) The two carbon-oxygen bond lengths in sodium formate
are equal
(c) Maleic acid is a stronger acid than fumaric acid, but
(c) The carbon-oxygen bond length in formic acid is less than
maleate monoanion is a weaker acid than fumarate
that in sodium formate
monoanion.
(d) The carbon-oxygen bond length in formic acid is greater
(d) Maleic acid is a stronger acid than fumaric acid, but the than that in sodium formate
corresponding monoanions have similar acidic strength.
11. Tollen’s reagent reacts with
5. Which of the following compound can be methylated by (a) formaldehyde (b) acetaldehyde
diazomethane ?
(c) acetone (d) formic acid
(a) C2H5COOH (b) C2H5NH2
12. Pyroligneous acid, obtained by destructive distillation of wood,
(c) C6H5OH (d) CH3COCH2COOC2H5 can be used for the manufacture of
6. Which of the following compound is decarboxylated on heat- (a) methyl alcohol (b) acetaldehyde
ing ? (c) acetic acid (d) propanol
13. Which are correct statements?
CH 2 COOH
(a) | (b) C2H5CH(COOH) 2 (a) Methyl malonic acid is converted into propanoic acid on
CH 2 COOH heating
(b) Succinic acid forms succinic anhydride on heating
O (c) 3-Hydroxy propanoic acid forms acrylic acid on heating
COOH
(c) CH3COCH2COOH (d) O
||
(d) CH 3 – C – CH 2 COOH forms acetone on heating
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14. Which can be used as fire-extinguisher?
O
(a) CH3COOH + NaHCO3 (b) OH
(b) Pyrene
(c) Formalin
OH
(d) Dry ice (c) OH
15. CH3COOH can be obtained by

(a) Mg/ether
2 3 CO /H O + OH
CH 3 Br ¾¾¾¾¾
® ¾¾¾¾¾¾®
OH
(d)
(b) AgCN H O+
CH3 Br ¾¾¾¾
® ¾¾¾¾
3 ®

(c) CH 3 CH = CHCH 3 ¾¾¾¾®

4 KMnO 21. Formic acid and acetic acid can be distinguished by the action of
(a) conc. H2SO4
aq. KOH H O+
(d) CH 3 CCl 3 ¾¾¾¾¾ 3
® , ¾¾¾¾® (b) Tollen’s reagent

16. Decarboxylation will take place on heating : (c) Fehling solution

(a) methyl malonic acid (d) heating of sodium salt

(b) succinic acid
O
(c) 2, 2-dimethyl acetoacetic acid ||
H+
22. C6 H 5 - C - OH + H2O18 ¾¾¾
® Product
(d) Glutaric acid
17. Which of the following will liberate CO 2 on reaction with Here the product may be
NaHCO3 : (a) C6H5CO 18OH (b) C6H5COO 18H
(c) C6H5COOO 18H (d) C6H5CO 18OOH
(a) —OH (b) CH3COOH

O O INSTRUCTION for Q. 23 to 34 : Read the passages given below and

CH CH2 OH CH 2 OH answer the questions that follow.
(c) | (d) |
OH CH2 OH
HO HO
PASSAGE 1
18. Which of the following compounds can be used as an
Alkyl halides can be converted easily into carboxylic acids through two
acylating agent ?
routes,
(a) CH3COCl (b) (CH3CO)2O
(i) through Grignard reagent formation, and
(c) CH3COOH (d) CH3CH2COCl.
19. Which of the following statement is true for the following (ii) through hydrolysis of nitriles.
reaction ?
(i ) CO
(i) CH 3 Br + Mg ¾
¾® CH 3MgBr ¾¾ ¾¾
2 ® CH COOH
3
RCOOH + LiAlH4 ¾¾¾® RCH2OH (ii ) H 3O +

(a) The first step of the reaction is the formation of AlH3

+
and H2. NaCN
(ii) CH 3CH 2 Br ¾¾ ¾ ¾® CH 3COOH + NH +4
(i ) H
¾® CH 3CH 2 CN ¾¾ ¾
(b) A hydride ion is transferred from AlH3 to the
carboxylate carbon. Other methods, generally opted in laboratory are oxidation of alcohols,
1° alcohols give carboxylic acids with same number of carbon, while 2°
(c) An aldehyde is formed as an intermediate.
alcohols give acids with lesser number of C atoms.
(d) Aldehyde is not the intermediate in this reaction

O 23. Dimethyl propanoic acid can be prepared easily from 2-chloro-

O (i) CH Mg Br
3
¾¾¾¾¾¾ 2-methylpropane through
20. + ¾
® Z, Z may be
(ii) H 3 O
(a) Grignard reagent route
(b) nitrile route
OH
(a) OH (c) both routes
(d) none of the two
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29. The C = O part in carboxylic acids and their derivatives make
acyl compounds more reactive than alkyl compounds toward
chromic acid nucleophilic attack because
24. Carboxylic acid
(a) The carbonyl group is electron donating
(b) The alkyl group is electron donating
The carboxylic acid formed in the above reaction is
(c) Attack of a nucleophile on a flat acyl compound is less
(a) 2-tert-butyl-3, 3-dimethylbutanoic acid
sterically hindered
(b) 2-(1, 1’-dimethylethyl)-3, 3-dimethylbutanoic acid
(d) Tetrahedral carbon atoms cannot have pentavalent
(c) Methanoic acid transition states

(d) Tricarballylic acid 30. Aldehydes and ketones react with nucleophiles to give addition
product rather substituion because
*
25. During oxidation of CH 3 C OCH 2 CH 2 CH 3 , labelled carbon is (a) They are more acidic
mainly found in (b) They are less acidic
(c) They are sterically hindered
* *
(a) CH 3 C OOH (b) CH 3 CH 2 CH 2 C OOH
(d) The C – H & C – C bonds do not break easily

* *
(c) H C OOH (d) CH 3 CH 2 C OOH
PASSAGE 3
Hell-Volhard-Zelinsky (HVZ) reaction involves the reaction of aliphatic
PASSAGE 2 carboxylic acid with bromine in the presence a trace of PBr3 to form a-
bromocarboxylic acid.
Although the carboxyl group consists of C=O and – OH, it is the – OH
that undergoes change, either loss of H+ or replacement by another 2 3 Br /PBr
CH3 CH 2COOH ¾¾¾¾¾ ® CH 3 CH 2COBr
group takes place. However, the carbonyl group markedly influences
the reactions of carboxylic acids. The presence of the C = O part is also
H O
responsible for nucleophilic substitution reactions in acid derivatives. ¾¾
® CH3 CHBrCOBr ¾¾¾
2 ® CH CHBrCOOH
3

Presence of an electron withdrawing group increases the acidity of

aliphatic as well as aromatic acids. On the other hand, electron releasing
31. When two equivalents of the reagent are used, the product
groups imparts opposite effect.
formed in the above reaction will be

(a) CH3CHBrCOBr (b) CH2BrCHBrCOOH

26. The marked acidity of RCOOH over ROH is due to the presence of (c) CH3CBr2COOH (d) both (b) and (c)
(a) – OH (b) C=O 32. What will be the product when three equivalent of Br 2 is treated
(c) Both (d) None with 2,2-dimethylbutanoic acid?

27. Chloroacetic acid is more acidic than acetic acid because

CH2 Br CH2 Br
(a) electron withdrawing group destabilizes the acid | |
(a) CH 2 Br - C - COOH (b) Br2CH - C - COOH
| |
(b) electron donating group stabilizes the acid
CH2 Br CH3
(c) electron withdrawing group stabilizes the carboxylate ion

(d) all the three

CH3
28. Which statement is correct when an acid weakening group is |
(c) Br3C - C - COOH (d) No reaction
present in benzoic acid? |
CH3
(a) Acid weakening groups activate the ring towards
electrophilic substitution
33. What product will be formed when PBr3 in the given set of
(b) Acid weakening groups deactivate the ring towards reactions is replaced by PCl3?
electrophilic substitution

(c) Acid weakening groups activate the ring toward nucleophilic Cl Br

| |
substitution (a) CH 3 - CHCOOH (b)
CH 3 - CH - COOH
(d) None of the above (c) Both (d) Reaction not possible
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34. When Br2 in the above given set of reactions is replaced by Cl2, 36. Statement 1 : The pKa of acetic acid is lower than that of phenol.
the product formed will be
Statement 2 : Phenoxide ion is more resonance stabilised.

Cl Br 37. Statement 1 : During the preparation of esters from a carboxylic

| |
(a) CH3 - CH - COOH (b) CH3 - CH - COOH acid and an alcohol in the presence of an acid catalyst, the water
or the ester should be removed as fast as it is formed.

Cl Cl Statement 2 : The reaction between an acid and an alcohol in the

| |
(c) CH 3 - CH - COCl (d) CH 3 - CH - COBr presence of an acid catalyst is a reversible reaction.

38. Statement 1 : A carboxylic acid is a stronger acid than phenol

Statement 2 : The conjugate base of carboxylic acid, a carboxylate

ion, is stabilised by two equivalent resonance structures in which
Instructions for Q. 35 : Following questions are Multiple Matching the negative charge is at the more electronegative oxygen atom.
type Questions :
39. Statement 1 : C6H5COOH is stronger than CH3COOH.

Statement 2 : C6H5COOH is weaker than HCOOH.

35. Column - I Column - II
40. Statement 1 : Dichloro and trichloro acids are stronger than
(Compound) (Oxidation product) monochloroacetic acid.

COOH Statement 2 : An increase in the number of electronegative

(A) (a) groups on the alkyl chain increases the strength of the acid.

41. Statement-1 : The pKa value of acetic acid is lower than that
of phenol.
NH2 COOH
Statement-2 : Phenoxide ion is more resonance stabilized
COOH
(B) (b) 42. Statement-1 : Nitration of benzoic acid gives m-nitrobenzoic
acid.

Statement-2 : Carboxyl group increases the electron-density

at meta-position.

(C) (c) Oxidation difficult 43. Statement-1 : RCOCl, (RCO)2O and RCOOR’ all react with
Grignard reagents to form 3º alcohols.

Statement-2 : RCOCl reacts with R2Cd to form ketones but

(RCO)2O and RCOOR' do not react at all.

(D) (d) (CH3)3CCOOH

Instructions for Q. 44 : Following questions are Integer Type
Questions :

Instructions for Q. 36 to 43 : Following questions are Assertion and

Reasoning Type Questions : 44. Amongst the following, the total number of compounds soluble
in aqueous NaOH is
Note : Each question contains STATEMENT-1 (Assertion) and
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c),
H3C CH3
(d) and (e) out of which ONLY ONE is correct. N COOH OCH2CH3 OH
CH2OH
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1.
(c) Statement -1 is True, Statement-2 is False. NO2 OH CH2CH3 COOH
CH2CH 3
(d) Statement -1 is False, Statement-2 is True.
(e) Statement -1 is False, Statement-2 is False.
N
H3C CH3
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EXERCISE 17.3 (Subjective Problems)

1. (a) Give the common and IUPAC names for the straight 7. Give steps involved in the following transformations :
chain saturated carboxylic acids containing 5, 6, 8, 10 and
12 carbon atoms. (a) Toluene to a-bromophenylacetic acid

(b) Give the structural formula and IUPAC name for each of (b) Benzene to a-methylphenylacetic acid.
the following :
(c) n-Butanol to 2-pentenoic acid.
(i) Isovaleric acid
8. (a) Arrange the following in order of decreasing acidic char-
(ii) Trimethylacetic acid acter.

(iii) a, b-Dimethylcaproic acid (i) CH3COOH, CH º CH, NH3, C2H6, C2H5OH, H2SO4,
H2O
(iv) a-Methyl-g-ethyloctanoic acid.

2. Write equations to obtain n-butanoic acid from (a) n-propanol (ii) Acetic acid, malonic acid, succinic acid
(two different methods), and (b) 2-pentanone.
(b) Arrange the monosodium salts of the acids given in (a) (i)
3. Write the products obtained from the reaction of n-valeric acid in order of decreasing basicity.
with
9. Complete the following reactions :
(a) Al (b) CaO
CH 3 MgBr ( i) CO 2
(c) NH3(aq) (d) H2, Ni, 20°C, 1 atm (a) CH º CH ¾¾¾¾¾® A ¾¾¾¾¾®
(ii) H +

(e) LiAlH4 (f) hot KMnO4

H 2SO 4 / HgSO 4 KMnO 4
B ¾¾¾¾¾® C ¾¾¾¾¾® CH2(COOH)2
(g) Br2/P (h) Br2/Fe

(i) fuming H2SO 4 (j) HNO3/H2SO 4 LiAlH 4 HBr (i) Mg

(b) CH3COOH ¾¾¾® A ¾¾® B ¾¾¾¾®
( ii) CO 2

(k) n-Valeryl alcohol.

Ag2O Br2
4. Give balanced equations for the reaction of each of the follow- C ¾¾¾® D ¾¾® E
ing reagents with phenylacetic acid.
10. Compare the reaction of CH3CH2COOH with excess of (i)
(i) SOCl2 (ii) PCl3
CH3MgBr and (ii) CH3Li.
(iii) PCl5 (iv) (CH3CO)2O
11. (a) Use simple chemical tests to differentiate among the fol-
(v) CH3OH/H2SO4 (vi) NH3 followed by heat. lowing dry compounds. n-Butanol, n-butanoic acid, bu-
tane, butanal and ethyl methyl ether.
5. Write the equations for converting isobutyric acid into each of
the following. (b) Differentiate between (i) CH3COOH and HCOOH, (ii)
oxalic acid and malonic acid ; and (iii) CH3CH2COCl and
(a) Isobutyramide (b) Isobutyl alcohol
CH3CH2COOH.
(c) Butane (d) Magnesium isobutyrate.
(c) Name the reagent or test that can be used for distinguish-
6. Give steps involved in the following conversions : ing between the members of each of the following pairs.

(a) 14CO 2 ¾¾¾® CH3CH2CH2 14 COOH (i) Acrylic acid, CH2=CHCOOH and propionic acid,
CH3CH2COOH.
(b) 14CO2 ¾¾¾® CH3CH2 14 CH 2 COOH
(ii) Mandelic acid, C6H5CHOHCOOH and benzoic acid,
(c) 14CO2 ¾¾¾® CH314CH2CH2COOH C6H5COOH.

(d) 14CH3OH ¾¾¾® 14CH3CH2CH2CH2COOH (iii) Mesotartaric acid and o-chlorobenzoic acid.
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12. (a) Define the term neutralization equivalent of an acid. How 14. Give schematic pathways for separation for each of the follow-
many equivalents of NaOH would be neutralized by one ing mixtures.
mole of a polycarboxylic acid whose MW is 210 g/mol
and NE is 70 g/eq. ? (a) Caproic acid and ethyl carproate (both liquids).

(b) Can you predict the NE of melittic acid, C6 (COOH)6 ?

(b) n-Butanoic acid and 1-hexanol (both liquids).
13. Compare acetic acid and sodium acetate with respect to fol-
lowing properties. (c) Sodium benzoate and triphenylmethanol (both solids).

(a) m.p. (b) b.p. 15. Benzoic acid and o-chlorobenzoic acid, both are water insoluble
(c) Solubility in water and ether solids, and are separated by treatment with an aqueous solu-
tion of sodium formate. Explain.
(d) acidity and basicity.
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EXERCISE 17.1
1 (c) 6 (a) 11 (b) 16 (d) 21 (d) 26 (a) 31 (c) 36 (c) 41 (b) 46 (b) 51 (c) 56 (b) 61 (d) 66 (b)
2 (b) 7 (a) 12 (c) 17 (d) 22 (b) 27 (a) 32 (d) 37 (d) 42 (b) 47 (c) 52 (c) 57 (d) 62 (b) 67 (c)
3 (d) 8 (c) 13 (b) 18 (b) 23 (c) 28 (d) 33 (b) 38 (c) 43 (c) 48 (c) 53 (c) 58 (b) 63 (b)
4 (b) 9 (b) 14 (b) 19 (c) 24 (c) 29 (a) 34 (d) 39 (b) 44 (b) 49 (b). 54 (b). 59 (c) 64 (b)
5 (b) 10 (c) 15 (d) 20 (d) 25 (b) 30 (c) 35 (c) 40 (d) 45 (c) 50 (a) 55 (d) 60 (d) 65 (c)

1. Here it is not essential to indicate the position (2) of the double bond, because no other position for the double bond is possible.
2. Since chloride is 3°, it will undergo elimination reaction with CN – ion, hence route (a) can’t be applied. Route (b) is a successful
Grignard synthsis.
3. Neither method can be used because the halide is 3° and undergoes elimination reaction rather than substitution. Further, the presence
of —OH group in the compound prevents the preparation of organometallic compound. A successful synthesis can be achieved by
first protecting the OH group and then carrying carbonation.

4.

CH3 CH3
H ½ Q CO ½ +

5. CH3CH2CH2CH2OH or CH3CH2CH(CH3) OH ¾¾¾¾¾® CH 3CH 2CH ¾¾¾® CH3CH 2 CHCOOH

sec-Butyl cation H2O 2 - Methylbutanoic acid

6. The charged end loses CO2 (for details, see mechanism in text).
7. Carbanion formed from simple carboxylate anions can’t be stabilized, while other carbanions are quite stable.
¾¾® –
CH3CH2CH2COOH ¬¾¾ CH3CH2CH2COO– ¾¾¾® CH 3CH 2CH 2
- CO2
Not stable, hence not formed
8. Higher the stability of the carbanion formed after loss of CO2, more will be the ease of decarboxylation. Carbanion from 2, 4, 6-
trinitrobenzoic acid is stabilised by the dispersal of charge due to strong–I effect of the three —NO 2 groups

Wt. of acid ´ 1000 0.187 ´ 1000

9. N.E. of acid = = = 103 g
Molarity of NaOH ´ Vol. of NaOH 0.972 ´ 18.7
Thus the equivalent wt. of the acid is 103 which coincides with the molecular/wt. (and eq. wt.) of ethoxyacetic acid, C 2H5OCH2COOH
(Mol. wt. and eq. wt. = 104).
OH -
10. RCX3 ¾¾¾® RC(OH)3 ¾¾¾¾® RCOOH
- H2O
11. LiAlH4 reduces halides to alkanes.
Br2 Br2 H O
2
12. (i) CH3CH2COOH ¾¾¾® CH3CH2COCl ¾¾¾® CH3CH(Br) COCl ¾¾¾® CH3CH(Br) COOH.
PCl 3

Cl 2 Cl H O
2 2
(ii) CH3CH2COOH ¾¾¾¾® CH3CH2COBr ¾¾¾® CH2CHClCOBr ¾¾¾® CH3CH(Cl)COOH.
PBr3
13. Precipitates in two cases is due to different compounds.
CH3CH 2CH 2COO - Ag + (Soluble in HNO3) AgCl (Insoluble in HNO 3 )
From propanoic acid From chloropropanoic acid
14. Reduction of alkynes by Na-C2H5OH occurs in trans-manner.
15. B2H6 selectively reduces a carboxylic group in presence of an ester.
CH 3 CH3
H+ ½Å + rearranges
CO ½
16. CH3CH2CH2CH2OH ¾¾¾¾® CH3CH 2CH 2 CH 2 ¾¾¾¾® CH 3CH 2 CH ¾¾¾® CH3CH 2 CHCOOH .
- H2O
1° Carbocation 2° Carbocation

17.
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18. Hydrogen bonding is maximum in acids, and minimum in aldehydes.
19. In (c), weaker electron-withdrawing group (Br) is present maximum away from —COOH group.
20. Theoretical.
O O
½½ 14 ½½
21. CH3CH 2 C ¾ OH + NaH C O3 ¾¾® CH3CH 2 C ¾ O - Na + + H2O + 14
CO2 .
22. —COOH and —C º CH are more acidic than enolic group = C(OH).
P2O 5
23. CH3COOH + HOOCCH3 ¾¾¾® CH3COOCOCH3 + H2O
red P / Cl 2 alc. KOH
24. CH3CH2COOH ¾¾¾® CH3CHClCOOH ¾¾¾® CH2 = CHCOOH.
KMnO 4 / OH -
25. CH3CHOH COOH ¾¾¾¾® CH3COCOOH.
26. An optically active reagent reacts with different rate with the two enantiomers, with the result the products formed will be unequal in
amounts and hence mixture (product) will be optically active.
27. Steric factor is responsible for relative esterification.
KMnO 4
28. CH3CH2CH2CH2OH ¾¾¾¾® CH3CH2CH2COOH
Intermediate P

29. CH3C º CCH3 ; CH3CH2COCH3 ; CH3CH2COOH

[X] [Y] [Z]
30. Option (i) and (ii) will form CH3COO– ions, not free CH3COOH.
heat
31. CH2(COOH)2 + P2O5 ¾¾¾¾® O = C = C = C = O + H3PO 4
Carbon suboxide

CH2COOH P/ Br2 CH 2COOH alc. KOH CHCOOH CF3CO 3 H

32. ½ ¾¾¾¾® ½ ¾¾¾¾® ½½ ¾¾¾¾¾¾® rac-Tartaric acid.
HVZ reaction anti - hydroxylation
CH2COOH BrCHCOOH CHCOOH
Maleic acid
33. Lesser the pKa value, stronger is the acid. Benzoic acid is strongest because benzoate ion is highly stabilized by resonance.
+ +
34. Me 3 N CH2COOH is strongest acid, because of powerful – I effect of the Me3 N — group , while Me3CCH2COOH is the least acidic
because of powerful + I effect of the Me3C — group.
35. CH3COOH + O = C = CH2 ¾¾¾¾® CH3COOCOCH3 .
36. NaBH4 reduces only C = O group and not —COOH group. The product formed undergoes cyclization to form g-lactone (six-
membered rings are formed easily).

37.

38.

39. tert-Alkyl groups are resistant to oxidation.

40. The three —NO2 (electron-withdrawing) groups in o- and p-positions make phenolic —OH group highly acidic. Moreover, the
corresponding phenoxide is highly stable.
41. Lower the pKa value higher is the acidity. The acidity of the three isomeric nitrobenzoic acids follows the order :
 www.crackjee.xyz
839

42.

43. b-Keto carboxylic acids undergo decarboxylation very easily.

CH 3 CH 3
½ heat ½
44. C6H5CO CHCOOH ¾¾® C 6H5CO CH 2
b-keto acid
45. —COOH group when present along with activating group like —OH is easily eliminated as CO 2.

46. + H3O+

47.

PCl5 C6 H 6 C 6H 5CO3 H
48. C6H5COOH ¾¾® C 6H5COCl ¾¾¾® C 6H5COC6H5 ¾¾¾¾¾¾¾¾¾¾® C 6H5OCOC6H5
AlCl 3 Baeyer-Villiger oxidation
49. —OH group is activating, hence electrophilic substitution will be taking place w.r.t. —OH. Future, bromine in CH 3COOH is a mild
brominating agent, hence only monobromo product will be the main product. p-Substituted is major product due to steric factor.
51. (c) Conjugate bases of both of the compounds, formic acid and 2, 4, 6-trinitrophenol, are highly stable.
–
O
O2N NO2
O
P
H — C— O -
formate ion NO2
(- ve charge dispersed (–ve charge dispersed due to three
due to resonance)
electron-withdrawing –NO2 groups)

52. (c) Phosphorus converts a little of the acid into acid chloride which is more reactive than the parent carboxylic acid. Thus it is the acid
chloride, not the acid itself, that undergoes chlorination on the a-carbon.

3 2 PCl from P + Cl Cl
CH 3 CH 2COOH ¾¾¾¾¾¾¾¾ ® CH 3 CH 2 COCl ¾¾¾
2®

Cl Cl
| |
H O
CH 3 CHCOCl ¾¾¾
2 ® CH CHCOOH
3

53. (c) 1, 6- and 1, 7-dicarboxylic acids on heating form cyclic ketones (Blanc rule)
54. (b) b-Keto carboxylic acids and b, g-unsaturated carboxylic acids undergo decarboxylation easily because the corresponding carbanion
is quite stable due to resonance.
O O O
+
–H – –CO 2
CH3 – C – CH2 – COOH CH3 – C – CH2 – C – O
III
–
O O
– +
H
CH3– C – CH 2 CH3– C = CH 2

OH O

CH3 – C = CH 2 CH 3 – C – CH 3
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O
– –CO2
CH3CH = CHCH2 – C – O
II

O
– –CO – –
CH3CH = CH – CH2 CH3CH – CH = CH2

+
H
CH3CH = CHCH 3 3 2 2
Major

O
–CO2 –
CH2= CH – C – O – CH2= CH
I (Unstable)

55. (d) If the key atom of the side chain of a benzene ring is 1º or 2º, it is oxidised to –COOH irrespective of its nature.

2º Carbon

COOH
KMnO4
hot

In case the key atom of the side chain is 3º, i.e. when it is not having any H, oxidation is very difficult. However, on vigorous
oxidation, benzene ring is oxidised instead of side chain.

3º Carbon
CH3
alk. KMnO 4
HOOC or HOOC – C – CH3
heat
CH3

O O OH O
NaBH4
56. (b) 5 3 1
does not reduce 6
OH –COOH group 4 2 OH

3 2 3 2
1 (Cyclisation) 1
or
4 O 4
O
OH
5 OH 5 O
6
6
d - Hydroxy acid d - Lactone

57. (d) V is most stable because its anion is stabilized to a greater extent through H – bonding with H atom of OH present on both ortho-
positions ; followed by II in which one OH group is present. Compound IV comes next to II because here –OCH 3 group is present
in ortho position which although is not capable of forming H–bonding yet more acidic than p-HOC6H4COOH (III) due to ortho
effect. Compound III is less acidic than benzoic acid because of electron-releasing group in the para position. Thus

COOH COOH COOH COOH COOH

HO OH OH OCH
OCH3
> > > >
V II IV I
OH
III
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58. (b) Note that when some activating group, e.g. –OH is present along with –COOH in ortho or para position substitution occurs with respect
to –OH preferably at para position due to steric factors. In case the reagent used is strong, electrophile enters at all possible positions even
with the replacement of –COOH group.

OH OH OH
Br Br COOH COOH
Br2 Br 2 in
water CH3COOH
(strong (weak reagent)
Br reagent) Br
[Y] [X]

O O O O
P P P P
59. (c) CH 3 - C - O - H ¾¾
® CH 3 - C - O - + H+ ; CH 3 - C - O - O - H ¾¾
® CH 3 - C - O - O -
Acetic acid Conjugate base Peroxyacetic acid Conjugate base
(Re sonance possible, (Re sonance not possible,
hence stable and weak base) hence unstable and strong base)

60. (d) Decarboxylation of b-keto acids involves transfer of the acidic hydrogen to the group followed by loss of CO2 via a cylic six-
membered transition state.

R R
CH CH
R–C C=O R–C C=O
O O O O
H H

R
CH CH
C=O C=O CO2 + R – C R – C – CH2R
OH O
(enol) (keto)

61. (d) Remember that LiAlH4 reduces both >C = O as well as –COOH to alcohols, while NaBH4 reduces only C = O without affecting
–COOH.

LiAlH4 +
H
heat
O O OH OH CH2 O
O
H [X]

NaBH 4 +
H
heat
O O OH OH O O O
H O
[Y]

O + O O
(i) NaIO, H heat
66. (b) (haloform reaction) + CO2
COOH

b-keto acid
67. (c) o - hydroxybenzoic acid is strongest acid and the decreasing order of acidity is
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EXERCISE 17.2

1 (a,b) 2 (b, d) 3 (a,b,c) 4 (a,b,d) 5 (a,c,d)

6 (b,c,d) 7 (a,c,d) 8 (b, c) 9 (a, c, d) 10 (a, b, d)

>1 CORRECT
11 (a, b, d) 12 (a, c) 13 (a, b, c, d) 14 (a, b, d) 15 (a, c, d)
OPTION
16 (a, c) 17 (b, c) 18 (a, b, d) 19 (a, b, c) 20 (b, c)

21 (a, b, c, d) 22 (a, b)

PASSAGE 1 23 (a) 24 (b) 25 (a)

PASSAGE 2 26 (b) 27 (d) 28 (a) 29 (c) 30 (d)

PASSAGE 3 31 (c) 32 (d) 33 (b, a) 34 (b, a)

MATCH THE
35 (A) - b, (B) - b, (C) - a, (D) - c, d
FOLLOWING
36 (b) 37 (a) 38 (a) 39 (b) 40 (a)
A/R
41 (b) 42 (c) 43 (b)

INTEGER 44 4

O OH OH OH
½½ H +
½ H2O 18 ½ -H + ½
C H ¾C = O
1. C6H 5 ¾ C ¾ OH ¾¾¾® C H ¾ C ¾ OH ¾¾¾®
6 5 C6 H 5 ¾ C ¾ OH ¾¾¾® C6 H 5 ¾ C ¾ OH ¾¾® C6 H 5 ¾ C ¾ OH + 6 5
Å ½ ½½ ½
½
OH O 18 OH
18OH 2 18 18
Å

Remember that C ¾ O18 bond is difficult to break than the C—O bond.

2. Theoretical.
3. Consult mechanism of the reaction in text.
4. Maleic acid is stronger because its monoanion is stabilized due to H-bonding between the cis COOH and COO– ; while there is no such
stabilization factor in fumarate monoanion (trans isomer), hence its formaton, i.e. dissociation of fumaric acid is less than that of
maleic acid.
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843
5. Diazomethane is used for methylating acidic groups ; compound (c) has enolic —OH group, hence it can also be methylated by
CH2N2.

6. Dicarboxylic acids having two —COOH groups on the same carbon atom ; and b-keto acids are easily decarboxylated on heating.

7. When pH is greater than seven, medium is alkaline hence the Zwitterion of anthranilic acid is converted to an anion.

18. (a,b,d) Stronger the basic nature of the leaving group, weaker will be its leavability. In CH3COOH, OH– is a strong base so it can’t be
+
removed easily to form CH3 C O required for acetylation (acylation).

19. (a,b,c) Consult mechanism of the reaction in text.

20. (b,c)

21. (a,b,c,d)

O OH OH OH
½½ H +
½ H2O 18 ½ - H + ½
22. (a,b) C6H 5 ¾ C ¾ OH ¾¾¾® C6 H 5 ¾ C ¾ OH ¾¾¾® C6 H 5 ¾ C ¾ OH ¾¾¾® C6 H 5 ¾ C ¾ OH
Å ½
½
18OH 2 18 OH
Å

¾¾® C6H 5 ¾ C ¾ OH + C6H 5 ¾ C = O

½½ ½
18 O 18OH

Remember that C ¾ O18 bond is difficult to break than the C—O bond.

31. (c) The HVZ reaction brings about halogenation only at the a-carbon of the fatty acid. In case the acid has two a-H's, a-dihalo
product will be formed when 2 equivalents of halogen are used.

32. (d) The acid does not have an a–H, necessary for the reaction.

33–34.(b, a)

The a-halogen comes from halogen (Cl2 or Br2) whatever might the nature of PX3 which is used for converting acid to acid halide.

41. (b)

42. (c) The correct reason : Carboxyl group only marginally decreases the electron density at m-position relative to o- and p-positions.

43. (b) The correct explanation : RCOCl, (RCO)2O and RCOOR' all add two molecules of Grignard reagents to give 3º alcohols.
44. 4.
All carboxylic acids and phenols are soluble in aqueous NaOH. Four compounds are soluble in aqueous NaOH.
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EXERCISE 17.3
1. (a) C-5 : n-Valeric, pentanoic C-6 : n-Caproic, hexanoic C-8 : n-Caprylic, octanoic
C-10 : n-Capric, decanoic C-12 : Lauric, dodecanoic.

(b) (i) (ii) (iii) (iv)

PBr3 (i) CN -
2. (a) n-C 3H7OH ¾¾¾® n-C 3H7Br ¾¾¾®
+
n-C3H7COOH
(ii) H

or

(i) NaOI - ,( ii) H +

(b) CH3COCH2CH2CH3 ¾¾¾¾¾® CHI3 + CH3CH2COOH
(haloform raction)

3. (a) (n-C4H9COO)3 Al (b) (n-C 4H9COO)2Ca

(c) n-C 4H9COONH4 (d), (f), (h), (i) and (j) no reaction.
(e) n-C 4H9CH2OH (g) n-C 3H7CHBrCOOH
(k) n-C 4H9COOCH2C4H9-n.
4. (i) C6H5CH2COOH + SOCl2 ¾¾® C 6H5CH2COCl + SO2­ + HCl ­
(ii) 3C 6H5CH2COOH + PCl3 ¾¾® 3C6H5CH2COCl + H3PO 3
(iii) C6H5CH2COOH + PCl5 ¾¾® C 6H5CH2COCl + POCl3 + HCl
(iv) 2C 6H5CH2COOH + (CH3CO)2O ¾¾® C6H5CH2COOCOCH2C6H5 + 2CH3COOH
H 2SO 4
(v) C6H5CH2COOH + CH3OH ¾¾® C 6H5CH2COOCH3 + H2O
D
(vi) C6H5CH2COOH + NH3 ¾¾® C 6H5CH2COONH4 ¾¾¾® C 6H5CH2CONH2 + H2O.
SOCl 2 NH 3
5. (a) Me 2CHCOOH ¾¾¾® Me2CHCOCl ¾¾¾® Me2CHCONH2
LiAlH 4
(b) Me 2CHCOOH ¾¾¾® Me2CHCH2OH
(c) Me 2CHCOOH + n-C4H9MgBr ¾¾® n-C4H10
Mg
(d) Me 2CHCOOH ¾¾¾® (Me2CHCOO)2 Mg.
14 14
6. (a) CO 2 + CH3CH2CH2MgBr ¾¾® CH3CH2CH2 COOH

14 14 LiAlH 4 14 SOCl 2 14 (i) CN - 14

(b) CO 2 + C2H5MgBr ¾¾® C 2H5 COOH ¾¾¾® C 2H5 CH 2 OH ¾¾¾® C2H5 CH 2 Cl ¾¾¾®
+
C 2H5 CH 2 COOH
(i) H

14 14 LiAlH 4 14 (i) PBr3 14 ethylene 14

(c) CO 2 + CH3MgBr ® CH3 COOH ¾¾¾® CH3 CH 2 OH ¾¾¾® CH3 CH 2 MgBr ¾¾¾® CH3 CH 2 CH2CH2OH
(ii) Mg oxide

KMnO 4 14
¾¾¾® CH3 CH 2 CH2COOH

14 (i) PBr3 14 HCHO 14 (i) PBr3 14 ethylene 14

(d) CH 3 OH ¾¾¾® CH 3 MgBr ¾¾¾® CH 3 CH2OH ¾¾¾® CH 3 CH2MgBr ¾¾¾® CH 3 CH2CH2CH2OH
(ii) Mg (ii) Mg oxide

KMnO 4 14
¾¾¾® CH 3 CH2CH2COOH

7. It is advisable to proceed backward.

P,Br2 (i) CN - Cl 2 , heat

(a) C 6H5 CH COOH ¬¾¾¾ C 6H5CH2COOH ¬¾¾¾ C 6H5CH2Cl ¬¾¾¾ C 6H5CH3
(ii) H 3 O +
½
Br
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845
CO 2 Mg HCl
(b) C6H5 CHCOOH ¬¾¾¾ C6H5 CHMgCl ¬¾¾¾ C6H5 CHCl ¬¾¾¾ C6H5 CHOH
½ ½ ½ ½
CH 3 CH3 CH 3 CH 3

Br2 Mg CH3CHO
C 6H6 ¾¾¾® C6H5Br ¾¾¾® C6H5MgBr
FeCl 3

alc. KOH P, Br2

(c) CH3CH2CH = CHCOOH ¬¾¾¾ CH3CH2CH2 CHCOOH ¬¾¾¾ CH3CH2CH2CH2COOH
|
Br

(i) P Br3 CO2

CH3CH2CH2CH2OH ¾¾¾® CH3CH2CH2CH2MgBr
(ii) Mg
8. (a) (i) H2SO 4 > CH3COOH > H2O > C2H5OH > CH º CH > NH3 > C 2H6
(ii) HOOCCH2COOH > HOOCCH2CH2COOH > CH3COOH
(b) The weaker the acid , the more basic will be its anion.
NaC2H5 > NaNH2 > NaC º CH > NaOC2H5 > NaOH > NaOOCCH3 > NaHSO4
CH 3 MgBr (i) CO 2 H SO / HgSO
2 4 4
9. (a) CH º CH ¾¾¾® HC º CMgBr ¾¾¾®
+
HC º CCOOH ¾¾¾¾¾®
A (ii) H B

tautomerises KMnO 4
HC = CHCOOH ¾¾¾¾¾® H C ¾ CH 2 — COOH ¾¾¾¾® CH 2 (COOH) 2
OH ½½ C
O
Note that compound B on hydration may also give ketone but it will not be oxidised to malonic acid, C.
H 2SO 4 / HgSO 4 KMnO 4
HC º CCOOH ¾¾¾¾¾® H2C = CCOOH ¾¾¾¾¾¾
tautomerises
® H3C— C ¾ COOH ¾¾¾¾® CH3COOH
½ ½½
OH O
LiAlH 4 HBr (i) Mg Br
(b) CH3COOH ¾¾¾¾® CH3CH2OH ¾¾¾® CH3CH2Br ¾¾¾® CH3CH2COOH ¾¾® CH3CH2COOAg ¾¾®
2
CH3CH2Br
A B (ii) CO 2 C D E
10. Excess or limited amount of CH3MgBr forms CH4, while excess of CH3Li forms ketone.
(i) CH3CH2COOH + CH3MgBr ¾¾® CH4 ­ + CH3CH2COO– (MgBr)+
(ii) CH3CH2COOH + CH3Li ¾¾® CH4 ­ + CH3CH2COO– Li+
Since Li is more electropositive than Mg, R from R—Li will bear a more negative charge than R from R—MgX, hence RLi is a stronger
nucleophile and capable of adding to the C = O of —COO–.

-
O OLi + OH
½½ ½ ½
- + CH 3 Li H2O - H 2O
CH3CH2 C ¾ O Li ¾¾¾® CH3CH2 C ¾ O - Li + ¾¾¾® CH3CH2 C ¾ OH ¾¾¾® CH3CH2 C = O
½ ½ ½
CH3 CH 3 CH3

11. (a) (i) n-Butanoic acid gives effervescences of CO2 with aq. NaHCO3 solution.
(ii) Butanal gives a silver mirror on addition of Tollen’s reagent, [Ag(NH3)2]2+ (a solution of AgNO3 in aq. NH3).
(iii) n-Butanol evolves H2 with metallic sodium.
(iv) Ether (methyl ethyl ether) dissolves in conc. H2SO 4 with the evolution of heat.
(v) Alkane (butane) remains inert to all tests.
(b) (i) Formic acid (HCOOH) has an aldehydic type of hydrogen, hence it is readily oxidized by acidified KMnO4 (indicated by
decolourization of purple colour), and Tollen’s reagent (indicated by formation of silver mirror).
(ii) Oxalic acid (HOOCCOOH) is oxidized by acidic KMnO4, again indicated by decolourization of purple colour. Malonic acid
loses CO2 (g), on heating.
(iii) Here aq. NaHCO3 solution will give CO2 with both (acid chlorides are readily hydrolysed in alkaline as well as acidic
medium), hence AgNO3 solution in presence of HNO3 should be used which will give white precipitate of AgCl with
CH3CH2COCl insoluble in HNO3.
(c) (i) KMnO4 or Br2/CCl4 (ii) CrO3/H2SO 4 (positive for mandelic acid)
(iii) Hot KMnO4 (positive for mesotartaric acid) ; elemental analysis for chlorine (positive for o-chlorobenzoic acid).
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12. (a) Neutralization equivalent (NE) is the equivalent weight (g/eq.) of an acid as determined by titration with standard NaOH
solution.
No. of eq of NaOH = No. of ionizable H’s (No. of eq of acid)
MW
= (Q NE = ME/No. of ionizable H’s)
NE

210 g / mol
= = 3 eq / mol
70 g / eq

MW 342 g / mol
(b) NE = = = 57 g/eq
No. of ionizable H’S 6 eq / mol

13. Acetic acid. Low m.p. ; low b.p. , soluble in water as well as in ether, stronger acid and weaker base.
Sodium acetate. High m.p. (decomposes), high b. p. (d), soluble in water, insoluble in ether, weaker acid and stonger base.
14. (a)

(b)

Butyric acid is very much soluble in water, hence water should be evaporated from the aqueous solution.
(c)

RCOONa, Ph3COH
ether, filter
Insoluble Soluble
evaporate
RCOONa Ph3COH + Ether ¾¾¾¾¾ ® Ph 3 COH
ether
(Insoluble)

15. Separation by sodium formate is similar like that by sodium bicarbonate ; sodium formate is so selected because formic acid is stronger
than benzoic acid and weaker than o-chlorobenzoic acid.

C6 H 5COOH HCOO - ®
¬¾¾ C6 H5 COO - HCOOH
Weaker acid + Weaker base
+
Stronger base Stronger acid

o-ClC6H4COOH + HCOO– ¾¾¾® o-ClC6H4COO– + HCOOH

¬¾

Stronger acid Stronger base Weaker base Weaker acid

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18 .1 Structure of Carboxylic Acid Derivatives 18 .5 Cyclic Esters or Lactones

18 .2 Nucleophilic Acyl Substitution 18 .6 Analysis of Carboxylic Acid Derivatives
18 .3 Preparation of Acid Derivatives 18 .7 Illustrative Examples
18 .4 Properties of Acid Derivatives EXERCISE
SOLUTIONS

Four closely related functional derivatives of carboxylic acids are obtained by replacing —OH of the carboxylic
group by —Cl, —OCOR, —NH2, or —OR.

O O O O
R—C R—C R—C R—C
Cl O NH2 OR
R—C
O
Acid chloride Acid anhydride Amide Ester

O
||
They all contain the acyl group R C , and may be hydrolyzed to the parent acid using dilute OH– or H3O+
.

O O + – O
H or OH
R—C ; R—C + H2O R—C + HX
X OH
Acyl group Carboxylic acid Water Carboxylic acid Conjugate acid
derivative of leaving group
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Acid derivatives are named from either the common name or the IUPAC name of the corresponding carboxylic
acid. For example, four derivatives of acetic acid, CH3COOH (IUPAC name : ethanoic acid ) are named as below.
(a) Acid chlorides. Change –ic acid to –yl chloride.
(b) Acid anhydrides. Change acid to anhydride.
(c) Acid amides. Change –ic acid of common name (or –oic acid of IUPCA name) to –amide.
(d) Esters. Change –ic acid to –ate, preceded by name of alcohol or phenol group.

O
O CH3—C O O
(a) CH3— C (b) O (c) CH3—C (d) CH3—C
Cl CH3—C NH2 OC2H5

O Acetamide Ethyl acetate

Ethanamide Ethyl ethanoate
Acetyl chloride Acetic anhydride
(Ethanoyl chloride) (Ethanoic anhydride)

1. Write IUPAC names of the following :

Br
O O
Br
(i) (ii) (iii) (iv) COCl
Cl Cl
O

O O O N(CH3)2
(v) (vi) COOCH3 (vii) (viii)
O O CH3 O
(ix) CH3NHCONHCH3 (x) (CH3)2NCONH2
2. Write structural formula for each of the two following compounds.
(i) 2-Phenylbutanoyl chloride (ii) 2-Phenylbutanamide (iii) 2-Phenylbutanoic anhydride
(iv) N-Ethyl-2-phenylbutanamide (v) Butyl-2-phenylbutanoate (vi) 2-Phenylbutyl butanoate.
3. Why nitriles are often classified as acid derivatives ?

18.1 Structure of Carboxylic Acid Derivatives

Like other carbonyl containing compounds (aldehydes, ketones and carboxylic acids), derivatives of carboxylic
acids have a planar arrangement of bonds to their carbonyl group. An important structural feature of these derivatives is
that the atom attached to the acyl carbon bears an unshared pair of electrons that is capable of interacting with the
carbonyl p system.

– –
O: :O: O:
:

: :

+
R—C ¬¾® R—C ¬¾® R—C
+
X: X:
: :

X:
: :

I II III
This interaction of the unshared electron pair (structures II and III) stabilizes the carbonyl group and decreases
its electrophilic character. The extent of this electron delocalization due to X dependes upon the nature of the substituent
X. More is the electronegativity of X, lesser is the electron donation to the carbonyl group and thus lesser will be the
stabilizing effect ; consequently more will be electrophilic character of the carbonyl group and hence higher will be the
reactivity of the derivative toward nucleophiles.
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The atom X in acid chlorides, acid anhydrides, esters and amides is Cl, O, O and N respectively. Since
electronegativity of these atoms follows the order Cl > O > N, we can say that carbonyl group of acid chlorides are weakly
stabilized, while that of acid amides are greatly stabilized due to resonance.

–
O: :O:

:
R—C ¬¾® R—C
+
Cl : Cl :

:
:
Acid chloride

Weak resonance stabilization due to —I effect of chlorine as well as poor

overlaping of 3p orbital of Cl with the p orbital of the carbonyl carbon.

–
O:

: :
O:

:
R—C ¬¾® R—C
+
NH2 N H2
:
Acid amide

Very effective resonance stabilization due to least —I effect of N

as well as better overlaping of 2p orbital of N with p orbital of carbonyl carbon

As far as acid anhydrides and esters are concerned, carbonyl group of an ester is stabilized more than that of an
acid anhydride because in acid anhydride there is a competition between two acyl groups for the oxygen lone pair, with
the result each carbonyl group is stabilized less than the single carbonyl group of an ester.

O O ..
O

..
R C .. C R R C ..
O
.. OR
..
Acid anhydride Ester
(Each carbonyl group is less (Carbonyl group is more stable)
stabilized than that of an ester)

Thus the relative stability of the carbonyl group of the four acid derivatives follows the order.
Acid chloride < Acid anhydride < Ester < Amide
Hence electrophilic character of the carbonyl group of these derivatives will be
Acid chloride > Acid anhydride > Ester > Amide
(Decreasing electrophilic character (and hence reactivity toward nucleophiles of the carbonyl group)
Carbonyl group of carboxylate anion is extremely stabilized because the negatively charged oxygen (substituent
X) is a powerful electron donor to the carbonyl group, hence carboxylates do not react with nucleophiles.

–
: :

O: O:
:

R—C ¬¾® R—C

–
:
:

O: O:
:

Relative stability and reactivity of carboxylic acid derivatives.

Derivative Formula Stabilization Relative Rate of hydrolysis
Acid chloride RCOCl Very Small 1011
Anhydride (RCO)2O Small 10 7
Ester RCOOR Moderate 1.0
Amide RCONH2 Large < 10–2
Carboxylate anion RCOO– Very large

Rates are relative to ester as standard substrate at pH 7.

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18.2 Nucleophilic Acyl Substitution

As in aldehydes and ketones, the carbonyl group in carboxylic acids and their derivatives performs two functions.
(i) It provides a site for nucleophilic attack.
(ii) It increases the acidity of a-hydrogens. This aspect is partly discussed in carboxylic acids and will be further
discussed at a later stage.
Acyl compounds (carboxylic acids and their derivatives) typically undergo nucleophilic substitution in which
—OH, —Cl, —OCOR, —OR, or —NH2 is replaced by some other basic group, of course stronger than the group to be
removed. Substitution at acyl carbon takes place much more readily than at a saturated carbon atom, i.e. at alkyl carbon in
alkyl halides, R—X. Greater reactivity of carbonyl group toward nucleophiles is due to both electronic and steric factors :
(a) the capability of oxygen to acquire electrons, and (b) the relatively unhindered transition state leading to tetrahedral
intermediate from the trigonal reactant.

R X R R Nu
–
Nu : + C Nu C—X C + :X

O O– O
Trigonal C Tetrahedral C (Stable)
attack relatively (negative charge on O)
unhindered

Acyl nucleophilic substitution

S 2 –
Nu : + C—X ¾¾
N
¾ Nu - - - C - - - X ¾¾® Nu—C + :X
½

Tetrahedral C Pentavalent C
attack relatively hindered (unstable)

Alkyl nucleophilic substitution.

Thus toward nucleophiles, acid chlorides are more reactive than alkyl chlorides, amides are more reactive than
amines, and esters are more reactive than ethers. Nucleophilic substitution at acyl carbon (nucleophilic addition-
elimination) is similar to some extent (first step or initial step) to the nucleophilic addition to aldehydes and ketones. The
two reactions differ in the second step. The tetrahedral intermediate from an aldehyde or ketone accepts a proton to form
a stable addition product. In contrast, the tetrahedral intermediate from an acyl compound eliminates a leaving group
leading to regeneration of the carbon oxygen double bond (a trigonal compound) and thus the net result is a substitution
product. Therefore, the overall process in the case of acyl substitution occurs by a nucleophilic addition-elimination
mechanism.

Nu Nu Nu
---

R
: Nu ½ H
+ ½
C = O ¾¾® R—C- - ¾¾® R—C ¾¾® R—C
- d–
R¢ R¢ O R¢ O– R¢ OH
Reactant Transition state Intermediate Addition product
(Trigonal) (Becoming tetrahedral) (Tetrahedral)

Nucleophilic addition on aldehydes and ketones

Nu Nu
R ½ R
: Nu
C = O ¾¾® R—C- - ¾¾® R—C ¾¾® C=O + :X
-
X X Od– X O– Nu
Reactant Intermediate Product Leaving
(Trigonal) (Trigonal) group

Nucleophilic addition-elimination on acyl compounds.

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Now the question arises why the two classes of compounds differ in their reaction toward nucleophiles. The
difference lies in the nature of the substituent present on acyl carbon ; in aldehydes and ketones, this substituent (R ¢) is
either H or an alkyl group while in acyl compounds, it (X) is OH (in carboxylic acids), Cl (in acid chlorides), OCOR, COR,
or NH2. The ease with which, :X is lost depends upons its basicity ; the weaker the base, the better the leaving group. For acid
chloride, acid anhydrides, esters, and amides, :X is respectively
- -
Cl - , -
OOCR , OR and NH 2
very weak base moderately weak base strong base stronger base

Hence Cl– is lost with maximum ease and hence acid chlorides are the most reactive, while NH2– is lost with the
most difficulty hence acid amides are the least reactive toward nucleophilic substitution. In general, the overall order of
reactivity is

RCOCl > RCOOCOR > RCOOR¢ > RCONH 2

Acid chloride Acid anhydride Ester Amide

For an aldehyde or ketone to react by nucleophilic addition-eliminiation way, their intermediate would have to
eliminate a hydride ion (H:–) or an alkanide ion (R:–), both of which are the strongest bases of all and hence very poor
leaving groups. Thus the intermediates of aldehydes and ketones undergo addition reaction. Remember that alkanide ion
from the haloform reaction behaves as a good leaving group, this is because here the leaving group is a weakly basic
trihalomethyl anion, X3C:–.
Thus nucleophilic acyl substitution proceeds by two steps. Generally, the overall rate is affected by the rate of
both steps, but the first step (formation of tetrahedral intermediate) is more important. As in nucleophilic additions on
aldehydes and ketones, here also the first step is (a) favoured by electron withdrawal, which stabilizes the developing
negative charge in the transition state, and (b) hindered by the presence of bulky groups, which become crowded together
in the transition state. The second step depends on the basicity of the leaving group, :X (weaker a base, more readily it will
be lost).
Acyl nucleophilic substitution takes place readily and even by weaker nucleophiles in presence of acid because
protonation of carbonyl oxygen makes carbonyl carbon more electrophilic and hence more reactive toward nucleophile.
Futher, here oxygen can now acquire p electrons without having a negative charge.

Nu Nu
R R R
---

H
+
+ : Nu ½
¾¾
C=O ¬ ¾¾
® C = OH ¾ ¾® R—C - - ¾ ¾® R—C ¾¾® C = O + H: X
- d+
X X X OH X OH Nu
Undergoes nucleophilic
attack more readily

Thus we can explain why acid derivatives are hydrolyzed more readily in acidic solution (here : Nu is H2O:)
than in neutral medium. Acid derivatives are also more readily hydrolyzed in alkaline medium than in neutral medium.
Here the reason being the fact that the alkaline solutions provide a strong nucleophile (OH–).

–
O O O
R ½ –
– OH
C = O + : OH ¾¾® R—C—OH ¾¾®
– R—C ¾¾® R—C
(— : X )
X ½ OH O–
X
A strong
nucleophile

1. Which of the compound of each pair undergoes hydrolysis rapidly ?

(i) Cl3CCOCl and F3CCOCl. (ii) CH3COOCH3 and COOCH3

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COOCH3 COOCH3 COOCH3 COOCH3

H3C CH3

(iii) and (iv) and

NO2 CH3

(v) CH3COOCH3 and CH3CONHCH3.

2. Give the structure of the product obtained when each of the following compound is treated with ammonia.

(i) CH3CHClCOOH (ii) ClCH2COCl (iii) Cl (iv) COOH

OH
3. Although ketones do not undergo nucleophilic substitution, following reactions occur. Explain.

OH
-
(i) RCOCCl3 ¾¾® RCOOH + CHCl3

O O
–
½½ NH2 ½½
(ii) C ¾¾¾® C—NH2 + F
NH3

18.3 Preparation of Acid Derivatives

We will come across many instances where one acid derivative is converted into other. The order of reactivity (or
the stabilization order) of acid derivatives given earlier gives us a clue as to which syntheses are practical and which are
not. In general, a more stable (less reactive) acyl compound can be synthesised from less stable (more reactive), but the
reverse is usually difficult and, when possible, requires special reagents. For example, an ester can be made from the
corresponding acid chloride or anhydride, but not from amide. In general, for synthesis of acid derivatives by acyl transfer
the reactant must have a better leaving group at the acyl carbon than the product.
(a) Preparation of acid chlorides. Since acyl chlorides are the most reactive of the acid derivatives, we must use
special reagents to prepare them. We use acid chlorides of inorganic acids, viz PCl5 (an acid chloride of phosphoric
acid), PCl3 (an acid chloride of phosphorous acid), and thionyl chloride (an acid chloride of sulphurous acid).
Reactions have already been given in properties of carboxylic acids. All of these reactions are examples of acyl
nucleophilic substitution reactions.
(b) Preparation of acid anhydrides. Of the four carboxylic acid derivatives, acid anhydrides are less reactive (i.e.
more stable) only from acid chlorides ; hence acid anhydrides can be prepared only from acid chlorides.

O O O O
½½ ½½ Pyridine ½½ ½½
R— C ¾ Cl + HO— C ¾ R ¢ ¾¾¾® R— C ¾ O — C ¾ R ¢ + HCl
This method is applicable to the preparation of both symmetrical (R and R¢ are same) and mixed anhydrides.
Sodium salts of carboxylic acids also react with acyl chlorides to give anhydrides.

O O O O
½½ ½½ ½½ ½½
R— C ¾ Cl + Na+ O — C ¾ R ¢ ¾¾¾¾® R— C ¾ O — C ¾ R ¢ + NaCl
In this reaction a carboxylate anion acts as a nucleophile and brings about nucleophilic substitution at the acyl
carbon of the chloride.
Cyclic anhydrides can sometimes be prepared by simply heating the appropriate dicarboxylic acid. However,
this method succeeds, only when anhydride formation leads to a five- or six -membered ring.
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O O O O

OH OH
¾300°C
¾¾® O ; ¾130°C
¾¾® O
OH
OH
O O O O
Succinic acid Succinic anhydride Maleic acid Maleic anhydride

O O

OH
OH ¾230°C
¾¾® O

O O
Phthalic acid Phthalic anhydride

1. Explain the following.

(a) Adipic acid (1, 6-hexanedioic) does not form a cyclic anhydride on heating, but forms a cyclic ketone ; while suberic acid (1,
8-octanedioic acid) does not form a cyclic ketone.
(b) Benzoic anhydride is formed in excellent yield by adding one molar equivalent of water to two molar equivalents of benzoyl
chloride.

The most important member of acid anhydrides, acetic anhydride, is prepared by the reaction of acetic acid with
ketene, CH2 = C = O, which itself is prepared by high temperature dehydration of acetic acid.

AlPO 4 , 700 ° C CH 3 COOH

CH3COOH ¾¾¾¾¾¾® CH2 = C = O ¾¾¾¾® (CH 3 CO)2 O
( - H2 O) Acetic anhydride

(c) Preparation of esters. Esters are usually prepared by the reaction of alcohols (or phenols) with acids or acid
chlorides.
1. From carboxylic acids (esterification). Carboxylic acids react with alcohols to form esters through a
condensation reaction known as esterification, or Fischer esterification.
O O
½½ HA ½½
R— C ¾ OH + R¢—OH R— C ¾ OR ¢ + H2O
Esterifications are acid catalyzed (conc. H2SO4 or HCl), and proceed very slowly in the absence of strong
acids. Since the reaction is reversible, the yield of ester can be increased in two manners. (For details,
consult chapter on “Carboxylic Acids”).
(a) By using excess of either the carboxylic acid or the alcohol depending on the availability and cost.
(b) By removing water from the reaction mixture as soon as it is formed .

Mechanism of esterification. This is a typical mechanism of acid-catalyzed nucleophilic addition-

elimination at acyl carbon atom.
An important question about the mechanism of acid-catalyzed esterification is the origin of alkoxy oxygen
of the ester, i.e. whether it is coming from carboxylic acid or alcohol. In other words whether it is the C—O bond of the
alcohol or of the carboxylic acid that is broken during esterification. It has been proved by isotopically labelled experiment
that the C—O bond of the carboxylic acid is broken .
O O
½½ 18 HA ½½ 18
C6H5—C—OH + CH3—O—H ¾¾®
¬¾¾ C6H5 —C—O—CH3 + H2O
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The essential steps of the mechanisum are summarised below

:
O: OH : OH

:
½½ + ½½ ½ Å
¾¾¾® ¾¾¾®

:
: :

: :
R—C—OH + H ¬¾¾¾ R—C—OH ¬¾¾¾ R—C—OR¢
+ ½ H
R¢OH : OH

:
Carboxylic acid accepts Alcohol attacks the protonated A proton is lost at
proton from strong carbonyl group to give a one oxygen and gained
acid catalyst tetrahedral intermediate at another

Å
O:

:
: OH
:

:
O—H + H2O
: :
½ ½½ ½½
¾¾® R—C—OR¢ ¾¾® ¾¾¾® R—C—OR¢ + H +O :

:
¬¾¾ ¬¾¾ R—C—OR¢ ¬¾¾¾ 3

:
½
Å OH
2
:

Loss of a molecule Transfer of a Ester is

of water gives a proton to a base formed
protonated ester (water)

Salient features of acid-catalyed esterification

(i) All steps of the reaction are reversible, so steps leading to forward reaction constitute mechanism of
acid-catalyzed esterification of an acid. However, the reverse steps of the reaction constitute the mechanism
of acid catalyzed hydrolysis of an ester.
(ii) The reaction can be forced to proceed in a particular direction by changing the conditions. The reaction
can be forced to esterification by taking excess of alcohol and removing water (product) as soon as it is
formed. On the other hand, for carrying out the reverse reaction (i.e. for acidic hydrolysis of an ester),
large excess of water should be used, i.e. the ester is refluxed with dilute aqueous HCl or dil. aqueous
H2SO4.
(iii) Both reactions i.e. acid-catalyzed esterification of an acid as well as acid-catalyzed hydrolysis of an
ester are affected by steric factors.
(iv) Mineral acid speeds up both processes by protonating carbonyl oxygen and thus rendering carbonyl
carbon more susceptible to nucleophilic attack. In esterification, the nucleophile is an alcohol molecule
and the leaving group is a water molecule ; in acidic hydrolysis, the roles are exactly reversed.
(v) Both processes involve similar type of C—O cleavage (acyl-oxygen cleavage).

O O
½½ 18 H
+
½
½ 18
Esterification. C6H5—C—O—H + CH3—O—H ¾¾® C H —C—OCH + H O
¬¾¾ 6 5 3 2

O O
½½ 18 H
+
½½ 18
Hydrolysis. C6H5—C—OCH3 + H—O—H ¾¾® C6H5 —C—OH + CH3OH
¬¾¾

2. Esters from acid chlorides and acid anhydrides. Since acid chlorides and acid anhydrides are more
reactive toward nucleophilic substitution than carboxylic acids, the reaction of an acyl chloride with an
alcohol occurs rapidly in an irreversible manner and in absence of an acid catalyst. However, pyridine is
often added to the reaction mixture to remove HCl (pyridine may also react with the acyl chloride to form an
acylpyridinium ion which is more reactive toward the nucleophile even than the acyl chloride).

O O
½½ ½½
R— C ¾ Cl + R¢OH + ¾® R— C ¾ OR ¢ +
–
N N + Cl
H
:
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Aromatic acid chlorides (ArCOCl) are considerably less reactive than the aliphatic acid chlorides.
(RCO)2O + R¢OH ¾¾® RCOOR¢ + RCOOH
Cyclic anhydrides react with one molar equivalent of an alcohol to form compounds that are both esters
and acids.

O O CH3
OH
½
½ 110°C OCHCH2CH3
O + CH 3CHCH2CH3 ¾¾¾®
OH

O O
Phthalic anhydride sec-Butyl hydrogen phthalate

3. Transesterification. When an ester is treated with an alcohol in presence of acid (H2SO4 or dry HCl) or base
(usually alkoxide ion), alcoholysis (cleavage by an alcohol) of an ester takes place to form new ester.

O O
½½ +
H or OR
– ½½
R— C ¾ OR ¢ + R²OH R— C ¾ OR ² + R¢OH
High boiling High boiling Higher boiling Lower boiling alcohol
Since the reaction is reversible, to carry out the reaction toward completion, it is necessary either to use a
large excess of the alcohol or to remove one of the products from the reaction mixture (when the alcohol
formed has low boiling point).
HA
CH2 = CHCOOCH3 + CH3CH2CH2CH2OH CH2 = CHCOOCH2CH 2CH 2CH 3 + CH3OH
Methyl acrylate Butyl alcohol Butyl acrylate
(d) Preparation of amides. Among the four acid derivatives, amides are the least reactive, hence these can be
prepared by treating acyl chlorides, anhydrides, or esters with ammonia or amines (acylation of amines or
ammonia). As expected, acid chlorides are the most reactive and carboxylate ions are the least.

RCOCl + 2NH 3 ¾¾® RCONH2 + NH4Cl

14442444 3
1 : 2 molar ratio

+
(RCO)2 O + 2R ¢NH 2 ¾¾® RCONHR¢ + RCOO–H N R¢
1444 424444 3 3
1 : 2 molar ratio

RCOOR¢ + R ² 2 NH ¾¾® RCONR2² + R¢OH

144424443
1 : 1 molar ratio

Note that two molar equivalents of amine are required in the reaction with acyl chlorides and acid anhydrides
; one molecule of amine acts as a nucleophile while the other as a Bronsted base to remove the acid formed during
these reactions. In case the amine used is costly or available only in small quantities, the reaction is carried out
successfully using one molar equivalent of amine in presence of some other base like NaOH to react with the
acid (HCl or RCOOH) formed. In case acid chloride (or acid anhydride) and ammonia are taken in 1 : 1 molar
ratio, whole of the reactant will not be converted into product as is evident by following example.

1 1 1
RCOCl + NH3 ¾¾® RCONH2 + NH4Cl + RCOCl
2 2 2
In industry, amides are more often made by heating ammonium salts of carboxylic acids.

NH 3 evaporate to dryness
RCOOH ¾¾® RCOO– NH4 ¾¾¾¾¾¾¾¾® RCONH2 + H2O
Since carboxylate ion has low reactivity toward nucleophilic addition-elimination, further reaction does not
take place in aqueous solution. However, if the dry ammonium salt is heated, dehydration takes place forming
amide.
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1. (a) Predict which of the reaction takes place easily.

(i) CH3COCl + H2O ¾¾® CH3COOH + HCl (ii) CH3COOH + NH3 ¾¾® CH3CONH2 + H2O
(iii) (CH3CO)2O + NaOH ¾¾® CH3COOH + CH3COONa (iv) CH3COBr + C2H5OH ¾¾® CH3COOC2H5 + HBr
(v) CH3CONH2 + NaOH ¾¾® CH3COONa + NH3 (vi) CH3COOCH3 + Br– ¾¾® CH3COBr + OCH3–
(b) Give chemical reaction used for preparing ter-butyl acetate from acetic acid.
(c) RCOCl cannot be perpared by the reaction of HCl with RCOOH. Explain.

18.4 Properties of Acid Derivatives

1. The presence of the C = O group in acid derivatives makes them polar and thus these compounds have definite
dipole moments. Dipole-dipole interactions contribute to the intermolecular attractive forces and hence these
compounds have higher boiling points than hydrocarbons of similar shape and molecular weight. Further, they
lack a hydrogen attached to electronegative oxygen (except amides in which H is attached to N), their molecules
cannot form strong hydrogen bonds to each other ; hence their boiling points are lower than those of acids and
alcohols of comparable molecular weight. The boiling points of these derivatives (except amides) are about the
same as those of comparable aldehydes and ketones. However, amides have quite high boiling points because
they are capable of forming strong intermolecular hydrogen bonding. Since N, N-disubstituted amides cannot
form hydrogen bonds to each other, they have lower melting and boiling points.

R
H ½
½ C
O N—H O N—H
C ½
½ H
R

2. Lower esters and amides are soluble in water as these are capable of forming hydrogen bonding with water.
3. Acid chlorides have sharp, irritating odors, at least partly due to their ready hydrolysis to HCl and carboxylic
acids. Low molecular weight esters are fairly volatile and have pleasant odors ; hence these are often used in the
preparation of perfumes and artificial flavourings.

(A) Reactions of Acyl Chlorides

(i) Since acyl chlorides are the most reactive of the acyl derivatives, they are easily converted to less reactive
ones, viz. anhydrides, esters, and amides and also acids very easily (Reactions discussed earlier).

O O O
½½ OH – ½½ H 2O ½½
R— C ¾ O + Cl– ¬¾¾¾ R— C ¾ Cl ¾¾® R— C ¾ OH + HCl
H2 O
O O O O
½½ R ¢ OH
½½ NaOOCR ¢
½½ ½½
R— C ¾ OR¢ ¬¾¾ R— C ¾ Cl ¾¾¾® R— C ¾ O — C ¾ R ¢ + NaCl
base
O O O O
½½ ½½ RNH 2 ½½ 2NH 3 ½½
R— C ¾ NR2 or R— C ¾ NHR ¬¾¾¾¾ R— C ¾ Cl ¾¾¾® R— C ¾ NH 2 + NH4Cl
or R 2 NH
In the laboratory, amides and esters are usually prepared from the acid chloride rather than from the acid
itself since both the steps (preparation of acid chloride and its reactions with ammonia or an alcohol) are
rapid and irreversible.
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O O O O
½½ SOCl2 ½½ NH 3 , cold ½½ ½½
R— C ¾ OH ¾¾® R— C ¾ Cl ¾¾¾¾¾¾® R— C ¾ NH2 or R— C ¾ OR ¢
heat or R ¢ OH/pyridine

Acetyl chloride is frequently used in acetylation (acylation, in general) ; a reaction in which hydrogen of
alcoholic, phenolic, amino, or imino group is replaced by acetyl (CH3CO –) group.
(ii) Friedel-Carft acylation.
O O
½½ AlCl3 or other ½½
R— C ¾ Cl + ArH ¾¾¾¾¾® R— C ¾ Ar + HCl
Lewis acid

A ketone
(iii) Reaction of organometallic compounds. Recall that ketones are formed with Grignard reagents,
organolithium compounds, and organocopper compounds ; however the latter are preferred because
organocopper reagents do not react with many of the functional groups with which Grignard reagents
and organolithiums do react, viz., —NO2, —CN, —CO—, —COOR, etc.
R¢ O
CuX ½ RCOCl ½½
R¢—Li ¾¾¾® R¢— CuLi ¾¾¾® R¢— C ¾ R
(iv) Reduction
O O
LiAlH 4 ½½ LiAlH (OBu -t )3 ½½
R—CH2OH ¬¾¾¾¾¾ R— C ¾ Cl ¾¾¾¾¾¾¾¾¾¾¾® R— C ¾ H
or Rosenmund reduction

1. Write the structure of the tetrahedral intermediate formed in the reaction of benzoyl choride with each of the following :
(a) CH3COOH (b) C2H5OH (c) (CH3)2NH (d) H2O.
2. The values of Ka for hydrazoic acid (HN3) and acetic acid (CH3COOH) are 2.6 –5 –5
× 10 and 1.8 × 10 respectively. Place the acyl azides
(RCON3) at proper place regarding reactivity of acyl derivatives.
3. List the reagent for converting benzoyl chloride to
(a) benzaldehyde (b) benzamide (c) benzyl alcohol (d) benzyl benzoate
(e) benzoic anhydride (f) N-benzylbenzamide (g) benzoyl azide, C6H5CON3.
4. Give the products of reaction of Me2CuLi followed by hydrolysis with each of the following

(a) NC (CH2)4COCl (b) CH3CO— —COCl (c) H5C2O2C(CH2)4COCl.

(B) Reactions of Acid Anhydrides.

(i) Acid anhydrides undergo the same reactions as acid chlorides, but a little more slowly. Compounds
containing acetyl group are often prepared from acetic anhydride because it is cheap, readily available, less
volatile and more easily handled than acetyl chloride and it does not form corrosive hydrogen chloride.

O O O
½½ CH 3 OH ½½ NH3 ½½
R— C ¾ OCH3 + RCOOH ¬¾¾¾¾ R— C ¾ OCOR ¾¾¾® R— C ¾ NH 2 + RCOONH4

O O O
½½ OH – ½½ H2 O ½½
RCOO– + R— C ¾ O ¬¾¾¾¾ R— C ¾ OCOR ¾¾¾® R— C ¾ OH + RCOOH
H2O

Like acetyl chloride, acetic anhydride is used in acetylation (acylation) of alcohols, phenols, amines and
imines.
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(ii) Friedel-Craft acylation.

O
AlCl 3
½½
(RCO)2O + ArH ¾¾® Ar— C ¾ R + RCOOH

O O O

AlCl 3 Conc. H SO
O + 2
¾¾¾¾¾®4

Friedel-Craft Cyclisation
acylation C
O OH O
O
Phthalic anhydride o-Benzoylbenzoic acid 9, 10-Anthraquinone

1. Write down the structures of the major organic product of each of the following reactions.

H+ H+
(a) Acetic anhydride + CH3OH ¾¾® (b) Acetic anhydride + 2CH3OH ¾¾®
(c) Acetic anhydride + NH3 (1 mol) ¾¾® (d) Succinic anhydride + (CH3)2NH (2 mol) ¾¾®

H3O+
(e) Succinic anhydride + NaOH (2 mol) ¾¾® (f) Acetic anhydride + 2CH3MgBr ¾¾®

3 AlCl
(g) Succinic anhydride + Benzene ¾¾®
2. (a) Give the possible ways for preparing following anhydrides :

O O O O
½½ ½½ ½½ ½½
(i) CH3 C —O— CCH2 CH3 (ii) H— C ¾ O — C ¾ CH3

(b) Can formic anhydride be prepared by heating formic acid ?

3. Predict the products of the following reactions :

AlCl 3 Conc. H2 SO 4
Toluene + Phthalic anhydride ¾¾® [A] ¾¾¾¾® [B]
heat

(C) Reactions of Esters.

Esters are less reactive than acyl chlorides and acid anhydrides toward nucleophilic substitution. The three
important reactions are conversion to amides, other esters (transesterification or alcoholysis) and hydrolysis.
(i) CH3COOC2H5 + NH3 ¾¾® CH3CONH2 + C2H5OH
(ii) CH3COOC2H5 + CH3OH ¾¾® CH3COOCH3 + C2H5OH

H + or OH -
(iii) CH3COOC2H5 + H2O ¾¾¾® CH3COOH (or CH3COO–) + C2H5OH
Since acid catalyzed esterification and acid hydrolysis of esters are reversible, if we reverse the mechanism of
esterification (discussed earlier), we get the mechanism of acid catalyzed ester hydrolysis.

Mechanism of base promoted ester hydrolysis. Unlike acid catalyzed, base promoted hydrolysis of ester, also
known as saponification, forms an alcohol and sodium salt of the acid.

O O
½½ ½½
R— C ¾ OR ¢ + OH– ¾¾® R— C ¾ O – + R¢OH
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The carboxylate ion is very unreactive toward nucleophilic substitution because it is quite stable and negatively
charged, hence base-catalyzed hydrolysis of ester is an irreversible reaction. Since base is consumed in the reaction, we
generally speak base-promoted rather than base-catalyzed. The base-promoted hydrolysis of an ester is also an example of
nucleophilic addition-elimination at the acyl carbon

:
:O:
R
½
– ¾slow
¾® ¾ ¾®

: :
C = O + : OH

: :
¬¾¾ R—C—O—H ¬¾¾
R¢—O ½
:O—R'

:
–
OH attacks the The tetrahedral intermediate
carbonyl carbon expels an alkoxide ion
(acyl-oxygen fission)

O O
½½ ½½ –
: : + –: O—R’ ¾¾® R—C—O : + H—O—R'

: :

: :
: :
R—C—O—H
Transfer of a proton leads to
more stable carboxylate ion

Evidence for the above acyl-oxygen fission.

(a) Istotopically labelled experiment. When ethyl propanoate labelled with 18O in the ether type oxygen of the
ester is subjected to hydrolysis with aqueous base, all of the 18O is found to be present in ethanol, and none
in the propanoate ion. This indicates that the bond between acyl group and oxygen is cleaved during
hydrolysis.

Acyl-oxygen fission
O Alkyl-oxygen fission
O
½½ 18 – ½½ –
18
OH + HOC2H5
C2H5—C—O—C2H5 ¾¾¾¾¾® C2H5—C—O
(acyl-oxygen
fission) (Products formed)
O
–
OH ½½ 18–
C2H5—C—O + HOC2H5
alkyl-oxygen fission (Not isolated)

(b) Stereochemical evidence. Saponification of esters of optically active alcohols proceeds with retention
of configuration.

O H H
C6H5 C6H5
½½ OH
–
–
CH3—C—O—C ¾¾® CH3COO + HO—C
Acyl CH3 CH3
(R)-(+)-1-Phenylethyl acetate (R)-(+)-Phenylethyl alcohol
(same optical purity as ester)

Retention in configuration in the chiral alcohol indicates that none of the bonds to the stereogenic
center are broken which is possible when acyl-oxygen fission takes place. Had alkyl-oxygen fission
occurred, it would have been accompanied by inversion of configuration since bond to the stereogenic
carbon is cleaved to form carbocation, and the product would have been (S)-(–)-1-phenylethyl alcohol.
(iv) Reaction with Grignard reagents. Esters react with two equivalents of a Grignard reagent to produce
tertiary alcohols. Since two of the three alkyl groups of the tertiary alcohol come from the Grignard reagent,
hence these must be identical.
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O OH
½½ (i) diethyl ether ½
R— C ¾ OR ¢ + 2R²MgX ¾¾¾¾¾® R ¾ C ¾ R² + R¢OH
(ii) H 3O + ½
R²

OH
(i) ether ½
COOC2H5 + 2 CH3MgI ¾¾¾¾®
+ C—CH3 + C2H5OH
(ii ) H3O
½
Ethyl cyclopropanecarboxylate CH3

Na/C2 H 5 OH, or Li AlH 4 , or

(v) Reduction. RCOOR¢ ¾¾¾¾¾¾¾¾¾¾® RCH2OH + R¢OH
H 2 , Copper chromite,
high pressure, 150 °C

Hydrogenolysis (cleavage by hydrogen) of esters may also be carried out by heating ester with H2 in
presence of Pd/C.
Pd/C
C6H5COOCH2C6H5 + H2 ¾¾® C6H5COOH + CH3C6H5
Note that here acidic part of the ester is not reduced, hence this type of hydrogenolysis is used for regenerating
the protected acidic group.
SOCl2 C6 H 5 CH 2 OH H 2 ; Pd/C
—COOH ¾¾® —COCl ¾¾¾¾¾® —COOCH2C6H5 ¾¾¾¾® —COOH + CH3C6H5

1. (a) An ester has two oxygen atoms, carbonyl oxygen and carboxyl oxygen, which of the two is more basic?
(b) An ester group has three carbon-oxygen bonds, can you think about their relative bond lengths ?
O
z
y x
R—C—O—R¢
2. How we can explain the lower rate of esterification and hydrolysis of esters when the alcohol, the acid, or both are highly branched?
3. (a) Predict the relative rate of alkaline hydrolysis of following esters.
Ethyl acetate, isopropyl acetate, methyl acetate, ter-butyl acetate
I II III IV
What two factors are responsible for their relative rate of hydrolysis ?
(b) Predict the order of reactivity toward alkaline hydrolysis of methyl acetate (I), methyl formate (II), methyl isobutyrate (III),
methyl propionate (IV), and methyl trimethylacetate (V).
4. Arrange the following esters in decreasing ease of alkaline hydroysis.

CH3 OCH3 Cl NO2

(a)

COOC2H5 COOC2H5 COOC2H5 COOC2H5 COOC2H5

I II III IV V

NH2 CH3 NO2

(b)
CH2COOCH3 CH2COOCH3 CH2COOCH3 CH2COOCH3
I II III IV
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5. (a) Give the structural formula for the products in each of the following reaction.

(i) CH3CH2COOCH3 + 2C6H5MgBr (ii) + 2CH3MgBr

O O

(iii) + CH3NH2 (iv) CH3COOC2H5 + H2NNH2

O O
(v) C6H5COOC2H5 + NH2OH.
(b) Write down structure of the products formed in the following reaction.
(i) heat
CH3CH = CHCH2COOCH2CH2Br + NaOH ¾¾¾®
(ii) H +

(c) Give the structure of the product obtained by hydrogenolysis of n-butyl oleate over copper chromite.
6. Esters of which acid would give secondary alcohols on reaction with Grignard reagents ? Give chemical reaction involved in the
preparation of 4-heptanol by the reaction of an ester with a Grignard reagent.
7. Explain the following anamoly in the acid-catalyzed hydrolysis of the following two esters.

O CH3 CH3
½½ ½ H 2 O18 , H + ½
(a) CH3— C — O ¾ C¾ C2 H5 ¾¾¾¾® HO18 — C — C2 H5 + CH3COOH
½ ½
C6 H5 C6 H5
(+) – (±) –

O CH3 CH3
½½ ½ H 2 O18 , H + ½
(b) CH3— C — O ¾ C ¾ C2 H5 ¾¾¾¾® HO— C ¾ C2H5 + CH3 COO18 H
½ ½
H H
(+) – (+) –

(vi) Claisen condensation. An a-hydrogen in an ester is weakly acidic (similarity to aldehydes and ketones)
and again like aldehydes and ketones the negative charge of the carbanion of esters is dispersed to the
carbonyl group through resonance.

Q O Q O

H2C C R H2C C OR
Carbanion of aldehyde / ketone Carbanion of an ester

Due to acidic nature of a-hydrogens, esters when treated with a strong base (generally C2H5ONa) undergo
condensation to form b-keto ester.

O O O
½½ ½½ (i) C H
2 5 ONa/C H
2 5 OH ½
½
CH3 COC 2H 5 + CH3 COC 2H 5 ¾¾¾¾¾¾¾¾® CH 3CCH 2COOC 2 H 5 + C H OH.
2 5
(ii) H O + Ethyl acetoacetate *
3
(Acetoacet ic ester)

The reaction, known as Claisen condensation, is related to aldol condensation given by aldehydes and
ketones : both reactions involve the attack of a carbanion (a nucleophile) on an electron deficient carbonyl carbon.
However, the two reactions differ in the next step : in the aldol condensation, nucleophilic attack leads to
addition, the typical reaction of aldehydes and ketones, while in the Claisen condensation, nucleophilic attack
leads to substitution, the typical reaction of acyl compounds.
Mechanism.

O O
½½ ® ½½
Step 1. CH 3 ¾ C ¾ OC2H 5 + –OC2H5 ¬¾¾ –CH — C ¾ OC H
2 2 5
Ethyl acetate

* The systematic name of ethylacetoacetate is ethyl 3-oxobutanoate.

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–
O O O O
½½ ®
Step 2. CH3—C—OC2H5 + –CH2— COC 2H5 ¬¾¾ CH3—C—CH2COC2H5
Ethyl acetate (2nd mole)
OC2H5

O O
® ½½ ½½
¬¾¾ CH3— C ¾ CH2 COC 2 H5 + –OC2H5

Although the products at the end of the second step are acetoacetic ester and ethoxide ion, the reaction does
not stop at this step ; had it so been, the yield of the b-keto ester would have been very little because the
overall equilibrium upto this point is favourable to reactants and not to products.
In b-keto esters (e.g. acetoacetic ester), a-hydrogens are surrounded at both ends by carbonyl groups,
hence such compounds are much stronger acids than ordinary esters because the negative charge can be
delocalised into two carbonyl groups instead of one in ordinary esters. Due to stronger acidic nature than ethyl
alcohol, the b-keto ester formed at step 2 reacts with ethoxide ion to form ethyl alcohol and an anion.

O O O O
½½ ½½ ½½ - ½½
¾¾® CH — C —
Step 3. CH3— C ¾ CH 2 ¾ COC 2 H 5 + –OC2H5 ¬¾ 3 CH — COC 2H 5 + C2H5OH
Stronger acid Anion of acetoacetic ester Weaker acid
(pKa = 11) (pKa = 16)
Note that the position of equilibrium for this step is favourable, and can be made more favourable by
distilling ethanol from the reaction mixture. Although, the reaction is complete at step 3, an acid is added
to the reaction mixture to obtain the product in its neutral form.

O O O O
½½ - ½½ H3O + ½
½ ½
½
CH3— C — CH — COC 2H 5 ¾¾® CH 3 — C — CH 2 — C OC 2H 5 + H2O
Acetoacetic ester

Like aldol condensation, Claisen condensation always involves bond formation between the a-carbon
atom of one molecule and the carbonyl carbon of another.

O O O
½½ a b (i) C 2H 5ONa ½½ ½½
2CH 3 CH 2 C OCH 2 CH 3 ¾¾¾¾¾® CH3 CH2 C ¾ CHCOC2 H5 + CH3CH2OH
(ii) H 3O +
½
CH3
Ethyl propanoate Ethyl 2-methyl-3-oxopentanoate
Unlike aldol condensation, Claisen condensation is possible only for esters having two a hydrogen
atoms; i.e. for the type RCH2COOR¢, but neither for R2CHCOOR¢ nor for R3CCOOR¢.
Intramolecular Claisen condensation (Dieckmann reaction). Esters of dicarboxylic acids undergo
intramolecular Claisen condensation, provided a five or six-membered ring can be formed

O O
O O O
½½ ½½ C—OC2H5 COC2H5
C2H5O C(CH 2 ) 4 COC 2H 5 or H2CCOOC2H5 (i) C2H5ONa
¾¾ ¾¾¾ ¾®
+
(ii) H3O

Diethyl hexanedioate Ethyl 2-oxocyclopentanecarboxylate

(Diethyl adipate)
Note that the a hydrogen atom and the ester group for the condensation are coming from the same molecule.
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Crossed Claisen condensation. Like a crossed aldol condensation, a crossed Claisen condensation is
possible when one of the reactants has no a -hydrogen and thus is incapable of undergoing self-
condensation ; this component acts as an acylating agent.

O O
O O
½½ (i) - OC2H 5
— COC2H5 + CH3 COC 2H 5 ¾¾¾¾® — C—CH2COC2 H5
+(ii) H 3O

Ethyl benzoate Ethyl acetate Ethyl benzoylacetate

(no a hydrogen)

O O O
½½ ½½ (i) C2H 5 ONa ½½
C6 H 5 CH 2 COC2 H 5 + C 2H 5 OCOC2H 5 ¾¾¾¾® C 6H 5 CHCOC 2H 5
Ethyl phenylacetate Diethyl carbonate (ii) H 3 O+ ½
(no a carbon) COOC2 H 5
Diethyl phenylmalonate
(Phenylmalonic ester)
In such cases, an ester without an a-hydrogen is mixed with the base, and then ester carrying a-hydrogen
is added.

1. (a) Write structural formulas for the Claisen condensation products of each of the following.
(i) CH3CH2CH2CH2COOCH2CH3 (ii) C6H5COOCH2CH3 (iii) C6H5CH2COOCH2CH3
(b) Give the structure of the product obtained when ethyl phenylacetate (C6H5CH2COOCH2CH3) is treated with each of the
following esters in presence of sodium ethoxide.
(i) ethyl formate (ii) diethyl oxalate (iii) ethyl phenylacetate (iv) ethyl benzoate.
2. Can we replace C2H5ONa by other base like CH3ONa or NaOH in the following reaction?
C H ONa
2CH 3 COOC 2 H 5 ¾¾2¾5¾¾ ¾® CH 3 COCH 2 COOC 2 H 5
3. Although ethyl propanoate gives good yield in the Claisen condensation, ethyl-2-methylpropanoate gives poor yield. Explain.
4. Name the starting material used for getting following product by Claisen condensation.

O O
O O

(i) (ii) OC3H7-iso

OCH3

5. Following b-keto esters are formed by crossed Claisen condensation, write down the structure of the two components in each of the
following.

O
H5C2O2C COOC2H5

(i) C6H5COCH (C6H5) COOC2H5 (ii) (iii) COOC2H5

O O
O
6. Give the different possible reactant(s) from which each of the following can be prepared using Claisen condensation.

O O O
COOC2H 5
(a) COC 6H5 (b) (c)
O O
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7. (a) Write the structure of the Dieckmann cyclization product formed on treatment of each of the following diesters with sodium
ethoxide followed by acidification.
(i) CH3CH2OOC(CH2)5COOC2H5 (ii) C2H5O2CCH2CH2 2 CH2 COOC2H5
½
CH3
(iii) C2H5O2C CHCH2CH2CH2COOC2H5
½
CH3
(b) Do you expect Dieckmann condensation when ethyl succinate or ethyl glutarate is treated with sodium ethoxide ?
8. Draw the structures of the starting diesters from which the following keto esters can be prepared using Dieckmann condensation.
O OC2H5 O
O C O
O C – OCH3
(a) (b) (c) O (d)
COOCH3 COOCH3
O
9. Give the product(s) in the following reaction.
O

BF3
CH3COOH

(D) Reactions of amides

1. Amides are slowly hydrolyzed when heated under either acidic or basic conditions.
OH - H+
RCOO– + NH3 ¬¾¾ RCONH2 + H2O ¾¾® RCOOH + NH4+
heat heat
The mechanism for acid hydrolysis of an amide is similar to that for acid hydrolysis of an ester. Water acts
as a nucleophile and attacks the protonated amide ; the leaving group is ammonia (or an amine). In basic
hydrolysis of amides, hydroxide ion acts as nucleophile as well as base.
2. Unsubstituted amides are converted to RCOOH with HNO2, and are dehydrated to RCN with P2O5, SOCl2,
POCl3 or PCl5.
RCONH2 + HONO ¾¾® RCOOH + N2 + H2O
P2 O5
RCONH2 ¾¾® RCN + H2O
Heat
3. Hofmann degradation of amides. On treatment with bromine in basic solution, unsubstituted amides are
degraded to amines with one carbon atom less. This is a useful method for the preparation of 1° amines,
and discussed in detail in amines.
RCONH2 + Br2 + 4OH– ¾¾® RNH2 + 2Br– + CO32– + 2H2O
4. Conversion to imides. Compounds containing acidic as well as amide group in the same molecule at the
two ends when heated, lose a molecule of water and produce a cyclic compound in which two acyl groups
have become attached to nitrogen ; such compounds are called imides.
O
CONH2 +
CONH2
2NH 3 H
O ¾¾® ¾®
– +
COO NH 4 COOH
O
Phthalic anhydride Phthalamic acid
heat, 300°C

N
H
3 ,h at
ea he
t
O

NH

O
Phthalimide
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1. (a) Outline all steps in the synthesis of succinimide from succinic acid.
(b) Outline an efficient synthesis of 1-propanamine from butanoic acid.
2. Arrange the following in decreasing order of acidity : Benzamide, phthalimide and ammonia.
3. Give structure of the product obtained by acidic hydrolysis of each of the following amides.

O
H O
N
(a) N, N-Dimethylacetamide (b) HOOC. CHNHCO CHNH2 (c) (d)
½ ½ NH
N O
CH3 C2 H5 H
4. Arrange the following amides in increasing ease of base-promoted hydrolysis.

NHCOCH3 NHCOCH3 NHCOCH3 NHCOCH3

NO2
NO2
I II III IV

5. How do amides (1°, 2° and 3°) react (a) with organometallic reagents ; and (b) with nitrous acid.
6. Give the products of reactions of LiAlH4 with
(i) C6H5CH2COOCH3 (ii) (CH3CO)2O (iii) C6H5COCl (iv) CH3CH = CHCH2CONHC6H5

O
H3C

(v) O (vi) NHCOCH 3 (vii) O

O
O

18.5 Cyclic Esters or Lactones

Certain hydroxy acids have the capacity to form cyclic esters, also known as lactones. This intramolecular
esterification takes place spontaneously and is especially favourable when the ring formed is 5- or 6-membered. Lactones
containing 5- and 6-membered cyclic esters are referred to as g-lactones and d-lactones respectively, because these are
derived from the corresponding (g- or d-) hydroxy carboxylic acids.

+
O H + H2O
¾¾® O
OH OH O
g-Hydroxybutyric acid g-Butyrolactone

O O
OH + O
OH H + H 2O
¾¾®
d-Hydroxyvaleric acid g-Valerolactone

A lactone is named by replacing the -oic acid ending of the parent carboxylic acid by -olide and identifying its
oxygenated carbon by number. Thus g-butyrolactone and d-valerolactone may be named as 4-butanolide and 5-pentanolide,
respectively.
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Reactions that are expected to produce hydroxy acids often yield the derived lactones provided a 5- or 6-
membered ring can be formed, e.g.

O OH
½½ (i) NaBH 4 ½
(a) CH 3 CCH 2 CH 2 CH 2 COOH ¾¾¾® + CH3 CHCH2 CH2CH2 COOH ¾¾® O
5-Oxohexanoic acid (ii) H 3 O
5-Hydroxyhexanoic acid O
(d -Hydroxy carboxylic acid)
CH 3
A 5-hexanolide

O OH
½½ Ni/H 2 ½
(b) CH 3 CCH 2 CH2 COOH ¾¾® CH3 CHCH2CH2 COOH ¾¾®
200 ° C O
A g-hydroxy carboxylic acid
CH3 O

OH OH
½ CH = CH H3O
+
H 2/Lindlar
(c) CH 3 CHCH2 C º CCOOH ¾¾¾¾® CH3CHCH2 ¾¾® O
catalyst COOH O
cis-Alkene
CH3
A d -hydroxy carboxylic acid

O é CH3 ù
½½ (i) 1 CH 3MgBr ê | ú H3C
(d) CH3 CCH 2 CH2COOCH3 ¾¾¾¾¾® +
ê CH 3 CCH 2 CH 2 COOH ú ¾¾¾¾®
(ii) H 3O ê | ú ¾ CH 3OH H3C O O
ë CH3 û
A g - hydroxy acid

Remember that a ketonic group is more reactive than an ester toward Grignard reagent.
Lactones whose rings are 3- or 4-membered (a-lactones and b-lactones) are very reactive, making their isolation
difficult. However, if attempt is made to prepare a b-lactone from a b-hydroxy acid, b-elimination usually occurs forming
a, b-unsaturated acid.

OH
½ H + or heat
RCHCH 2 COOH ¾¾¾¾® RCH = CHCOOH + H2O

Similarly, when a-hydroxy acids are heated, they form cyclic diesters called lactides.

O
OH C O
½ heat
2RCHCOOH ¾¾® RCH CHR
a -Hydroxy acid
O C
O

A lactide (cyclic diester)

Lactones react nearly in the same way as ester, e.g.
–
OH –
(i) O COO
+
O H OH
d-Valerolactone d-Hydroxypentanoate
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NH 3
(ii) d-Valerolactone ¾¾® HOCH2CH2CH2CH2CONH2

CH 3 OH/H 2 SO 4
(iii) d-Valerolactone ¾¾¾¾¾¾® HOCH2CH2CH2CH2COOCH3

(i) LiAlH 4
(iv) d-Valerolactone ¾¾¾¾® HOCH2CH2CH2CH2CH2OH
(ii) H 2 O

Like esters, lactones (cyclic esters) are inert to NaBH4

(i) THF
(v) O + BrMg(CH2)3 MgBr ¾ ¾ ¾ ¾+ ®
O (ii) H3O

OH CH2CH2OH

Ester group reacts with both parts of Grignard reagent forming a diol.

18.6 Analysis of Carboxylic Acid Derivatives

1. Carboxylic acid derivatives are recognized by their hydrolysis products. We know that the ease of hydrolysis of
the four products follows the following order.
Acid chlorides > Acid anhydrides > Esters > Amides
(hydrolyzed by water) (hydrolyzed when heated (hydrolyzed when
briefly with NaOH) refluxed with NaOH)

2. Saponification equivalent of ester. An ester is hydrolyzed with excess, but known amount of base, and the
amount of base used is measured and used to give the saponification equivalent ; the equivalent weight of the
ester, which is similar to the neutralization equivalent of an acid.

RCOOR¢ + OH - ¾¾® RCOO– + R¢OH

One equivalent One equivalent

However, unlike neutralization equivalent, saponification equivalent of esters is less useful in identification of
esters because of great number of possible combinations of the two alkyl groups present in an ester, RCOOR¢.

1. Identify each type of acid derivative which responds following test :

(a) gives white precipitate insoluble in nitric acid, on treatment with alcoholic silver nitrate.
(b) gives ethyl alcohol when heated with acid or base.
(c) gives only propanoic acid on hydrolysis.
(d) reacts immediately with cold NaOH to liberate a gas that turns moist litmus paper blue.
(e) reacts with boiling NaOH and produce a gas that turns moist red litmus paper blue.
2. What is the saponification equivalent of n-propyl acetate ? Is this equivalent possible for any other ester or carboxylic acid ? Give
their structures.
3. (a) What is the saponification equivalent of methyl phthalate ?
(b) What is the relation between saponification equivalent and the number of ester groups per molecule ?
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18.7 Illustrative Examples

Example 1 :
Identify the braketed compound(s) in the following reactions :
CH2CO
AlCl Zn(Hg) SOCl 2 AlCl
(i) + O ¾¾¾3¾
® [A] ¾¾¾¾ ® [B] ¾¾¾¾ ® [C] ¾¾¾3¾ ® [D]
CH2CO HCl

H2 /Pt H SO , heat Pt, heat

¾¾¾¾ 2 4
® [E] ¾¾¾¾¾¾® [F] ¾¾¾® [G] + H2

COOH COOH
heat COOH heat
(ii) COOH ¾¾® [A] + [B] (iii) ¾¾® [A] + [B]
COOH
COOH
O O
NaBH 4 H 2 SO 4 heat C6H 5 CO 3H
(iv) ¾¾¾® [A] ¾¾® [B] (v) Calcium adipate ¾¾® [A] ¾¾¾¾® [B]
heat
OH

CH 3 OH PCl 5 CH 3 NH 2 NH 3 heat
(vi) O ¾¾¾® [A] ¾¾® [B] ¾¾¾® [C] (vii) Phthalic acid ¾¾® [A] ¾¾® [B]
300° C

3 2CH COOH heat (i) excess of CH 3 Mg Br

(viii) CH º CH ¾¾¾¾® [A] ¾¾® [B] (ix) [A] ¾¾¾¾¾¾¾¾¾® 2, 3-Dimethyl-2-butanol
(ii) H3 O +

Hg 2 +/H 2SO 4 Al (OC2 H 5 )3 C 2H 5 ONa

(x) CH º CH ¾¾¾¾¾® [A] ¾¾¾¾¾® [B] ¾¾¾¾® [C]
Solution :

(i) ; ; ;

HOOC HOOC ClOC

O
[A] [B] [C] [D]

; ;

H OH
[E] [F] [G]

COOH COOH
heat heat CO
(ii) ¾¾¾® ¾ ¾¾ ® O
COOH (—CO2 ) ( —H2O )
COOH COOH
cis- and trans- cis- and trans-Anhydride
Cyclohexane-1, 2-dicarboxylic acid [A] and [B]
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O
COOH
C

(iii) O
C
COOH
O
trans-1, 2-Cyclobutane-dicarboxylic acid cis-Anhydride
[A] [B]
Remember that unlike above reaction, trans-dicarboxylic acid cannot form the anhydride because a 5- and 4-
membered ring cannot be fused trans.
OH O

(iv) O
OH O
[A] [B]

(v) O (through Baeyer-Villeger reaction)

O

[A] [B]

O O O

OCH3 OCH3 OCH3

(vi)
OH Cl NHCH3

O O O
[A] [B] [C]

O
COONH4
(vii) NH
COONH4
O
[A] [B]

(viii) CH3CH(OCOCH3)2 CH3CHO

[A] [B]
(ix) Recall that tert-alcohols (2, 3-dimethyl-2-butanol) are formed by the action of excess of Grignard reagents on
esters. Hence the compound A should be an ester. Now further recall that in the tert-alcohol, two identical alkyl
groups are introduced by the alkyl group of the RMgX, so the third alkyl group (which may be different or
identical) is coming from the acidic moiety to the ester. So here first examine the structure of the tert-alcohol and
then write down the structure of the ester.

OH O
½ (i) 2CH 3 MgBr ½
½
CH 3 ¾ C ¾ CH ¾ CH3 ¬¾¾¾¾¾ +
RO — C ¾ CH ¾ CH 3
½ (ii) H3 O ½
½
CH3 CH3 CH3
2, 3-Dimethylbutanol-2 [A]

Tischenko Claisen
(x) CH 3 CHO ¾¾¾¾® CH 3 COOC2H 5 ¾¾¾¾®
condensation
CH 3 COCH 2 COOC2 H 5 .
reaction
[A] [B] [C]
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Example 2 :
Give steps involved in the following reactions :
(i) C2H5OH to CH3CN (ii) C6H5CH3 to p-NO2C6H4CN
(iii) C6H5CH3 to p-NO2.C6H4.CH2CN (iv) C6H5CH3 to C6H5CH2CN
(v) C6H5CH2CH2COOH to 1-Phenylpropane.
Solution :

Cr2 O 7 2 -/H+ 5 PCl (i) NH 3

(i) C2H5OH ¾¾¾¾® CH3COOH ¾¾® CH3COCl ¾¾¾® CH3CN
(ii) P2 O 5

CH3 CH3 COOH CONH2 CN

–
Conc. HNO3 MnO4 (i) SOCl2 P2O5
(ii) ¾ ¾¾ ¾ ¾ ® ¾¾¾ ® ¾¾¾¾® ¾¾®
+
Conc. H2 SO4 H (ii) NH3

NO2 NO2 NO2 NO2

CH3 CH3 CH2Br CH2CN

–
Nitration NBS CN
(iii) ¾¾¾¾® ¾¾® ¾¾®

NO2 NO2 NO2

CH3 CH2Br CH2CN

–
NBS CN
(iv) ¾¾¾® ¾¾®

LiAlH 4 H 2SO 4 H 2/Pt

(v) C6H5CH2CH2COOH¾¾¾® C6H5CH2CH2CH2OH ¾¾¾® C6H5CH2CH = CH2 ¾¾® C 6 H 5 CH 2 CH 2 CH 3
( ¾ H 2O) 1-Phenylpropane

Example 3 :
Prepare 2-methylbutanoic acid from ethanol as the only organic compound, of course you can use inorganic reagents;
you require.
Solution :

CH3CH2OH
½Oxidation
½
¯
3PBr Mg in (i) CH3CHO
C2H5OH ¾¾® C2H5Br ¾¾® C2H5MgBr ¾ ¾ ¾ ¾+® C2H5CHCH3
ether (ii) H3O
½
OH

PCl (i) CO 2
3 Mg
¾¾® C2H5 CHCH 3 ¾¾® C2H5 CHCH3 ¾¾¾® C2H5 CHCH3
(ii) H 3 O+
½ ½ ½
Cl MgCl COOH
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Example 4 :
Give all steps involved in the following conversions.

CH2OH

¾ ¾¾ ®

COOH COOH

Solution :
The conversion involves simply addition of water molecule in anti-Markovnikov way which can best be achieved by
the use of BH3. THF. However, this reagent also reacts with —COOH group so the latter must first be protected which
is done by converting it into —COOCH2C6H5.

CH2OH CH2OH

(i) SOCl2 BH3 .THF H2

¾ ¾¾ ¾ ¾ ¾ ® ¾¾¾¾® ¾¾®
(ii) C6H5CH2OH Pd/C

COOH COOCH2C6H5 COOCH2C6H5 COOH

Note that tert-butyl group can’t be used as a protective group in place of —CH2C6H5 group because its removal as
isobutene requires H+ which would dehydrate the —CH2OH group giving back the starting material.

Example 5 :
Give reaction(s) involved in the conversion of (CH3)3CCHOHCH3 to (CH3)3 CCH = CH2.
Solution :
Although the reaction seems to be achieved simply by dehydration, but in such case a 2° carbocation would be
formed as an intermediate which will rearrange to 3° carbocation and thus the major product would be
(CH3)2 C = C(CH3)2 . To avoid this, pyrolyze the acetate ester of the given alcohol.
CH 3 COCl heat
(CH3)3CCHOHCH3 ¾¾¾¾® (CH3)3C CHCH3 ¾¾¾¾¾® (CH3)3CCH = CH2
( ¾ CH 3 COOH)
½
OCOCH3

Example 6 :
Give steps involved in the following conversion :

¾¾¾®
OC2H5 OH
O O
Solution :
The reaction involves simply conversion of —COOC2H5 to —CH2OH, which can be easily accompanied by reducing
either —COOC2H5 or —COOH to —CH2OH by means of LiAlH4. However, since LiAlH4 also reduces ketonic group so
it should first be protected. Hence the various steps are as follows.
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O O
+ OH
H3O
OH
¾¾® ¾¾¾®
OC2H5 OH
O O
O
(i) LiAlH4
¾ ¾ ¾ ¾+®
OH (ii) H3O
OH
O O O

Example 7 :
Give steps involved in the following conversion :

O OH
COOCH3
(CH2)5 into
COOCH3

Solution :
Note that the product is a tert-alcohol which is prepared by the interaction of an ester with excess of RMgX which here
must be CH3CH2MgX because the tert-alcohol has two CH3CH2— groups ; the third alkyl group here is substituted
cyclohexyl. Further, recall that esters of dicarboxylic acids can be converted into cyclic b-keto esters by means of
Dieckmann reaction (intramolecular Claisen condensation). Thus the various steps can be written as below.

O O
– COOCH3
OCH3 (i) OC H CH OH.CH OH
¾ ¾ ¾2 +¾5 ® ¾ ¾2 ¾ ¾ ¾¾
2
®
COOCH3 (ii) H (protection of
the keto group)

O
O O OH
COOCH3
(i) C2H5 MgBr
¾ ¾ ¾ ¾ ¾+¾ ®
(ii) H3O

Example 8 :
Explain the products formed by the pyrolysis of
(a) CH3CH2COOCH2CH2CH2CH3 (b) CH3COOCH(CH3)CH2CH3
Solution :
The reaction is believed to proceed through a cyclic six-centre transition state, and involves simultaneous syn-elimination
of a b hydrogen of the alcohol and the acetoxy group.

O O
O
(a) CH3CH2C CH2 CH3CH2C CH2
heat
¾¾® CH3CH2C + CH3CH2CH = CH2
O CCH2CH3 O CCH2CH3
H H OH
H H
Transition state
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O
(b) CH3C CHCH3
OH
½½ ½
O C heat
¾ ¾ ¾ ® CH3C + CH3CH = CHCH3
H ½
H CH3 O
2-Butene
Two b -H¢s are present

(OR)
O
CH3C CHCH2CH3
OH
½½ ½
O C ¾¾¾®
heat
CH3C + CH3CH2CH = CH2
H ½ H
H OH
1-Butene
Three b -H¢s are present

Since there are two b-hydrogens that may be eliminated to give 2-butene and there are three b-hydrogens
which may lead to 1-butene, hence 2-butene and 1-butene are formed in 2 : 3 ratio.

Example 9 :
Trimyristin (C45H86O6), obtained from coconut oil, when heated with aqueous sodium hydroxide followed by
acidification, gives glycerol and tetradecanoic acid as the only products. Can you assign a structure to trimyristin?
Solution :
Molecular formula and hydrolysis products of trimyristin indicate that it is a triester of glycerol with tetradecanoic
acid, CH3(CH2)12COOH.

O O
½½ ½½
CH3(CH2)12CO OC(CH2)12CH3
OC(CH2)12CH3
½½
O

Example 10 :
Alar (C6H12O3N2), a growth regulator for apples, itself is harmless but on hydrolysis it gives a dicarboxylic acid
[X] of molecular formula C4H6O4 and a carcinogenic compound, unsymmeterical dimethylhydrazine (UDMH).
Compound X on heating yields an anhydride. Assign structure to alar.
Solution :

Alar H 2O
¾¾® C 4 H 6 O 4 + H 2 NN(CH 3 )2
C 6 H12 O 3 N 2
X UDMH
(i) Since alar, on hydrolysis, gives a carboxylic acid and a substituted amine, it must be an amide.
(ii) The dicarboxylic acid (X), C4H6O4 on heating gives an anhydride, the two —COOH groups must be present
on different carbon atoms, so X should be succinic acid. Hence alar should be an amide of succinic acid and
UDMH.

2 H O
HOOCCH 2 CH 2 COOH + H2 NN(CH3 )2 ¬¾¾ HOOCCH2 CH 2 CONHN(CH 3 )2
Succinic acid, X UDMH Alar
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Example 11 :
An organic compound (A) of the formula C5H10O is treated with perbenzoic acid to form compound (B) of the
formula C5H10O2. Compound (B) on acidic hydrolysis gives acetic acid and an alcohol (C) which responds haloform
tert. Identify compounds (A) to (C).
Solution :

C6 H 5 CO 3 H
H +
C5H10O ¾¾¾¾® C5H10O2 ¾¾® CH3COOH + RCHOHCH3
[A] [B]
Given reactions indicate that compound [B] is an ester of acetic acid and the alcohol RCHOHCH3, so B (C5H10O2)
should be an ester of the formula CH3COO CHCH3 or CH3COO CHCH 3 ; hence [A] should be a ketone. Recall that
½ ½
R CH3
ketones when treated with per acids give esters (Baeyer-Villeger oxidation).

RCO3 H
CH3COCH(CH3)2 ¾¾¾® CH3COOCH(CH3)2 ¾¾® CH3COOH + HOCH(CH3)2
[A], C5H10O [B], C5H10O2 [C], responds
haloform test

Example 12 :
An organic ester (A) of the formula C8H16O2 reacts with phosphorus pentachloride and gives two compounds (B)
and (C) . When (B) is treated with palladised-hydrogen supported over barium sulphate, it gives another
compound (D) which on reduction with LiAlH4 forms a primary alcohol (E) of the formula C4H10O ; E can also be
produced from (C), which has a branched alkyl group, by reaction with aqueous sodium hydroxide. Identify
compounds (A) to (E) and explain the reactions involved.
Solution :
Let us summarise the given facts
PCl
(A) ¾¾¾
5
® (B) + (C) ¾ ¾ ¾ ¾ ¾
Ester, C8H16 O2
½ H2/Pd, aq. NaOH
½ BaSO4
¯ LiAlH4
(D) (E)
(i) Since the given compound (A) is an ester, with PCl5 it will form an acid chloride and alkyl halides which are (B)
and (C).
O O
½½ ½½
R ¾ C ¾ O ¾ R ¢ + PCl5 ¾¾® R¾ C ¾ Cl + R¢—Cl + POCl3
A B and C
(ii) The given statement indicates that the compound (B) is reduced by Rosenmund reduction (specific reduction for
acid chloride), so (B) should be acid chloride and (C) should be alkyl chloride. Now let us write down the given
reactions of (B).
O O
½½ H 2/Pd ½
½ LiAlH 4
R ¾ C ¾ Cl ¾¾® R¾ C ¾ H ¾¾¾® RCH 2OH
(B) BaSO 4 (D) (E), C 4H10 O

So (E) can now be written as C3H7CH2OH.

(iii) Nature of (C) as an alkyl halide is confirmed by its conversion to (E), a primary alcohol by reaction with aq.
NaOH.

aq. NaOH
(C) ¾¾¾® RCH 2 OH
(E), C 4 H 10 O
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Hence the structure of (C) can be expanded as RCH2Cl or C3H7CH2Cl. Since (C) has a branched alkyl group, it
should be (CH3)2CHCH2Cl and thus (E) as (CH3)2CHCH2OH.
(iv) Now going backward, we can write the structure of (D), (B) and hence (A).

LiAlH 4 2 H /Pd
(CH 3 )2 CHCH 2 OH ¬¾¾¾ (CH 3 )2 CH.CHO ¬¾¾ (CH 3 )2 CHCOCl
(D) BaSO 4 (B)
(E)

O
PCl 5 ½½
2 (CH 3 )2 CHCOCl + ClCH 2 CH(CH 3 )2 ¬¾¾ (CH 3 )2 CHCOCH 2 CH (CH3)2
(B) (C) A, C8 H16 O 2

Example 13 :
A reaction mixture of (±)-2-phenylpropanoic acid on esterification with (+) -2-butanol gives two esters. Mention the
stereochemistry of the two esters produced.
Solution :

COOH COOH

H C6H5 + C6H5 H Enantiomers

CH3 CH3

2-Phenylpropanoic acid

½ (+) – CH3CHCH2CH3
½ ½
¯ OH

CH3 CH3
½ ½
COOCHCH2CH3 COOCHCH2CH3

H C6H5 + C6H5 H Diastereomers

CH3 CH3
(+)-(+)-Ester (–)-(+)-Ester

Example 14 :
Although alcohols are neither acidic enough nor basic enough to form stable salts, these are frequently resolved.
Outline the steps used for resolving racemic mixture of sec-butyl alcohol using (+)-base as a resolving agent.
Solution :
Although alcohols, themselves, are not strong acids or bases, these are converted into acidic compounds (alkyl hydrogen
phthalate) on reaction with phthalic anhydride. The enantiomers of the racemic modification of alkyl hydrogen
phthalate, being acidic, react with an optically active base to form diastereomeric salts which can be separated by
fractional crystallisation (remember that enantiomers have similar solubility while diastereomers have different
solubilities). The two separated diastereomers are then hydrolyzed to give optically active alcohols. Since hydrolysis of
a carboxylic ester does not usually involve cleavage of the alkyl-oxygen bond, there is no loss of optical activity in the
hydrolysis step.
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O + (± ) – ROH

O
Phthalic anhydride
½
½
¯
COOR(+) COOR(–)
+ Enantiomers

COOH COOH
½
(+) – B (An optically active base)
½
¯
COOR(+) COOR(–)
+ Diastereomers
– + – + (separable by fractional
COO (+) – BH COO (+) – BH crystallisation)

Resolve by fractional
crystallisation
½ OH– ½ OH–
¯ ¯
– –
COO COO
+ (+) – ROH ; + (–) – ROH
COO– COO–

Example 15 :
When benzoic acid is esterified by methanol in presence of a little sulphuric acid, the final reaction mixture
contains five substances : benzoic acid, methanol, water, methyl benzoate and sulphuric acid. Outline a procedure
used for the separation of the pure ester (methyl benzoate).
Solution :
H 2 SO 4
C6H5COOH + CH3OH ¾¾® C6H5COOCH3 + H2O
(i) The mixture containing five substances, viz. C6H5COOCH3, H2O (formed as products), C6H5COOH, CH3OH
and H2SO4 (left as residual amounts) is shaken with benzene which dissolves only methyl benzoate and
benzoic acid ; while the other three substance (CH3OH, H2O and H2SO4) remain in water layer.
(ii) Benzene extract is now treated with aq. Na2CO3 which converts benzoic acid to water soluble sodium benzoate
which is thus removed as water layer.
(iii) Benzene layer containing methyl benzoate and some residual water is distilled when benzene and water
distils over first, followed by distillation of methyl benzoate at high temperature (200°C).

Example 16 :
Identify the bracketed compounds from [A] to [D] in the following sereies of reactions.

2 3 K CO aq. 2 (i) HCN -H O

Me 2 CHCHO + HCHO ¾¾¾¾¾® [A] ¾¾¾¾® [B] ¾¾¾¾® [C]
+
(ii) H 3 O

2 H NCH CH CONHCH CH SH
2 2 2 2 aq. NaOH
¾¾¾¾¾¾¾¾¾¾¾¾¾® [D] ¾¾¾¾¾® Products
heat
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Solution :
Me2C CHOH
CH2OH
|
CH2OH CH2OH
| | H2C C=O Me 2 C - CH - CONHCH 2CH 2 CONHCH 2 CH 2SH
|
Me 2 CCHO Me2 C CHOHCOOH O OH
(A) (B) (D)
(from crossed aldol (C)
condensation)

CH2 OH
|
Me 2 C - CHCOO- + H 2 NCH 2 CH 2 COO- + H2 NCH2 CH 2 S -
|
OH
Products

Example 17 :
Write stereochemical formulas for the compounds A to G.
-
(a) cis-3-Methylcyclopentanol + C6 H 5 COCl ¾¾ OH
® [A] ¾¾¾® [B]
reflux
-
OH
(b) cis-3-Methylcyclopentanol + C6 H 5 SO 2 Cl ¾¾
® [C] ¾¾¾® [D]
heat
acetone
(c) (R)-2-Bromoheptane + OH– ¾¾¾¾® [E]

2 OH - , H O
(d) (R)-2-Bromoheptane + CH3COONa ¾¾
® [F] ¾¾¾¾¾® [G]
reflux
Solution :
H H H H H H H OH
(a) (b)
H3C OCOC6H5 H3C OH H3C OSO2C6H5 CH3 H
cis -(A) cis -(B) cis -(C) trans -(D)

H – H
OH , heat
(c) C – Br (inversion)
HO – C
C5 H11 C5 H11
CH3 CH3
(E)

H – + –
CH3COO Na H OH , heat H
(d) C – Br (inversion) AcO – C reflux HO – C
C5 H11 C5H11 C5H11
CH3 CH3 CH3
(F) (G)

Example 18 :
Esters (or carboxylic acids), and amides have two major resonance contributors, one of which involves charged
structures.
.. ..– .. ..–
O: :O: O: : O:
C .. C + C .. C +
R OCH
.. 3 R OCH
.. 3 R NH2 R NH2
Account for the fact that the charged structure in amides has a significant contribution than in esters or in
carboxylic acids.
Solution :
In amides, positive charge resides on a lesser electronegative element (N) than that in esters or carboxylic acids
where positive charge is present on a more electronegative element (oxygen).
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Example 19 :
Arrange the following compounds in order of their decreasing boiling points.
Carboxylic acids, alcohols, esters, amides, nitriles
Solution :
For knowing the relative boiling point of different compounds of comparable molecular weights, consider following
factors, dipole-dipole interaction, hydrogen bonding, van der Waal forces, etc. Here no specific compounds are given,
so it is assumed that the vander waal forces are nearly similar in each case, hence other two factors are responsible for
their following relative boiling points.
Amides > carboxylic acids > alcohols » nitriles >>> esters.
(i) Boiling points of esters are lower than the boiling points of alcohols because their molecules can't form hydrogen
bonds with each other. However, boiling points of esters (also for acyl chlorides, aldehydes, and ketones) are higher
than those of ethers because of polar carbonyl group. Further, due to resonance polarity is less than in nitriles.
(ii) Boiling point of nitriles are similar to that of alcohols becasue the former have a strong dipole-dipole interactions,
while alcohols have strong hydrogen bonds.
(iii) Carboxylic acids have relatively high boiling points than alcohols because they can form hydrogen-bonded
dimers, giving them larger effective molecular weight.
(iv) Amides have the highest boiling points, because here the dipole-dipole interactions are strong than in nitriles
because here dipole-dipole interaction involves separated complete charges (recall that in an amide resonating
structure having separated charges contribute significantly to the hybrid).
Dipole-dipole Intermolecular Dipole-dipole
interaction hydrogen bond interaction
d– d+
+ R
Nº C – R
O HO R 2N = C
R–C C–R O–
R –C º N
d+ d– OH O –O
C = NR2
R +
Nitriles, RC º N Carboxylic acids, RCOOH Amides, RCONR2

Further if an amide has a hydrogen, bonded to nitrogen as in RCONH2 or RCONHR, the molecules also form
intermolecular hydrogen bonds.

Example 20 :
Predict the products in the following reaction with proper explanation.
O
C – OCH3
H3C CH3 – 18 18
OH, H2O
A + B

CH3
Methyl mesitoate

Solution :
Although base promoted hydrolysis of an ester involves the attack of –OH on the carbonyl carbon to form a tetrahedral
intermediate which is then converted to carboxylic acid and alcohol. Here it is not so, steric hindrance due to two
ortho-methyl groups prevents formation of the tetrahedral intermediate; and thus the nucleophile attacks on the
alkyl carbon of the alcoholic portion instead of the acyl carbon of the acidic portion leading to alcohol having –OH
provided by nucleophile.
O O
–18 –
C – O – CH 3 + OH C–O
H3C CH3 18 H3C CH3 18
H2O
+ CH3 – OH

CH3 CH3
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EXERCISE 18.1 (MCQ - ONE option correct)

1. Bouvealt-Blanc reduc tion of an ester (CH 3 COOC 2 H 5 7. Predict the nature of the product P in the following reaction:
Na/C2 H 5OH dil . NaOH
¾¾¾¾¾¾® C 2H5OH) involves
(+)-C6H5 CHCH = CHCH3 ¾¾¾® P
(a) reduction by H2
½
(b) reduction by nascent H OCOC2H5
(c) electron transfer from Na to C = O
(d) none of the three. OH
½
2. Benzoic anhydride is formed according to following reaction
(a) (+) – C6H5 CHCH = CHCH3
C6H5COCl + C6H5COONa ¾¾® C 6H5COOCOC6H5 + NaCl
Here the nucleophile is provided by OH
(a) C6H5COCl ½
(b) C6H5COONa (b) (±) – C6H5 CHCH = CHCH3
(c) either of the two
(d) It is not an example of nucleophilic substitution. OH
½
3. Which of the following is different regarding nucleophilic
(c) (+) – C6H5CH=CH CHCH3
substitution ?
(a) CH3COCl + CH3COONa ¾¾® CH3COOCOCH3 OH
(b) CH3COONa + CH3CH2Br ¾¾® CH3COOCH2CH3 ½
H
+ (d) (±) – C6H5CH = CH CHCH3 .
(c) CH3COOC2H5 ¾¾® CH3COOH + C2H5OH 8. Aspartame, an artificial sweetening agent, has following structure
(d) CH3COOCOCH3 + CH3OH
Å
¾¾® CH3COOCH3 + CH3COOH COOCH3 N H3
4. Which of the following ester can be used as acylating agent in ½ ½ Q
mixed Claisen condensation ? C6H5CH2 CHNHCO CHCH 2COO .
O
On hydrolysis with dil. HCl, it will give
½½
(a) H ¾C ¾ OCH3 (a) three neutral molecules.
(b) one neutral molecule and two molecules as cations
O (c) two neutral molecules and one molecule as cation.
½½
(b) C6 H 5 ¾C ¾ OCH 3 (d) three molecules, all in the form of cations.
9. Unlabelled 4-butanolide is allowed to stand in an acidic solution
O O in which water has been labelled with O 18. When the lactone is
½½ ½½ extracted from the solution after 4 days, what will you expect ?
(c) C2H5O ¾ C ¾C ¾ OC2H5
(a) Both oxygen of 4-butanolide should have O18
(d) All
(b) Only carbonyl oxygen should have O 18
5. The product P in the following reaction will be
(c) Oxygen other than carbonyl group should be O 18
CH MgBr (excess)
3 (d) Both oxygen should have O 16.
Ethyl ester ¾¾¾¾¾¾¾¾
®P
10. An ester molecule reacts with two eq. of a Grignard reagent and
forms
(a) (b)
(a) a 3° alcohol having at least two identical alkyl groups.
(b) a 3° alcohol having all the three identical alkyl groups.
(c) a 2° alcohol having both identical alkyl groups.
(d) both (a) and (c).
(c) (d) 11. Hydrolysis of an ester may be achived under acidic as well as
basic conditions. Pick up the correct statement regarding this
(a) Acidic hydrolysis is faster than alkaline hydrolysis.
(b) Alkaline hydrolysis is faster than acidic hydrolysis.
(c) Both occur at the same rate.
6. Predict the nature of B. (d) In both, the first step is protonation of the —OH part of
heat Li Al H 4 the —COOH group.
H2NCH2CH2CH2COOH ¾¾® A ¾¾® B
12. In an ester molecule there are three C—O bonds,
(a) H2NCH2CH2CH2CH2OH
(b) CH2 = CHCH2CH2OH O
(c) CH3CH2CH2CH2OH ½½ b
g a
R ¾ C ¾ O ¾ R¢. What do you expect regarding their relative
(d) bond lengths ?
(a) a>b>g (b) b=g>a
(c) g>b>a (d) a = b = g.
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13. C2H5COOCH3 + 18OH– ¾¾® A + B 18. An enantiomerically pure acid is treated with racemic mixture
In the above reaction, products A and B respectively are of an alcohol having one chiral carbon. The ester formed will be
(a) optically active mixture
O
½½ (b) pure enantiomer
18
(a) C2H5 C ¾ O– + CH3 O H (c) meso compound
(d) racemic mixture.
O 18 -
½½ 18 19. Reactivity order of different nucleophiles (OH–, O COCH3 and
(b) C2H5— C ¾ O – + CH3OH NH2–) toward RCOCl + : Z ¾¾® RCOZ + Cl– is
(a) OH– > –OCOCH3 > NH2–
O –OCOCH – > NH –
(b) 3 > OH 2
½½ 18
(c) C2H5— C ¾ O – + CH3OH (c) NH2 > OH > –OCOCH3
– –
(d) OH– > NH2– > –OCOCH3.
O 18 20. Acidic hydrolysis is minimum in
½½
(d) C2H5— C ¾ O– + CH3OH
14. In the following reactions, X and Y are
(a) (b)
Y

(a) X is and

(c) (d)
Y is

(b) X is and
21. Which of the following amide undergoes alkaline hydrolysis
most easily ?
Y is

(c) Both are

(a) (b)

(d) Both are

15. Acetic acid is dissolved in water having oxygen as O 18, What do

you expect about the resulting acetic acid ? It should be
(c) (d)
O O
½½ ½½
(a) CH3 C ¾ OH (b) CH3— C ¾ O18 H

O 18 O 18
½½ ½½ 22. A keto lactone is reduced by different reagents to give A and B
(c) CH3— C ¾ OH (d) CH3— C ¾ O18 H.
16. When butyramide is boiled with aqueous NaOH and then
acidified, the resulting product contains
LiAlH 4 NaBH 4
(a) CH3CH2CH2COO– + NH3 [B] ¬¾¾¾ ¾¾¾® [A]
(b) CH3CH2CH2COO – + NH4+ + Cl– CH 3OH
(c) CH3CH2CH2COONa + NH3
(d) CH3CH2CH2COOH + Na+ + Cl–.
17. The product of acid hydrolysis of P and Q can be distinguished
by Here [A] and [B] respectively are

(a)

(a) Lucas reagent (b) 2, 4-DNP

(c) Fehling solution (d) NaHSO3.
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26. Predict the nature of the product P in the following reaction.

(b)

(a) (b)
(c)

(c) (d)

27. Give the structure of the compound A formed in the following

reaction.
(d) in both cases

(i) 1 CH 3CH 2MgI

¾¾¾¾¾® A
( ii) H 3 O +

(i) H + / H 2 O
23. ¾¾¾® Z. Here Z is
( ii) heat

(a)

(a) (b)

(b)

(c) (d)

(c)
24. Lactones A and B are respectively named as

(A) (B)
(d)

(a) g-Pentanolactone, 2-methylbutyrolactone

(b) g-Butyrolactone, 2-methyl-g-butyrolactone
(c) g-Butyrolactone, b-Butyrolactone
(d) a-Pentanolactone, 2-methyl a-butyrolactone.
25. Which of the following represents the structure of g - 28.
pentanolactone ?

(a) (b)

Here R and R¢ respectively are

(c) (d) (a) Pt/ H2, H3O+ (b) H2/Pd, H3O+
(c) Li/NH3, H3 O + (d) Ni/H2.
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29. Predict the respective compounds A and B in the following 35. Which of the following reaction is possible ?
reaction :
(i) CH 3COCl + H 2O ® CH 3COOH + HCl
C 6 H 5 CO 3 H H 3 O+
CH3CH2COCH3 ¾ ¾¾¾® [ ] ¾¾® A + B (ii) CH 3COOCH3 + HBr ® CH 3COBr + CH 3OH
(a) CH3CH2COOH, CH3OH
(iii) CH 3CONH 2 + HBr ® CH 3COBr + NH 3
. (b) CH3CH2COOH, CH3COOH
(c) CH3CH2OH, CH3COOH (iv) CH 3COOCOCH 3 + H 2O ® 2CH 3COOH
(d) CH3CH2COCH3, C6H5COOH.] (a) (i) and (iv) (b) (i), (iii) and (iv)
(c) (i), (ii) and (iv) (d) All the four
30. In the given series of reactions, the final product D is
36. Acid amides do not undergo the usual properties of carbonyl,
P2 O 5 (i) CH 3 MgI Ca(OH) 2 / I 2 C = O group because
¾¾® [A] ¾¾¾¾® [B] ¾¾¾¾® [C]
+
(ii) H 3 O (a) it is a weak base
(b) it is a weak acid
(c) it is amphoteric
heat
¾¾® [D] (d) its carbonyl carbon is not electron deficient
37. Which of the following will undergo alkaline hydrolysis most
(a) (b) rapidly ?

COOCH3 COOCH3

(c) (d)
(a) (b)

CH3
O
||
31. C2H 5 O - C - OC2H 5 + 2CH 3 MgBr ¾¾
® A ; A is COOCH3 COOCH3

OH OH
| |
(a) (CH 3 )2 C - C2 H 5 (b) C2H 5 - C - CH3 (c) (d)
|
C2H 5
(c) CH3COOH (d) CH3COCH3 Cl NO2
32. Which of the following reagent can be used for carrying out the
reaction outlined below? 38. Hydrolysis of esters in presence of an acid is a reversible reaction,
what is true about ester hydrolysis in presence of a base?
O OH O (a) It is irreversible because salts of carboxylic acids are
Reagent insoluble.
H OC2H5 (b) It is irreversible because salts of carboxylic acids have
(a) BrMgCH2COOC2H5 (b) BrZnCH2COOC2H5 high melting points.
(c) LiCH2COOC 2H5 (d) Any of the three (c) It is irreversible because carboxylate ion is resonance
stabilized.
O (d) It is reversible reaction.
39. Compound A is formed by the interaction of
33. Product . CH3

Here the product is O O

CH2COOH
O O
CH3
[A]
(a) O (b) O

(a) CH3COOH and HO CHO

COOH COOH
(b) CH3CHO and HO COOH
(c) (d)
O COOH OH

34. Acetyl chloride does not react with CHO

(c) CH3COCH2COOH and HO
(a) Water OH
(b) Sodium acetate OH
(c) 2-methylpropene
(d) It reacts with all the three (d) CH3CHO and HO COOH
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40. The yield of ester in esterification can be increased by 45. Which of the following can be used for introducing a ketonic
CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O group in the compound ?
(a) removing water (a) Claisen rearrangement (b) Claisen reaction
(b) taking ethanol in excess (c) Pinacol rerarrangement (d) All the three
(c) taking acetic acid in excess 46. Which statement is true regarding reaction of an acid chloride
(d) all the above factors (RCOCl) and ammonia when taken in 1 : 1 molar ratio?
41. The yield of a cid amide in the reaction, (a) Wholeof acid chlorideisconverted into RCONH2
(b) One-half of acid chloride is converted into RCONH2 and
RCOCl + NH 3 ® RCONH 2 , is maximum when
the other half into RCOONH4
(a) acid chloride and ammonia are treated in equimolar ratio
(c) One-half of acid chloride is converted into RCONH2 and
the remaining half remains unreacted
(b) acid chloride and ammonia are treated in 1 : 2 molar ratio
(d) None of the three is correct
47. Esterification of acid chloride with ethanol is usually carried
(c) acid chloride and ammonia are treated in 2 : 1 molar ratio
out in the presence of pyridine. The function of pyridine is
(d) All the three gives nearly similar result (a) to remove HCl formed in the reaction
(b) to react with acid chloride to form an acylpyridinium ion
COOC2H5 C2H 5ONa
(c) both (a) and (b)
42. Z. Here Z is
COOC2H5 (d) as a catalyst

O O O
(a) (b) C –
COOC2H5 PCl5 LiAlH4 PCC OH
48. O [A] [B] [C] [D]
O O C
(c) (d)
COOC2H5
COOC2H5 O

43. Both aldol and Claisen condensations are given by compounds Compound D is
having a-hydrogen atom to a C = O group. Pick up the – –
compound which responds aldol condensation but not Claisen COO COO
condensation. (a) (b)
COO– CH2O–
CH 3CH 2COOC 2 H 5
I –
COO CH 2OH
(CH 3 ) 2 CHCOOC 2 H 5 (CH 3 ) 3 CCOOC 2 H 5 (c) (d)
II III CH2OH CH 2OH
(a) II (b) III 49. The product of acid hydrolysis of P and Q can be distinguished
(c) II and III (d) None of the three by
44. BrMg MgBr
OCOCH3 H3C
P = H2C Q=
,
+
H O CH3 OCOCH3
+ CH 3 COOC 2 H 5 ® [ ] ¾¾3 ¾
¾® A . Compound A is
(a) Lucas Reagent (b) 2,4–DNP
O
(c) Fehling’s Solution (d) NaHSO3
(a) OH
CH MgBr
Ethyl ester ¾ ¾ ¾ ¾¾® P . The product P will be
3
50.
excess
OH
OH
(b)
(a) (b)
CH3
(c)
OC2H5

CH3
(c) (d)
(d)
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51. An enantiomerically pure acid is treated with a racemic mixture (a) Only II (b) I, II, III and IV
of an alcohol having one chiral carbon. The ester formed will be (c) II, III and V (d) II, III and IV
(a) Optically active mixture (b) Pure enantiomer 58. The reason for greater reactivity of acetyl chloride for
(c) Meso compound (d) Racemic mixture nucleophilic substitution than methyl chloride is due to
52. Which of the following statement is not upto the mark? (i) capability of oxygen to acquire electrons
O O (ii) difference in the nature of carbon of the intermediate: a
|| || tetrahedral in case of acetyl chloride and a pentavalent in
OH -
(a) R - C - OR ¢ ¾¾¾® R - C - O - + R ¢OH case of methyl chloride
(A base-catalysed reaction) (iii) difference in attack of nucleophile on the compound
(b) OH - (iv) better leavability of –COCl than –Cl
CH 3 COOC 2 H 5 ¾¾¾® CH 3COOH + C 2 H 5 OH (a) (i) and (ii) (b) (i) and (iii)
(reaction involves acyl-oxygen fission) (c) (i), (ii) and (iii) (d) (iv)
(c) H+ 59. The driving force for the completion of Claisen condensation
C 6 H 5COOH + CH 3OH ¾¾®
¾ C 6 H 5COOCH 3 + H 2 O between ethyl acetate and sodium ethoxide to ethyl acetoacetate
(reaction involves acyl-oxygen fision)
is
OH -
(d) CH3 COOCH(CH3 )C 2 H 5 ¾¾¾® CH 3COO - (a) the presence of reactive methylene group in ethyl
acetoacetate
+ HOCH(CH3 )C2 H5 (b) the phenomenon of keto enol tautomerism
(configuration of the reactant is retained)
(c) the presence of at least a-hydrogen atom in ester
53. The products in the following reaction are
(d) all the three factors
H -Pd / C 60. Which of the following compound undergoes Claisen
C 6 H 5 COOCH 2 C 6 H 5 ¾¾2 ¾ ¾
¾®
condensation in presence of C 2 H 5 ONa ?
(a) C 6 H 5CH 2OH + C6 H 5CH 2OH
(b) C 6 H 5CH 3 + C6 H 5CH 3 (i) CH 3CH 2COOC 2 H 5
(c) C 6 H 5CH 2OH + C 6 H 5CH 3 (ii) (CH 3 ) 2 CHCOOC 2 H 5 (iii) ClCH 2 COOC 2 H 5
(a) only (i) (b) (i) and (ii)
(d) C 6 H 5COOH + C 6 H 5CH 3 (c) (i) and (iii) (d) all of the three
CH 3 H3O +
61. Ester + CH3MgBr (excess) ¾¾ ¾¾® C4 H10 O (Alcohol)
|
54. Pyrolysis of CH 3COO C HCH 2 CH 3 gives The alcohol formed gives white ppt. with ZnCl 2/HCl
(a) 1-butene and 2-butene in equimolar ratio immediately, the ester may be
(b) 1-butene and 2-butene in 1 : 2 molar ratio HCOOC 3H 7 CH 3COOC 5H11
(c) 1-butene and 2-butene in 3 : 2 molar ratio I II
(d) 1-butene and 2-butene in 2 : 3 molar ratio
55. The relative stability of the four acid derivatives towards CH 3COOCH 3 C 2 H 5COOCH 3
nucleophiles is III IV
(a) Amide > Ester > Acid anhydride > Acid chloride (a) II (b) II and III
(b) Amide > Acid anhydride > Ester > Acid chloride (c) II and IV (d) I
(c) Acid Chloride > Acid anhydride > Ester > Amide
(d) Acid Chloride > Ester > Acid anhydride > Amide 62. In the reaction
56. Which of the following statement is true about the hydrolysis O (1) NaOH/Br2
of acetic anhydride ? H3C C T
(i) It is more easily hydrolysed in acidic medium than in O
neutral NH2 (2) C
(ii) It is more easily hydrolysed in alkaline medium than in Cl
neutral
the structure of the product T is :
(iii) It is equally hydrolysed in all the three medium
(iv) It is more easily hydrolysed in neutral than in acidic O
medium (a) H3C C O
(v) It is more easily hydrolysed in neutral than in alkaline O C
medium
(a) (i) and (ii) (b) (iii)
(c) (iv) and (v) (d) (i) and (v)
57. Which of the following compounds can undergo nucleophilic
substitution easily ? (b) NH
O O O C CH3

C C–O–C O

I II
O O (c) H3C NH
C
C– CCl3 C F
O
O
III IV O
O F (d) H3C C
NH C
C

V
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11. (a) What is an ortho ester, give its general formula ? Give the
product obtained by the mild hydrolysis of ethyl
orthoformate.
(b) Write down the steps involved in the preparation of ethyl
orthoformate by the reaction of chloroform with sodium
(iii)
ethoxide.
12. Give the ester or combination of esters required to prepare the
following products by a Claisen condensation.

O CH 2C6 H 5
½½ ½
(a) C6H5CH2CH2 C CHCOOCH 3

CH 3
½
(b) C2H5COO.CO. CHCOOC2 H 5

C6 H 5
½
(c) OHC CHCOOCH 3
13. Compare the reactants, conditions, and products of the
(iv) CH3COOC2H5, CH3COCl, (CH3CO)2O Hofmann, Lossen, Curtius and Schmidt reactions.
and CH3CONH2. 14. Compare the acidity of the N—H in
(c) Compa re the rea ctivity of benzoyl chloride with (a) an acid amide (e.g., CH3 CONH2) and a sulphonamide
cyclohexanecarboxyl chloride. (e.g., CH3SO2NH2).
8. Predict the product of the reaction of g-butyrolactone with (b) benzamide (C6H5CONH2),a phthalimide and ammonia.
15. Explain the following :
(a) ammonia (b) LiAlH4 (c) C2H5OH + H2SO 4.
(a) Dimethyl sulphate is a good methylating agent.
9. Describe simple chemical tests that would serve to distinguish
between (b) An acyl chloride undergoes nucleophilic attack more
rapidly than does an alkyl chloride.
(a) Acetyl chloride and acetic anhydride.
(c) Trialkyl phosphates are readily hydrolyzed with OH– to
(b) n-Butyryl chloride and n-butyl chloride. dialkyl phosphate salts, while the hydrolysis of dialkyl
(c) Benzoyl bromide and p-bromobenzoic acid. hydrogen phosphates and alkyl dihydrogen phosphates
(d) Propanoic acid and ethyl acetate. with OH– becomes increasingly more difficult.
(e) Acetic anhydride and n-butyl alcohol. (d) Hydrolysis of the ester (A) with 5 M NaOH gives optically
(f) Ammonium benzoate and benzamide. active alcohol, C6H5 while hydrolysis with dil. NaOH gives
optically inactive alcohol.
(g) Glyceryl monopalmitate and glyceryl tripalmitate.
(e) The reaction ‘CH3COOC2H5 + H2O ¾¾® CH3COOH +
10. (a) Write an equation for the reaction of CH3COOC2H5 with
C2H5OH’ is slow in the beginning, but fast subsequently.
CH3MgI.
16. An ester (A) of the formula C5H8O2 on acidic hydrolysis gives
(b) Why a ketone is not isolated from the reaction of an ester an acid (B) which reduces Tollen’s regent and an alcohol (C)
with one equivalent of CH3MgI ? which gives iodoform test. Ester (A) can also be converted into
(c) Can you prepare a 2° alcohol from an ester and an alcohol (B) by reaction with excess of Grignard reagent (D).
organometallic reagent ? Identify (A) to (D).
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1. (i) 3, 3-Dimethylbutanoyl chloride (ii) 2-Bromopentanoyl bromide (iii) 3-Hexenoyl chloride

(iv) Cyclopentyl methanoyl chloride (v) Propanoic hexanoic anhydride (vi) Methyl cyclopentanecarboxylate
(vii) 1-Methylpropyl propenoate (viii) N, N-Dimethylpropanamide (ix) N, N¢-Dimethylurea
(x) N, N-Dimethylurea.

2. (i) (ii) (iii)

(iv) (v) (vi)

3. Nitriles are hydrolyzed by H+ or OH– to acids.

1. Recall that the first step in nucleophilic substitution at acyl carbon is the addition of a nucleophile at acyl carbon which is facilitated by
(a) any factor that increases the electrophilic character of the acyl carbon ; and (b) less steric hindrance at carbonyl carbon. Thus
(i) F3CCOCl is more reactive due to strong electron-withdrawing nature of F.
(ii) CH3COOCH3 is more reactive because the other compound has benzene ring which decreases the electrophilic character of carbonyl
carbon by supplying electrons due to resonance,

(iii) O2N— —COOCH3 is more reactive due to electron-withdrawing nature of the —NO2 group.

(iv) —COOCH3 is more reactive due to less steric hindrance.

(v) An ester is more reactive (less stable) than an amide.

2. (i) CH3CH(Cl) COO–NH4+. Here addition of nucleophile takes place on —COOH. Recall that alkyl halides (CH3CHCl —) react very
slowly with nucleophiles than acyl compounds.
(ii) ClCH2CONH2 (Acyl nucleophilic substitution is very fast than alkyl nucleophilic substitution).
(iii) C6H5Cl does not react with NH3 at room temperature.

(iv)

3. Aldehydes and ketones do not undergo nucleophilic substitution (nucleophilic addition-elemination) because generally the eliminated
anions (H:– or R:–) are strongly basic and hence poor leaving groups. In the two given cases, the leaving anions are stabilized by powerful
electron withdrawing groups ; hence these are weak bases and behave as good leaving groups.

Stabilized by three electron-withdrawing groups Stabilized by powerful electron withdrawing ortho F

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1. (a) Formation of anhydride from adipic acid would produce a seven-membered ring which is too difficult to be formed. Instead, it
loses a molecule of CO 2 and converted into a cyclic ketone with five-membered ring.

Suberic acid (1, 8-octanedioic acid) does not form cyclic ketone because again here seven-membered ring would be formed which
is too difficult to be formed.
O O
½½ ½½
(b) C6 H5 ¾ C ¾ Cl + H2O ¾¾® C6 H5 ¾ C ¾ OH + HCl

O O O O
½½ ½½ ½½ ½½
C6 H5 ¾ C ¾ Cl + HO ¾ C ¾ C6H 5 ¾¾® C6 H5 ¾ C ¾ O ¾ C ¾ C6 H5 + HCl

1. (a) Nucleophilic substitution of acyl compounds takes place readily (i) if the final product is more resonance stabilized than the
reactant or (ii) if the incoming group (nucleophile) is a stronger base than the leaving group.
(i) Yes. CH3COOH is more resonance stabilized than CH3COCl ; also OH– is a stronger base than Cl– .
(ii) No. CH3CONH2 is lesser resonance stabilized than CH3COOH. NH3 reacts with RCOOH to form RCOO–NH4+ which does
not react. Amides are prepared from RCOOH by strongly heating dry RCOO – NH4+ because now reaction is catalysed by acid
(NH4+).
(iii) Yes. CH3COO– is more stabilized than (CH3CO)2O ; also the leaving group RCOO– is a weaker base than OH–.
(iv) Yes. CH3COOC2H5 is more stabilized than CH3COBr, and also Br– is a much weaker base than HOC2H5.
(v) Yes. CH3COO– is highly stable than CH3CONH2 ; although NH2– (the leaving group) is a stronger base than OH– (the
nucleophile).
(vi) No. CH3COBr is less stable than CH3COOCH3 (ester) ; also Br– is a weaker base than OCH3–.
NaOH (CH 3 ) 3 CBr
(b) CH3COOH ¾¾® CH3COO–Na + ¾¾¾® Elimination reaction.
Conc. H 2SO 4
Hence CH3COO– Na+ + (CH3)2 C = CH2 ¾¾¾¾® CH3COOC (CH3)3
(c) Since acyl chloride is more reactive than the carboxylic acid, it will react with water rapidly to give the starting material
RCOOH + HCl RCOCl + H2O
Water (one of the products) cannot be removed as it is formed because here HCl (being gas) would escape.

OH OH OH OH
½ ½ ½ ½
1. (a) C6 H5 ¾ C ¾ OCOCH3 (b) C6 H5 ¾ C ¾ OC2H5 (c) C6H 5 ¾ C ¾ N(CH3 ) 2 (d) C6H 5 ¾ C ¾ OH
½ ½ ½ ½
Cl Cl Cl Cl

2. Since hydrazoic acid (HN3) is slightly more acidic than acetic acid (CH3COOH), the azide ion (N3–) is slightly less basic than the acetate
ion (CH3COO–). Thus azide ion will be slightly better leaving group than the acetate ion ; hence acyl azide (RCON 3) will be a little more
reactive than the anhydride (RCOOCOR). Thus the position of acyl azide in the order of reactivity of various acyl derivatives will be
between acyl chlorides and acid anhydrides.
RCOCl > RCON3 > (RCO)2O
3. (a) Pd/C, poisoned with quinolione and S or LBAH (b) NH3 (c) LiAlH4 (d) C6H5CH2OH + H+
(e) C6H5COO–Na + or heat with (CH3CO)2 O (f) C6H5CH2NH2 (g) NaN3 (sodium azide).
4. In each case, the less reactive organometallic Me2CuLi reacts with the more reactive —COCl group to form methyl ketone.

(a) NC (CH2)4 COCH3 (b) 2 (c) H5C2OOC (CH2)4 COCH3.

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1. (a) CH3COOCH3 + CH3COOH (b) 2CH3COOCH3

CH 2CON(CH 3 ) 2 CH 2COO - Na +
1 1 1
(c) CH3CONH2 + CH3COO–NH4+ + (CH3CO)2O (d) ½ (e) ½
2 2 2
CH 2COO - H 2 N + (CH 3 ) 2 CH 2COO - Na +

(f) (CH3)3COH (g)

2. (a) Mixed anhydrides are prepared by reacting the acid chloride of one of the acids with the carboxylic salt of the other. Thus
O O
½½ ½½ O O
(i) CH3 ¾ C ¾ Cl + Na+ –O— C ¾ CH2CH3 ½½ ½½
or ¾¾® CH3 ¾ C ¾ O ¾ C — CH2CH3

O O
½½ ½½
CH 3CH2 ¾ C ¾ Cl + Na+ –O— C ¾ CH3

O O O O
½½ ½½ ½½ ½½
(ii) CH 3 ¾ C ¾ Cl + Na + -O — C ¾ H ¾¾® CH3 ¾ C ¾ O ¾ C ¾ H
Acetic formic anhydride
Since HCOCl is not stable, HCOCl + CH3 COO–Na – does not constitute the alternate pair for preparing acetic formic
anhydride.
(b) No. On heating, formic acid undergoes dehydration intramolecularly rather than intermolecularly.
HCOOH ¾¾® CO + H2O

3.

1. (a) . The p electrons of the C = O bond are more easily displaced than the s electrons of the C—O bond with the result the
carbonyl oxygen acquires negative charge, hence acyl oxygen (or carbonyl oxygen) is more basic.
(b) The three C—O bonds have different bond lengths, because of relative displacement of electrons along their bonds ;

The relative value of bond lengths is x > y > z.

2. The carbonyl carbon of RCOOH and RCOOR¢ is trigonal sp 2 hybridised, while that of the intermediate is tetrahedral sp 3 hybridised. If
alkyl group in alcohol or in acid is extensively branched, transition state will be crowded leading to slow reaction and with difficulty too.
3. (a) CH3COOCH3 > CH3COOC2H5 > CH3COOCHMe2 > CH3COOCMe3
III I II IV
Steric effect, and relative basic character of the leaving groups. Basic character of the leaving groups is
Me 3CO – > Me2CHO– > C 2H5O– > CH3O–
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(b) HCOOCH3 > CH3COOCH3 > CH3CH2COOCH3 > Me2CHCOOCH3 > Me3CCOOCH3
II I IV III V
Remember that an alkyl group releases electrons, and thus destabilizes the transition state by intensifying the negative charge
developing on oxygen. Thus lesser is electron releasing character of an alkyl group, more will be the stability of the transition state.
4. Presence of electron-withdrawing group speeds up the reaction since it helps to disperse the negative charge developing on oxygen.
(a) V > III > IV > I > II (b) III > IV > II > I.

C6 H5
½
5. (a) (i) CH3CH2 COH
½
C6 H5

(ii)

(iii) (iv) CH 3CONHNH 2 (v) C6 H 5CONHOH

Acetyl hydrazide Benzoylhydroxamic acid

(b)

(c) CH3(CH2)7 CH = CH (CH2)7 COOC4H9-n ¾¾® CH3 (CH 2 ) 16 CH2OH + n-C 4H9OH
1- Octadecanol
6. Esters of formic acid, when treated with excess of Grignard reagents, give secondary alcohols having similar alkyl groups.

O
½½
H— C ¾ OC2H5 + 2 n-C 3H7MgBr ¾¾® n-C3H7 ¾ CH ¾ C3H7-n
½
OH
4 - Heptanol

7. (a) However, with 3° alcohols, ester hydrolysis occurs by alkyl-oxygen cleavage leading to a 3° carbocation which being planar gives
racemic product.

(b) Hydrolysis of esters having 2° or 1° alcohol occur by acyl-oxygen cleavage. Since no bond to chiral carbon is broken, configuration
is retained and O18 from water appears in acidic part.

O CH3
H+ , H 2O18½½ ½
¾¾¾® CH — C ¾ O18 H + HO ¾ C ¾ C2 H5
3
½
H
(+ ) -

O O
½½ ½½
1. (a) (i) CH3CH2CH2CH2 C CHCOOCH 2CH3 (ii) Not possible (iii) C6H5CH2 C CHCOOCH 2CH3
½ ½
CH 2CH 2CH 3 C 6H 5

CHO COCOOC 2 H 5 COCH 2C 6 H 5 COC6 H 5

½ ½ ½ ½
(b) (i) C6H5 CHCOOC2 H5 (ii) C6H5 CHCOOC 2 H 5 (iii) C6H5 CHCOOC 2 H 5 (iv) C6H5 CHCOOC 2 H 5 .
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2. The side reaction with sodium methoxide is transesterification. The starting material, and therefore the product, would be a mixture of
methyl and ethyl esters. Sodium hydroxide would irreversibly saponify the ester, completely stopping the claisen condensation as the
carbonyl no longer has a leaving group attached to it.
–
CH3 O CH3 O CH3 O
–
OC2H5
3. CH3 – CH – COC2H5 CH3 – .C. – COC2H5 CH 3 – C = COC 2H5
–

O –
O CH3 O O CH3 O
–
(CH 3)2CHCOC2H5 –C2H5O
(CH3) 2CH – C — C – C – OC 2H 5 (CH3)2CH – C – C – COC2H 5

OC 2H5 CH3 CH3

The two reasons for the poor yield in this reaction are
(i) The nucleophilic carbon in the enolate is 3° and attack is hindered.
(ii) More important, the final product has no hydrogen on the a-carbon, so the deprotonation by base which is the driving force in
Claisen condensation can't occur. Thus, the product will be an equilibrium mixture of product (minor) and starting materials
(major).
4. Dissect the a,b-bond of the b-keto ester. Add the appropriate alcohol (ROH) to the two carbon atoms (RO – to the carbonyl carbon and H+
to other carbon).

O OC3H7-iso
(i) (ii)
OCH 3
O
Note that in (b) the product of Claisen condensation would be formed in low yield because it does not have acidic hydrogen between two
C = O groups to be removed to form the stable carbanion (driving force for the reaction).
5. Remove the acyl group of the product in the form of an ester.

(i)

CH 2 COOC2 H 5
COOC2 H 5 ½
(ii) ¬¾¾ ½ + CH 2
COOC2 H 5 ½
CH 2 COOC2 H 5

(iii) ¬¾¾ + H3CCOOC2H5

O
O O
O
OCH 3
6. (a) + CH3O – C – C 6H5 or C6H 5 (b) O
C
OC2H5
O
Crossed Claisen Intramolecular Claisen

O O O
O

(c) + C2H5O – C – OC2H 5 or O OC2H5

C
O OC2H5

7. (a) (i) (ii) (iii)

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(b) Since three and four membered rings are difficult to form, ethyl succinate and ethyl glutarate do not undergo Dieckmann reaction.
However, ethyl succinate on prolonged treatment with sodium ethoxide undergoes double Claisen condensation to form six-
membered cyclic compound.

COOCH3
8. (a)
COOCH3
(b) It is a g-keto ester, hence can't be prepared by Dieckmann condensation.
O

OCH3
COOC2H5
(c) (d) COOCH3
COOC2H5
O O

Ketonic group is protected to avoid aldol condensation.

9. ˆˆ†
CH3 COOH + BF3 ‡ˆˆ CH3 COOBF3- +H +

O O O
+
+
H
+

3° carbocation

O O
+
–H
+

(major)

1. (a)

SOCl 2 NH 3 Br2 / NaOH

(b) CH3 CH2 CH 2 COOH ¾¾® CH3CH2CH2COCl ¾¾® CH3CH2CH2CONH2 ¾¾¾¾® CH 3CH2CH2 NH2
Butanoic acid 1-Propanamine
2. Let us draw the structure of the conjugate base and study their relative basicity.

Resonance in conjugate base of benzamide.

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In conjugate base of NH3, i.e. NH2–, the negative charge is localised. Thus the order of basic character of the three conjugate bases is
NH2– > C 6H5CONH– > Conjugate base of phthalimide
Acidity order is Phthalimide > Benzamide > NH3
+
3. (a) CH3COOH + Me2 N H2 (b) COOH. CHNH3+ + COOH CHNH3 +
½ ½
CH3 C 2H 5

COOH
(c) (d) + ½
COOH

4. Hydrolysis of amides is an example of nucleophilic addition-elimination reaction which is enhanced in presence of electron-withdrawing
group. Thus II < I < IV < III
5. (a) RCONH2 + R¢Li ¾¾® RCONH–Li+ + R¢H
1° amide metal salt
RCONHR¢ + R²Li ¾¾® RCON–R¢Li+ ¯ + R²H
2° amide
RCONR2¢ + R²Li ¾¾® RCOR² + R2¢NLi
3° amide
(b) RCONH2 + HONO ¾¾® RCOOH + N2 + H2O
1° amide

RCONHR¢ + HONO ¾¾® RCO N — N = O

½
R¢
N-Nitrosoamide

RCONR2¢ (3° amide) does not react with nitrous acid.

6. (i) C6H5CH2CH2OH + CH3OH (ii) 2CH3CH2OH
(iii) C6H5CH2OH (iv) CH3CH = CHCH2CH2NHC6H5

(v) HOCH2 CHCH 2CH 2OH (vi) (vii)

½
CH 3

1. (a) RCOCl (b) RCOOC2H5 (c) (CH3CH2CO)2O

(d) RCOO–NH4+ (e) RCOO–NH4+, RCONH2, or RCN.
2. CH 3COOC3 H7 -n + OH– ¾¾® CH3COO– + n-C 3H7OH
n-Propyl acetate
One mole of the ester requires one mole of OH– for hydrolysis (saponification), thus Saponification equivalent (SE) = M.W. of ester = 102
(C 5H10O2).
Number of esters (RCOOR¢) having C5H10O2 as the molecular formula can be ascertained by taking different possibilities for R and R ¢
(total number of C in R and R¢ should be 4). Since R¢ is coming from alcohol part, it can CH3, C2H5, n-C 3H7, iso-C 3H7, n-C 4H9, iso-C 4H9,
sec-C 4H9, or tert-C 4H9 ; while R (coming from acidic part) can be n-C 3H7, iso-C 3H7, C2H5, CH3, or H. Thus nine different esters are
possible, including n-propyl acetate.
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(i) HCOOC4H9-n (ii) HCOOC4H9-iso (iii) HCOOC4H9-sec (iv) HCOOC4H9-tert
(v) CH3COOC 3H7-n (vi) CH3COOC3H7-iso (vii) C2H5COOC2H5 (viii) n-C 3H7COOCH3
(ix) iso-C3H7COOCH3.
Number of carboxylic acids (RCOOH) having C5H10O2 as molecular formula. Since here one carbon atom is present as —COOH, so the
remaining four carbon atoms must be present as butyl group, i.e.

CH3
½
CH3CH2CH2CH2COOH (CH3)2CHCH2COOH C2H5 CHCOOH (CH3)3C.COOH
Butanoic acid Isobutanoic acid sec. Butanoic acid tert-Butanoic acid

3. (a) + 2CH3OH

Methyl phthalate Phthalate anion

(M.W. = 194)
Since 1 mole of phthalate used 2 moles of OH– ; S. E. = M.W./2 = 194/2 = 97
(b) S.E. = M.W./No. of ester groups per molecule.

EXERCISE 18.1
1 (c) 6 (d) 11 (b) 16 (d) 21 (c) 26 (d)
2 (b) 7 (d) 12 (a) 17 (c) 22 (b) 27 (c)
3 (b) 8 (b) 13 (c) 18 (a) 23 (d) 28 (b)
4 (d) 9 (b) 14 (a) 19 (c) 24 (c) 29 (c)
5 (a) 10 (d) 15 (d) 20 (d) 25 (c) 30 (d)

1. In Bouvealt-Blanc reduction, reduction involves the transfer of electron from metal (Na or Li).

O Od –
½½ d +½
½
2. C6H5— C ¾ O– is a nucleophile, while C6 H5 — C ¾ Cl acts as an electrophile.

3. Only reaction (b) is S 2 while the others are acyl bimolecular nucleophilic substitution.
N
4. In mixed condensation, an ester not having any a-hydrogen atom acts as acylating agent because it does not form enolate ion.
5. Esters (other than formates) react with excess of RMgX forming 3° alcohols having two alkyl groups corresponding to alkyl part of the
RMgX. Since here RMgX is CH3MgBr, so the 3° alcohol formed should have at least two methyl groups which is only option (a).
6. Like g- and d-hydroxy acids, g- and d- amino carboxylic acids form corresponding lactam.

7. In presence of dil. NaOH, esters are hydrolysed via SN1 mechanism which involves the formation of carbocation, hence the product
(alcohol) will be optically inactive, provided chiral carbon is present in the parent ester. Further, carbocation is formed as an intermediate
which rearranges to the more stable carbocation, thus the rearranged product is formed as the final product.
OH
dil. NaOH + + OH -
½
C6H5 CHCH = CHCH 3 ¾¾¾® C6H5 C HCH = CHCH3 ¬¾® C6H 5CH = CHCHCH3 ¾¾® C6H 5CH = CHCHCH3 .
½ More Stable ( ±) - Alcohol
OCOC2H5
Å Å
COOCH 3 O N H3 CO OH N H3
½ ½½ ½ H 3OÅ ½ Å ½
8. C6 H 5CH 2CH ¾ NH ¾ C — CHCH 2 COO Q ¾¾® C6 H5CH 2CH NH3 + HOOC. CHCH 2COOH + CH3OH
9. Consult mechanism of lactone (or ester) hydrolysis by acids.
OH OH
½ ½
10. HCOOR + R¢MgX (excess) ¾¾® H ¾ C ¾ R ¢ ; RCOOR² + R¢MgX (excess) ¾¾® R ¾ C ¾ R ¢¢
½ ½
R¢ R¢
A 2° alcohol (A 3° alcohol)
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11. Alkaline hydrolysis is irreversible because here RCOO– is isolated ; moreover the product RCOO – stabilizes itself due to resonance.
12. The g-carbon-oxygen bond is shortest because it has double bond character. The b-C—O bond is shorter because it also has some double
bond character due to resonance. The a-C—O bond is longest because it is always a single bond.

13. Esters undergo acyl-oxygen cleavage during hydrolysis.

14.

15.

OH - HCl
16. CH3CH2CH2CONH2 ¾¾® CH3CH2CH2COO– Na+ ¾¾® CH3CH2CH2COOH + Na+ + Cl–
(- NH 3 )

17.

Acetone and propanal can be distinguished by Fehling solution.

18. Remember that the two enantiomers react differently i.e. at different rate with an optically active reagent leading to the formation of two
isomers (diastereomers) in different amounts, hence the resulting mixture will be optically active.
19. Stronger a nucleophile, more will be its reactivity toward nucleophilic substitution.
20,21. Recall that presence of electron-withdrawing group in p- or o-position increases nucleophilic substitution, while electron-releasing group
decreases the reactivity.
22. Only ketonic group is reduced by NaBH4, while LiAlH4 reduces both ketonic as well as lactone group to the —OH groups.

23.

Remember that b-keto acids undergo decarboxylation on heating.

24,25. In lactones, the root word is derived from the name of the parent carboxylic acid prefix a, b or g- is inserted on the basis of relative
positions of the —OH and —COOH groups in the parent hydroxy acid.
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26.

27.

28. (i) Since the product has a C = C bond, so C º C should be partially reduced to C = C.
(ii) Since the final prouct is a cyclic, the intermediate should be cis- or syn- alkene, because anti-alkene will not be able to undergo
cyclisation. Hence the reagent R should be H2/Pd (Lindlar catalyst) which gives syn-alkene. The second reagent R¢ is H3O+.
29. In Baeyer Villeger oxidation (conversion of ketones to esters by per acids), oxygen is introduced between the larger alkyl group and the
C = O carbon.
O O
½½ C 6 H 5 CO 3H
½½ H+
CH3CH2— C ¾ CH3 ¾¾¾¾® CH3CH2 ¾ O ¾ C ¾ CH 3 ¾¾¾® CH3CH2OH + CH3COOH

30.

EXERCISE 18.2 MCQ > 1 1 (a ,b,c) 2 (a,b,c) 3 (a ,c,d) 4 (c,d)

CORRECT 5 (a,b,d) 6 (a , b, c, d) 7 (a , b, c, d) 8 (a , b, c)
OPTION 9 (a, c) 10 (a , b, c, d) 11 (a , d)
PA SSAGE 1 12 (c) 13 (c) 14 (b)
15 (A ) - (b, c), (B) - ( d), (C ) - (a ), (D ) - (a )
Ma tch the
16 (A ) – b; (B) – d; (C) – c; (D ) – a
following
17 (A) - a , b; (B) - a , b; (C) - c; (D) - d
A/R 18 (c) 19 (a ) 20 (c) 21 (c)

1. Alkyl isonitriles are not hydrolysed to acids, all others give carboxylic acids on hydrolysis.
2. The first three are examples of nucleophilic addition elimination reaction, option (c) is although ketone, it
undergoes acyl type of nucleophilic substitution, i.e. nucleophilic addition elimination because the leaving
group here is an aryl anion having electron withdrawing F in the o-position making the carbanion stable.
Thus it is a weaker base and better leaving group than the ordinary Ar –. In (d) –OH is a poor leaving group.

é ù
O ê O O- ú OH
½½ ê ½½ ½ ú H+ ½
-
3. CH 3 ¾ C ¾ OC2 H5 ¾¾® ê CH 2 ¾ C ¾ OC2 H 5 ¬¾® CH 2 = C ¾ OC2 H 5 ú ¾¾® CH 2 = C ¾ OC2H5 .
ê More stable ú An enol
ë û

4. Nature of the final products indicate that Q is an ester, and hydrolysed by alkali. Thus P must be (CH3)2 CHCHO which
undergoes Tischenko reaction.
5. Stronger the basic nature of the leaving group, weaker will be its leavability. In CH 3COOH, OH– is a strong base so it can’t be removed
+
easily to form CH3 C O required for acetylation (acylation).
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EXERCISE 18.3
1. (a) C6H5COCH2CH3 (b) CH 3CH 2 CONHOH (c) CH 3CH 2CONHCH 3 (d) CH 3CH 2COC3 H 7-n
Propiophenone Propanehydroxamic acid N-Methylpropanamide 3-Hexonone
(Ethyl phenyl ketone)

O O
½½ ½½
(e) CH3CH2CHO (f) CH3CH 2 C ¾ O ¾ O ¾ CCH2CH3
Propanal Propionyl peroxide

2. (a) CH3(CH2)3NH2 (b) CH3(CH2)3NH2 (c) No reaction (d) CH3(CH2)2 COOC2H5

3. (a) The hydrolysis involves O-acyl cleavage and hence configuration of the alcohol is retained. The products formed are
CH 3
½
CH3COO–Na + + (R) – HO CHCH 2CH 3

CH 3
½
(b) Here also O-acyl cleavage occurs. CH3COOH + (R) – HO CHCH 2CH 3
(c) In presence of a high concentration of nucleophile (5 M NaOH), the ester undergoes bimolecular nucleophilic acyl substitution, with
the O-acyl cleavage. Further since the bond to the chiral carbon is not broken, configuration of the alcohol is retained.

(d) In presence of a low concentration of nucleophile (dil. NaOH), ester undergoes S N 1 reaction involving alkyl-oxygen fission. Further
note that carbocation is formed as an intermediate, so it stabilizes to the more stable benzylic- allylic cation having double bond in
conjugation with the ring. Since carbocation is planar, the product formed will be racemic mixture.
OCOR OH
½ dil. NaOH Å OH -
½
(R)–C6H5CHCH = CHCH 3 ¾¾¾® C6H5— CHCH3 ¬¾® C6H5CH = CH ¾ C HCH3 ¾¾® C6H5CH = CH — CHCH3
More stable racemic mixture

O
½½
(e) C6H5CH2OH + C2H5OH (f) C6 H 5 C ¾ O ¾ O - Na + + C6H5COOCH3 (g)
Sod. peroxybenzoate

(h)

OH
½
4. (a) C6H5 ¾ C ¾ C3H7-n (b) C6H5COOCH2CH(CH3)2
½
n-C3H7

4-Phenyl-4-heptanol Isobutyl benzoate

O O
½½ ½½
(c) HCONH 2 + HOCH 2 (CH 2 ) 3 CH 3 (d) CH3CH 2CH 2 —C ¾ O ¾ C ¾ CH2CH 3 .
Formamide 1-Pentanol Butyric propionic anhydride

5. (a) CH3CH2CH2COOH + C6H5CH2OH (b) m-ClC6H4COOH + CH3OH

(c) HOCH2CH2CH (CH3) COOH (d) CH3CH = CHCH2COOH +

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6. (a) (CH3 ) 2 CHCH 2CuLi , C6H5COCH 2CH(CH3 ) 2 (b) C6H5CH 2C(OH)(n -C4 H9 )2
[A] [B] [C]
(c) CH2 = CHCH2COC6H5
[D]

(d) Br CH2 COOH Br Zn CH 2COOC2 H5 (CH 3 ) 2 C(OH)CH 2COOC2 H 5 (CH3 ) 2 C = CHCOOH (CH3 ) 2 C = CHCH 2OH
[E] [F] [G] [H] [I]

7. (a)

Greater the partial +ve charge on carbonyl carbon, higher is the reactivity of carbonyl group towards nucleophilic substitution.
(b) (i) CH3COOCH3 > CH3COOCH2CH3 > CH3COOCH(CH3)2 > CH3COOC(CH3)3
Size of the alkyl group of the alcoholic part increases from left to right, steric hindrance increases, and hence rate of hydrolysis
decreases.
(ii) HCOOCH3 > CH3COOCH3 > (CH3)2CHCOOCH3 > (CH3)3CCOOCH3
Size of the alkyl group of the acidic part increases from left to right.
(iii) – I group disperses negative charge in transition state and thus increases reactivity of ester for hydrolysis. Thus the relative order
of ester hydrolysis is

-
(iv) Lesser thebasic character of theleaving group (Cl– < O COCH3 < –OC2H5 < NH2–), more easily it is removed.
CH3COCl > (CH3CO)2O > CH3COOC2H5 > CH3CONH2
(c) Cyclohexanecarboxyl chloride reacts faster than benzoyl chloride.
8. (a) HOCH2CH2CH2CONH2 (b) HOCH2CH2CH2CH2OH (c) HOCH2CH2CH2COOC2H5.
9. (a) On reaction with water, acetyl chloride reacts with water and liberates HCl which is detected by giving a white precipitate of AgCl
on adding AgNO3. Acetic anhydride on reaction with water liberates only acetic acid and no HCl.
(b) n-Butyryl chloride (n-C 3H7COCl) gives pleasant smelling ester with ethyl alcohol.
(c) Only benzoyl bromide (C6H5COBr) gives yellow precipitate of AgBr with alcoholic AgNO 3.
(d) Only propanoic acid gives CO2 with aqueous NaHCO3 solution.
(e) Only acetic anhydride reacts with aq. NaHCO3 solution and evolve CO 2.
(f) Ammonium benzoate evolves ammonia immediately on treatment with cold aq. NaOH.
(g) Glyceryl monopalmitate has two free alcoholic groups ; hence it is oxidised by CrO 3 / H2SO 4.

O OMgI CH3 CH3

½½ CH 3 MgI ½ - MgI (OC2H5 ) CH 3 MgI ½ H+ ½
10. (a) CH3—C ¾ OC2H5 ¾¾¾® CH3 ¾ C ¾ OC2H5 ¾¾¾¾¾® CH3—C = O ¾¾¾® CH3 ¾ C ¾ OMgI ¾¾® CH3 ¾ C ¾ OH
½ ½ ½ ½
CH3 CH3 CH3 CH3
Acetone (as intermediate) tert-Butanol
(b) Ketones are more reactive than esters towards RMgX.
(c) A formate ester when treated with 2 eq. of Grignard reagent gives 2° alcohol with identical alkyl groups.

O OH
½½ (i) 2RMgBr ½
H— C ¾ OC2H5 ¾¾¾¾® H¾C¾R
(ii) H 3O + ½
R
A 2° alcohol
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11. (a) An ortho ester has three alkoxy groups (– OR) attached to the same carbon atom ; thus the general formula for ortho esters is
RC(OR¢)3 ; where R = H or an alkyl group, while R¢ = an alkyl group.
mild hydrolysis
HC(OC 2H 5 )3 ¾¾¾¾¾® HCOOC 2 H 5 + 2C H OH
2 5
Ethyl orthoformate Ethyl formate

C 2 H 5O -
(b) CHCl3 + 3C2H5ONa ¾¾¾® HC(OC2H5)3 + 3NaCl
Mechanism. Dichlorocarbene, formed from chloroform, inserts between H and O of C2H5OH to form a, a-dichloromethyl ethyl
ether which solvolyses rapidly via SN1 in ethyl alcohol.
C2H 5O - C 2 H 5O ¾ H - Cl -
HCCl3 ¾¾¾® : CCl2 ¾¾¾¾® C 2H5O—CHCl2 ¾¾®

OC 2 H 5
é + ù C 2 H 5 OH ½ C 2H 5OH
ê C HCl ¬¾® C 2H5 O + = CHCl ú ¾¾¾® C 2H5O— CHCl ¾¾¾® HC (OC2H5)3
ë .. û (- HCl)
12. In the Claisen condensation, the bond formed is between the carbonyl carbon of one ester and the carbon which is a to the —COOR group
of the ester molecule. Thus work backward by breaking this C—C bond and adding OR to the carbonyl carbon and H to the other carbon.
Mixed Claisen condensations are practical, when one ester has a H.

O CH 2 C6 H 5
(i) C 2 H 5 ONa ½½ ½
(a) ¬¾¾¾¾ C6H5CH2CH2 C ¾ OC2H5 + CH 2 COOCH 3
( ii) - C 2 H 5OH

O CH 3
(i) C 2 H 5ONa½½ ½
(b) ¬¾¾¾¾ C2H5OOC— C ¾ OC2H5 + CH 2COOC2H 5
(ii) - C 2H 5OH

O C6 H 5
(i) C 2 H 5 ONa ½½ ½
(c) ¬¾¾¾¾ H— C ¾ OC2H5 + CH 2 COOCH 3
( ii) - C 2 H 5OH

13. Reaction Reactant Reagents/Conditions Product

Hofmann RCONH2 (Amides) Br 2, OH– RNH2
H 2O
Lossen RCONHOH OH– RNCO ¾® RNH2
Hydroxyamic acids
Curtius RCON3 (i) heat in benzene (i) RNCO
Acid azides (ii) heat in H2O or R¢OH (ii) RNH2 or RNHCOOR¢
Schmidt RCOOH HN3, H2SO 4, OH– RNH2
Carboxylic acids
14. More stable a conjugate base of an acid, higher will be its acidic character.
(a) Since the conjugate base of the sulphonamide is stabilized by delocalization of the negative charge to two oxygens, the parent
compound sulphonamide will be more acidic than the acid amide, CH3CONH2, where delocalization is possible to only one
oxygen.
 www.crackjee.xyz
899
(b) Amides are much more acidic than NH3 because the negative charge on :NH2– from ammonia is localised, while in amides it is
delocalized to the oxygen of C = O. Since phthalimide has two C = O¢s, while benzamide has only one, the imide anion from
phthalimide is more stabilized than the amide anion from benzamide.

Thus the acidic character of the three compounds follows the order :
Phthalimide > Benzamide >>> NH3.
15. (a) Dialkyl sulphates, in general, are good alkylating agents, because the alkyl sulphate anion, e.g. CH3OSO3– is the conjugate base
of a strong acid , methyl sulphuric acid, CH3OSO3H. Thus due to very weak basic nature of the methyl sulphate anion, it is a good
leaving group.

OH - CH 3 - OSO2OCH 3
C6 H5OH ¾® C 6H5O– ¾¾¾¾¾¾® C 6H5OCH3 + - OSO OCH
2 3
Phenol Methyl sulphate anion
(b) Acyl chlorides are more reactive than alkyl chlorides due to following factors.
(i) Presence of C = O in acid chlorides makes the acyl carbon more electrophilic by attracting electrons.
(ii) The transition state of the acyl chloride leading to tetrahedral intermediate is less sterically hindered than the transition state
with the petavalent carbon in the SN2 reaction of RX.
(iii) In the formation of an alkyl transition state, a stronger s-bond must be partially broken , while a weaker p-bond is broken in
the acyl case.
(c) In the hydrolysis of trialkyl phosphates, OH– attacks on the neutral molecule (having no charge), while in the dialkyl and monoalkyl
phosphates the substrates have –1 and –2 charges which make the attack of OH– progressively more difficult.

O- O- O
OH - ½ OH - ½ OH -
½½
-
(RO)3 P = O ¾¾¾® (RO)2 P = O ¾¾¾® RO ¾ P = O ¾¾¾® O ¾ P ¾ O–
( - ROH) (- ROH) (- ROH)
½ ½
O- O-

Trialkyl phosphate Dialkyl phosphate Monoalkyl phosphate Phosphate ion

(neutral) (carries –1 charge) (carries –2 charge)

(d) Recall that concentration of the reagent affects the kinetics of the SN reaction. In presence of high concentration of nucleophile,
reaction opts SN2 mechanism, while in low concentration (dil. NaOH) SN1 mechnism is followed. Since in SN2 reaction configura-
tion is retained, so the optically active ester will be hydrolysed to optically active alcohol.

* 5 M NaOH *
C6H5 CHCH = CHC2H5 ¾¾¾® C 6H5 CHCH = CHC2H5
½
(SN 2) ½
OCOCH3 OH

Optically active Optically acitve

However, in SN1 reaction since carbocations are formed as intermediate which may rearrange, if possible, to the more stable
carbocation. Thus rearranged product may be formed. Further, carbocation being planar, may be attacked on either side of the face
forming racemic mixture.
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900

dil. NaOH é + +
ù
C6H5 CH ¾ CH = CHC2H5 ¾¾¾® ê C6H5 CH — CH = CHC2H5 ¬¾® C6H5CH = CH ¾ CHC2H5 ú
S 1 ë More stable û
½ N
OCOCH3
OH -
¾¾® C6H5CH = CH— CHCH 3
½
OH
Rearranged (optically inactive) alcohol
(e) Acetic acid formed in the reaction, catalyses the hydrolysis of ester by providing H +.

O O
½½ ½½
16. H— C ¾ OCH(CH3 ) 2 H— C ¾ OH HOCH (CH3)2 CH3MgI
[A] [B] [C] [D]
 www.crackjee.xyz
CARBONYL COMPOUNDS
PAST YEAR QUESTIONS JEE ADVANCED/IIT-JEE (2013 - 2017)
MCQs with One Correct Answer MCQs with One or More Than One Correct
1. The compound that does NOT liberate CO2, on treatment 1. In the following reaction, the product(s) formed is(are)
with aqueous sodium bicarbonate solution, is [JEE Adv. 2013]
[JEE Adv. 2013]
(a) Benzoic acid (b) Benzenesulphonic acid
(c) Salicylic acid (d) Carbolic acid (Phenol)
2. The major product in the following reaction is
O 1. CH3MgBr, dry ether, 0°C
Cl 2. aq. acid
CH3
[JEE Adv. 2014]
O
(a) H3C
CH3
OH

(b) H2C CH3

CH3

(c)
CH2
O
CH3 (a) P (major) (b) Q (minor)
(c) R (minor) (d) S (major)
(d) 2. After completion of the reactions (I and II), the organic
O CH3 compound(s) in the reaction mixtures is(are)
3. The correct order of acidity for the following compounds is [JEE Adv. 2013]
CO2H CO2H
CO2H CO2H
HO OH OH
Reaction I :
OH
OH
I II III IV
[JEEAdv. 2016]
(a) I > II > III > IV (b) III> I > II > IV
(c) III > IV > II > I (d) I > III > IV > II Reaction II :
4. The major product of the following reaction sequence is
[JEEAdv. 2016]
O
(i) HCHO (excess)/NaOH, heat
+
(ii) HCHO/H (catalytic amount)

O O O O OH
(a) (b)

O OH
HO O O (a) Reaction I : P and Reaction II : P
(b) Reaction I : U, acetone and Reaction II : Q, acetone
(c) (d) (c) Reaction I : T, U, acetone and Reaction II : P
OH (d) Reaction I : R, acetone and Reaction II : S, acetone
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A-2

3. The major product of the following reaction is 6. Reagent(s) which can be used to bring about the following
[JEE Adv. 2015] transformation is (are) [JEEAdv. 2016]

O i. KOH, H 2O
ii. H,+ heat
O O O O
C O C
CH3
O H OH
O O
COOH COOH
CH3 CH3
O O (a) LiAlH4 in (C2H5)2O (b) BH3 in THF
(a) (b) (c) NaBH4 in C2H5OH (d) Raney Ni/H2 in THF
7. Compounds P and R upon ozonolysis produce Q and S,
respectively. The molecular formula of Q and S is C 8H8O. Q
O O CH3 undergoes Cannizzaro reaction but not haloform reaction,
CH3
(c) (d) whereas S undergoes haloform reaction but not Cannizzaro
reaction [JEE Adv. 2017]
4. Positive Tollen’s test is observed for [JEE Adv. 2016] i) O /CH Cl
(i) P ¾¾¾¾¾¾
3 2 2
ii) Zn/H O
® Q
2 (C8 H8O)
H O
CHO i) O / CH Cl
H (ii) R ¾¾¾¾¾¾
3 2 2® S
(a) H (b) ii) Zn / H 2O (C8H8O)

H The option(s) with suitable combination of P and R,

respectively, is(are)
OH
O H3C
Ph (a) and
(c) Ph (d) CH 3
O Ph Ph
CH3 H3C
5. The correct statement(s) about the following reaction CH3
sequence is(are) [JEE Adv. 2016] (b) and
H3C CH3
(i) O2 CHCl3 / NaOH
Cumene(C9 H12 ) ¾¾¾¾
+
¾® P ¾¾¾¾¾¾®
(ii)H3O
H3C
Q (major) + R (minor) CH3
CH3
NaOH CH3
Q ¾¾¾¾¾ ®S (c) and
PhCH 2 Br
CH3 CH3
(a)R is steam Volatile
(b)Q gives dark violet coloration with 1% aqueous FeCl3
solution H3C
(c) S gives yellow precipitate with 2, 4–dinitro- (d) H3C and
phenylhydrazine CH3
(d) S gives dark violet coloration with 1% aqueous FeCl3
solution
Match the Following
1. Different possible thermal decomposition pathways for peroxyesters are shown below. Match each pathway from List-I with an
appropriate structure from List-II and select the correct answer using the code given below the lists. [JEE Adv. 2014]
P · ·
R + R¢O
– CO2
O Q
O · · · ·
R + R¢O R + X + carbonyl compound
R O R¢
– CO2
(Peroxyester)
R · · · ·
RCO2 + R¢O R + X¢ + carbonyl compound
– CO2

S · · · ·
RCO2 + R¢O R + R¢ O
– CO 2
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A-3

List-I List-II
O
O
P. Pathway P 1. C 6H 5CH 2 O CH3
O
O
Q. Pathway Q 2. C6H5 O CH3
O
O CH3
R. Pathway R 3. C6H5CH2 O CH3
CH2C6H5
O
O CH3
S. Pathway S 4. C6H5 O CH3
C6H5
Code :
P Q R S P Q R S
(a) 1 3 4 2 (c) 4 1 2 3
(b) 2 4 3 1 (d) 3 2 1 4
Comprehension Based Questions
PASSAGE-1 (b)
P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize
Br2/H2O. On heating, P forms the cyclic anhydride. Upon treat-
ment with dilute alkaline KMnO4, P as well as Q could produce
one or more than one from S, T and U.

(c)

[JEE Adv. 2013]

1. Compounds formed from P and Q are, respectively
(a) Optically active S and optically active pair (d)
(T, U)
(b) Optically inactive S and optically inactive pair PASSAGE-2
(T, U) In the following reactions
(c) Optically active pair (T, U) and optically active S Pd - BaSO 4
C8 H6 C8 H8 ¾¾¾¾¾¾¾ (i) B2 H6
(ii)H 2 O2 , NaOH, H 2O
®X
(d) Optically inactive pair (T, U)) and optically inactive S H2
2. In the following reaction sequences V and W are respectively H2O
HgSO 4 ,H 2SO 4
Δ (i) EtMgBr, H O
C8 H 8 O ¾ ¾(ii)¾ ¾ ¾® 2
H + , heat
Y

3. Compound X is [JEE Adv. 2015]

(a) (b)

(a)

(c) (d)
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A-4

4. The major compound Y is [JEE Adv. 2015] 8. The product S is [JEEAdv. 2017]
H3C
CH3
(H3C)3C
(a)
(a)

COCH3
(b) COCH3
(H3C)3C CH3
(b)

H3COC
(c)
(H3C)3C H3C CH3
(c)

HO3S

(H3C)3C O CH3
(d)
(d)

COCH3
PASSAGE-3
9. The reactions, Q to R and R to S, are [JEEAdv. 2017]
By appropriately matching the information given in the three
(a) Dehydration and Friedel–Crafts acylation
columns of the following table. [JEE Adv. 2017] (b) Aromatic sulfonation and Friedel–Crafts acylation
Columns 1, 2 and 3 contain starting materials, reaction conditions, (c) Friedel–Crafts alkylation, dehydration and Friedel–
and type of reactions, respectively. Crafts acylation
Column 1 Column 2 Column 3 (d) Friedel–Crafts alkylation and Friedel–Crafts acylation
(I) Toluene (i) NaOH/Br2 (P) Condensation Integer Value Correct Type
(II) Acetophenone (ii) Br 2/hv (Q) Carboxylation 1. The total number of carboxylic acid groups in the product
(III) Benzaldehyde (iii) (CH3CO)2O/ (R) Substitution P is [JEE Adv. 2013]
CH3COOK O O
(IV) Phenol (iv) NaOH/CO2 (S) Haloform +
1.H 3O .D
5. For the synthesis of benzoic acid, the only CORRECT O 2.O3 P
combination is 3.H2 O2
(a) (II) (i) (S) (b) (IV) (ii) (P) O O
(c) (I) (iv) (Q) (d) (III) (iv) (R) 2. Consider all possible isomeric ketones, including
6. The only CORRECT combination that gives two different stereoisomers of MW = 100. All these isomers are
independently reacted with NaBH4 (NOTE: stereoisomers
carboxylic acids is are also reacted separately). The total number of ketones
(a) (II) (iv) (R) (b) (IV) (iii) (Q) that give a racemic product(s) is/are [JEE Adv. 2014]
(c) (III) (iii) (P) (d) (I) (i) (S) 3. Among the following, the number of reaction(s) that
7. The only CORRECT combination in which the reaction produce(s) benzaldehyde is [JEE Adv. 2015]
proceeds through radical mechanism is
(a) (III) (ii) (P) (b) (IV) (i) (Q) CO, HCl
I. ¾¾¾¾¾¾¾¾¾
®
(c) (II) (iii) (R) (d) (I) (ii) (R) Anhydrous AlCl3 /CuCl

PASSAGE-4
The reaction of compound P with CH3MgBr (excess) in (C2H5)2O H O
II. ¾¾¾®
2
followed by addition of H2O gives Q. The compound Q on treatment 100°C
with H2SO4 at 0ºC gives R. The reaction of R with CH3COCl in the
presence of anhydrous AlCl3 in CH2Cl2 followed by treatment with
H2O produces compound S. [Et in compound P is ethyl group] III. ¾¾¾¾¾
2 ®
H
Pd - BaSO 4
(H3C)3C CO2Et Q R S
DIBAL–H
¾¾¾¾¾¾®
IV. Toluene,–78°C
H 2O
P
 www.crackjee.xyz
A-5

PAST YEAR QUESTIONS JEE MAIN/AIEEE (2013 - 2017)

1. The most suitable reagent for the conversion of (b) CH3MgBr, H+/CH3OH, [Ag(NH3)2]+ OH–
R - CH 2 - OH ® R - CHO is: [JEE M 2014] (c) CH3MgBr, [Ag(NH3)2]+ OH–, H+/CH3OH
(a) KMnO4 (d) [Ag(NH3)2]+ OH–, CH3MgBr, H+/CH3OH
(b) K2Cr2O7 5. The major product obtained in the following reaction is :
(c) CrO3 [JEE M 2017]
(d) PCC (Pyridinium Chlorochromate)
2. In the reaction, O
LiAH PCl Alc.KOH
CH 3 COOH ¾¾¾¾
4 ® A ¾¾¾
5 ® B ¾¾¾¾® C,

the product C is: [JEE M 2014] DIBAL–H

(a) Acetaldehyde (b) Acetylene
(c) Ethylene (d) Acetyl chloride
3. In the following sequence of reactions : [JEE M 2015] COOH
OH OH
KMnO SOCl H / Pd
Toluene ¾¾¾¾
4
® A ¾¾¾
2
® B ¾¾¾®
2
BaSO
C
4

the product C is : (a) CHO (b) CHO

(a) C6H5CH2OH (b) C6H5CHO
COOH CHO
(c) C6H5COOH (d) C6H5CH3
4. The correct sequence of reagents for the following (c) CHO (d) CHO
conversion will be : [JEE M 2017]
O HO CH3 COOH CHO
6. Sodium salt of an organic acid 'X' produces effervescence
with conc. H2SO4. 'X' reacts with the acidified aqueous CaCl2
solution to give a white precipitate which decolourises acidic
HO–CH3 solution of KMnO4. 'X' is : [JEE M 2017]
CHO CH3 (a) C6H5COONa (b) HCOONa
(a) [Ag(NH3)2]+ OH–, H+/CH3OH, CH3MgBr (c) CH3COONa (d) Na2C2O4

SOLUTIONS
PAST YEAR QUESTIONS JEE ADVANCED/IIT-JEE (2013 - 2017)
MCQs with One Correct Answer –
1. (d) Carbolic acid (Phenol) is weaker acid than carbonic COOH COO
acid and hence does not liberate CO2 on treatment
with aq. NaHCO3 solution.
2. (d)
(i) CH 3 MgBr OH OH
(III) (stabilizes by –I effect)
(ii) aq. acid
O –
Cl O Cl O COOH COO
–
O O
3. (a) H H
COOH C
HO OH O O

OH OH
(IV) (destabilizes by +M effect)
(I) (stabilizes by more H-bonding)
–
\ acidity order is I > II > III > IV
O O 4. (a)
COOH H OH
O O
OH O O CH2
H–C–H / NaOH
H
[Cross aldol reaction]
(II) (stabilizes by H-bonding)
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A-6

OH OH
OH OH O O
O CH2 CH2 O
H–C–H / NaOH – +
+ HCOO H–C–H / H
[Cross cannizaro
Acetal formation
reaction]

MCQs with One or More Than One Correct

OH O OH
CHO

1. (b, d) CHCl +
¾¾¾¾
-
3®
OH

H3C CHCl2 (S)

(Minor)
CH3 CH3 (Major)
(Q)
-
® :CCl2 + H 2 O + Cl-
CHCl3 + OH ¾¾
– –
OH O O O OH OH
–
CCl2 CHCl2 CHO
- H ˆˆ† -
+ OH ¾¾
® +H2O ; +: CCl2 ¾¾
® ¾¾¾
OH ®

CH3 CH3 CH3 CH3 CH3 CH3 (major)

–
O O O

¾¾
® H 2O
¾¾¾ ®
–
: CCl2 H3C CCl2 H3C CHCl2 (minor)
CH3
O O
Br (1.0 mol)
2. (c) Reaction I : ¾¾¾¾¾
2 ® CH3COONa + CHBr3 +
CH3 CH3 Na ÅOH e CH3 CH3
(T) (U)
1.0 mol (unreacted)
O O
Br (1.0 mol)
Reaction II : ¾¾¾¾¾
2 ®
CH3 CH3 CH COOH3 CH3 CH2Br
1.0 mol (P)

KOH,
KOH,HH2OO
3. (a)

(Minor) (Major)
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A-7

4. (a, b, c) Aldehydes and a-Hydroxyketones show positive Tollen's test.

H O CHO
Tollen's Tollen's
H ¾¾¾¾® Silver mirror ¯ ¾¾¾¾® Silver mirror ¯
Reagent Reagent
H
H
OH O
Ph Tollen's Ph
Ph ¾¾¾¾® Silver mirror ¯ + Ph
Reagent
O O
Diketone

OH OH OH
CHO
(i) O2 CHCl3/NaOH
5. (b, c) +
(ii) H 3O+
P Q
(Major) CHO
R (Minor)

OH O – CH2Ph
CHO CHO
NaOH
PhCH 2Br
S

Q is steam volatile not R.

Q and R show positive test with 1% aqueous FeCl 3 solution.
Q, R, S give yellow precipitate with 2, 4-dinitrophenyl hydrazine.
6. (c, d)
LiAlH4/(C2H5)2O : Reduces to esters, carboxylic acid, epoxides and aldehydes and ketones.
BH3 in T.H.F : Reduces to –COOH and aldehydes into alcohols but do not reduce to esters and epoxides.
NaBH4 in C2H5OH : Reduces only aldehydes and ketones into alcohols but not to others.
Raney Ni in T.H.F. : Do not reduce to –COOH, –COOR and epoxide but it can reduce aldehyde into alcohols.
7. (a, b)
O O
(i) O 3, CH 2Cl 2
(c) CH3 Q (C8H8O), i.e., CH3 C + H – C– H
(ii) Zn, H2O
(Q) H
(P)
(+ve cannizaro reaction)
O
C O
(i) O 3, CH 2Cl 2
CH3
(ii) Zn, H2O
+ H – C– H

(R) CH3 (S) (+ve haloform reaction)

CH3 O O
O3, CH2Cl2
(d) C + CH3 – C– H
Zn, H2O
H
CH3 (+ve cannizaro reaction)
CH3
(P) (Q)

CH3 O
C C O
CH3 O3, CH2Cl 2
CH3 + CH3 – C– CH3
C
Zn, H2O
CH3
(R) CH3
(+ve haloform reaction)
(S)
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A-8

Match the Following

1. (a)
O O
(1) C6H 5CH2—C—O CH3 C6H 5CH 2 + CO 2 + CH 3 – O
O O
C O C
(2) C 6H5 O CH3 C 6H 5 O + CH 3 — O
O CH3
O CH3
(3) C6H5CH2—C—O C— CH3 CO2 + C6H5CH2 + CH3—C—O
CH2 – C6H5 CH2—C6H5
O
C O CH3 O CH3
(4) C6H5 O C—CH3 C6H5— C — O + O — C — CH3
CH3 CH3
Comprehension Based Questions
COOH
1. (b) HOOC COOH Cold alk. H OH
C=C ¾¾¾¾®
KMnO 4
H H
'P' (Cis) (Syn addition) H OH

COOH
Meso (S), optically inactive
COOH COOH
H COOH Cold alk. H OH OH H
C=C ¾¾¾¾® +
KMnO 4
HOOC H
'Q' (trans) (Syn addition) OH H H OH

COOH COOH
T U
(Racemic Mixture), optically inactive
O

H / Ni
2. (a) HOOC–CH=CH–COOH ¾¾¾¾
2
D
® O

Q O
V
O O
OH OH
Zn -Hg
H3PO 4
Anhydrous AlCl
+ O ¾¾¾¾¾¾3¾
® ¾¾¾¾ ®
O HCl O

O O
V
OH
3. (c) Pd-BaSO4 i. B 2H6
C8 H 6
H2 ii. H2 O2 , NaOH, H2O

H2O i. Et MgBr, H2O

4. (d) C8H6
HgSO4 , ii. H,+ Heat
H2SO4
Y
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A-9

COOH
+
H2O/H
5. (c)

6. (d) Perkin condensation of benzaldehyde with (CH3CO)2O/CH3COOK yields cis and trans form of cinnamic acid.
(i) CH 3 COONa
C6H5CHO + (CH3CO)2O ¾¾¾¾¾®   C6H5CH = CHCOOH
Benzaldehyde Acetic anhydride (ii) H+ Cinnamic acid
cis and trans
7. (a) Alkylbenzenes when treated with Br2 at high temperature, in the presence of sunlight and absence of halogen carrier
undergo halogenation in the side chain. Thus
CH3 CH2 Br CHBr2 CBr3

Br 2 / heat Br2 Br2

¾ ¾ ¾ ¾® ¾ ¾¾ ¾ ® ¾¾ ¾ ¾®
light heat, light heat, light
Toluene Benzyl chloride Benzyl chloride Benzo trichloride
8. (a) & 9. (d)
–+
O OMgBr
(CH3)3C C OEt (CH3)3C CH3 C CH3
CH MgBr(excess)/(C H ) O
¾¾¾¾¾¾¾¾¾¾¾®
3 2 5 2

(P)
H2O
H + H
O O H

(CH3)3C C(CH3)2 (CH3)3C CH3 C CH3

H SO
¬¾¾¾
2 4¾
0°C

(Q)
–H2O O
CH3
CH3 CH3
+ CH3 CH3 C Cl/AlCl3 (CH3)3C
(CH3)3C C(CH3)2 (CH3)3C (Friedel Craft Acylation)
(Friedel Craft
alkylation)

(R) COCH3
(S)

Integer Value Correct Type

O O O O O
COOH
1. (2) 1.H OÅ D O /H O HOOC
O ¾¾¾¾
3 ® ¾¾¾¾
–2CO
® ¾¾¾¾¾
3 2 2®
2 HOOC
COOH
O O O O O
No. of –COOH group is '2'
2. (5) General molecular formula for ketones is CnH2nO \ CnH2nO = 100 or 12n + 2n + 16 = 100, n = 6
Possible isomeric ketones with 6 carbon atoms are
O
O O
CH3 O CH3—CH—CH2—C—CH3
CH3CH2CH2 CH2—C—CH3 CH3CH2CH2—C—CH2CH3 *
CH3CH2CH—C—CH3 CH3
(I) (II) (III) (IV)
CH3 O
CH3 O CH3—C — C—CH3
CH3—CH—C—CH2CH3 CH3
(V) (VI)
Note that only isomer III has a chiral carbon so on reduction with NaBH4 it will give diastereomeric alcohols, while all other
five isomers will give racemic mixture.
 EBD_7090
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A-10

CHO

CO, HCl
3. (4) Anhyd AlCl3 /CuCl
(Gatterman Koch Reaction)

OH
CHCl 2 CH CHO
H2O OH
100°C – H2O

COCl CHO
H2
(Rosenmund Reduction)
Pd–BaSO 4

COOMe CHO
DIBAL–H
Toluene, –78°C H2O

PAST YEAR QUESTIONS JEE MAIN/AIEEE (2013 - 2017)

1. (d) An excellent reagent for oxidation of 1° alcohols to aldehydes is PCC.

PCC
R - CH 2 - OH ¾¾¾
® R - CHO
LiA1H PCl5 Alc. KOH
2. (c) CH3COOH ¾¾¾¾
4 ® CH CH OH
3 2 CH3CH2Cl CH2 = CH2
(A) (B) (C)
Hence the product (C) is ethylene.
CH3 COOH COCl CHO

KMnO4 SOCl2 H2/Pd

3. (b) BaSO 4

(A) (B) (C)

Rosenmund’s
reaction

O O O
CH3
H+/CH3OH
4. (a) [Ag(NH3)2]OH (esterification) CH3MgBr
Tollens reagent

CHO CO2H C H3C – C – CH3

O OCH3
OH
5. (b) DIBAL-H is an electrophilic reducing agent. It reduces both ester and carboxylic group into an aldehyde at low temperature.
O
O OH O

DIBAL - H
¾¾¾¾®
CHO
CO2H
6. (d) Na2C2O4 + H2SO4 ® Na2SO4 + CO­ + CO2­ + H2O
'x' (conc.)
Na2C2O4 + CaCl2 ® CaC2O4¯ + 2NaCl
' x' (white ppt.)
5CaC2O4 ¯ + 2KMnO4 + 8H2SO4 K2SO4 + 5CaSO4 + 2MnSO4 + 10CO2 + 8H2O
(purple) (colourless)