CHAPTER 4

Carboxylic Acid
Derivatives
Introduction to Carboxylic
Acid Derivatives
a) Acyl halides
b) Acid anhydrides
c) Ester
d) Amides
 Acyl Halides

• Acyl halides are compounds that have a

halogen atom in place of the OH group
of a carboxylic acid.

O O
R C OH R C Cl
• The most common are acyl chlorides and
acyl bromides.

O O

R C Cl R C Br
acyl chloride acyl bromide
Example 1:

O
CH3 C Cl

2C is ethane, “e” is removed and replaced

with “oyl chloride”

The name is ethanoyl chloride

Example 2:

O
CH3CHCH2CH2 C Br
CH3

4-methylpentanoyl bromide
 Acid Anhydrides

• Anhydrides means without water.

• Loss of water from two molecules of

carboxylic acid.
Example:

O O
R C OH + HO C R'
carboxylic acid carboxylic acid

O O
R C O C R' + H2O
acid anhydride
 Types of Anhydride

• If two carboxylic acids are the same, the

anhydride is a symmetrical anhydrides.

• If two carboxylic acids are different, the

anhydride is a mixed anhydrides.
 Naming of Acid Anhydrides
• Symmetrical anhydrides are named by
using the acid name and replace “acid”
with anhydride”.

O O
CH 3 C O C CH3

Ethanoic acid ethanoic anhydride

• Mixed anhydrides are named by stating
the names of both acids in alphabetical
order, followed by “anhydride”.

O O
CH3 C O C CH2CH2CH3

Butanoic ethanoic anhydrides

 Esters

• The general structure of ester:

O
R C O R'

• The general formula of ester is CnH2nO2.

 Naming of Esters

R C O R'

acid alcohol

The alcohol part is name first, followed by

the name of “ic acid” modified with “ate” at
the end of the name.
Example 1:

O
CH3CH2 C O CH2CH3

ethylpropanoate
Example 2:

CH3 O C

methylbenzoate
Naming Salts of Carboxylic Acids

• Salts of carboxylic acids are named in

the same way.

• The cation is named first, followed by

the name of the acid and “ic acid”
replaced by “ate”.
Example 1:

O
CH3 C O- Na+

Sodium ethanoate
Example 2:

C O- K+

Potassium benzoate
 Amides
• Amides are compounds in which a
carbonyl group is connected to a
nitrogen atom.

C NH2

• General formula is RCONH2.

 Naming of Amides

• The I.U.P.A.C name is based on the

longest continuous carbon chain that
includes the amide group.

• If a substituent is bonded to the nitrogen,

the name of the substituent is stated
first, followed by the name of the amide.
• Amides are named by replacing the ending
“oic acid” with “amide”.

O O

CH3 C OH CH3 C NH2

ethanoic acid ethanamide
Example 1:

O
CH3CH2CH2 C NH2

butanamide
Example 2:

CH3CH2CONH2

propanamide
Example 3:

C NH2

benzamide
• If there is more than one substituent
bonded to the nitrogen, they are stated
alphabetically.

• The name of each substituent is

preceded by a capital –N to indicate that
the substituent is bonded to nitrogen.
Example 1:

O CH2CH3
CH3CH2CH2 C N CH2CH3

N,N-diethylbutanamide
Example 2:

O CH3
CH3CH2CH2CH2 C N CH2CH3

N-ethyl-N-methylpentanamide
 Classification of Amides

• Amides can be classified as primary (1°),

secondary (2°) or tertiary (3°) amides.
 Primary Amides
• Nitrogen atom is attached to two
hydrogen atoms.
O
CH3 C NH2
ethanamide

O
CH3CH2CH2 C NH2
butanamide
 Secondary Amides
• Nitrogen atom is attached to one
hydrogen atoms.

O CH3

CH3 C NH
N-methylethanamide
 Tertiary Amides

• No hydrogen atom is attached to the

nitrogen.

O CH3
CH3CH2 C N CH2CH3
N-ethyl-N-methylpropanamide
 Nucleophilic Acyl Substitution

• The characteristic reaction of carboxylic

acid derivatives is nucleophilic acyl
substitution.

• The general mechanism for nucleophilic

acyl substitution is a two-step process;
nucleophilic attack followed by loss of the
leaving group.
The mechanism:
1) The nucleophile attacks the carbonyl
group, cleave the pi bond and form
intermediate with a new C-Nu bond.

O O- O
[1] [2] -
R C Z R C Z R C + Z

-
Nu Nu
Nu
intermediate

2) Elimination of the leaving group

forms the substitution product.
Relative Reactivity of Carboxylic Acids
and Their Derivatives

• Carboxylic acids and their derivatives

differ in reactivity towards nucleophiles.

Increasing LG ability

-NH
2
-
OH -
OR RCOO- Cl-
 Order of Reactivity
Increasing reactivity

O O O O O O

C C C C C C
R NH2 R OH R OR' R O R Cl
R'
least reactive most reactive

Weaker base,
therefore it is a
better leaving group