Chapter 21.

Carboxylic Acid
Derivatives: Nucleophilic Acyl
Substitution Reactions
21.1 O O
CH3OH
C C
CH3CH2 O CH2CH3

• Ethanoic acid + ethanol

• methyl ethanoate + Propanoic acid
• ethyl ethanoate + Ethanoic acid
• methyl propanoate + Propanoic acid
• ethyl propanoate + Ethanoic acid
21.1 answer
• Ethanoic acid + ethanol
• methyl ethanoate + Propanoic acid
• ethyl ethanoate + Ethanoic acid
• methyl propanoate + Propanoic acid
• ethyl propanoate + Ethanoic acid

An anhydride reacts with an alcohol to give a carboxylic acid

and an ester.
Alcoholysis 醇解
 O
21.2
CH3CH2CH2NH2
C
CH3CH2 OCH3

• N-Propyl propanamide + methanol

• N-Propyl ethanamide + ethanol
• N-Ethyl propanamide + methanol
• N-Ethyl ethanamide + ethanol
• N-Ethyl ethanamide + propanol
Level 3
Challenging
 21.2 answer

• N-Propyl propanamide + methanol

• N-Propyl ethanamide + ethanol
• N-Ethyl propanamide + methanol
• N-Ethyl ethanamide + ethanol
• N-Ethyl ethanamide + propanol
Aminolysis 胺解
An ester reacts with an amine to produce an amide
and an alcohol.
Level 3
Challenging
 O
21.3 HCl
C
CH3CH2 NHCH3 heat

O
O
(a) (b)
NH2
H

(c) CH3COOH (d)

COOH
21.3 answer
O
O
(a) (b)
NH2
H

(c) CH3COOH (d)

COOH

Hydrolysis 水解
21.4
Predict the outcome of the following
reaction.
O

OH SOCl2

1. 2. 3.
O O
OH
H Cl

4. 5.
O
O
S
OH S OH
O
 21.4 answer
O

OH SOCl2

1. 2. 3.
O O
OH
H Cl

4. 5.
O
O
S
OH S OH
O
 O
21.5 1. 2CH3MgBr
C
+
CH3CH2 Cl 2. H3O

(a) (b)

HO
OH

(c) (d)

OH HO
21.5 answer

(a)
(b)
HO
OH

(c) (d)

OH HO
21.6 O
1) LiAlH4

NH2 2) H2O

O
(a) COOH (b)

NH2

(d)
(c)
CH2NH2 CH2NHCH3
 21.6 answer

O
(a) COOH (b)

NH2

(d)
(c)
CH2NH2 CH2NHCH3
21.7 O
1) LiAlH4

NHCH3 2) H2O

O
(a) COOH (b)

NH2

(d)
(c)
CH2NH2 CH2NHCH3
 21.7 answer

O
(a) COOH (b)

NH2

(c) (d)
CH2NH2 CH2NHCH3
 O O
21.8
C C
CH3CH2 Cl
+ -
HO CH3

a.Ethanoic methanoic anhydride

b.Methanoic propanoic anhydride
c.Ethanoic anhydride
d.Ethanoic propanoic anhydride
21.8 Answer

a.Ethanoic methanoic anhydride

b.Methanoic propanoic anhydride
c.Ethanoic anhydride
d.Ethanoic propanoic anhydride

An acid halide reacts with a carboxylic acid

to form an anhydride.
 21.9
What sequence of reagents will accomplish the
following transformation?
OH
OH

1. 2.
+ +
H 2 PhMgBr H3O H3O+
2 PhMgBr
CH3OH Et2O Et2O

3. 4.
H+ H+ 2 PhOH

PhOH CH3OH

5.
SOCl2 2 PhOH
 21.9 answer
OH
OH

1.
+
2.
H +
2 PhMgBr H3O 2 PhMgBr H3O+

CH3OH Et2O Et2O

3. 4.
H+ H+ 2 PhOH

PhOH CH3OH

5.
SOCl2 2 PhOH
1.

5.