Aldehyde & Ketone : 10/

Reaction with Halogen

Mechanism & Application

-H of compound if replaced by halogen atom ; the substitution reaction is known

as -halogenation reaction

REACTION ON ALDEHYDE & KETONE

Substrate : Reagent :

Product :

Acid-catalysed Mechanism :

Summary : Successive halogenation become slower compare to previous.

H
H3C H2O
C
+
O H

Dr. Pallab Sarkar M.Sc , Ph.D

Aldehyde & Ketone : 10/

H
H3C H2O
C Cl
+
H
O

H3C H2O
C Cl
+
Cl H
O

Base catalysed mechanism :

Summary : Successive halogenation become faster compare to previous.

Attachment of electronegative halogen atom makes -H more acidic which

favors deprotonation by OH–.

H H H
H3C H3C
OH OH H3C OH
C C Cl Cl
C
O Cl 2 Cl 2 Cl 2
O O Cl

Acidic character of -H gradually increases

O +
H

+ Br2
OH

Dr. Pallab Sarkar M.Sc , Ph.D

Aldehyde & Ketone : 10/

Haloform Reaction

Substrate :

Reagent :

Product :

Mechanism :

Summary : Methyl of ‘ketone methyl gr.’ converted into CHX3 & counter
part oxidized into carboxylic acid salt
-
R CH3 R O
KOH
+ Br 2
+ CHBr 3
O O

1. AlCl 3 (anhy)
CH3 +
KOH H3O P 2O 5 2. C6H6
CH3 + I2 yellow ppt. + A B C D
NaOH
E
+
3. H3O CaO /
O

Dr. Pallab Sarkar M.Sc , Ph.D

Aldehyde & Ketone : 10/

Haloform reaction do not affect any unsaturation

CH3
KOH
+ I2
O

Acid derivative can’t participate in haloform reaction

Acid derivative mostly participate into basic hydrolysis as -H atoms are even
less acidic than aldehyde & ketone.

H3C Cl
KOH
+ I2
O

Me O Et
KOH
+ I2
O O

If an ester on hydrolysis produce such an alcohol that can participate in

haloform reaction, we will observed positive response to X2 / OH–

H3C O
KOH
+ I2
O

Presence of active methylene gr. alter the expected product

KOH
+ I2
O O

Dr. Pallab Sarkar M.Sc , Ph.D

Aldehyde & Ketone : 10/

REACTION ON ACID DERIVATIVES

Extent of anolisation :

O
tautomerism
H3C C OH
(carboxylic acid)

tautomerism
H3C C O C CH3
O O
(anhydride)

tautomerism
H3C C OEt
O
(ester)

tautomerism
H3C C NH2
O
(amide)

Dr. Pallab Sarkar M.Sc , Ph.D

Aldehyde & Ketone : 10/

tautomerism
H3C C Cl
O
(acid halide)

Hell-Volharde-Zelinsky Reaction

Substrate :

Reagent :

Product :

Mechanism :

Summary :

Dr. Pallab Sarkar M.Sc , Ph.D

Aldehyde & Ketone : 10/

H3C OH Br2 / Red P

H2O
O

OH Cl 2 / Red P
H2O
O

Synthetic Application

H2O

H3C OH Br2 / Red P MeOH

A
O

NH3

1. OH
+
2. H3O
H3C OH Br2 / Red P NH3
A C
H2O
O
1. KCN
+
2. H3O

+ 1. LAH / THF 1.DIBAH

H3O + +
2. H3O 2. H3O

E F G

Dr. Pallab Sarkar M.Sc , Ph.D

Aldehyde & Ketone : 10/

Harpp modification : Use of SOCl2 instead of Cl2 / Red P

Dr. Pallab Sarkar M.Sc , Ph.D