Chapter 22.

Carbonyl Alpha-
Substitution Reactions
22.1
Which of the following reagents will not form
an enolate upon reaction with a ketone?
2.
1.

3.
4.
22.1 answer

2.
1.

LDA

3.
4.
22.2 O O
O O
O
O
O
A B C D

Which of the above carbonyl compounds is

most acidic?

1. A
2. B
3. C
4. D
22.2 answer O O
O O
O
α
 O
O
A B C D

Which of the above carbonyl compounds is

most acidic?

1. A
2. B
3. C -Dicarbonyl Compounds
4. D
22.3
O O O O O O O

OCH3 CH3O OCH3 OH

A B C D

Rank the above from least to most acidic.

1. A<B<C<D
2. D<B<A<C
3. D<A<C<B
4. D<A<B<C
5. C<B<A<D
22.3 answer
O O O O O O O

OCH3 CH3O OCH3 OH

A B C D
pKa = 9 pKa =11 pKa =13 pKa = 5
Rank the above from least to most acidic.
1. A<B<C<D
2. D<B<A<C
3. D<A<C<B
4. D<A<B<C
5. C<B<A<D
 O
22.4 C
CH3
NaOH

excess Br2

O O

(a) (b)
C C
C6H5 CBrH2 C6H5 CBr2H

O
O

(c) C (d)
C
C6H5 CBr3 - + CHBr3
C6H5 O
22.4 answer

O O

(a) (b)
C C
C6H5 CBrH2 C6H5 CBr2H

O
O

(c) C (d)
C
C6H5 CBr3 - + CHBr3
C6H5 O

Haloform Reaction 鹵仿反應

 O
22.5
1. Br2/PBr3
C
CH3CH2CH2 OH 2. H2O

O O

C (b)
(a) C
CH3CH2CH2 Br
CH3CH2CHBr OH

O O

(c) C (d) C
CH3CHBrCH2 OH
CH3CH2CBr2 OH
22.5 answer
O O

C (b)
(a) C
CH3CH2CH2 Br
CH3CH2CHBr OH

O O

(c) C (d) C
CH3CHBrCH2 OH
CH3CH2CBr2 OH

α - Bromination of Carboxylic Acids:

The Hell–Volhard–Zelinskii (HVE) Reaction
22.6 O O 1. NaOCH2CH3
CH2 C
CH3CH2O 2. CH3CH2CH2Cl
OCH2CH3 3. H3O+ heat

(a)
(b)

COOH COOH

(c)
(d)

COOCH2CH3 COOCH2CH3
 22.6 answer
O O
CH2 C
CH3CH2O
OCH2CH3
(a)
(b) 2 C carboxylic acid

COOH COOH

(c)
(d)

COOCH2CH3 COOCH2CH3

Malonic ester ,Diethyl malonate is alkylated. The

derivative is hydrolyzed then decarboxylated.
 O O 1. NaOCH2CH3

22.7 C CH2 C
2. CH3CH2Cl
H3C OCH2CH3 +
3. H3O heat

(a)
(b)
COOCH2CH3 COOH

(c)
O (d)

O
 O O

22.7 answer
C CH2 C
H3C OCH2CH3

3 C ketone
(a)
(b)
COOCH2CH3 COOH

(c)
O (d)

Ethyl acetoacetate is alkylated. The

derivative is hydrolyzed and
decarboxylated.
 22.8
Predict the product of the following sequence of
reactions.

heat

1.
2.

3.
4.

5.
None of these
22.8 answer

heat

1.
2.

3.
4.

5.
None of these