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Introduction
Aldehydes and ketones are the compounds containing a carbonyl group, >C=O, in which a
carbon atom is linked to an oxygen atom by a double bond. They have the same general formula
O O
|| ||
CnH2nO. The general structure of aldehydes is R − C − H and that of ketones is R − C − R where
R and R may be same or different. Formaldehyde represents the simplest aldehyde in which the
O
||
carbonyl group is attached to two hydrogen atom, i.e., H − C − H . Formaldehyde is exceptional in
that the carbonyl group carries two hydrogen atoms and no alkyl substituents. It is, therefore, not
surprising that it displays characteristic properties.

Nomenclature
The common name of aldehydes are derived from the names of the corresponding carboxylic
acids by replacing –oic acid by –al.
The IUPAC names of aldehydes follow the usual pattern. The longest chain containing the –CHO
group is considered the parent structure and named by replacing –e of the corresponding alkane
by –al. The position of the substituent is indicated by a number, the carbonyl carbon always
being considered C-1. Here, as with the carboxylic acids, the C-2 of the IUPAC name
corresponds to alpha of the common name.
H H H3C H3C H

H H3C H

O O O O
formaldehyde acetaldehyde propionaldehyde butyraldehyde
H H
O2 N H3C
O O O
benzaldehyde 4-nitrobenzaldehyde 4-methylbenzaldehyde
CH3

H
OH
1-(2-hydroxyphenyl)ethanone O
phenylacetaldehyde
CH3
H H
H
H3C O H3C O H3C

O
CH3 H3C 4-methylpentanal
2-methylpentanal 3-methylpentanal

The simplest aliphatic ketone has the common name acetone. For most other aliphatic ketones we
name the two groups that are attached to carbonyl carbon and follow these names by the word
ketone. A ketone in which the carbonyl group is attached to a benzene ring is named as a-
phenone, all illustrated below. According to IUPAC system, the longest chain carrying the

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carbonyl group is considered the parent structure, and is named by replacing –e of the
corresponding alkane with one. The positions of various groups are indicated by numbers.
CH3 H3C H3C CH3
H3C CH3
O O O
acetone butan-2-one pentan-2-one
H3C H3C CH3

O CH3 H3C O CH3

pentan-3-one 3-methylbutan-2-one O
1-phenylacetone
NO 2
2 3

4
CH3
6 5
CH3 5 6

H3C 4

O O 3 2 O
O
1-phenylethanone 1-phenylbutan-1-one benzophenone (4-methylphenyl)(4-nitrophenyl)methanone

Structure of Carbonyl Group

A carbonyl group consists of a carbon-oxygen double bond. Here the carbon atom utilizes its
three sp2 hybrid orbtials to form bonds with three atoms, one of them being oxygen. An
unhybridized p orbital is left on the carbon atom. The oxygen atom on the other hand, has two sp
hybrid orbitals, one of which contains one electron and forms a  bond with carbon atom. The
other sp hybrid orbital of oxygen has a pair of electrons and points away from the  bond
(between carbon and oxygen). As a result of hybridization in oxygen, two unhybridized p orbitals
are left. One of them accommodates an electron whereas the other p-orbital contains a pair of
electrons. The p-orbital of oxygen containing a single electron is parallel to the unhybridized p-
orbital of carbon. These two orbitals overlap sideways forming the  bond between the two
atoms.

Thus in a carbonyl compound, the carbonyl carbon, oxygen and the other two atoms (attached to
the carbon) are coplanar and are directed at an angle of 120° from each other. The structure of
carbonyl group may thus be written as below with formaldehyde as an example.
p-p- overlapping

H p − orbital
 bonds C O
H sp − hybrid orbital

 bonds
Fig. Orbital formulation of formaldehyde

Because of the difference in the electronegativities of carbon and oxygen, the  electron density
around oxygen is more than that at the carbon. Hence, carbon and oxygen atoms assume partial
positive and negative charges, respectively.

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 bond
H H + −
120 C O or C O
H H

Methods of Preparation
Aldehydes by Oxidation of 1° Alcohol: Aldehydes can be prepared from 1° alcohol by
oxidation with pyridinium chlorchromate (PCC) In CH2Cl2 solvent.
O O
R [O]
R
[O]
R
[H] [H]
OH H OH
O
−
R
⎯⎯⎯⎯⎯⎯⎯⎯
C6 H5 NHCrO3Cl (PCC)
CH Cl
→ R
2 2

OH H

Ketones by Oxidation of 2° Alcohol

OH O

⎯⎯⎯⎯
→H 2 CrO4

R R' R R'

Secondary alcohols can be oxidized to ketones. The reaction usually stops at the ketone stage
because further oxidation requires the breaking of C – C bond.

Aldehydes by Reduction of Acyl Chlorides, Esters and Nitriles: Theoretically, it ought

to be possible to prepare aldehydes by reduction of carboxylic acids. In practice, it is not
possible, because the reagent normally used to reduce carboxylic acid directly is LiAlH 4 and
when any carboxylic acid is treated with LAH, it is reduced all the way to 1° alcohol. This
happens because LAH is a powerful reducing agent and aldehydes are very readily reduced. Any
aldehydes that might be formed in the reaction mixture is reduced by the LAH to 1° alcohol.

O O

⎯⎯⎯⎯
→
LiAlH 4 ⎯⎯⎯
LiAlH 4
⎯→ R
R OH R H
OH
1° alcohol

The secret of success here is not to use a carboxylic acid itself, but use a derivative of carboxylic
acid that is more readily reduced, and to use an aluminium hydride derivative that is less reactive
than LAH. We shall study derivative of carboxylic acid, but suffice it to say here that acyl
chlorides, esters and nitrile are all easily prepared from carboxylic acid, and they all are more
easily reduced. Two derivative of aluminium hydride that are less reactive than LAH (in part
because they are much more sterically hindered and therefore, have difficulty in transferring
hydride ion) are lithium tri-tert-butoxyaluminium hydride and diisobutyl aluminium hydride
(DIBAL-H).

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CH3 CH3

O CH3
H CH3
CH3 Al CH3
Li + O Al
H3C O H
H3C CH3
CH3
CH3 H3C CH3
Diisobutylaluminium hydride
i-Bu2OH or DIBAL-H

Lithium tri-tert-butoxyaluminium hydride

The following scheme summarises how these reagents are used to synthesise aldehydes from acid
derivatives.
O O
i) LAH (o-t-bu)3 ; −78C
⎯⎯⎯⎯⎯⎯⎯ ii) H O
⎯→
2
R Cl R H
O O

i) DIBAL-H, hexane;− 78 C

⎯⎯⎯⎯⎯⎯⎯⎯ ii) H O
⎯→
R OR` 2
R H
O

R N ⎯⎯⎯⎯⎯⎯⎯
i) DIBAL-H, hexene
ii) H O
→
2
R H

Aldehydes from Acyl Halides: Acyl chlorides can be reduced to aldehydes by treating them
with lithium-tri-tert-butoxyaluminium hydride, LiAlH[OC(CH3)3]3, at –78°C (carboxylic acids
can be converted to acyl chlorides by using SOCl2).
O O
O

+ SOCl2 ⎯⎯
→ ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
i) LiAlH(0-t-Bu)3 , Et 2 O, - 78°C
→
R Cl
ii) H O 2 R H
R Cl
OH

The following is a specific example.

O O

Cl H
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
i) LiAlH(0-t-Bu) 3 , Et 2O, - 78°C
ii) H O
→
2

H3C H3C

O O
H3C H3C
3-methoxy-4-methylbenzoyl chloride

Mechanism for the Conversion of RCOCl To RCHO

CH3 CH3
H CH3 H CH3
H3C - O + H3C - O
O Al O Li Al
O CH3 + O CH3
R Li H3C O H C ⎯⎯
→R H3C O H C
H3C 3 H3C 3
Cl Cl
CH3 CH3
H3C H3C

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CH3
CH3
H3C
O CH3
H Li CH3 O CH3
+ CH3 -
O Li Al O H3C
CH3
O Al
R H3C O ⎯⎯
→ R H H3C O O ⎯⎯
→
H3C CH3
Cl CH3 Cl
CH3 H3C CH3
CH3
CH3
H3C CH3
H3C
CH3
CH3 O CH3 CH3
H3C O O CH3
Li + +
O O
− LiCl
R O
⎯⎯⎯ → CH3 ⎯⎯⎯ → R
O CH3 + H2O
+
H3C Al H3C Al
O H3C
H3C H
O H
H
CH3
H3C
R
Cl

Aldehydes from Esters and Nitriles: Both esters and nitriles can be reduced to aldehydes
by DIBAL-H. Carefully controlled amounts of reagents must be used to avoid over reduction,
and the ester reduction must be carried out at low temperatures. Both reductions results in the
formation of a relatively stable intermediate by the addition of a hydride ion to the carbonyl
carbon of the ester or to the carbon of –C  N group. Hydrolysis of the intermediates liberates the
aldehyde.

Mechanism of Ester Reduction

i-Bu
i-Bu Al
i-Bu
+ - O i-Bu
O H Al O Al i-Bu
⎯⎯
→ R H ⎯⎯
→
R i-Bu ⎯⎯
→ R H
OR' OR' OR'

i-Bu

Al O
+
O i-Bu
⎯⎯⎯
H2O
→
R H
R H

Mechanism of Reduction of Nitriles to Aldehydes

i-Bu

i-Bu i-Bu N Al
+
H3C N H Al ⎯⎯
→ H3C N i-Bu ⎯⎯
→ H3C i-Bu

i-Bu H H
H2 O
O
R
H

By heating calcium salt of fatty acids: Aldehydes are obtained by heating calcium salts of
fatty acids with calcium formate to about 675 K.

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O
O
H3C
O
O
2+ 2+ H
Ca + Ca ⎯⎯⎯
675K
→ 2CH 3CHO + 2CaCO3
O H
H3C O
O O
Calcium acetate Calcium formate Acetaldehyde

Ketones are formed by distilling calcium salt of the fatty acid alone.
O
H3C
O
O
Ca 2+ ⎯⎯⎯
675K
→ H3C + CaCO3
O
CH3
H3C acetone
O
Calcium acetate

Rosenmund Reduction: A classical method for the preparation of an aldehyde from the
corresponding acid chloride involves catalytic reduction over partially deactivated (by sulphur or
quinoline) palladized barium sulphate or carbonate (Rosenmund reduction). The following
mechanism seems to operate.
H
O O OH O
+
− Cl −H
R ⎯⎯⎯→
H 2 (Pd)
R Cl ⎯⎯ ⎯ → R ⎯⎯⎯ → R
BaSO 4

Cl H H H

The partial deactivation of the catalyst is necessary to obviate further reduction of the product
aldehyde.

Hydroboration of Alkynes: Hydroboration proceeds faster with alkynes than with alkenes
and the treatment of the products (vinylboranes) with alkaline hydrogen peroxide gives aldehydes
if the double bond is located at the end of the chain.
R
R 2 B− H
H3C ⎯⎯⎯⎯ → H3C B
CH
Vinyl borane
R

H 2 O 2 , OH

H3C OH
H3C O

Hydration of Alkynes: Hydration of alkynes not only requires the catalytic assistance of acids,
but also mercuric ions. Mercury ions form a complex with a triple bond and the reaction then
proceeds as shown bellow:

2+ H O
H H OH
Hg
+
HC CH ⎯⎯⎯→
HgSO 4
⎯⎯⎯
H2O
→ ⎯⎯→
H H
H 2SO 4
2+ H H H
Hg OH H

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Gattermann-Koch Reaction: Benzaldehyde and many aromatic aldehydes are

conveniently synthesized by treating benzene (or other aromatic compounds) with a mixture of
carbon monoxide and hydrogen chloride (compounds of formyl chloride) in the presence of an
equimolecular quantity of Lewis acid and a trace of copper (I) chloride. The initially formed
cation (C+HO) adds to the benzene nucleus to give the  complex which yields the aldehyde.
+ −
⎯⎯
→ C HO + CuCl + AlCl4
CuCl  CO + HCl+AlCl3 ⎯
⎯
O
H O

+ HC O ⎯⎯
→ ⎯⎯⎯
AlCl4
→ + HCl + AlCl3

Gattermann Reaction: In Gattermann reaction, the electrophile is CH = NH, instead of

CHO, which is readily formed by utilizing hydrogen cyanide in place of carbon monoxide.
Hydrolysis of the aldimine, formed as a result of electrophilic substitution on the aromatic ring,
yields the corresponding aromatic aldehyde.
+ −
⎯⎯
→ C H = NH + AlCl4
HCN + HCl + AlCl3 ⎯
⎯

NH
H NH

+ HC CH2 ⎯⎯
→ ⎯⎯⎯
AlCl4
→ + HCl +AlCl3

NH O

⎯⎯⎯
H2O
→

Aldimine

Freidel Crafts Acylation: Aromatic ketones can be obtained by Friedel Crafts acylation in
presence of anhydrous aluminium chloride.
O CH3

O
+ H3C ⎯⎯⎯⎯→
anhy.AlCl3
+ HCl

Cl
benzene acetyl chloride 1-phenylethanone

Similarly, treatment of benzene with benzoyl chloride in the presence of AlCl 3 gives
benzophenone.
O
O
+ H5 C 6 ⎯⎯⎯
AlCl3
− HCl
→ + 2HCl
Cl
benzene benzophenone

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Benzophenone can also be prepared by Friedel Crafts reaction of phosgene (COCl2) with excess
of Benzene.
O
O
+ Cl ⎯⎯⎯⎯⎯
Anhy. AlCl3
→ + 2HCl

Cl
benzene benzophenone

By Oxidation of Alkyl Benzenes: Aromatic aldehydes are obtained by the oxidation of side
chain in the aromatic ring. For example, benzaldehyde is obtained by the oxidation of toluene
with chromium trioxide in acetic anhydride. In this case the benzaldehyde formed is trapped by
acetic anhydride to form benzal diacetate. As a result, further oxidation of benzaldehyde to
benzoic acid is prevented. However, benzaldehyde can be regenerated by hydrolysis of benzal
diaceate.
O CH3

O O O O
CH3

CH3
⎯⎯⎯⎯
CrO3 , [O]
CCl
→ + H2O
⎯⎯⎯ → + 2CH3COOH
4

toluene Benzal diacetate benzaldehyde

Etard’s Reaction: The reaction involves the oxidation of toluene with chromyl chloride
(CrO2Cl2) in CCl4.
O
CH3 CH(OCrCl2OH)2

+ H2O
⎯⎯⎯⎯
CrO 2 Cl2
CCl
→ ⎯⎯⎯ → + 2CH3COOH
4

toluene Complex benzaldehyde

In the case of side chains bigger than CH3 group the end carbon atom of the chain is oxidized by
CrO2Cl2 to –CHO group.
O
CH3
⎯⎯⎯⎯→
i) CrO 2 Cl2
ii) H O
2

ethylbenzene phenylacetaldehyde

Physical Properties
Polarization of the carbonyl group creates dipole - dipole interactions between the molecules of
ketones and aldehydes, resulting in higher boiling points than for hydrocarbons and ethers of
similar molecular weights. Ketones and aldehydes have no O – H or N – H bonds, however, so
they cannot form hydrogen bonds with each other. The following compounds of molecular
weight 58 or 60 are ranked in order of increasing boiling point. The ketones and the aldehyde are
more polar and higher-boiling than the ether and the alkane, but lower boiling than the hydrogen-
bonded alcohol.

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O O
OH
CH3 O CH3 H3C H3C
H3C H3C propan-1-ol bp 97°C
H3C H CH3
butane bp 0°C ethyl methyl ether by 8°C
propionaldehyde bp 49°C acetone bp 56°C

The melting points, boiling points, and solubilities in aqueous medium of some representative
ketones and aldehydes. Although pure ketones and aldehydes cannot engage in hydrogen
bonding with each other, they have lone pairs of electrons and can act as hydrogen bond
acceptors with other compounds having O – H or N – H bonds. For example, the – OH of water
or an alcohol can form a hydrogen bond with the unshared electrons on a carbonyl oxygen atom.

O O
H H H R
 
O O
|| ||
C C
H R R R

Because of this hydrogen bonding, ketones and aldehydes are good solvents for polar hydroxylic
substances such as alcohols. They can also be remarkably soluble in water i.e. acetaldehyde and
acetone are miscible (soluble in all proportions) with water, and other ketones and aldehydes
with up to four carbon atoms are appreciably soluble in water. These solubility properties are
similar to those of ethers and alcohols, which also engage in hydrogen bonding with water.

Formaldehyde and acetaldehyde are the most common aldehydes. Formaldehyde is a gas at room
temperature, so it is often stored and used as a 40 percent aqueous solution called formalin. When
dry formaldehyde is needed, it can be generated by heating one of the solid derivatives of
formaldehyde, usually trioxane units. Paraformaldehyde is a linear polymer, containing many
formaldehyde units. These solid derivatives form spotaneously when a small amount of acid
catalyst is added to pure formaldehyde.
H H
C
O O
H H heat
O HO OH
C C
H O H H–C–H ⎯⎯ ⎯→ H – C – H
H 2O

Trioxane (metal form aldehyde) Formaldehyde bp – 21C formalin

heat

 H H H H 
 | | | | 
−
 | C − O − C − O C − O − C − O − 
| | |
 H H H H 
 
Paraformaldehyde
(a polymer of formaldehyde)

Acetaldehyde boils near room temperature, and it can be handled as a liquid. Acetaldehyde is
also used as a trimer (paraldehyde) and a tetramer (metaldehyde), formed from acetaldehyde
under acid catalysis. Heating either of these compounds provides dry acetaldehyde. Paraldehyde
is used in medicines as a sedative, and metaldehyde is used as a bailt and poison for snails and
slugs.

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Illustration 1: Boiling point of aldehydes are in between of corresponding alcohols and

alkane – explain.

Solution: In aldehydes, dipole-dipole interaction exists between the molecules. In

alkanes Vander Wall’s interaction exists which is weaker than this and in
alcohols hydrogen bonding exists which is stronger than dipole-dipole
interaction. So their boiling points are in between alcohols and alkanes.
H CH3 CH3 H
O O C O H
O O || O C
CH3 CH3 ⎯⎯ CH3 − C− H ⎯⎯→ CH3
heat heat
CH3
C Acetaldehyde, bp 20C C O
C
H O H H O H
C
Paraldehyde, bp 125C
(a trimer of acetaldehyde)
CH3
Metaldehyde, mp 246C
(a tetramer of acetaldeyde)

Relative Reactivities of Carbonyl Compounds

As we know that the carbonyl group is polar, since oxygen being more electronegative than
carbon, has a greater share of electrons of the double bond. Because of the partial positive charge
of the carbonyl carbon, carbonyl compounds are attacked by nucleophiles.
O −

+
Nu
R (R)H

Aldehydes are more reactive towards nucleophilic attack than are ketones. Because alkyl groups
are electron donating compared to a hydrogen, an aldehyde has a greater partial positive charge
on its carbonyl carbon, making it more susceptible to attack by a nucleophile.
O O O

 
H H R H R R

Since steric factor also contribute to the greater reactivity of the aldehyde compared with a
ketone. Because, the hydrogen attached to the acyl group of an aldehyde group is smaller than the
alkyl group attached to the acyl group of a ketone, the carbonyl carbon of an aldehyde is more
accessible to the nucleophile than is the carbonyl carbon of a ketone. For the same reason,
ketones with small alkyl groups bonded to the carbonyl carbon are more reactive than ketone
with large alkyl groups.

Relative Reactivities towards Nucleophilic addition

O
H3C O H3C O

 
H3C CH3
H3C CH3 H3C CH3
H3C

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How does the reactivity of an aldehyde or ketone towards nucleophiles compared with the
reactivity of the carbonyl compounds? Aldehydes and ketones are less reactive than acyl halides
and acid anhydrides but are more reactive than esters, carboxylic acids, and amides.

Rate of Nucleophilic Substitution

Acyl Halides  Acid Anhydride  Ester  Amide

Because the carbonyl compounds have a pair of non-bonding electrons on an atom attached to
the carbonyl group, these compounds (acid derivatives) has a resonance contributor that
aldehydes and ketones do not have. This resonance contributor places some of the positive
charge on the atom adjacent to the carbonyl carbon. We have seen that the reactivity of these
carbonyl compounds is related to the basicity of the Y–. The weaker the basicity of Y–, the more
reactive the carbonyl group, because weak bases are better able to withdraw electrons inductively
from the carbonyl carbon and are less apt to donate electrons by resonance to the carbonyl
carbon.
O O

R Y R Y

So aldehydes and ketones are not as reactive as carbonyl compounds in which Y– is a very weak
base (acyl halides and acid anhydrides) but are more reactive than carbonyl compounds in which
Y– is relatively stronger base (carboxylic acids, ester and amides).

Reactivitiy Considerations: As we know that the acyl group of a carboxylic acid or a

derivative is attached to a group that can be replaced by another group. These compounds
therefore, react with nucleophiles to form substitution products.
O O

+ Z ⎯⎯
→ + Y−
R Y R Z

In contrast, the acyl group of an aldehyde or a ketone is attached to a group (H or R) that is too
basic (H– or R–) to be replaced by another group. Therefore, aldehydes and ketones react with
nucleophiles to form an addition product. Thus, aldehydes and ketones undergo nucleophilic
addition reactions while carboxylic acids and their derivative undergo nucleophilic substitution
reactions.
O OH

+ HZ ⎯⎯
→ R Z
R Y
R

If the nucleophile that adds to the aldehyde or ketone is a good nucleophile will readily attack the
carbonyl carbon. The resulting addition product can be protonated either by the solvent or by
added acid.

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O O OH
H+
+ Z ⎯⎯
→ R R R R
− H+
R Y
Z Z

A poor nucleophile requires an acid catalyst to make the nucleophilic reaction occur at a
reasonable rate. The acid protonates the carbonyl oxygen, which increases the susceptibility of
the carbonyl carbon to nuclophilic attack.

O OH OH
H+
+ Z ⎯⎯
→ R R
− Z+ R R
R R
Z

If the attacking atom of the nucleophile has a pair of non-bonding electrons in the addition
product, water will be eliminated from the addition product. This is called a nucleophilic addition
– elimination reaction.
H
OH HO
R R
H+
R R + R R + H2O
−H
Z
Z Z

Addition of Carbon Nucleophiles

Addition of Grignard Reagents: Addition of a Grignard reagent to a >C = O compound is a
versatile reaction that leads to formation of a new carbon –carbon bond. Because both the
structure of the carbonyl compounds and the structure of the Grignard reagent can be varied, the
reaction can produce compounds with a variety of structures.

O MgBr OH

O
MgBr ⎯⎯
→ CH3 ⎯⎯⎯
+ CH3
+
H3O
→
H3C
CH3 CH3
H3C H

A ketone reacts with a Grignard reagent to produce a 3° alcohol.

O
O MgBr OH

+ H C MgBr ⎯⎯
→ H3C H3O +
⎯⎯⎯→ H3C
H3C CH3 3
CH3 CH3
H3C H3C
3° alcohol

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OH

H3C CH3 ⎯⎯⎯⎯⎯

i) CH3MgBr
ii) H3O +
→
H3C CH3 CH3
O

H3C OH

H
O
MgBr

⎯⎯⎯⎯⎯⎯⎯
i)
ii) H O +
→
H3C H 3

1-phenylbutan-1-ol

A Grignard reagent can react with CO2 to form carboxylic acids with one more carbon than the
Grignard reagent.

O O

MgBr +

OMgBr ⎯⎯⎯→ H3C

H3O
⎯⎯
→ H3C OH
O C O + H3C

Addition of Acetylide Anions: We have seen that a terminal alkyne can be converted to
acetylide anion by a strong base.

NaNH / NH
H3C CH ⎯⎯⎯⎯⎯⎯
2 3(l)
→ H3C C

An acetylide anion is another example of a carbon nucleophile that adds to aldehydes and
ketones when the reaction is over, acid is added to reaction mixture to protonate the oxyanion.

O O HO
+

+ H3C C C ⎯⎯
→ CH3 ⎯⎯→
H
CH3

H3C H
CH3 CH3

Addition of HCN: HCN adds to aldehydes and ketones to form cyanohydrins. This reaction
increases the number of carbon atoms in the reactant by one. In the first step of the reaction, the
cyanide ion attacks the carbonyl carbon. The oxyanion then accepts a proton from an
undissociated molecule of hydrogen cyanide.

O OH
O
H −C N
H3C + C N H3C CH3 H3C CH3

CH3 CN
Cyanohydrin
N

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Compared with other carbon nucleophiles, cyanide ion is relatively weak base (pKa of HCN =
9.14, pKa of CH  CH = 25, pKa of CH3CH3 ~ 50), which means cyano group is most easily
eliminated from the addition product. Cyanohydrins, however, are stable because the neutral –
OH group does not have sufficient driving force to eliminate the cyano group. But if the one
group loses its proton, the cyano group is eliminated. Therefore, in basic solutions, a cyanohydrin
is converted back to the carbonyl compound.
N
N
HO O O

HO − + CN
H2O

The addition of HCN to aldehydes and ketones is synthetically useful reaction because of
subsequent reactions that can be carried out in the cyanohydrin. For example, acid catalysed
hydrolysis of a cyanohydrin forms an -hydroxycaboxylic acid.
OH OH O
+
N ⎯⎯⎯⎯
H , H 2O

→
H3C H3C OH
H3C H3C
An -hydroxy carboxylic acid

The catalytic addition of hydrogen to a cyanohydrin produces a 1° amine with an OH group on

the -carbon.
OH
H3C
NH2
⎯⎯⎯
H 2 / Pt
→
H3C
N OH

Problem 12: Complete the reactions

a) +
H3C N + MgBr ⎯⎯
→(A) ⎯⎯⎯
H 3O
→(B)

b) O
+
− H2O
MgBr ⎯⎯
→(A) ⎯⎯⎯ →(B) ⎯⎯⎯ →(C) ⎯⎯⎯⎯⎯ →(D)
H 3O i) CH3 MgBr
H3C + H3C ii) H3O +

O
H5C 2

c)
+ NBS ⎯⎯
→(A) ⎯⎯⎯
Mg
Ether
→(B) ⎯⎯⎯⎯
i) CH3CN
ii) H O+
→(C)
3

Solution: a) H3 C N
MgBr
O

A= B=
CH3

[Type text]
[Type text]

b) O MgBr
H3C OH O
H3C
A= O B= C= H3 C
H3C OH
H3C CH3
C 2 H5
CH3
H3C
D=
OH
H3C

c) Br MgBr O

A= B= C=
H3C

Illustration 2: Complete the following reaction:

H3C ⎯⎯⎯⎯
i) HCN
→
ii) H O+
3

O
CN OH
Solution: +
H3C ⎯⎯⎯
HCN
→ H3C ⎯⎯⎯⎯→
2HOH / H
− NH
H3C
3

O OH O
HO
Lactic acid

Haloform Reactions
Chlorine or bromine replaces one or more -hydrogen atoms in aldehydes and ketones, e.g.,
acetone may be brominated in glacial acetic acid to give monobromoacetone :

CH 3COCH 3 + Br2 ⎯⎯
→ CH 3COCH 2 Br + HBr (43–44%)

The halogenation of carbonyl compounds is catalysed by acids and bases. Let us consider the
case of acetone. In alkaline solution, tribromoacetone and bromoform are isolated. Thus, the
introduction of a second and a third bromine atom is more rapid than the first. In aqueous sodium
hydroxide, the rate has been shown to be independent of the bromine concentration, but first
order with respect to both acetone and base i.e.,

rate = k [acetone] [OH–]

O O

CH 3COCH 3 + OH – H 2O + CH 3CCH 2− ⎯
→ CH 3C = CH 2 ⎯⎯→
slow Br2
fast

CH3COCH 2 Br +Br –
Another point that we shall discuss here is: How is it possible for a C—H bond to be broken so
readily? This has been explained as follows. Owing to the inductive effect of the carbonyl group,
the electrons of the C—H bonds on the -carbon atom are displaced towards the carbon atom,
thus facilitating the release of a proton from C . At the same time, the anion produced has

[Type text]
[Type text]

greater resonance stabilization than the parent carbonyl compound, i.e., the conjugate base is
stabilized with respect to its acid.

The inductive effect is very much weaker on a -carbon atom since the I effect falls off rapidly
from the source. Hence proton release is far less easy than on -carbon. Also, if a proton were
released from the —C, this negative atom would be `insulated’ from the CO group by the
intervening saturated carbon atom, and consequently such an anion would not have increased
resonance stabilization. Thus, because of the increased reactivity of hydrogen in a methylene
group (—CH2—) or in a methyne group (=CH—) when adjacent to a carbonyl group or any other
strongly electron-attracting group, these groups are referred to as the `active’ methylene or
methyne group.
Aldehydes and ketones with -hydrogen atoms readily react with sulphuryl chloride at room
temperature in the absence of a catalyst, to replace -hydrogen atoms only, e.g.,
CH3COCH3 ⎯⎯⎯
SO2 Cl2
→ CH3COCH 2 Cl

Illustration 3: Complete the following equations:

O
+
(a) + Br2 ⎯⎯⎯
H
− HBr
→ ? ⎯⎯⎯⎯
alc. KOH

→ ? ⎯⎯⎯⎯ i) O3
ii) H O / Zn
⎯→ ⎯⎯⎯
H 2 O2
→?
2

CH3 CH3
− +
Soda −lime
(b) H3C ⎯⎯⎯
I2
OH −
→ ? ⎯⎯⎯
OH
→ CHI3 + ? ⎯⎯→
H
? ⎯⎯⎯⎯ 
→

CH3 O

Solution: (a) a)O +

O O O O
+
O O O
⎯⎯⎯⎯
Br2 / H
− HBr
→ ⎯⎯⎯⎯
alc. KOH
− KBr
→ ⎯⎯⎯⎯ i) O3
ii) H O / Zn
⎯→ ⎯⎯⎯⎯
Br2 / H
− HBr
→ ⎯⎯⎯⎯
alc. KOH
− KBr
→ ⎯⎯⎯⎯ i) O3
ii) H O / Zn
⎯→
2 2
− H2O − H2O
Br O Br O
2-bromocyclohexanone 2-bromocyclohexanone
O O
O O O O

O O
⎯⎯⎯
H 2 O2
→ HO ⎯⎯⎯
H 2 O2
→ HO

OH OH
(b) I Formatted
I +
CH3 CH3 CH3 O Na
CH3
I
H3C ⎯⎯⎯
3I 2
−3HI
→ H3C ⎯⎯⎯
NaOH
− CHI3
→ H3C

O CH3 O CH3 O
CH3

CH3 OH H3C
Soda − lim e
⎯⎯→
H +
H3C ⎯⎯⎯⎯→

CH3
− CO 2

O H3C
CH3

BRAIN TEASER 1:
A ketone A which undergoes haloform reaction to give compound B on reduction. B on heating
with sulphuric acid gives compound C, which forms mono-ozonide D. The compound D on

[Type text]
[Type text]

hydrolysis in presence of zinc dust gives only acetaldehyde. Identify A, B, C and D. Write down
the reactions involved.

Aldol Condensations
Two molecules of an aldehyde or a ketone undergo condensation in the presence of a base to
yield a -hydroxyaldehyde or a -hydroxyketone. This reaction is called the aldol condensation
which may be exemplified by the reaction of acetaldehyde to give acetaldol (3-hydroxybutanal).
HO
−
2H3C ⎯⎯⎯
HO
H O
→
2

O H3C O
H
Since aldehydes and ketones lacking -hydrogens do not undergo aldol condensation, a key step
of the reaction is the formation of the enolate anion (carbanion) by removal of an -hydrogen by
base. Like other nucleophiles, the carbanion then attacks the carbonyl carbon of the second
molecule and the anion so formed accepts a proton from the solvent molecule to yield the
product.

Step I: O
H O
slow
HO + O H2C H2C + H 2O

H H H
Step II: H
H
fast
H3C + H2C H3C

O O O O

H H
+ HO
H3C + H2O H3C

O O OH O

Crossed aldol condensation between two different carbonyl compounds – both having -
hydrogen – yields a mixture of four possible products. For example, the condensation of
acetaldehyde and propionaldehyde may occur in the following manner:
OH
OH −
H3C + H3C ⎯⎯⎯
H2O
→ H3C
O O
H3C O
or
−
H3C H3C ⎯⎯⎯
OH
→ H3C
+ H O
2

O O

HO O

[Type text]
[Type text]

In addition, the reaction will also yield both, the dimmer of acetaldehyde and the dimmer of
propionaldehyde by self-condensation of the reactants.

However, when one of the reactants has no -hydrogen (e.g., benzaldehyde and formaldehyde)
and therefore cannot form an enolate, mixed aldol condensation can be of some synthetic utility.
For example.
O
O O
−

H3C + H ⎯⎯⎯
OH
H2O
→ H3C OH

CH3 H

Aldol condensations are also catalysed by acids. The reaction of benzaldehyde with
acetophenone in the presence of acid was found to be first-order in both the reactants and it
appears quite reasonable to believe that acid catalyses the conversion of acetopheone into the
enol when they reacts with the protonated benzaldehyde.

OH OH OH
O
H5 C 6 H5 C 6 H5C 6 + H
H5 C 6 + H
CH3 CH3 CH2
CH3 enol
OH OH
O
H5 C 6 H5 C 6
H5 C 6 + H

OH OH H5 C 6 C 6 H5 H5 C 6 C 6 H5
+ H
H5 C 6 + H5 C 6
OH OH O OH
CH2

Usually the aldol products are easily dehydrated under acidic conditions.
O C 6 H5 O C 6 H5
O C 6H5
H − H 2O
⎯⎯⎯ → H C
H5C 6 OH2 5 6
H5C 6 OH
H

The appearance of dehydrated product is not only confined to acid-catalysed reactions, but many
aldol condensations employing strong bases, such as alkoxide or hydroxide ions also yield the
dehydrated products. Their mechanism of formation involves an enolate ion which subsequently
eliminates a hydroxide ion.
H H
O O
+ C2 H5O + C2 H 5OH
H5 C 6 H5 C 6
OH C 6 H5 OH C 6 H5

[Type text]
[Type text]
O

H
O H5C 6 C 6H5
H5C 6
OH C 6H5
`
This forms the basis of the Claisen-Schmidt reaction which may be defined as a base-catalysed
condensation of an aldehyde or ketone to form an , -unsaturated aldehyde or ketone.
O OH H3C

2 H3C ⎯⎯⎯H
⎯→ H3C ⎯⎯⎯H
or OH
⎯→
or OH

CH3 CH3 O H3C O

H3C H3C
diacetone alcohol mesityl oxide

Mesityl oxide (III) is thermodynamically favoured product and hence lies at a lower energy level
than either acetone or diacetone alcohol (II).

base catalysed
acid catalysed

Diacetone alcohol

G Acetone

Mesityl oxide

Reaction coordinate
Fig. Reaction coordiante diagram for the aldol condensation of acetone

It becomes apparent from an inspection of figure that dehydration of the initially formed aldol
product is an extremely facile process in the presence of acids.

Illustration 4: Give the mechanism of the following cyclization via aldol condensation:
O

OH −
O ⎯⎯⎯ O
→
H3C
CH3

[Type text]
[Type text]

Solution: O O O
H

H
+ H2O H + H O
H + OH H
CH3 CH3 CH3
H

O
O O
OH H
H

H + H 2 O + OH
+ OH CH3
CH3

O O

Claisen Condensation
When two molecules of ester undergo a condensation reaction, the reaction is called Claisen
Condensation. The product of the Claisen condensation is a -keto ester.
CH3

i) CH3CH 2 ONa +
O CH3
O CH3
H3C + H3C
2 H3C ii) H +
OH
O O
O
-keto ester

After nucleophilic attack, the aldol addition and the Claisen condensation differ. In the Claisen
condensation, the negatively charged oxygen reforms the carbon oxygen -bond and eliminates
the OR group.

O CH3
H H3C O CH3
O O
O EtO −
H3C CH3 H3C CH3
H3C O O
O O
H3C
O
H3C
CH3

O CH3
EtO − + H3C

O O

The elimination step in the Claisen condensation is a reversible reaction since the alkoxide ion
can readily attack the keto group of the -keto ester. The reaction can be driven to completion by
removing a proton from the -keto ester. This is easily to do because, since the central -carbon
of the -keto ester is flanked by two carbonyl groups and its hydrogens are more acidic than the
-hydrogens of the reacting ester. Consequently, a successful Claisen condensation requires an

[Type text]
[Type text]

ester with two -hdyrogens and an equivalent amount of base rather than a catalytic amount of
base. When the reaction is over, addition of acid to the reaction mixture reprotonates the -keto
ester anion.
CH3 CH3

O O
CH3 ⎯⎯⎯→ H3C
CH3O
H3C CH3

O O O O
H+

O O
CH3

H3C CH3

[Type text]
[Type text]

Mixed Claisen Condensation

O O O O

O CH3 − O CH3
CH3 ⎯⎯⎯⎯⎯ →
i) CH3CH 2 O
+ H3C O ii) H +

H3C
-keto ester

A reaction similar to a mixed Claisen condensation is the condensation of the ketone and an
ester. Because the -hydrogens of a ketone are more acidic than those of an ester, primarily one
product is formed if the ketone is added slowly to a mixture of the base and excess ester. The
product is a -diketone.

O O O
O
− CH3
+ ⎯⎯⎯⎯⎯
i) CH3CH 2O
ii) H +
→ + H3C
H3C O CH3
excess OH
-diketone

A -keto aldehyde is formed when a ketone condenses with formate esters.

O O O O

H O CH3 + ⎯⎯⎯⎯⎯
i) CH3CH 2 O
→ + H3C
ii) H +

OH
-keto aldehyde

A -keto ester is formed when a ketone condenses with diethyl carbonate.

O O O O

−
+ ⎯⎯⎯⎯⎯
i) CH3CH 2 O
→ O CH3 + H3C
H3C O O CH3 ii) H +
diethyl carbonate OH
(excess) -keto ester

Intramolecular Claisen Condensation

Dieckmann Condensation: The addition of base to a 1,6-diester causes the diester to
undergo intramolecular Claisen Condensation, thereby forming a five membered ring -keto
ester. An intramoelcular Claisen Condensation is called a Dieckmann Condensation.

[Type text]
[Type text]

O O
CH3 −
⎯⎯⎯⎯
i) CH 3O
ii) H +
→ + CH3O
O
O
O H3C

O O

CH3

O
CH3 O
+
−
⎯⎯⎯⎯
i) CH 3O
ii) H +
→ H3C OH
O CH3
O

O
H3C
O O

O CH3 CH3O − O CH3

H3C O H3C O

O H O

O
O O O
+ −
⎯⎯
H
⎯⎯⎯
CH3O
O
O O O
H3C
O H3C O H3C O H3C O O

H3C

Perkin Reaction: In Perkin reaction, condensation has been effected between aromatic
aldehydes and aliphatic acid anhydride in the presence of sodium or potassium salt of the acid
corresponding to the anhydride, to yield , -unsaturated aromatic acids.

The acid anhydride should have at least two -H.

C6 H5CHO + (CH3CO) 2 O ⎯⎯⎯⎯⎯→

AcONa
170 −180 C, 5h
C6 H 5 − CH = CH − COOH
O
⎯⎯⎯⎯⎯⎯⎯
(CH3CO) 2 O, AcONa

→
O O
OH
O
3-(-furyl)acrylic acid

[Type text]
[Type text]
O

O
OH

O ⎯⎯⎯⎯⎯⎯⎯
(CH3CO)2 O, AcONa

→ O

O O
Phthalyl acetic acid

Mechanism: It is observed that the acetate ion abstracts a proton from the -carbon of the
anhydride producing a carbanion which then attacks the carbonyl group of the aldehyde. The
product then abstracts a proton from the acid to form – aldol type compound. The latter then
undergoes dehydration in the presence of hot acetic anhydride.

CH 3COONa CH 3COO − + Na +

H O O
H2C
H3C COO + O O
H3C H3C
O O
O O H O

H2C O O
O O HO
CH3COOH
O O
H5 C 6 O
H H
H5 C 6 CH3 H5 C 6 CH3
H H3C
O -H2O
170°

O O O
H5C 6 O
H3C +
⎯⎯
⎯ H C
H2O
O CH3
5 6
OH
OH

Prolonged heating (about 5 hours) and high temperature is required, since a weak base (acetate
ion) has to react with a weak acid (anhydride).

Meta directing groups in the aromatic ring promotes the reaction. When anhydride with one -H
atom is used, no dehydration is possible and an aldol type product is isolated.

Knoevenagel Reaction: Condensation of aldehydes and ketones with compounds having

active methylene group in the presence of basic catalyst to form , -unsaturated compounds is
called Knoevenagel Reaction. The basic catalyst may be ammonia or its derivative. Thus 1°, 2°,
3° amines i.e., aniline, di-or tri-alkyl amines, pyridine or piperidine are used.
O O

O H5C 6 O H5 C 6 O
R ⎯⎯⎯⎯ ⎯→
i) H 2O
C6 H5CHO + R ⎯⎯⎯⎯
Pyridine /
Piperidine
→ ii)  , -CO 2

O O OH
Cinnamic acid
O R O R
Malonic Ester

Mechanism

[Type text]
[Type text]
O O
O O
+
R3N + H R R3 N H + R
O O
O R O R
O O O
O O HO O
O O
R 3 NH
+ R R' R R
R' −R3N

O H O R' O
H
O R O R O R

-H2O
O

R' O O

⎯⎯⎯⎯
i) H 2O
ii)  , - CO
⎯ R
2

OH R' O
O R

High reactivity of the methylene group of the active methylene group of the active methylene
compound prevents self condensation of the aldehyde.

H3C CH3 H3C COOH

H3C
O ⎯⎯⎯→
i) H 2 O
⎯⎯⎯⎯⎯
CH3COONa
→
O + H3C R CH3COOH
ii) 

H3C O H3C H
H3C O
2-methylprop-1-enoic acid
O R

Cannizzaro Reaction
Mechanistically, Cannizzaro reaction is a characteristic reaction of aromatic aldehydes and of
aliphatic aldehydes without -hydrogen. In the presence of a strong base, such aldehydes
undergo self-oxidation-reduction yielding salt of carboxylic acid and an alcohol.

CH3 CH3 CH3

O

2 H3C ⎯⎯→ H3C

HO
+ H3C

O O CH3 OH
CH3 CH3

When the Cannizzaro reaction is performed in D2O, the alcohol formed has no carbon-bound
deuterium thereby establishing that the reaction sequence involves a direct transfer of hydrogen
from one molecule of aldehyde to the other. An aldehyde molecule produces an anion by
interaction with a hydroxide ion which transfers a hydride ion to the carbonyl carbon of the
second aldehyde molecule.

O
O
fast
HO + H5C6 H5 C 6 H

H OH

[Type text]
[Type text]

O O O
slow
H5C 6 H + H5C 6 H5 C 6 + H5 C 6

H OH O
OH
fast

O
H5 C 6 + H5 C 6

O OH

Aldehydes that possess -hydrogens do not undergo this reaction, because base-catalysed aldol
condensation becomes the dominant process.
The Cannizzaro reaction between two dissimilar aldehyde moelcuels (crossed Cannizzaro
reaction) may yield all possible products. However, when one of the aldehydes is formaldehyde
the formate ion and the alcohol corresponding to the other aldehyde are formed exclusively. The
exclusive formation of the formate ion is due to the high reactivity of formaldehyde which
preferentially adds a hydroxide ion before losing one of its two hydrogens as hydride ion to the
less reactive aldehyde.
CH3 CH3 O
O
H3C + H ⎯⎯→
HO
H3C + H

CH3 O H CH3 OH O

HO + H − CH 2 − CHO H 2 O + CH 2 − CHO

O O

H + H2C H

H O H O

H2O

OH HO
HO ⎯⎯⎯⎯
OH, CH 2 O

H H O
O
HO, CH2O

OH OH

HO ⎯⎯⎯
HO
→ HO + HCOO
CH 2 O

HO HO
O OH
(I)
Illustration 54: Write the structure of the major organic product expected from each of the
following reactions.
H3C
O + HCHO + KOH ⎯⎯
→
O

[Type text]
[Type text]

Solution: It is crossed-Cannizzaro reaction

CH3 CH3
O O


+ KOH ⎯⎯ → + HCOO-

O + HCHO HO

Reformatsky Reaction
A similar reaction like the addition of organometallic compounds on carbonyl compounds that
involves the addition of an organozinc reagent to the carbonyl group of an aldehyde or ketone.
This reaction, called Reformatsky reaction, extends the carbon skeleton of an aldehyde or ketone
and yields -hydroxy esters. It involves treating an aldehyde or ketone with an -bromo ester in
the presence of zinc metal; the solvent most often used is benzene. The initial product is a zinc
alkoxide, which must be hydrolysed to yield the -hydroxy ester.
Br

Zn
O O O OH O
⎯⎯⎯⎯ →
Zn / C6 H6 +
O + Br ⎯⎯⎯
H 3O
→
O O R O R
Aldehyde
or ketone R -hydroxy ester
-Bromoester

The intermediate in the reaction appears to be an organozinc reagent that adds to the carbonyl
group in a manner analogous to that of a Grignard reagent.

ZnBr
O O O O OH O
O
+

Br ⎯⎯⎯
Zn
→ BrZn ⎯⎯⎯⎯⎯⎯
→ ⎯⎯⎯
H3O
→
C6 H 6

O O O R O R
-hydroxy ester
R R

Illustration 56: Complete the following reactions:

CH3
O O
+ Zn + Br C 2H5 ⎯⎯⎯
H 2O
→ Products

[Type text]
[Type text]

Solution: CH3 CH3

OZnBr
O O
+ Zn + Br C 2H5 ⎯⎯
→
O
O
O C 2H5
CH3
OH

⎯⎯⎯
H2O
→
O
O C 2H5

Addition of Nitrogen Nucleophiles

Aldehydes and ketones react with primary amines and other ammonia derivative (Z – NH2) to
form imines. An imine is a compound with a carbon – nitrogen double bond.
R R
O + H 2 NZ NZ + H 2 O
R R
An imine

Compounds such as hydroxyl amine (NH2OH), hydrazine (NH2NH2), semi-carbazide

(NH2NHCONH2) and primary amines (R – NH2) are all derivatives of NH3 because each has a
substituent in place of one of the hydrogens of ammonia (H – NH2).

The imine obtained from the reaction of a carbonyl compound and a primary amine is called a
Schiff’s Base. The imine obtained from the reaction with NH2OH is called an oxime; the imine
obtained from the reaction with hydrazine is called a hydrazone; and the imine obtained from the
reaction of a semi-carbazide is called Semi-carbazone.
H3C H2N H3C N
O + + H2O
CH3
H3C
1° amine A Schiff's Base

O
+ H2N OH
N OH
Oxime

+ H2N NH2

O N
H3C H3C NH2
(Hydrazone)

[Type text]
[Type text]

H2N NH
O + N O + H 2O
O
NH
H2N NH2
Semicarbazone

Phenyl substituted hydrazines react with aldehydes and ketones to form phenyl hydrazones.
H2N
+ NH N + H 2O
O
NH

cyclopentanone phenylhydrazone

H3C
H2N N
H3C + NH NO2 NH NO2
O
O2 N O2N
(1E)-propanal (2,4-dinitrophenyl)hydrazone

Mechanism and pH dependence of Rate of Reaction of Imine

(>C = N-) Formation
O H+
OH − H+ OH
O + R NH2 − H+ H+
NH2 NH2 NH
Ketone 1 amine R R R
− H+ H+

H
+
H+ O
N NH H
− H+
NH
R R
An imine R

H3C H3C H3C

H3C OH OH
O − H+
H+
O + H2N OH −H + H+
H
H H
NH2 NH2 NH
H
HO HO HO

− H+ H+

H
H3C H3C H3C +
− H2O
O
H+
N NH H2O
H
− H+
H
H OH H OH NH
oxime
HO

The addition of nitrogen nucleophile to the aldehyde or ketone is unlike the addition of hydrogen
or carbon nucleophile, more than a simple addition reaction. The addition of a carbon or
hydrogen nucleophile to an aldehyde or a ketone forms a stable tetrahedral compound. Because
the nitrogen atom in the tetrahedral compound formed when a nitrogen nucleophile adds to an

[Type text]
[Type text]

aldehyde or a ketone still has a non-bonding pair of electrons, the tetrahedral compound is not
stable. The non-bonding electrons on nitrogen cause water to be eliminated. Loss of proton from
a resulting imine(protonated) results in stable imine. Overall the reaction is a nucleophilic
addition – elimination reaction: nucleophilic addition of an amine followed by loss of water.
Aldehydes and ketones undergo a nucleophilic addition reaction with a carbon and hydrogen
nucleophile and undergo nucleophilic addition – elimination reaction with a nitrogen nucleophile.

The pH at which imine formation is carried out, must be carefully controlled. There must be
sufficient acid present to protonate the tetrahedral intermediate so that H2O rather than the much
more basic OH– is the leaving group. However, if too much acid is present, it protonates the
reactant amine. Protonated amine are not nucleophiles, so they cannot react with carbonyl
groups.

A plot of the observed rate constant for the reaction of acetone with NH2OH as a function of pH
of the reaction mixture is shown in figure. This type of a plot is called pH – rate profile. The pH
rate profile is a bell shaped curve with maximum rate occu rring at pH = 4.5. As the acidity

increases below pH = 4.5, the rate of the reaction

decreases because more and more of the amine
becomes protonated. As a result less and less amine is
present in the nucleophilic non-protonated form. As the
Kobs (min-1)

acidity decreases above pH = 4.5, the rate decreases

because the less and less of the tetrahedral intermediate
is present in the reactive protonated form. The pKa of
protonated hydroxylamine is 4.5. Apparently, the
maximum rate is obtained at a pH at which half of the 1 2 3 4 5 6 7
amine is active as a nucleophile and the other half is pH
Dependence of Rate of reaction of acetone with NH2OH on the
protonated. pH of the reaction mixture

Imine formation is a reversible reaction. In aqueous acidic solutions, imines are hydrolysed back
to the carbonyl compound and amine. In an acidic solution, amine is protonated and is unable to
participate in the reverse reaction.

+
+ H 2 O ⎯⎯→
H
+ H3C

N O NH3

CH3

Imine hydrolysis is a necessary step in the conversion of a nitrile to a ketone. Reaction of a nitrile
with a Grignard reagent forms an imine that is hydrolysed to a ketone.

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[Type text]

H3C H3C
H3C +
+ R -MgBr ⎯⎯
→ N MgBr ⎯⎯→
H
R
N
R H2 N
+
H /H2O

H3C

NH +4 + R
O

Addition of Secondary Amines: Formation of Enamine: The reaction of an aldehyde or

ketone with a secondary amine produces an ENAMINE. An enamine is an ,  - unsaturated
tertiary amine. Notice that the double bond is in the part of the molecule that come from ketone.
The name ENAMINE comes from “ene” + “amine” with the ‘e’ omitted in order to avoid two
successive vowels.
CH3

O N
CH3

+ H3C NH CH3 + H 2O

N,N-diethylcyclopent-1-en-1-amine

O N

+ + H2O
N
cyclohexanone H
1-cyclohex-1-enyl-1-pyrrolidine
pyrrolidine

Mechanism for Enamine Formation

O OH − H+ OH
H+ R
O + R R R H+
NH − H+ N
NH NH
R
R R R

H+ − H+
H
R R
H+ +
OH
N R
N − H+ N
R R
An Enamine R
H
+ H 2O
In aqueous acidic solution, an enamine is hydrolysed back to the carbonyl compound and
protonated secondary amine.

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[Type text]

N O

+
+ H 2 O ⎯⎯→
H +
+
N
H
H

Addition of Ammonia: Reductive Amination: The imine formed from the reaction of an
aldehyde or a ketone with ammonia is not stable. There must be a substituent other than a
hydrogen bonded to the nitrogen of an imine in order to stabilize it The unstable imine, however,
is a useful intermediate. For example, if the reaction with NH3 is carried out in the presence of H2
and on appropriate metal catalyst, Ni add to the C = N bond as it is formed, forming a primary
amine.
CH3 CH3 CH3

O + NH 3 ⎯⎯
→ NH ⎯⎯⎯⎯
H2
Raney Ni
→ NH2
excess
H3C H3C H3C

Similarly secondary and 3° amines can be prepared from imines and enamines by reduction of
imines or enamines. Commonly used reducing agents are hydrogen and a metal catalyst. The
reaction of an aldehydes or a ketones with ammonia (or with an amine) in the presence of
reducing agent is called reductive amination.

+ H3C ⎯⎯
→ ⎯⎯⎯⎯
H2
→
Raney Ni
O N NH
NH2
CH3 CH3
CH3
O + H3C NH ⎯⎯
→ N
CH3
CH3

Addition of Oxygen Nucleophile

Addition of Water: Water adds to an aldehyde or a ketone ot form a hydrate. A hydrate is a
molecule with two OH groups on the same carbon. Hydrates are also called gem-diols.

O OH

R + H 2O R R(H)

R (or H) OH
A gem diol (or hydrate)

The mechanism for the addition reaction involves nucleophilic attack by water on carbonyl
carbon. Loss of a proton from the oxonium ion and gain of a proton by the oxyanion forms the
DIOL.

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[Type text]

Mechanism

O O OH

H3C + H 2O H3C H H3C H

H +
O OH
H H Acetaldehyde hydrate (58%)

Water is a poor nucleophile, therefore, adds relatively slowly to a carbonyl group, but the rate of
the reaction can be increased by an acid catalyst. Notice that the catalyst has no effect on the
position of the equilibrium. The catalyst affects the rate at which an aldehyde or a ketone is
converted to the hydrate.

Mechanism for Acid-Catalysed Hydrate Formation

OH OH
O OH
− H+
H+ H3C H
H3C H3C + H2O H3C H H+
− H+
+
H H O OH
(42%) H H (58%)

The extent to which an aldehyde or a ketone is hydrated in an aqueous solution depends on the
aldehyde or the ketone. For example, only 0.2% acetone is hydrated at equilibrium, but 99.9% of
formaldehyde is hydrated. Why is there such a great difference?
OH
O
H3C + H2O H3C CH3 K eq = 2  10−3

CH3 OH
(99.8%) (0.2%)
OH
O
H3C + H 2O H3C H K eq = 1.4

H OH
(42%) (58%)

O OH

H + H 2O H H K eq = 2.3  103

H OH
formaldehyde (99.9%)
(0.1%)

The equilibrium constant (Keq) for hydrate formation depends on the relative stabilities of the
carbonyl compound and the hydrate. We have seen that the electron donating alkyl groups make
the carbonyl compound more stable (less reactive), so acetone is more stable than formaldehyde.
However, alkyl groups have the opposite effect on the stability of the hydrate, they make the
hydrate less stable, so the hydrate of acetone is less stable than that of the formaldehyde.

Relative stabilities of carbonyl compounds

CH3COCH3  CH3CHO  HCHO

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Relative stabilities of hydrates of carbonyl compounds

OH OH OH

H3C CH3  H3C H  H H

OH OH OH

Steric interaction between the alkyl groups are responsible for the decreased stability of the
hydrate. The electron cloud of the alkyl groups in the carbonyl compound do not interfere with
each other, since the bond angle between them is 120°. However, the bond angle in the hydrate is
reduced to 109° 5’. So the alkyl groups are closer to each other. Hydrates of aldehydes and
ketones are generally too unstable to be isolated and exist only in an aqueous solution.
O OH

CH3
H3C CH3 H3C
120° CH3
109° 5'

The reaction co-ordinate diagrams in figure shows how the opposing effects of substituents on
the stabilities of the carbonyl compounds and the hydrate can have a dramatic effect on the
equilibrium constant for hydrate formation.

H H OH
Free Energy

O
H3C CH3

OH
H 3C H OH
O
H3C H

OH
H 3C CH3 OH

H H

OH

Progress of Reaction

If the amount of hydrate formed from the reaction of H2O with a ketone is too small to detect,
how do we know that the reaction has even occurred? We can prove that it occurs by treating the
ketone with 18O-labelled water and isolating the ketone after the equilibrium has been
established. Finding that the labeled O18 is incorporated into the ketone proves that the reaction
has occurred.
O OH OH OH

H+ 18 − H+
+ H2 O H3C CH3 H3C CH3
− H+ H+
H3C CH3 H3C CH3
+ OH
O 18
H 18 H

−H + H+
18 H
O 18OH
OH

H+ H3C CH3
H3C CH3 H3C CH3
− H+

OH
18

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[Type text]

Illustration Cl

76:
H3C Cl ⎯⎯⎯
Alkali
Boil
→

Solution: Gem dihalide on hydrolysis gives aldehyde

H3C H3C H3C

OH ⎯⎯
→ O + H2O
2KOH
Cl ⎯⎯⎯⎯ →
( aq )
boil
−2KCl
Cl HO

Addition of Alcohols
Hemiacetals: Dissolving an aldehyde or ketone in an alcohol causes the slow establishment of
an equilibrium between these two compounds and a new compound called a hemiacetal. The
hemiacetal results by nucleophilic addition of the alcohol oxygen to the carbonyl carbon of the
aldehyde or ketone.

Mechanism for the Reaction

H
R R + H3C
O O
O + HO - R  R' R'
H H3C
R O O H
Aldehyde Alcohol
(or ketone) Hemiacetal (usually too
unstable to isolate)

The essential structural features of a hemiacetal are an –OH and an –OR group attached to the
same carbon atom.
Most open-chain hemiacetals are not sufficiently stable to allow their isolation. Cyclic
hemiacetals with five-or six membered rings, however, are usually much more stable.

O O two O
HO + steps
O H O H H

Ketones undergo similar reactions when they are dissolved in an alcohol. The products (which
are also unstable as open-chain compounds) are called hemiacetals.
R
R R H3C
+ O
O
O + HO - R  R' R'
H H3C
R O O H
Ketone Hemiacetal

The formation of hemiacetals is catalyzed by acids and bases.

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[Type text]

Acid-Catalyzed Hemiacetal Formation

R' H R'
+ +
O + O R' O + O R'
+ −
H H H H H

R' H R'
+ O R'
O O H
H +
R' O R" O + O R'

H H H H H

Base-Catalyzed Hemiacetal Formation

R' R'
O O
R'
O R' H OR'
O R" O R' O + O R'
+ −
H H H H

Acetals: If we take an alcohol solution of an aldehyde (or ketone) and pass into it a small
amount of gaseous HCl, the hemiacetal forms, and then a second reaction takes place. The
hemiacetal reacts with a second molar equivalent of the alcohol to produce an acetal. An acetal
has two – OR groups attached to the same carbon atom.
OH OR'

R OR'
HCl( g )
⎯⎯⎯
R − OH
⎯
→ R OR' + H 2O

R" R"
Hemiacetal (R" may be H) An acetal R" may be H)

Acid-Catalyzed Acetal Formation

H H R"
+ +
O + O R' O + O R'
+ −
R H R H H

R' H R'
+ O R'
O O H
H +
R" O H O + O R'

R H R H H

R' H R'
+
O O R' O H
H +
H OH2
+ O + H2O
H O
H R R'
R R

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[Type text]

H +
R' R'
H O O
R' O H R' O H
O
+
H O H O + R 'OH +2

R R' R R' R R'

If we place the acetal in water and add a small amount of acid, all of the steps reverse. Under
these conditions (an excess of water), the equilibrium favours the formation of the aldehyde. The
acetal undergoes acid catalysed hydrolysis.

OR' O
H3C
H 3O +
+ H 2O R + 2R 'OH
(several steps)
H3C OR' H
Acetal Aldehyde

Acetal formation is not favoured when ketones are treated with simple alcohols and gaseous HCl.
Cyclic acetal formation is favoured, however, when a ketone is treated with an excess of a 1,2-
diol and a trace of acid.
R' R' O
HO
H3O +
O + + H 2O
HO O
R R
Ketone (excess) Cyclic acetal

This reaction, too, can be reversed by treating the acetal with aqueous acid:

R' O R'
OH
+ H 2O
H3O +
O +
R O OH
R

Acetals are Protecting Groups: Although acetals are hydrolyzed to aldehydes and ketones
in aqueous acid, they are stable in basic solutions:
R' OR'
−
+ H 2 O ⎯⎯⎯
OH
→ no reaction
R OR'
R' O
−
+ H 2 O ⎯⎯⎯
OH
→ no reaction
R O

Because of this property, acetals give us a convenient method for protecting aldehyde and
ketone groups from undesired reactions in basic solutions. (Acetals are really gem-diethers,
and, like ethers, they are relatively unreactive toward bases). We can convert an aldehyde or
ketone to an acetal, carry out a reaction on some other part of the molecule, and then hydrolyze
the acetal with aqueous acid.

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[Type text]

O O O
to
O OH
H5C 2
(A) (B)

Keto group are more easily reduced than ester groups. Any reducing agent (e.g. LiAlH 4 or H2/Ni)
that can reduce the ester group of A reduces the keto group as well. But if we “protect” the keto
group by converting it to a cyclic acetal (the ester group does not react), we can reduce the ester
group in basic solution without affecting the cyclic acetal. After we finish the ester reduction, we
can hydrolyze the cyclic acetal and obtain our desired product B:
O

O O O O O OH
⎯⎯⎯⎯⎯⎯
HA
→ ⎯⎯⎯⎯
i) LiAlH 4
Et O
→
HOCH CH OH
2 2
2
ii) H 2 O
O C 2 H5 O
O
H5 C 2 +
H3 O H2 O

O
OH

Addition of Sulphur Nucleophile

Addition of Sodium Bisulphite: Sodium bisulphite adds to most aldehydes, methyl ketones
and unhindered cyclic ketones to form crystalline addition products commonly referred to as
bisulphate addition products.

O Na OH
O
SO 3H SO 3 Na

Na SO 3H
+ -
OH H or OH
O + NaSO3H

SO 3 Na

H
SO 2 + H2O
SO 3H
OH
SO 3 + H2O

Addition of Thioalcohols: Formation of Thioacetals (RSH)

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[Type text]
O RS
SR'

H H

Aldehydes and ketones react with thiols to form thioacetals:

CH3
R R S
O + 2CH 3CH 2SH ⎯⎯→
HA
+ H 2O
H H S
CH3
Thioacetal
R R S
O + HSCH CH SH ⎯⎯
BF3
⎯→ + H2O
3 2

H H S
Cyclic thioacetal

Thioacetals are important in organic synthesis because they react with Raney nickel to yield
hydrocarbons. These reactions (i.e., thioacetal formation and subsequent “desulfurization” give
us an additional method for convert carbonyl groups of aldehydes and ketones to – CH2 – groups:

R S R

⎯⎯⎯⎯
Raney Ni
(H )
→ + H + NiS
2

H S R H

Oxidation of Aldehydes And Ketones

Tollen’s Reagent: Aldehydes are readily oxidized to carboxylic acids not only by the usual
reagents such as permanganate and dichromate, but also by the very mild oxidizing agents such
as silver ions. A test often employed for the characterization of aldehydes consist of treatment
with ammoniacal silver nitrate (Tollen’s reagent) in which the oxidation of the aldehyde is
accompanied by reduction of silver ion to free silver appearing in the form of a mirror under the
reaction conditions:

RCHO + 2Ag(NH3 ) 2 OH ⎯⎯
→ 2Ag + RCOONH 4 + H 2O + 3NH 3
Colourless solution Silver mirror

Since ketoens do not undergo oxidation under mild conditions, Tollen’s reagent is also used for
differentiating them from ketones. Tollen’s reagent also does not attack carbon-carbon double
bonds and hence the reaction provides a valuable method for the synthesis of , -unsaturated
acids from , -unsaturated aldehydes, which are available by the aldol condensation and
subsequent dehydration.
H3C
H3C O

⎯⎯⎯⎯⎯⎯
Tollens' reagent
→
H +
ONH4

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[Type text]

Fehling Solution: Fehling’s solution is an alkaline solution of copper sulphate containing

sodium potassium tartrate (Rochelle salt) as the complexing agent. Aldehydes on warming with
this solution, give a red precipitate of cuprous oxide.

R − CHO + 2Cu(OH) 2 + NaOH ⎯⎯

→ RCOONa + Cu 2 O + 3H 2 O
Red precipitate

Benedict’s Solution: Benedict’s solution is alkaline copper sulphate containing citrate ions as
complexing agent. Aldehydes on warming with this solution, give brick red precipitates.

RCHO + Cu 2+ (complex) ⎯⎯
→ Cu 2 O + RCOOH
Red precipitate

It must be noted that Fehling solution and Benedict’s solution are very weak oxidizing agents.
These can oxidize only aliphatic aldehydes but are not capable of oxidizing aromatic aldehydes
such as benzaldehyde.

Since Ketones are not oxidizied by weak oxidizing agents, such as Tollen’s reagent or Fehling
solution, therefore, such reagents may be used to distinguish between aldehydes and ketones.

Schiff’s Reagent: Schiff’s reagent is an aqueous solution of magenta or pink coloured

rosaniline hydrochloride which has been decolourised by passing SO2. When aldehydes are
treated with decolourised solution of Schiff’s reagent, its pink or magenta colour is restored. This
reaction is used as a test for aldehydes because ketones do not restore the pink colour of Schiff’s
reagent.
H2N CH3

NH2Cl

H2N
Rosaniline hydrochloride

Baeyer-Villiger Oxidation: Both aldehyde and ketones are oxidized by peroxy acids. This
reaction, called the Baeyer-Villiger oxidation, is especially useful with Ketones, because it
converts them to carboxylic esters. For example, treating acetophenone with a peroxy acid
converts it to the ester phenyl acetate.

[Type text]
[Type text]
O

R O
O H5C 6 O
OH
H5C 6 ⎯⎯⎯⎯⎯⎯→ O

CH3 H3 C
phenyl acetate
Mechanism
+
H O
O H A O O H
O O
+ ⎯⎯
→ H C
⎯
⎯ O
+
R
H3C C 6H5 H3C C 6H5 H O 3

C 6 H5 H
OH
A

H A H H
H + H A
O O O
OH O O
O O
O + H3C O O R O R
H3C H3C
R C 6 H5 C 6 H5 C 6H5

H3C O

C 6 H5

The product of this reaction show that a phenyl group has a greater tendency to migrate than a
methyl group. Had this not been the case, the product would have been C 6H5COOCH3 and not
CH3COOC6H5. This tendency of a group to migrate is called is migratory aptitude. Studies of the
Baeyer-Villiger oxidation and other reaction have shown that the migratory aptitude of groups H
 phenyl  3° alkyl  2° alkyl 1° alkyl  methyl. In all cases, this order is for groups migrating
with their electron pairs, that is, as anions.

Oppenauer Oxidation: The reaction is the reverse of Meerwein-Ponndorf-Verley reduction.

The reaction involves the oxidation of a secondary alcohol with a ketone and a base to the
corresponding ketone of the alcohol.

Commonly used ketones are acetone, methyl ethyl ketone and cyclohexanone. Commonly used
bases are aluminium ter-butoxide, aluminium isoporpoxide, potassium tri-tert-butoxide, etc.

Thus when a secondary alcohol in acetone or cyclohexanone is refluxed with aluminium tert-
butoxide in benzene or toluene solution, the secondary alcohol is dehydrogenated to a ketone and
the hydrogens are transferred to acetone or cyclohexanone converting them to alcohols.

[Type text]
[Type text]
R H3C R OH

OH + O
Al(OCMe3 ) 3
O + H3C

R H3C R CH3
2° Alcohol acetone ketone propan-2-ol

R
Al(OCMe3 )3 H
OH + O R 2 CO +
OH
R
cyclohexanone cyclohexanol

Primary alcohols may also be oxidized to aldehydes if ketones is replaced by a better hydrogen
acceptor, e.g., p-benzoquinone. The equilibrium can be controlled by the amount of acetone, an
excess of which favours the oxidation of the alcohol.

Mechanism: The mechanism is the reverse of Meerwein-Ponndorf-Verley reaction. The

alcohol and aluminium tri-tert-butoxide react to form aluminium derivative of the 2° alcohol.
Metal alkoxides undergo rapid acid-base exchange with their corresponding alcohols].

3R 2 CHOH + Al(OCMe3 )3 (R 2 CHO)3 Al + 3Me3C(OH)

The aluminium derivative then forms with acetone a cyclic transition state which undergoes
internal hydride ion transfer, resulting in the oxidation of the alcohol to ketone.
O
(R 2 CHO)3 Al + (CH3 )2 CO + R 2C Al(OCHR2)2 R 2 C = O + (CH3 ) 2 CHO − Al(OCHR 2 ) 2

H O

H3C CH3

Since the initial attack is on the alcoholic hydroxyl group, hindered alcoholic group react less
readily. Thus, in cyclohexanols, the axial hydroxyl groups are attacked less readily.

Oxidation of Aldehydes And Ketones With SeO2: Aldehydes and ketones with a methyl
or methylene group adjacent to the carbonyl group are oxidized by selenium dioxide at room
temperature to dicarbonyl compounds, e.g., acetaldehyde forms glyoxal, and acetone forms
methylglyoxal :
CH 3CHO + SeO 2 ⎯⎯ → OCHCHO+ Se + H 2O
CH3COCH 3 + SeO 2 ⎯⎯
→ CH 3COCHO + Se + H 2O

The reaction is usually carried out in acetic acid, and the actual reagent is selenous acid. A
probable mechanism is

O H O O
OH C
C C O C
O Se ⎯⎯⎯
– H2O
→ ⎯⎯⎯
→ – H2O
+ Se
CH2 CH C O C
OH O
H Se OH

[Type text]
[Type text]

Reduction of Aldehyde and Ketones

Addition of Hydride Ion: Addition of hydride ion (from NaBH4 or LiAlH4) to an aldehyde or
ketone forms an oxyanion that can subsequently be protonated by adding water or a weak acid to
the reaction mixture. The overall reaction is addition of H2 to >C = O group. The addition of H2
an organic compound is a reduction reaction.

O O OH
H+
R + H ⎯⎯
→ R H R OH
H H H
Aldehydes and ketones are reduced using NaBH4 as the source of hydride ion. Aldehydes are
reduced to primary alcohol and ketones are reduced to secondary alcohol. Notice that the source
of protons (water or weak acids) is not added to the reaction mixture until reaction with the
hydride donor is complete.
⎯⎯⎯⎯
i) NaBH 4
→ H3C OH
H3C O ii) H 2 O

1° alcohol

⎯⎯⎯⎯
i) NaBH 4
→ H3C OH
H3C CH3 ii) H 2 O

O OH
2° alcohol

Mechanism: The mechanism of reduction is similar to that of LiAlH4. The reaction proceeds by
complexing the oxygen atom of the carbonyl group with boron and simultaneous transfer of the
hydride ion to the carbonyl carbon. All the four hydrogens of the reagent are transferred to the
four molecules of the substrate. Subsequent hydrolysis gives alcohol.
3 O
O + NaBH 4 ⎯⎯
→ O ⎯⎯
→ O ⎯⎯⎯⎯⎯
→ O

BH3Na H BH3Na H BNa

4
H H2O

4 OH + NaOH + B(OH)3

NaOH + B(OH)3 ⎯⎯
→ NaH 2 BO3 + H 2 O

Meerwein-Ponndorf-Verley Reduction: The reaction involves reduction of aldehydes or

ketones to alcohol by treating it with aluminium isopropoxide in excess of isopropyl alcohol.

R OH OH O

+
Al(OCHMe 2 )3
O + H3C R H3C

R' CH3 R' CH3

The reaction is reversible. The reverse reaction, called OPPENAUR Oxidation, is employed for
the oxidation of alcohols, using aluminium tert-butoxide as catalyst in presence of excess
acetone.

The reaction shifts in the forward direction by the removal of acetone by distillation. The reaction
occurs under mild condition, is rapid, side reactions are negligible and the yield is high. The

[Type text]
[Type text]

reaction is specific for >C=O group, other reducible groups such as >C = C<, NO2 etc., present in
the substrate remain unaffected. If a compound contains two>C = O groups, one may be
protected by acetal formation and other is then reduced. Ketones with high enol content, e.g. -
diketones, -keto esters, etc. do not give this reaction.

Mechanism: The reaction probably involves a cyclic transition state (I) in which a H– ion from
the -CH bond of the alkoxide migrates to the >C = O carbon of the ketone to yield the mixed
alkoxide (II).

Al(OCHMe2)2
Al(OCHMe2 )2
R OAl(OCHMe2)2 H C
O O O R 3
CH3
O + ⎯⎯
→ R CH3 + O
- H
H H R'
R' CH3 R' CH3 H3C
(I)

An excess of isopropyl alcohol is used so that it exchanges with the mixed alkoxide (II) to
liberate the reduced ketone (III) i.e. the desired alcohol.

R H3C R
OAl(OCHMe2)2 H OH
+ ⎯⎯
→ + Al(OCHMe 2 )3
R' H3C R'
H OH H

Thus, for the reduction one hydrogen is supplied by the catalyst and the other hydrogen by the
solvent.

The Wolf Kishner Reduction: When a ketone or an aldehyde is heated in a basic solution of
hydrazine, the carbonyl group is converted to a methylene group this process is called
Deoxygenation because an oxygen is removed from the reactant. The reaction is known as the
Wolf-Kishner Reduction.
O
⎯⎯⎯⎯→
NH 2 , NH 2
OH − , 
CH3 CH3

Initially the ketone reacts with hydrazine to form a hydrazone. Hydroxide ion and heat
differentiate the Wolff-Kishner Reduction from ordinary hydrazone formation. After the
hydrazone is formed, OH– removes a proton from the NH2 group. Heat is required because these
protons are not easily removed. Resonance places some of the negative charge on carbon, which
abstracts a proton from water. The last two steps are repeated to from the deoxygenated product
and N2 gas

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[Type text]

Mechanism for Wolff-Kishner

H
O N N N NH2
−
+ H2N NH2 H ⎯⎯⎯
HO
→
CH3 CH3 CH3

H O
H H
N N
H −O − H
⎯⎯⎯ ⎯ + N2 ⎯
⎯
CH3 CH3 CH3

+OH − +OH −

Clemmensen Reduction: The reduction of carbonyl groups of aldehydes and ketones to

methylene groups with amalgamated zinc and concentrated hydrochloric acid is known as
Clemmensen reduction.
O
Zn − Hg, HCl
H5 C 6 ⎯⎯⎯⎯⎯
Reflux
→ H5 C 6

CH3 CH3
1-phenylethanone ethylbenzene

The reduction consists in refluxing the carbonyl compounds with amalgamated zinc and excess
of concentrated hydrochloric acid. The reduction is useful especially for ketones containing
phenolic or carboxylic groups which remain unaffected. Ketones are reducing more often than
aldehydes. Such reduction is also observed in Wolff-Kishner reduction but Clemmensen
reduction is easier to perform. The reduction, however, fails with acid-sensitive and high
molecular weight substrates. The , -unsaturated ketones undergo reduction of both the olefinic
and carbonyl groups.

Mechanism: Nakabayaski has suggested a mechanism on the assumption that the reducing
under acid condition involves protonated carbonyl group to which electrons are transferred from
the metal.

R R R H
R
+
O ⎯⎯ → ⎯⎯⎯ →
H Zn
OH ⎯
→ OH − Zn 2+
OH ⎯⎯⎯
2H
→ R OH2

R R R R R

-H2O

H R R
R H ⎯
H
⎯ H ⎯⎯Zn
⎯ H
− Zn 2+

R R R

[Type text]
[Type text]

Certain types of aldehydes and ketones do not give the normal reduction products alone. Thus, -
hydroxyl ketones give either ketones through hydrogenolysis of OH group or olefins and 1,3-
diketones give exclusively monoketones with rearrangement.
O
O O
H3C
⎯⎯⎯⎯⎯
Clemmensen
reduction
→
CH3
CH3 CH3
H3C

Certain cyclic 1,3-diketones give under Clemmensen reduction a fully reduced product along
with a monoketone with ring contraction.
H3C CH3
H3C CH3 H3C CH3

Zn − Hg
⎯⎯⎯→
HCl +
O O
1,1-dimethylcyclohexane
5,5-dimethylcyclohexane-1,3-dione O CH3
2,4,4-trimethylcyclopentanone

The latter probably is formed through a diradical with subsequent intramolecular C – C bond
formation and pinacol type rearrangement.
H3C CH3
H3C CH3 H3C CH3 H3C CH3 H3C CH3

− H2O
Zn − Hg
⎯⎯⎯→ ⎯⎯
→ ⎯⎯→
H +
⎯⎯⎯
− H+
→
HCl

O O HO OH HO OH HO OH2
O CH2

[H]

H3C CH3

O CH3

Other Reactions Of Aldehydes And Ketones

Wittig Reaction: Wittig reaction affords an important and useful method for the synthesis of
alkenes by the treatment of aldehydes or ketones with alkyldinetripheylphosphorate (Ph 3P =-
CR2) or simply known as phosphorane.
Ph Ph Ph Ph
Ph Ph
P + ⎯⎯
→ CH2 + P
CH2 Ph O O
Ph Ph Ph
(1-phenylvinyl)benzene triphenylphosphine oxide

The Wittig reagent, alkylidenetriphenylphosphorane, is prepared by treating trialkyl or

triarylphosphine usually the latter with an alkyl halide in ether solution. The resulting

[Type text]
[Type text]

phosphonium salt is treated with a strong base (such as C65Li, BuLi, NaNH2, NaH,
C2H5ONa, etc.

Ph Ph Ph
Ph Ph + +
P + H3C Br ⎯⎯
→ Ph P ⎯⎯⎯⎯
→ Ph
C6 H5 Li
P CH2 ⎯
→ Ph P CH2

Ph Br Ph Ph
Ph
(I) (II)
+ C6 H 6 + LiBr

Mechanism: The reaction probably proceeds by the nucleophilic attack of the ylide on the
carbonyl carbon. The dipolar complex (betain) so formed decomposes to olefin and
triphenyphosphine oxide via a four centred transition state.

Ph R Ph R
Ph R R'
Ph R R Ph
+
Ph P O
+ Ph P R ⎯⎯
→ ⎯⎯
→ P +
Ph P
O Ph
Ph R' Ph R R"
Ph R
O R' R"
R'
R"
O Betaine intermeidate
R"

The mechanism is supported by the fact that an optically active phosphonium salt reacts to
produce a phosphine oxide with retention of configuration.

Et Et
Et H5 C 6
+
CH2
+
P Br ⎯⎯⎯ ⎯
C6 H5 Li
→ P ⎯⎯⎯⎯→
C6 H5CHO
CH2 + Ph P O
Ph Ph
styrene
Ph
Ph Ph

Phosphorous yields react in the same manner with the C = O groups of ketones and isocyanates
as also with the N = O and C = N groups of nitroso and imine compounds respectively.
R 2 'C = C = O
R 2C = C = CR 2
Ketene
R N = C = O
R N = C = CR 2
Isocynate
Ph 3 P + − CR 2−
R N = O
R N = CR 2
Nitroso compound
R 2C = NR
R 2 C = CR 2
Imine

Illustration 6: Complete the following reaction

H5 C2
CH2Cl C O
(C6H5)3P C2H5ONa H5C2
(A) (B) (C)
H3C

[Type text]
[Type text]

C6H5
+
CH2Cl CH2 P C6H5 Cl-
Solution: (C6H5)3P
C6H5
H3C H3C C6H5Li
(A)
H5 C2
C2H5
C O CH P(C6H5)3
CH C H5 C2

C2H5
H3C
H3C
(C) (B)

Illustration 7: Complete the following reaction:

O

+ (C6 H5 )3 P = CH 2 ⎯⎯
→

BRAIN TEASER 2:
Complete the following reactions
a) C 6 H5
H C3
+ H3C P ⎯⎯
→
O C 6 H5
H5 C 6
H3C
b) C 6H5

+ H3C P ⎯⎯
→
O C 6 H5
H5C 6
c) CH3
H5 C 6
O
O + P CH3 ⎯⎯
→
H2C H5 C 6
C 6 H5 O
Pinacol-Pinacolone Rearrangement: The acid catalysed rearrangement of vic diols (1, 2-
diols) to ketones or aldehydes with elimination of water is known as pinacol or pinacol-
pinacolone rearrangement. The name was given from the classical example of the conversion of
pinacol to pinacolone.
CH3 CH3 CH3 O
+
H3C CH3 ⎯⎯⎯⎯⎯⎯
H (dil. H 2SO4 )

→ H3C

OH OH CH3 CH3
pinacol Pinacolone (methyl t-butyl ketone)
Ph H Ph H
+
Ph H ⎯⎯→
H

Ph

OH OH H O
1,1-diphenylethane-1,2-diol diphenylacetaldehyde

Elimination of water without rearrangement – the normal reaction of alcohols – may be achieved
under drastic conditions (Al2O3, 450°C).

[Type text]
[Type text]
CH3 CH3 H3C CH3

H3C CH3 ⎯⎯⎯⎯⎯

Al2 O3 , 450°C
→ + a little pinacolone

OH OH H2C CH2

The rearrangement has been successfully carried out with various polysubstituted glycols.

Mechanism:

CH3 CH3 CH3 CH3 CH3 CH3

+ − H2O 1,2 − Methyl shift
H3C CH3 ⎯⎯→
H
H3C CH3 ⎯⎯⎯→ H3C ⎯⎯⎯⎯⎯⎯ →

OH OH OH OH2 OH CH3
(I)
H3C CH3 H3C CH3 H3C CH3
+
−H
CH3 ⎯
→ CH3 ⎯⎯⎯ → CH3
HO CH3 HO CH3 O CH3
(II)

The carbocation (I), though tertiary, prefers to form (II) for its resonance stability.

The mechanism is supported by the fact that any carbocation in which the positive charge is on
 | |

the carbon adjacent to the one bearing the hydroxyl group  − C− C− OH  also undergoes similar
 |  
rearrangement. Thus,

CH3 CH3 CH3 CH3 CH3 CH3

− N2 1, 2-shift
H3C CH3
NaNO 2 + HCl
⎯⎯⎯⎯⎯ → H3C CH3 ⎯⎯⎯
→ H3C
5 C −H +
+ CH3
OH NH2 OH N OH

N
CH3 CH3 CH3 CH3 H3C CH3

CH3 ⎯
⎯
1,2 −shift
H3C CH3 Ag +
⎯⎯⎯ ⎯ → H3C ⎯⎯⎯⎯
+
→
(Ag 2 O) −H

OH Cl OH CH3 O CH3

The loss of water and migration of the alkyl group may be very rapid or simultaneous. Probably
the migrating group does not become completely free before it is partially bonded (III) to the
adjacent positively charged carbon, i.e., a type of intramolecular rearrangement is suggested.
R

(III)

Evidence in favour of this are (a) the migrating group retains its configuration, if chiral and (b)
no cross-over products are obtained when a mixture of two nearly similar 1,2-diols is treated with
acid.

[Type text]
[Type text]

Migratory aptitude: Migration order in general is H  aryl  alkyl

Ph H Ph H H H H
O
+
H+ H ⎯⎯→
H
Ph CH3 ⎯⎯→ Ph Ph Ph

CH3 OH OH H O
OH OH H

As the migrating group migrates with its electron pair, the more nucleophilic group might be
expected to migrate. Thus, the order of migration amongst the aryl groups is p-anisyl  p-tolyl 
phenyl  p-chlorophenyl, etc.

CH3 CH3 CH3

O
CH3
+
Ph Ph ⎯⎯→
H
Ph Ph
OH OH

Obviously, electron-withdrawing groups will retard the migration. The migratory aptitude
amongst the alkyl groups is Me3C  Me2CH > Me. However, the stability of the initially formed
carbocation may offset the migratory aptitude order. The initial carbocation is formed by the loss
of that hydroxyl group which results in the formation of the most stable carbocation. Thus, in the
compound 1, 1-dimethyl-2, 2-phenyl glycol, the resonance-stabilized carbocation (IV) is formed
instead of (V) and so it is the methyl group and not the phenyl group which migrates, contrary to
the above sequence.

Ph CH3 Ph O
1,2 − shift
CH3 ⎯⎯⎯⎯
− H+
→ Ph
Ph CH3
+ Ph OH CH3 CH3
H (IV)
Ph CH3
-H2O Ph CH3
OH OH
Ph Less stable than (IV)

OH CH3
(V)

Steric hindrance may affect the rate of migration- p-anisyl group migrates 1000 times faster than
o-anisyl group.

Illustration 8: Complete the following equations:

a) H C OH
3 +
⎯⎯→
H
?
H3C
OH

[Type text]
[Type text]

b) CH3 CH3
+
C 6H5 ⎯⎯→ ?
H
H3C

OH OH

CH3
Solution: a) H3C
OH
H3C H3C H

+ H +
H2O +
H3C H2 O
H3C OH
OH OH
H3C H3C
+
−H
⎯⎯⎯→
H shift
⎯⎯⎯ →

H3C O H H3C O
C 6 H5
b) CH3 CH3 CH3 CH3 H3C
− H2O
C 6 H5 + H CH3
+
H5 C 6 H5C 6 C 6 H5 + H2O

H5 C 6 OH
OH OH OH2 OH

C 6 H5 CH3 C 6 H5 O
⎯⎯
→ H C −H
⎯⎯⎯
+
→ H5 C 6
5 6

CH3 O CH3 CH3

H

Benzoin Condensation: The benzoin condensation is essentially a dimerisation of two

aromatic aldehydes under the catalytic influence of cyanide ions to give benzoin (I).
O
CN −
2C6 H 5CHO ⎯⎯⎯
→ H3C
OH
H5 C 6
(I)
The hydrogen atom attached to the carbonyl group of aldehyde is not active enough to be
removed easily but the addition of the cyanide ion to the carbonyl carbon places this hydrogen in
the alpha position of the nitrile thus rendering it relatively acidic. The carbanion, thus generated,
attacks the carbonyl carbon of the second aldehyde molecule in a rate-determining step forming
an unstable cyanohydrin of benzoin which immediately breaks down into benzoin and hydrogen
cyanide.
OH OH
O O
+
− H , +H +

H5C 6 + CN H5 C 6 ⎯⎯⎯⎯
CN ⎯⎯⎯ →
⎯ ⎯
→
H5C 6 CN H5C 6 C
H N
H

[Type text]
[Type text]

OH O
OH O
H5C 6 + ⎯⎯⎯
slow
C6H5 ⎯⎯ ⎯→ H3C CH3

CN H CN H

O OH O

H3C → H3C
CH3 ⎯⎯ + CN
OH
CN H
H5C 6

Benzoin condensation is not catlaysed by hydroxide ion, or by bases in general, but is

specifically catalyzed by cyanide ions. This unique catalytic property of cyanide ion is due to (a)
its good nucleophilicity which enables it to attack the carbonyl carbon. (b) its ability to stabilize
the carbanion, and (c) the ease with which cyanide ion departs in the last step.

Schimdt Reaction: This is the reaction between a carbonyl compound and hydrazoic acid in
the presence of a strong acid concentrated sulphuric acid. Aldehydes give a mixture of cyanide
and formyl derivatives of primary amines, whereas ketones give amides :

RCHO + HN 3 ⎯⎯⎯
H 2SO4
→ RCN + RNHCHO + N 2
RCOR + HN3 ⎯⎯⎯
H 2SO4
→ RCONHR + N 2

The mechanism of the reaction is uncertain. It has been shown to be intramolecular, and Smith
(1948) has proposed the following mechanism, which is an example of the 1, 2-shift (from
carbon to nitrogen); for ketones :
R R R R OH R R
C C C
⎯⎯→ H+ ⎯⎯⎯
→ R
HN3
C R ⎯⎯⎯
→
– H2O

+
O OH N N N
HN N N
-N2 R
+
C R ⎯⎯⎯
H2O
→ OH2 CR ⎯⎯⎯
–H
→O
NR NR NHR

In ketones, if the two groups are not identical, then two geometrical isomers of (I) are possible. It
is also reasonable to suppose that the anti group (to the diazonium nitrogen) is the group that
migrates. In this way it is possible to explain how steric factors may influence the isomer ratio of
amides formed:

[Type text]
[Type text]

1 2
R R
+
C
⎯⎯⎯
– N2
→ R 1 — N = C— R 2 ⎯⎯⎯
H 2O
→ R 1NHCOR 2
N N2
1 2
R R
+
C
⎯⎯⎯
– N2
→ R 1 — C = NR 2 ⎯⎯⎯
H2O
→ R 1CONHR 2
N2 N

For aldehydes, R 1 = H , and so the reaction maybe formulated :

H R
+
C +
⎯⎯
→ N 2 + HN = C— R ⎯⎯⎯
–H
→ RCN
N N2

R H
+
C
⎯⎯
→ N 2 + RN = C H ⎯⎯⎯
H2O
→ HCONHR
N N2

Benzilic acid Rearrangement: The addition of a strong base to a carbonyl group results in
the formation of an anion. The reversal of the anionic charge may cause expulsion of the attached
group X, e.g.

X X O

O
HO
O ⎯⎯
→

OH OH

However, in a 1,2-diketone the group X may migrate to the adjacent electron-deficient carbonyl
carbon forming -hydroxy acid.

Thus, benzil on treatment with a strong base forms benzilic acid (salt), whence the name benzilic
acid rearrangement.

O O OH O
O
C 6H5 ⎯⎯⎯
NaOH
→ H5C 6 ⎯⎯
→ H5C 6
H5C 6
C 6H5 OH C 6H5 ONa
O
benzil sodium salt of benzilic acid

[Type text]
[Type text]

Barium and thallous hydroxides are more effective than sodium or potassium hydroxides.
Alkoxide ions (methoxide, t-butoxide etc.) in place of hydroxide ion give the corresponding
esters.
O C 6 H5 O
C 6 H5 ⎯⎯⎯⎯
CH3ONa
→ H5 C 6
H5 C 6
OH O
O
H3C
Benzilic acid methyl ester

Phenoxide ions are too weak a nucleophile to attack. Besides aromatic 1,2-diketones, aliphatic
and heterocyclic diketones as also o-quinones undergo this rearrangement.

Mechanism: It has been seen the rate of reaction is proportional to the concentration of benzyl
and the hydroxide ion, i.e., rate  [C6H5COCOC6H5][OH–]

It has also been found that when the reaction is carried out in the presence of H 218O, benzyl
exchanges 18O faster than it rearranges.

On the basis of the above observations, it has been suggested that a fast reversible nucleophilic
attack occurs at the carbonyl carbon in the first step. The second step is the rate determining step
in which the migration occurs. Finally, a rapid proton transfer completes the process.

O O O O O O OH O

+ OH
fast
OH ⎯⎯⎯
slow
→ Ph ⎯⎯⎯
proton
transfer
⎯→ Ph

H3C Ph H3C Ph Ph OH Ph O

The rearrangement is analogous to intramolecular Cannizzaro reaction of glyoxal.

The carbonyl group which is attached to the less electron releasing of the two aryl groups is
relatively more positively charged and, hence, is attacked by OH–. Consequently, the less
electron donating aryl group migrates to the other carbonyl group.
O O O O
H3C
OH
H3C ⎯⎯⎯
slow
→ H3C
fast O
O C6H5 OH
H5 C 6
H5C 6 OH
OH O
+
⎯⎯⎯ H
⎯
transfer
→ H3C
C 6 H5 O

The Beckmann Rearrangement: The acid catalysed transformation of a ketoxime to an N-

substituted amide is known as the Beckmann rearrangement.

[Type text]
[Type text]

R R'
H+ NH
N ⎯⎯→
R' OH O R

The rearrangement is catalysed by a variety of acidic reagents such as H 3PO2, H2SO4, SOCl2,
PCl5, etc., and a simplified mechanism can be written in the following steps.
H
R R +
R' C +
H+ O H
N ⎯⎯→
⎯⎯ N − H2O
⎯⎯⎯→ ⎯⎯⎯
→ H2O

N R R'
R' OH R' OH2
N R
−H +
O O H
R' R'
NH R N R

The rearrangement is highly stereospecific in that the migrating group always approaches the
nitrogen atom on the side opposite to the oxygen atom.

R' O
R R'
− H2O
⎯⎯⎯→ ⎯⎯⎯→
i) H 2 O
ii) -H +
NH

N N R' R
OH2 R

In the above example, there is migration of the R group to the electron deficient nitrogen, which
is anti or trans to the hydroxyl group. The exclusive migration of the anti group has been
confirmed in a number of cases, most notably in the conversion of 2-chloro-5-nitro-
benzophenone oxime to a chlorobenzanilide. The configuration of this particular oxime has
earlier been established by its ready conversion of a nitro-substituted phenylbenzisoxazole,
showing that the nitrated benzene ring lies on the same side of the C = N linkage as the –OH
group. When this oxime undergoes Beckmann rearrangement, it is found that the phenyl group,
rather than the nitrated benzene ring, migrates to the nitrogen.
O C 6H5 C 6H5

O2N O2 N O2 N
NH N N
⎯⎯⎯
Beckmann
⎯ ⎯⎯⎯⎯
cold alkali
→
C 6 H5 rearrangement OH O
Cl Cl

Since it is always the anti group that migrates, it appears that either the breakage of the N – O
bond and the group migration are syunchronous or these two steps follow each other quickly. The
migration of the anti group is so much certain in the Beckmann rearrangement that it is normally
possible to establish the configuration of a particular oxime by identifying its rearrangement
products.
H5C 6 O
+
O ⎯⎯→
H O
N H5C 6 NH CH3
CH3
OH

[Type text]
[Type text]

H5C 6 O
O ⎯⎯
→ H5 C 6
HO N CH3 NH OCH3

Another mechanistic feature of the rearrangement has been worked out by Kuhara and later by
Chapman who established that the rearrangement does not take place in the oxime itself, but in
its acyl derivative which ionizes and subsequently rearranges. The ionization of the acyl
derivative has been shown to be the rate-controlling step of the rearrangement. Typically, the
benzene sulphonic ester of benzophenone oxime undergoes rearrangement without any acid
catalyst.
H5 C 6 C 6 H5 H5 C 6 OSO2Ph O
+
⎯⎯
→ ⎯⎯→
H H5 C 6 + C6 H5SO2 OH
N N
OSO2Ph C 6 H5 NH
H5 C 6

It is also observed that rates of isomerisation of various oxime esters run parallel to the strength
of the esterifying acids which is found to be in the following order.
C6 H 5SO 2 OH  C6 H 5COOH  CH 3COOH

Finally, the carbon atom of the migrating group retains its configuration in the Beckmann
rearrangement. By the following series of reactions. Kenyon and Young not only proved
retention of configuration but also correlated Beckmann and Hofmann rearrangements. Optically
active 3-heptylcarboxylic acid was converted to its amide and subjected to Hofmann
rearrangement. In another set of experiment the same acid was converted into 3-phenylmethyl
ketone and then the oxime of this ketone was rearranged by the Beckmann method. Both these
rearrangement yielded the same optical isomer of 3-heptylamine.
C 2H5 C 2H5 O C 2 H5

n-C 4H9 CO2H ⎯⎯

→ n-C 4H9 ⎯⎯⎯⎯
Hofmann
→ n-C 4H9 NH2

H H NH2 H
1. SOCl2
2. Cd(CH3)2 hydrolysis

C 2H5 C 2 H5 C 2 H5
O CH3

n-C 4H9 ⎯⎯
→ n-C 4H9 ⎯⎯⎯⎯
Hofmann
→ n-C 4H9 NH

CH3 N H O
H H
HO H3C

Since the retention of configuration at the migrating carbon has already been confirmed in the
Hofmann rearrangement, it therefore follows that the Beckmann rearrangement also takes place
with retention of configuration. Apparently the migrating group never becomes free from the
remainder of the molecule and it also appears reasonable to believe that the breakage of C – C
bond and the formation of the new C – N bond take place synchronously.
However, Beckmann rearrangement as a whole is not an intramolecular process since the
carbonium ion, once formed, may combine with a hydroxyl ion present in solution. The

[Type text]
[Type text]

rearrangement of benzophenone oxime into benzanilide was studied in presence of water

containing heavy oxygen (18O). The product incorporated the heavy isotope.
H5C 6 C 6H5 NH C 6H5

⎯⎯⎯⎯
i) PCl5
ii) H 218O
→ H5C 6
N 18
OH O

It is therefore evident that the Beckmann rearrangement does not proceed by an intramoelcular
exchange of the hydroxyl and the phenyl group; rather it passes through a carbonium ion which
accepts hydroxyl ion or a water molecule from the solvent. Thus there is complete loss of the
original oxime oxygen from the molecule during the reaction. A reasonable mechanism for the
Beckmann rearrangement may be summed up as under:
C 6H5
H5C 6 C 6H5 H5C 6 C 6H5
⎯⎯⎯
PCl5
→
N
N N
OH O
18
Cl Cl H 2O
P
Cl Cl 18 +
H5C 6 H5C 6 OH2
18 − H+
O ⎯⎯ ⎯
N
H5 C 6
H5C 6
In the presence of strong acids, the reaction is initiated by protonation of the oxime followed by
loss of water to yield the same species as obtained by the decomposition of ester.
Beckamnn rearrangement is not only confined to ketoximes, but some aldoximes have also been
shown to undergo this rearrangement. Thus, syn- and anti- benzaldoximes undergo
rearrangement under the influence of PPA.
H5C 6 H O
H+
⎯⎯→ H5C 6
N NH2
HO

The formation of benzamide in the rearrangement of the syn-isomer has been explained by the
ready conversion of some of the syn-form into the anti which then rearranges with a hydrogen
migration.
Beckmann rearrangement has also been used for the enlargement of rings. An example of
considerable industrial importance involves the rearrangement of cyclohexanone oxime to -
caprolactam used for the manufacture of nylon-6.
O

NH
+
N ⎯⎯→
H ⎯⎯
→ nylon-6
OH

Reaction of Formaldehyde with Ammonia: Formaldehyde reacts with ammonia to form

hexamethylene tetramine, (CH2)6N4 also known as urotropine.

[Type text]
[Type text]
N Formatted

CH2

6HCHO + 4NH 3 ⎯⎯
→ N
CH2 CH2
N N

Hexamethylene tetramine

Urotropine is used as a medicine to treat urinary infections. Nitration of urotropine under

controlled conditions gives an explosive RDX (Research and development explosive).
Answer to Brain Teasers
Brain Teaser 1: A = CH3COCH2CH3
B = CH3CHOHCH2CH3
C = CH3CH = CHCH3
D = H3C O
H CH3

O H
O

H3C C 6 H5 H5 C 6
Brain Teaser 2: a) H5 C 6 O
O + P CH3 ⎯⎯
→ P
H5C 6
H3C H5C 6 C 6H5

+ H3C CH3

CH3
(3E)-3-methylhept-3-ene
H5C 6
b) H5C 6
O
O + P CH3 ⎯⎯
→ + P
H5C 6 H5C 6
C 6 H5 C 6 H5
CH3
CH3 CH3
c)
H5 C 6
O O O
+ P CH3 ⎯⎯
→ H2C CH3
H2C
H5 C 6
C 6 H5 O O
H
H5 C 6
O
+ P
H5C 6
C 6H5

[Type text]