Aldehyde, Ketone and

04 Carboxylic Acid
Aldehyde and Ketone
Organic Compounds having C=O group are called carbonyl compounds and C=O group is known as
carbonyl group. It's general formula is CnH2nO (n = 1, 2, 3......) Carbonyl compounds are grouped into two
categories.
O
(a) Aldehydes: Aldehyde group is —C—H (also known as formyl group). It is a monovalent group
O
1°
Carbon atom of —C—H group is of 1° nature i.e. R—C=O
H
(b) Ketones: The carbonyl group C=O is a Ketonic group when its both the valencies are satisfied
by alkyl group. It is a bivalent group.
R 2°
Carbon atom of C=O group is of 2° nature i.e. C=O
R

Ketones are further classified as

R
(i) Simple or symmetrical ketones: Having two similar alkyl groups. C=O
R
R
(ii) Mixed or unsymmetrical ketones: Having two different alkyl groups. C=O
R’
Ex. (Ketones): Symmetrical Unsymmetrical

CH3 CH3CH2
C=O C=O
CH3 CH3
(Acetone or Dimethyl ketone) (Ethyl methyl ketone)
Propanone Butanone

Structure: In C=O compounds C-atom is sp2 hybridised which forms three  bonds and one 
bond. The unhybridised atomic orbital of C-atom and the parallel 2p orbital of oxygen forms the π
bond in C=O group.
C sp2 
C= O The C—C—O / H—C—O bond angle is 120°
C 

Due to electronegativity difference in C and O atoms, the C=O group is polar.

+ −
C=O Hence aldehydes and Ketones possess considerable dipole moment.

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General Methods of Preparation
1. From alcohol :
(a) By Oxidation of Alcohols
PCC
CH2Cl2
R—CH2—OH R—C—H
PDC O
1° alcohol CH2Cl2 Aldehyde
R O
[O]
R—CH—OH R—C—R
2° alcohol Ketones
R
[O]
R—C—OH No oxidation

R
3°alcohol
(b) Dehydrogenation of alcohols
Cu
CH3CH2OH 300°C CH3CHO (Acetaldehyde)

O
CH3—CH—CH3 Cu CH3—C—CH3 (Acetone)
300°C
OH
CH3 CH2
CH3—C—OH Cu CH3—C + H2O (Isobutylene)
300°C
CH3 CH3
2. From Hydrocarbons :
(a) By Reductive Ozonolysis Of Alkenes
O O
(i) O3
H3C—C CH—CH3 H3C—C—CH3 + CH3—C—H
(ii) Zn/H2O
CH3
(b) By Hydration of Alkynes (Kucherov Reaction)
OH O
dil.H2SO4/
H3C—C CH H3C—C CH2 H3C—C—CH3
HgSO4
enol keto
3. From Aromatic Hydrocarbons :
(a) Gatterman Koch Reaction
H O
C

+ CO + HCl AlCl3 or

Cu2Cl2

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Aldehyde, Ketone and Carboxylic Acid
(b) Etard reaction
Benzaldehyde is formed by oxidation of methyl benzene in presence of CrO2Cl2
CH3 CH(OCrOHCl2)2 CHO

CS2 H/H2O
+ CrO2Cl2

Toluene Chromyl (Chromium complex)

chloride
(c) Oxidation using CrO3 (Chromic oxide)
CH3 CH(OCOCH3)2 CHO

273-283 K H/H2O
+ CrO3 + (CH3CO)2O

(Acetic anhydride) (Benzylidene diacetate)
(d) By side chain chlorination followed by hydrolysis
Side chain chlorination of toluene gives benzal chloride which on hydrolysis gives benzaldehyde.
CH3 CHCl2 CHO

Cl2/hv H2O

4. From Cyanides :
(a) Stephen’s Reduction
Nitriles are reduced to corresponding imine with SnCl2 in the presence of HCl, which on hydrolysis
gives corresponding aldehyde.
H3O+
R—CN + SnCl2 + HCl R—CH=NH R—CH=O
DIBAL–H → Diisobutyl aluminum hydride [AlH(i-Bu)2]: is also used to obtain aldehyde from
cyanide/ester
1. AlH(i-Bu)2
R—CN R—CH=O
2. H2O
(b) Reaction with Grignard reagent
Treating a nitrile with Grignard reagent followed by hydrolysis yields a ketone.
ether CH3CH2—C NMgBr H3O+
CH3—CH2—CN + C6H5MgBr
C6H5

H3O+ O
CH3—CH2—C=NH C2H5—C + NH3
C6H5
C6H5
(1-Phenylpropanone)
5. From Acid Chloride :
2RMgX + CdCl2 → R2Cd + 2MgXCl
2R’—C—Cl + R2Cd → 2R’—C—R + CdCl2
O O
ketone

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BEGINNER’S BOX-1
1. Acids do not give the characteristic reactions of C=O group because of :-
(1) Dimerisation (2) Resonance
(3) Cyclic structures (4) Attached alkyl radical
2. Which reagent below cannot reduce an acid chloride to an aldehyde?
(1) H2/Pd-BaSO4 (2) NaH (3) LiAlH4 (4) DIBAL-H
3. Compound which gives only acetone on ozonolysis
(1) CH3–CH=CH–CH3 (2) (CH3)2C=C(CH3)2
(3) CH3–C=CH–CH3 (4) CH3CH=CH2
CH3
4. Catalyst SnCl2/HCl is used in
(1) Stephen’s reduction (2) Cannizzaro reaction
(3) Clemmensen reduction (4) Rosenmund’s reduction
5. Hydrogenation of benzoyl chloride in the presence of Pd gives
(1) Benzyl alcohol (2) Benzaldehyde (3) Benzoic acid (4) Phenol

Physical Properties
State: Only formaldehyde is gas, all other carbonyl compounds upto C11 are liquids and C12 onwards solid.

Solubility: C1 to C3 (formaldehyde, acetaldehyde and propionaldehyde) and acetone are highly soluble
+ −
in water due to polarity of C=O bond and can form H–bond with water molecule. C5 onwards are
insoluble in water.

H+
1
+ − + So lubility 
C=O H—O− Molecular weight

H-bonding

Boiling point: Boiling point  Molecular weight

Boiling point order is - Alcohol  Ketone  Aldehydes  Alkane (of comparable molecular mass)
This is because in alcohols intermolecular H-bonding is present but in carbonyl compounds H-bonding
doesn't exist, instead dipole-dipole and Vander Waal force of attraction is present. Alkanes are non-polar.
+ − + −
C=O C=O
Density: Density of carbonyl compounds is lower than water.

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Aldehyde, Ketone and Carboxylic Acid
Chemical Properties
Carbonyl compounds undergo following reactions:
1. Nucleophilic addition reactions (NAR) :
NAR is characteristic reaction of aldehydes and ketones
Mechanism
E
O O O
Nu E
C C C
rds fast
R R’ R R’ R Nu R’
Nu
Aldehyde/Ketone
Generally rate towards NAR  Electrophilicity of carbonyl group.
1

Steric hindrance
Generally, Rate towards NAR:
Aliphatic > Aromatic > Aliphatic > Aromatic
aldehyde aldehyde ketone ketone
O O O O
C C C C
R H H R R R

Stereochemistry of Reaction :
Nu
Nu
E C
C R’
R’ OE
R’ Nu O R
R
Enantiomers
C O
R R
Nu R OE
O E
Aldehyde/Ketone R’ C R’ C

Nu Nu

Note: If RR’ then racemic mixture will be formed.

(50 % ‘d’ and 50% ‘I’)
If R = R’ then racemic mixture is not obtained.
(i) Reaction with HCN/OH
HCN – weak acid
HCN + OH CN + H2O
Pure HCN – Rate of reaction is slow so reaction is base catalyzed.
Mechanism
O O OH
CN H–O–H
C C C
R R’ R R’ R R’
CN CN
Aldehyde/Ketone (Cyanohydrin)

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Illustration 1:
Which of the following will react with HCN to form racemic mixture ?
O O O O
(1) C (2) C (3) C (4) C
H H H3C H Ph Ph H3C CH3
Solution :
CN
CH3—C—H + H—CN CH3—C—H
O OH
Product has chiral carbon
In remaining no chiral carbon in product.

(ii) Reaction With NaHSO3 (sodium hydrogensulpite / sodium bisulphite)

O ONa OH
NaHSO3 H Bisulphite addition
C C C compound
transfer
R R’ R R’ R R’
SO3H SO 3Na
Aldehyde/ketone (White crystalline product)
(Water soluble)
Note: Reaction is sterically sensitive and given by all aldehydes, aliphatic methyl ketones
O O
—C—CH3 R—C—CH3
(methyl ketone) (aliphatic methyl ketone)
Note: The bisulphite addition compound can be converted back to the original carbonyl
compound by treating it with dilute acid or base.
Hence this reaction is useful for separation and purification of aldehydes (and some ketones)

(iii) Reaction With Grignard Reagent (RMgX)

O OH
(ii) H/H2O
CH3—MgBr + H—C—H H—C—H 1° alcohol

CH3
O OH
(ii) H/H2O
CH3—MgBr + H3C—C—H H3C—C—H 2° alcohol
CH3
O OH
(ii) H/H2O
CH3—MgBr + H3C—C—CH3 H3C—C—CH3 3° alcohol
CH3

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Aldehyde, Ketone and Carboxylic Acid
(iv) Reaction with ROH (Alcohol) (addition then elimination)
O OH OR’
R R’OH R
R’OH
C C C + H2O
dry HCl dry HCl
R H H OR’ H OR’
Hemi-acetal Acetal
O OH OR’
R R
R’OH R’OH
C C C + H2O
dry HCl dry HCl
R R R OR’ R OR’
Hemi-ketal Ketal

Note:
1. To move equilibrium in forward direction excess ROH is used and H2O is removed.
2. Aq. HCl not used as it will shift equilibrium in backward direction.
3. HCl used to make ‘C’ of carbonyl group more electrophilic.
H
O O OH
H
C C C
R H R H R H
more electrophilic
4. Acetals and ketals are hydrolysed with aq. mineral acid to yield corresponding aldehydes
and ketones.
Mechanism
H
O O OH OH2
R R
H R’OH
C C C C
R H R H H H–O–R’ H OR’

–H2O

R OR’ R H–OR’ R
C –H C R’OH C
H OR’ H OR’ H OR’

R H–O–R’ R OR’
–H2O
Directly C=O + C
H H OR’
H–O–R’
(v) Reaction with H2O
R R OH
H
C=O + H2O C
R' R’OH
Aldehdye/Keto Unstable hydrate
ne (generally)

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Mechanism
H
O O OH
H H2O
C C C
R R’ R R’ R R’
OH
(vi) Reaction with NH3 and It’s Derivatives (addition then elimination)
R pH 4-5 R
C O + H2N—H C N—H + H2O
R’ R’
Aldehyde/Ketone
R R
pH 4-5
C O + H2N—Z C N—Z + H2O
R’ R’
Aldehyde/Ketone NH2–Z – Ammonia derivatives
Ex : NH2OH (hydroxyl amine)
NH2NH2 (hydrazine)
Note:
1. Mild acidic medium used – To make ‘C’ of carbonyl group more electrophilic.
2. It is an addition elimination reaction.
R H R
C O+ N—NH2 C N—NH2
R’ H R’
(Hydrazine) (Hydrazone)
R H R
C O+ N—NH—Ph C N—NH—Ph
R’ H R’
(Phenyl hydrazine) (Phenyl hydrazone)
R H R
C O+ N—OH C N—OH
R’ H R’
(Hydroxyl amine) (Oxime)
O O
R H R
C O+ N—NH—C—NH2 C NH—C—NH2
R’ H R’
(Semi-carbazide) (Semi-carbazone)

O2N O2N
R H R
C O+ N—NH NO2 C N—NH NO2
R’ H R’

(2,4 Dinitrophenyl hydrazine) (2,4 Dinitrophenyl hydrazone)

(2,4-DNP or Brady’s reagent)

2,4-DNP Test: Aldehyes and ketone react with 2,4-DNP to give red, orange or yellow ppt.
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Aldehyde, Ketone and Carboxylic Acid

BEGINNER’S BOX-2
1. Which gives stable hydrate?
(1) CH3—C—H (2) Ph—CHO (3) CCl3—CHO (4) CH3—C—CH3
O O

Ph—CHO + Ph—NH2 H
2.

(1) Ph—CH2—Ph (2) Ph—CH2—NH2 (3) Ph—CH=NH—Ph (4) Ph—CH2—NH—Ph

3. Which is the best nucleophile ?
1 2 3
NH2—C—NH—NH2
O
(1) 1 (2) 2 (3) 3 (4) All are same
4. Which gives DNP test?
(1) Ph—CO—CH3 (2) Ph—CHO
(3) CH3—COCH3—CH3 (4) All of these
5. Which gives two oxime when reacted with NH2—OH?
(1) H—CHO (2) Ph—COPh (3) CH3—COCH3 (4) Ph—COCH3

2. Reduction of aldehyde/ketone:
The nature of product depends upon the reducing agent used.
(i) C=O ⎯→ CH2 Reducing agents are
⚫ Red P/HI at 150°C
⚫ Zn-Hg/HCl [Clemmensen reduction]
⚫ (i) N2H4 (ii) OH/ [Wolff Kishner reduction]

(ii) C=O ⎯→ CHOH Reducing agents are

⚫ Metal + H2 ⚫ LiAlH4
⚫ NaBH4 ⚫ Na + C2H5OH
3. Oxidation of aldehyde/ketone:
Aldehydes are easily oxidised to carboxylic acids on treatment with strong oxidising agents like
KMnO4, K2Cr2O7.
Ketones are oxidised under vigorous conditions, i.e., strong oxidising agents and at elevated
temperatures.
[O]
R—CHO R—COOH
[O]
R—CH2—C—CH2—R’ R—COOH + R’—CH2COOH + R—CH2COOH + R’—COOH
O (By clevage of C1—C2 bond) (By clevage of C2—C3 bond)

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Oxidation of only aldehyde
Reducing character: Aldehydes are easily oxidised so they are strong reducing agents.
(i) Tollens' reagent: It oxidises aldehydes. Tollens' reagent is ammoniacal silver nitrate
solution
(AgNO3+NH4OH) ⎯⎯→ [Ag(NH3)2]OH
RCHO+[Ag(NH3)2]OH ⎯⎯→ RCOO + Ag + H2O
Silver mirror
(ii) Fehling's solution: It is a mixture of aqueous CuSO4, NaOH and sodium potassium
tartarate.
Fehling solution A– aq. solution of CuSO4
Fehling solution B– Roschelle salt (Sodium potassium tartarate + NaOH)
Fehling solution A + Fehling solution B (Dark blue colour of cupric tartarate)
RCHO + Cu+2 + OH– ⎯⎯→ RCOO + Cu2O
(Cuprous oxide–Red ppt.)
Cu2+ ⎯⎯→ Cu+
(Cupric - Blue) (Cuprous - Red ppt.)

(iii) Benedict's solution: It is a mixture of CuSO4 + sodium citrate + NaOH. It provides Cu+2. It
is reduced by aldehyde to give red ppt of cuprous oxide.
RCHO + Cu2+ + OH– ⎯⎯→ RCOO + Cu2O
(Cuprous oxide–Red ppt.)
(iv) Schiff's reagent: Dilute solution of p-rosaniline hydrochloride or magenta dye, is a pink
coloured dye and is known as schiff's dye.
Its pink colour is discharged by passing SO2 gas and the colourless solution obtained is
called schiff's reagent aldehyde reacts with this reagent to restore the pink colour.
Note:
1. All above four methods are used to distinguished aldehydes and ketones.
2. Aromatic aldehyde does not give F.S. and B.S. test.
4. Oxidation of methyl ketone (haloform reaction) :
When methyl ketones react with halogen in the presence of base oxidation of methyl ketones takes place.
O O
R—C—CH3 + 3X2 + 4NaOH R—C—ONa + CHX3 (Haloform)
Salt of carboxylic acid
CHCl3 – Chloroform (liquid)
CHBr3 – Bromoform (liquid)
CHI3 – Iodoform (yellow solid)

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Aldehyde, Ketone and Carboxylic Acid
Ketones → Methyl ketones undergo haloform reaction
O
R—C—CH3
Aldehydes → Only acetaldehyde can undergo haloform reaction
O
H3C—C—H
Alcohols → Alcohols of the following type also undergo haloform reaction
OH

—CH—CH3
NaOH + X2 is also a mild oxidizing agent
OH O
NaOX
H3C—CH—CH3 H3C—C—CH3
(Gives iodoform test)

NaOX
H3C—CH2—OH H3C—CHO
(Gives iodoform test)
Illustration 2:
Which of the following compounds will give positive iodoform test?
O O
(i) H3C—CH2—C—H (ii) H3C—C—NH2

O
(iii)H3C—CH2—C—H (iv) H3C—CH2—CH—CH3
I OH
(v) Ph—CH2—OH (vi) Ph—CH—OH
CH3
Solution:
Ans. (iii), (iv), (vi)

5. Aldol Condensation :
Carbonyl compounds which contain -H atoms undergo condensation with dil. NaOH to give aldol.
Aldol contains both alcoholic and carbonyl group, which on heating in alkaline medium gets
converted into , -unsaturated carbonyl compound.
   
CH3—CH + HCH2CHO dil CH3—CH—CH—CHO OH/ CH3—CH=CH—CHO
NaOH –H2O
O OH H Crotonaldehyde

Mechanism of aldol condensation: It takes place in the following two stages:

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(i) Formation of Carbanion
(ii) Combination of carbanion with other carbonyl molecule.

(i) Formation of Carbanion: -H atom of C=O group are quite acidic which can be removed
as proton, by a base

+ −
OH + H—CH2—C—H CH2—C—H + H2O
O O
Base Acetaldehyde Carbanion
Carbanion thus formed is stable because of resonance –

CH2—C—H CH2=C—H
O O

(ii) Combination of carbanion with other carbonyl molecule:

Identical carbonyl compounds ⎯⎯

→ Simple or self aldol condensation.
Different carbonyl compounds ⎯⎯
→ Mixed or crossed aldol condensation.

Simple or Self condensation

CH3 CH3
   
CH3—C—CH3 + H—CH2COCH3 CH3—C—CH2—COCH3 CH3—C=CH—COCH3 + H2O

O OH Mesityl oxide

Mixed or Crossed aldol Condensation

  
CH3—CH + H—CH2COCH3 CH3—CH—CH2—COCH3 NaOH – H2O

O OH

6. Cannizzaro Reaction :
Those aldehydes which do not contain  - H atom give this reaction, with conc. NaOH or KOH:
Products are Salt of carboxylic acid and alcohol
In this reaction one molecule of aldehyde is oxidised to acid, while other is reduced to alcohol, such
type of reactions are called redox reaction.
Conc.
HCHO + HCHO ⎯⎯⎯ → HCOONa + CH3OH
NaOH,

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Aldehyde, Ketone and Carboxylic Acid
Mechanism involved in Cannizzaro’s reaction
Θ
(a) Rapid reversible addition of OH to one molecule of HCHO.
OH
OH
H—C—H H—C—H
O O

Θ
(b) Transfer of hydride ion H to second molecule of HCHO

OH OH O O OH

H—C—H + H—C—H H—C + H—C—H H—C + H—C—H

O O O H O H
acid salt alcohol

When molecules are same ⎯⎯

→Simple cannizzaro reaction
Two different molecules ⎯⎯
→Mixed cannizzaro reaction

Note:
1. In mixed or crossed cannizzaro reaction more reactive aldehyde is oxidised and less
reactive aldelyde is reduced.
NaOH
HCHO + C6H5CHO ⎯⎯⎯
→ HCOONa + C6H5CH2OH

Oxidized Reduced
(Sodium formate) (Benzyl alcohol)
2. Ketone does not give Cannizzaro due to poor leaving tendency.
CHO CH2OH
O O
Ex. conc. NaOH + H—C—ONa
+ H—C—H

7. Electrophilic Substitution Reaction :

Aromatic aldehydes and ketones undergo electrophilic substitution at the ring in which the
carbonyl group acts as a deactivating and meta-directing group.
CHO CHO
HNO3/H2SO4
273–283 K
NO2
Benzaldehyde m-Nitrobezaldehyde

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BEGINNER’S BOX-3
1. The compounds capable in reaction with Tollen's reagent is (are) :
(1) Formaldehyde (2) Formic acid (3) Acetaldehyde (4) All the above
2. Acetaldehyde reacts with NaOH to form :-
OH H
(1) CH3–CH2–CH–C=O (2)

(3) (4)

3. Fehling's solution is a :-
(1) Solution of magenta dye bleached by SO2
(2) Ammonical solution of AgNO3
(3) Mixture of a solution of CuSO4 and a solution of caustic soda and sodium potassium tartarate
(4) Alcoholic solution of 2,4-dinitrophenylhydrazine
4. The compound that will not give iodoform on treatment with alkali and iodine is:
(1) Acetone (2) Ethanol (3) Diethyl ketone (4) Isopropyl alcohol
5. Which of the following will not give the iodoform test?
(1) Acetophenone (2) Ethanal (3) Benzophenone (4) Ethanol
6. Which of the following give yellow precipitate with NaOH+I2?
(1) Acetone (2) CH3—C—Cl (3) Benzaldehyde (4) CH3—C—O—CH3
O O
7. How will you convert butan-2-one to propanoic acid?
(1) Tollens reagent (2) Felling’s solution
(3) NaOH/I2/ and H + (4) NaOH/NAI/H+
C—CH3 NaOH
8. P.P.T.
O I2

PPT of-
I
(1) CH3I (2) CHI3 (3) (4) CH2I2

Carboxylic acid
Organic compounds having –COOH group are called Carboxylic acids. This functional group is composed of
O

Carbonyl (—C—) and hydroxyl (–OH) group.

O O
—C— + —OH ⎯⎯→ —C—OH
Carbonyl group Hydroxyl group Carboxylic group
The properties of the carboxylic group are not simply the combined properties of these two groups, but it
has its own distinctive properties. The acidic nature of carboxylic acids is due to the presence of replaceable
H-atom in the Carboxylic group.
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Aldehyde, Ketone and Carboxylic Acid
Classification :
Monocarboxylic acid (RCOOH): Having one carboxylic group, also called monobasic acid.
General molecular formula - CnH2nO2 (n = 1, 2, 3, ........). Higher mono carboxylic acids are called fatty acids.

Dicarboxylic acid: Having two carboxylic groups, also called dibasic acid.
COOH
Ex. Oxalic acid
COOH

Tricarboxylic acid: Having three carboxylic groups also called tribasic acid.
CH2COOH
Ex. HO—C—COOH Citric acid
CH2COOH
Structure: The carbon atom of –COOH group is sp2 hybridised, this C- atom is in centre and thus bond
angle around C-atom is 120°.

General Methods of Preparation

1. By Oxidation of alcohols and carbonyl compounds :
Oxidation is carried out by acidified K2Cr2O7 or KMnO4.
[O] [O]
RCH2OH ⎯⎯⎯⎯⎯⎯
K Cr O /H SO
→ RCHO ⎯⎯→ RCOOH
2 2 7 2 4

Acids are third oxidation products of alkane.

[O] [O] [O]
R—H ⎯⎯ → R—OH ⎯⎯ → R—CHO ⎯⎯ → R—COOH

2. From Alkyl Benzenes :

Oxidation using

(a) KMnO4 /H

(b) KMnO4 /OH/ 

(c) K2Cr2O7 /H
C(H, , O) COOH COO

or

CH3 COOH

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(No oxidation)

(No hydrogen, no  bond, no oxygen)

3. By hydrolysis of alkane nitriles or cyanides :

Complete hydrolysis takes place in acidic medium (dil. HCl) or in alkaline medium
OH O O
H2O/H Tautomerism H2O/H
R—CN R—C=NH R—C—NH2 R—C—OH + NH3
 

4. From Grignard's reagent :

O O
H2O X
RMgX + O=C=O R—C—OMgX R—C—OH + Mg
OH
Carbon dioxide
Solid CO2 (dry ice) is used

5. By hydrolysis of acid derivatives :

O O
R—C—Z + H—OH R—C—OH + HZ
Z = —Cl, —OCOR, —OR, —NH2
Reactivity order of acid derivatives: RCOCl > (RCO)2 O > RCOOR > RCONH2

HOH
RCOCl ⎯⎯⎯
dil.acid
→ RCOOH + HCl
HOH
(RCO)2O ⎯⎯⎯
dil.acid
→ 2RCOOH
HOH
RCOOR' ⎯⎯⎯
dil.acid
→ RCOOH + R'OH
HOH
R—CONH2 ⎯⎯⎯
dil.acid
→ RCOOH + NH3

Physical Properties
Carboxylic acids from C1— C4 are completely soluble in water.
1
Solubility 
molecular weight

Solubility is due to intermolecular H - bonding with water molecules.

Boiling point: B. P.  Molecular weight

B. P. : Carboxylic acids > alcohol

This is because in acids two oxygen atoms take part in H - bonding (while in alcohol only one
O - atom takes part).

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Aldehyde, Ketone and Carboxylic Acid
Reactions of Carboxylic Acids (Chemical Properties)

1. Formation of Anhydrides :
H/
O O O O
R—C—OH + HO—C—R R—C—O—C—R
P2O 5

Note:
O
P2O 5
R—C—NH2 R—CN + H2O


2. Esterification Reaction :
Carboxylic acids react with alcohols or phenols in the presence of an acid (conc.H 2SO4 or dry HCl)
to form esters. This method is called Fischer esterification.
O
H
RCOOH + R’OH R—C—OR’ + H2O

O O
H
H3C—C—OH + CH3OH H3C—C—OCH3 + H2O
O O
18
C—OH C—OCH3
18 H
+ CH3OH + H2O

Mechanism
••
OH OH
••

••
O H O—H R’—OH
•• Proton
•• R—C—O—R’
R—C •• R—C R—C—O—R’
O—H O—H transfer
••
OH H OH2
••

Carboxylic acid ••

Tetrahedral intermediate
-H2O

O -H O—R’
R—C R—C ••
••
O—R’ O—H
••

Ester Protonated ester

1
Rate of esterification 
Steric hindrance

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 NEET : Chemistry
Reactivity of alcohols
CH3
H3C—C—OH < H3C—CH—OH < H3C—CH2—OH
CH3 CH3
3°Alcohol 2°Alcohol 1°Alcohol
Reactivity of acids
CH3
H3C—C—COOH < H3C—CH—COOH < H3C—CH2—COOH
CH3 CH3
3. Reaction with PCl3, PCl5, SOCl2 :

3R—COOH PCl3 3R—COCl + H3PO3

R—COOH PCl5
R—COCl + POCl3 + HCl

R—COOH SOCl2 R—COCl + SO2 + HCl

4. Reaction with Ammonia :


R—COOH + NH3 R—COONH4 R—CONH2 + H2O
(Ammonium carboxylate) (Amide)

 H3C—CONH2 + H2O
H3C—COOH + NH3 H3C—COONH4
(Acetic acid) (Ammonium acetate) (Acetamide)
COOH CONH2
NH3
+ H2O


COOH COONH4 CONH2

NH3  + 2H2O
COOH COONH4 CONH2
(Phthalic acid) (Ammonium phthalate) (Phthalamide)

Strong
–NH3 heating

O O CO
—C—NH—C— NH
(Imide) CO
(Phthalimide)

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Aldehyde, Ketone and Carboxylic Acid
5. Reduction :
Carboxylic acids are reduced to primary alcohols by lithium aluminum hydride or better with
diborane. Diborane does not easily reduce functional groups such as ester, nitro, halo, etc. Sodium
borohydride does not reduce the carboxyl group.
(i) LiAlH4/ether or B2H6
R—COOH R—CH2OH
(ii) H3O+

6. Decarboxylation :
Removal of CO2 from carboxylic acid is known as decarboxylation.
Reagent used: NaOH + CaO (Soda lime)
NaOH/CaO
CH3COOH CH4 + Na2CO3

-keto carboxylic acids
-keto acid can be easily decarboxylated by heating only (no need of sodalime)
O O
CH —C—CH —COOH  CH —C—CH —H + CO
3 2 3 2 2

(-Keto acid) (Acetone)

O O O O
COOH HOOC COOH
 
+ CO2 + 2CO2

7. Hell Volhard Zelinsky (HVZ) Reaction :

Carboxylic acids having  hydrogen atom are halogenated at the  position on treatment with chlorine
or bromine in the presence of small amount of red phosphorous to give -halocarboxylic acids.
 (i) X2/Red P 
R—CH2—COOH R—CH—COOH
(ii) H2O
X
Cl
 P/Cl2  P/Cl2
H3C—CH2—COOH H3C—CH—COOH H3C—C—COOH
Cl Cl
8. Ring Substitution :
Aromatic carboxylic acids undergo electrophilic substitution reactions in which the carboxyl group
acts as a deactivating and meta-directing group. They however, do not undergo Friedel-Crafts
reaction (because the carboxyl group is deactivating and the catalyst aluminium chloride (Lewis
acid) gets bonded to the carboxyl group).
COOH COOH

Conc. HNO3 +
(i)
Conc. H2SO4 NO2
m-Nitrobenzoic acid

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 NEET : Chemistry
COOH COOH

Br2/FeBr3
(ii)
Br
m-Bromobenzoic acid
••
Chemical Reaction of Acid Derivatives R—C—Z
O
•• •• •• •• ••
–Z may be → –OR, –X, –OCOR, –NH2

R—C—OR R—C—X R—C—O—C—R R—C—NH2

O O O O O
Ester Acid halide Anhydride Amide
Characteristic reaction of acid derivative is nucleophilic substitution reaction (NSR)
••
Ex. R—C—Z + E—Nu R—C—Nu + E—Z
O O
Acid derivative Product
Mechanism
••
O O
•• O
••
CH3—C + Nu CH3—C—Nu CH3—C—Nu + Z
Z Z
In this reaction Z is leaving group and weak bases are good leaving groups.
Reactivity order: CH3COCl > CH3COOCOCH3 > CH3COOC2H5 > CH3CONH2
1. Reaction with water (Hydrolysis) :
•• ••
Ex. R—C—Z + H—OH R—C—OH + Z—H
O O
Hydrolysis of acid derivative gives carboxylic acid.

(i) CH3—CH2—C—Cl + H—OH CH3—CH2—C—OH

O O
Acid halide

H
(ii) Ph—CH2—C—O—CH3 + H—OH Ph—CH2—C—OH + CH3—OH
O O
(ester)

(iii) H
CH3—C—NH—CH3 + H—OH CH3—C—OH + CH3—NH2
O O H CH3—NH3
(Amide)

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Aldehyde, Ketone and Carboxylic Acid
2. Reaction with Alcohol :
•• •• ••
R—C—Z + R—OH R—C—OR + Z—H
O O
(ester)
C—Cl –HCl C—O—CH2—CH3
(i) + CH3—CH2—OH
O O
(ii) CH3—C—O—CH2—CH3 + CH3—OH CH3—C—O—CH3 + CH3—CH2—OH
O O
Transesterification → formation of ester from another ester
3. Reaction with Ammonia :
•• •• ••
R—C—Z + NH2—H R—C—NH2 + Z—H
O O
(amide)
CH3—C—Cl + NH2—H Base CH3—C—NH2
••
(i)
O O
(ii) CH3—C—O—CH3 + R—NH—H CH3—C—NH—R + CH3—OH
O Amine O
Amide
(iii) CH3—C—O—C—CH3 + NH2—NH—H CH3—C—NH—NH2 + CH3—C—OH
O O O O
4. Reaction with Grignard reagent :
••
R—C—Z + RMgX NSR ••
R—C—R + ZMgX
O O
ketone
(i) CH3—C—Cl + EtMgCl CH3—C—Et + MgCl2
O O
ketone
If RMgX is used in excess then alcohol is obtained
CH3
C—Cl C—CH3 CH3MgCl C—CH3
+ CH3MgCl
O O OMgCl

CH3
C—CH3 H–OH

OH
NSR
(ii) CH3—C—O—CH3 + PhMgBr CH3—C—Ph
O O
ketone

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 NEET : Chemistry

BEGINNER’S BOX-4
1. Alkanoic acids can be prepared by hydrolysis of:-
(1) Trihaloalkanes (2) 1,1,1–trihaloalkanes
(3) Grignard reagents (4) Ketones
2. Acids have much higher boiling points than isomeric esters because :-
(1) Acids form dimers by H–Bonding
(2) Acids are volatile in steam
(3) Esters are non–volatile
(4) Acids can ionise to give protons in aqueous solution
3. Which of the following compounds can form intermolecular H–bonds :-
(1) Ethyl acetate (2) Methyl formate
(3) Acetamide (4) Acetic anhydride
4. Reaction of ethyl acetate with sodium ethoxide gives acetoacetic ester. This reaction is known with
the name of :-
(1) Claisen (2) Clemmensen
(3) Cannizaro (4) Etard

BEGINNER’S BOX ANSWER KEY

Que. 1 2 3 4 5
BEGINNER'S BOX-1
Ans. 2 3 2 1 1

Que. 1 2 3 4 5
BEGINNER'S BOX-2
Ans. 3 3 3 4 4

Que. 1 2 3 4 5 6 7 8
BEGINNER'S BOX-3
Ans. 4 2 3 3 3 1 3 2

Que. 1 2 3 4
BEGINNER'S BOX-4
Ans. 2 1 3 1

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