DECARBOXYLATION

Removal of CO2 is decarboxylation ,following compounds will undergo decarboxylation on heating:

(i)   keto acid

(ii) Gem-dicarboxylic acid
(iii)  ,   unsaturated acid
(iv) NaHCO3
(v) Sodalime process
(vi) On heating 1,6 or higher dicarboxylic acids in presence of acid anhydride will form
cycloketones with one carbon less (Blanc reaction)

On heating   keto acid it’s entropy increases and hence CO2 evolves.

H
OH O
O O heat
H3C H3C
H3C O -CO2
CH2 CH3
3-oxobutanoic acid prop-1-en-2-ol acetone

Transition state have aromatic character

H
OH O
O O heat
HO HO
HO O -CO2
CH2 CH3
malonic acid ethylene-1,1-diol acetic acid


H
CH2 O heat
-CO2 H3C
O
CH2
but-3-enoic acid prop-1-ene

O

COOH
heat
O

COOH

O
phthalic acid 2-benzofuran-1,3-dione


O O
O
heat
R R
-CO2
-
- CH2
O


CO2 always removes on heating   keto carboxylic acid or it’s salt. For acid pericyclic
mechanism follows and for it’s salt carbanion involves.
 DECARBOXYLATION

Q.1 Correct order of rate of decarboxylation among following is:

O2 N  CH 2  COO  , N  C  CH 2  COO  , Cl  CH 2  COO  F  CH 2  COO 
(I ) ( II ) ( III ) ( IV )

(a*) I  II  III  IV (b) I  II  III  IV

(c) I  II  IV  III (d) I  IV  II  III

Q.2 Identify product?

O

HOOC COOH
heat
HOOC COOH

(i)
O
HOOC heat
COOH
(ii)
O

COOEt
heat
+
H3O
(iii)
O
heat
Ph COOH

(iv) HOOC

OH
PCC heat
A B
H3C COOH
(v)

heat

COOH
(vi) O

CH3
O
O
H3C
COOEt
heat
+
H3O
(vii)
 DECARBOXYLATION

Q.3 Write relation between A & B?

CH3
HOOC heat
COOH A + B

H5 C2

Q.4 The total number of carboxylic acid groups in the product P is

O O
+
1. H3O ,
O P
2. O 3
3. H2O2

O O

Ans. 2

O
O
 CH3COOOH
OH A B
Q.5

The correct statement among the following is

(A*) Compound A is formed by heating adipic acid.

O
(B) Compound B is

(C) Compound A gives positive Tollen’s test

(D) None of these