addition to carbon - Hetero multiple

bonds

 Addition of Grignard Reagents

 Aldol condensation
 Perkin reaction.
 Knoevenagel reaction
 Reformatsky reaction
 Wittig reaction
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Aldol condensation

• Aldehydes containing alpha Hydrogen atoms undergo

self condensation in presence of base to form product
“aldol”
• Eg:
O O
HO O

H
C
CH3 + H
C
CH3 NaOH H C
3 CH CH2 C H
acetaldehyde acetaldehyde
3-hydroxybutanal

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Mechanism
• Reaction involves following steps

• Step:1-formation of carbanion from a molecule of

aldehyde the abstraction of proton by a base

O O
H + - + H O
CH2 H
:OH- :C H2 H 2
Carbanion
acetaldehyde

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Step:2-Attak of carbanion on the 2nd aldehyde

O -
O O O
C -
H3C H+ :C H2 C H H3C HC CH2 C H

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• Step:3-protonation of negatively charged

oxygen by water

- HO O
O O

H3C CH CH2 C H
H3C HC CH2 C H + H2O 3-hydroxybutanal

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 SDM College (Autonomous) Ujire

Benzoin condensation

• This reaction involves self addition of aromatic

aldehydes(which lack of alpha hydrogen) In presence of
aqueous alcoholic KCN to form alpha hydroxy ketones

O O
O H
KCN
C + C C C
H H2O,C 2H5OH
H
OH
benzaldehyde benzaldehyde
2-hydroxy-1,2-diphenylethanone
Benzoin

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 SDM College (Autonomous) Ujire

Step:1 Formation of carbanion by nucleophilic attak of CN-

on carbonyl group of benzaldehyde

-
O O OH
-
C H + CN C H
C
-
NC
benzaldehyde NC

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• Step:2 Attack of carbanion on the carbonyl group of the

2nd molecule of benzaldehyde to form a addition product

OH
O OH O-
-
C + C C C
NC
H NC H

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• Step:3- Proton transfer and loss of cyanide ion from the

addition product to form Benzoin

-
O OH
OH O -

-
Proton shift C C
C C NC H
NC H
-
-CN

O H
C C

OH
Benzoin
22-Jul-17 Executive summary
 Perkin reaction
• It involves the treatment of an aromatic aldehyde
with anhydride of an aliphatic acid and sodium salt
of the same acid to form alpha,beta-unsaturated
acid.
• Eg:

O
O CH 3COONa CH CH OH
C H + (CH3CO)2O
453
3-phenylprop-2-enoic acid
Cinnamic acid
Step:1 formation of anion by abstraction of an alpha
hydrogen from acetic anhydride by base.

O O O O

CH 3COO
-
+ H2C C O C CH3
-
:C H2 C O C CH3 + CH 3COOH
H

Step:2 Attack of anion on carbonyl group of benzaldeyde to

form a product with a –vely charged oxygen

O O O O
-
O O
-
C H + :C H2 C O C CH3 CH CH2 C O C CH3
 Step:3- protonation
-
O O O + HO O O
H
CH CH2 C O C CH3 CH CH2 C O C CH3

Step:4 –Elimination of water

HO
H O O O O
CH CH C O C CH3 CH CH C O C CH3
-H 2O

Step:5-Hydrolysis to give cinnamic acid

O O O
H2O
CH CH C O C CH3 CH CH C OH + CH 3COOH
3-phenylprop-2-enoic acid
 Knoevenagel reaction:
• An aldehyde or ketone on condensation with a active
methylene compound In presence of a base gives a
unsaturated compound.
• Eg

O O
O Pyridine C CH3
C CH3
H3C H
+ H2C + H3C CH C
C O CH3 H ,-H 2O C O CH3
O O
Acetoacetic ester
methyl 2-acetylbut-2-enoate
(unsaturated compound)
Mechanism
Step:1-Formation of carbanion by abstraction of hydrogen from
acetoacetic ester by the base
O O
C CH3 - C CH3
B: +HC C O CH3
CH
C O CH3
+ BH
++

H
O O

Step:2-Attack of the carbonyl group of aldehyde to form an

alkoxide ion

O - O
O O
C CH3
C CH3
H3C H
+ CH
- H3C HC CH
C O CH3
C O CH3
O O
Step:3-Protonation of alkoxide ion to give a hydroxy
compound

- O O
O + OH
C CH3 H C CH3
H3C HC CH H3C HC CH
C O CH3 C O CH3
O O

Step:4-Dehydration of the hydroxy compound.

O O
OH -H 2O C CH3
C CH3
H3C CH C
H3C HC CH C O CH3
C O CH3

O O
Unsaturated compound
 The reaction of α-haloesters with carbonyl compounds such as
aldehydes and ketones in the presence of zinc in an inert solvent
to produce β-hydroxyesters is known as Reformatsky reaction.

16
 The reaction involves the formation of an intermediate
organozinc compound which then adds to the carbonyl group.
The resulting complex is readily hydrolysed to β-hydroxyester.

17
 Wittig reaction

The Wittig reaction or Wittig olefination is a chemical

reaction of an aldehyde or ketone with a triphenyl phosphonium
ylide (often called a Wittig reagent) to give
an alkene and triphenylphosphine oxide.
Mechanism
 Examples:
O +
C + (C6H5)3P C-H2 CH CH2 + (C6H5)3PO
H Methylene triphenyl phospene (ylide)
Styrene

H3C H3C
+
O + (C 6H5)3P C H2
-
CH2 + (C6H5)3PO
H3C H3C
2-methylprop-1-ene
 4.Mannich reaction
Formaldehyde on condensation with an amine and a
compound capable of forming an enol gives a
product called Mannich base. this reaction is called
mannich reaction

O O
O

H3C
C +
CH3 H
C + (C2H5)2NH H3C C CH2 N(C 2H5)2 + H2O
H
Acetone Diethylamine 1-(diethylamino)propan-2-one
Oxidation of aldehydes & ketones
• Aldehydes can be oxidesd to carboxylic acids in
presence of sodium (pottasium) dichromate or
potassium permanganate in acedic medium.
• Eg:
O
H3C Na 2Cr 2O7
C O H3C C OH
H H2SO4
acetaldehyde acetic acid
O O
O
HNO3
H3C CH2 C CH3
H3C CH2 C OH + H3C C OH
propanoic acid acetic acid
butan-2-one
 Milder oxidising agents such as Tollens
reagent,Fehlings & Benidicts solutions ca be used

O O
2Ag(NH2)OH
C R C
-
O NH
+
+ 2Ag + H2O
4
R H

O O
- +
R
C
H
+ 2Cu(OH) 2 + NaOH R C O Na + Cu2O + 3H2O
Fehlings/Benidicts soln
Reduction of aldehydes and ketones
• Aldehydes & ketones can be redused to alkanes by
using reducing agents.

• Two important reactions are

• 1.Clemmensen reduction:
• 2.Wolf –Kishner reduction
 1.Clemmensen reduction:
• It is the reduction of aldehyde &ketones to alkanes
using zinc amalgum in HCl as reducing agent.
• Eg:
O
Zn/Hg
H3C
C
H
+ 4[H] H3C CH3 + H2O
HCl
acetaldehyde ethane

O
Zn/Hg
H3C
C
CH3 + 4[H] H3C CH2 CH3 + H2O
HCl
propan-2-one propane
2.Wolf –Kishner reduction
• It is the reduction of aldehyde &ketones to
alkanes using a basic solution of hydrazine
as redusing agent
O
H2N NH2

H3C
C
H
+ 4[H]
NaOH
H3C CH3 + H2O
acetaldehyde ethane
O

H3C
C
CH3 + 4[H] H2N NH2
H3C CH2 CH3 + H2O
NaOH
propan-2-one propane
Protecting Groups
• “A group that protect a functional group from
undergoing chemical reaction is called protecting
group.”
• The carbonyl function of aldehyde and ketone are
protected by using some protecting groups.
• Eg:
H2C CH2 H2C CH2 CH2

OH HO OH OH
1,2 diol 1,3 diol

• These react to form five or six membered ring acetals

or ketals respectively
 O H2C CH2
Eg:
H3C CH2 C H +H2C CH2 O O + H2O
propanal OH OH C
H3C H
1,2 diol
Five membered acetal
CH2

O H2C CH2

H3C CH2 C H + H2C CH2 CH2 O O + H2O

OH OH C
propanal H3C H
1,3 diol
Six membered acetal

• Protecting group can be removed by acid hydrolysis after

the reaction
 CH2
O O H2C CH2
CH2 CH2
H3C C CH2 CH2 C H + H2C O O O
4 -Oxypetanal OH OH H3C C CH2 CH2 C H
1,3 diol Six membered acetal

CH2
H2C CH2 HO O
CH 3MgBr +
OH H ,H 2O
O O
H3C C CH2 CH2 C H
H3C C CH2 CH2 C H
CH3
CH3

Aldehydes are more reactive than ketones.so

aldehyde part is protected then ,Grignard reagent
made to react with keto group. then it is
deprotected by hydrolysis