HIMILO UNIVERSITY

Course name: organic chemistry

chapter :8
Carboxylic acids And carboxylic acid derivatives
 Introduction
Carboxylic acids have the following general structure.

O O
Ar C OH R C OH

Aromatic carboxylic acid Aliphatic carboxylic acid

Condensed form of the functional group

COOH CO2H
 Esters

The general formula for esters:

O O O
R C O R Ar C O Ar Ar C O R

Examples of aliphatic and aromatic esters

 acyl group.

The acyl group is part of the functional group of the carboxylic

acid derivatives, including the esters, acid chlorides, acid
anhydrides, and amides.
 Carboxylic Acids

Structure and Physical Properties:

The carboxyl group consists of two very polar functional groups,

the carbonyl group and the hydroxyl group.

However carboxylic acids are very polar compounds.

They can form hydrogen bond to one another and to molecules of

a polar such as water.
As the presence of intermolecular hydrogen bonding, carboxylic
acid boil at higher temperatures than aldehydes, ketones, or
alcohols of comparable molecular weight.

The smaller carboxylic acids are soluble in water. so solubility

decreases dramatically as the carbon content of the carboxylic acid
increases because the molecules become more hydrocarbon like
and less polar.
The lower-molecular-weight carboxylic acids have sharp, sour
tastes and unpleasant aromas.

The longer-chain carboxylic acids are generally called fatty acids

and are important components of biological membranes and
triglycerides, the major lipid storage form in the body.
 Nomenclature
I.U.P.A.C. Nomenclature System

1. determine the parent compound, the longest continuous carbon

chain bearing the carboxyl group.

2. Number the chain so that the carboxyl carbon is carbon-1.

3. Replace the -e ending of the parent alkane with the suffix -oic
acid. If there are two carboxyl groups, the suffix -dioic acid is used.

4. Name and number substituents in the usual way.

 Example

O 4 3 2
O 1
2 1 O
CH3 C OH 3 2 1 CH3CHCH2 C OH
CH3CH2 C OH
CH3
Ethanoic acid Propanoic acid
3-Methylbutanoic acid
(acetic acid) (propionic acid)
(β -methylbutyric acid)
carboxylic acids with two carboxyl groups:

O1 2 3 4 5 O
6
HO C CH2CH2CH2CH2 C OH Hexanedioic acid
(adipic acid)

O O
1 2 3 Propanedioic acid
HO C CH2 C OH (malonic acid)
 Example
O O
5 4 3 2 1
8 7 6 5 4 3 2 1
a) CH3CH2CHCH2 C OH b) CH3CHCH2CHCH2CHCH2 C OH
OH Br Br Br
3-Hydroxypentanoic acid
3,5,7-Tribromooctanoic acid
 Practice Problem

Determine the I.U.P.A.C. name for each of the following structures. Remember
that -COOH is an alternative way to represent the carboxyl group.

CH2CH2CHCOOH
a) CH3CHCH2CHCOOH b)
Cl Cl
CH3 CH3

Cl
OH
d) CH3CH2CHCHCHCOOH
c) CH3CHCHCOOH
CH3 Br
OH
The carboxylic acid derivatives of cycloalkanes are named by
adding the suffix carboxylic acid to the name of the cycloalkane or
substituted cycloalkane.

O
C OH Cyclohexanecarboxylic acid
 common system of nomenclature
δ γ β α O
C C C C C OH

Example

γ β
O
α O
β α
CH3CHCH2 C OH CH3CH C OH
OH OH
β -Hydroxybutyric acid α-Hydroxypropionic acid
 Example
Naming Carboxylic Acids Using the Common System of
Nomenclature:

βO α
CH3CH2CH2CHCH2C OH β-Bromocaproic acid
Br

γ β O α
CH3CHCH2CH2C OH
γ-Chlorovaleric acid
Cl
 Practice Problem

Provide the common name for each of the following molecules.

Keep in mind that the carboxyl group can be represented as
COOH.
CH3
b) CH2CH2CHCOOH
a) CH3CHCH2CHCOOH
Cl Cl
CH3

Br
d) CH3CH2CHCH2CH2COOH
c) CH3CHCHCH2COOH
OH
Br
Reactions Involving Carboxylic Acids
Preparation of Carboxylic Acids

In the laboratory, carboxylic acids are prepared by the oxidation

of aldehydes or primary alcohols, in the presence of oxidizing
agents.
 Example

Write an equation showing the oxidation of 1-propanol to

propanoic acid.

Solution:
H
O O
H2CrO4
CH3CH2C OH CH3CH2C H Continued
Oxidation CH3CH2C OH
H

1-Propanol Propanal Propanoic acid

 Practice Problem

Write equations showing synthesis of

(a) ethanoic acid,

(b) butanoic acid, and

(c) octanoic acid by oxidation of the corresponding primary

alcohol.
 Acid-Base Reactions

The carboxylic acids behave as acids because they are proton

donors. They are weak acids that dissociate to form a carboxylate
ion and a hydrogen ion.

O O
+
R C OH R C O- + H

Carboxylic Carboxylate Hydrogen

Acid anion ion
The neutralization of acetic acid and benzoic acid in solutions of
the strong base NaOH.
O O
CH3 C OH + NaOH CH3 C O Na+ + H O H

Acetic acid Sodium Sodium acetate Water

hydroxide
(strong base)
 O O
C OH + NaOH C O Na+ +H O H

Benzoic acid Sodium hydroxide

Sodium benzoate Water
(strong base)
 Example

Write an equation showing the neutralization of propanoic acid

by potassium hydroxide.

Solution:
O O
CH3CH2 C OH + KOH CH3CH2 C O- K+ + H2O

Potassium Potassium salt of

Propanoic acid Water
hydroxide propanoic acid
 Esters
Structure and Physical Properties:

Esters are mildly polar and have pleasant aromas.

Many esters are found in natural foodstuffs.

Esters boil at approximately the same temperature as aldehydes or

ketones of comparable molecular weight.

The simpler ones are somewhat soluble in water.

 Nomenclature
Esters are named according to the following set of rules:

1. Use the alkyl or aryl portion of the alcohol name as the first
name.

2. The -ic acid ending of the name of the carboxylic acid is

replaced with –ate and follows the first name.
 Example

 The molecule shown below contributes to the flavor of

pineapple. Write the I.U.P.A.C. and common names for this
ester.
I.U.P.A.C. Common name
O
a) CH3CH2CH2 C OCH2CH3 Ethyl butanoate Ethyl butyrate
O
b) CH3CH2CH2 C OCH2CH2CH2CH2CH3 Pentyl butanoate Pentyl butyrate
 Practice Problem

Name each of the following esters using both the I.U.P.A.C. and
common nomenclature systems.
O O
a) CH3CH2CH2C OCH2CH2CH3 b) CH3CH2CH2C OCH2CH3

O O
c) CH3C OCH2CH2CH3 d) CH3CH2C OCH2CH2CH2CH3
 Reactions Involving Esters
Preparation of Esters

The conversion of a carboxylic acid to an ester requires heat and

is catalyzed by a trace of acid (H).

When esters are prepared directly from a carboxylic acid and an

alcohol, a water molecule is lost as in the reaction:

 O O
H+, heat
CH3CH2C OH + CH3OH CH3CH2C OCH3 + HO H

Propanoic acid Methanol Methyl propanoate water

Esterification is a dehydration reaction, so called because a water

molecule is eliminated during the reaction.
 Example

Write an equation showing the esterification reactions that would

produce ethyl butanoate and propyl ethanoate.

Solution:
O O
H+, heat
CH3CH2CH2C OH + CH3CH2OH CH3CH2CH2C OCH2CH3 + H2O

Butanoic acid Ethanol Ethyl butanoate

Similarly, the name propyl ethanoate reveals that the alcohol used
in this reaction is 1-propanol and the carboxylic acid must be
ethanoic acid.

O O
H+, heat
CH3 C OH + CH3CH2CH2OH CH3C OCH2CH2CH3 + H2O

ethanoic acid 1-propanol propyl ethanoate

 Practice Problem

Write an equation showing the esterification reactions that would

produce (a) butyl ethanoate and (b) ethyl propanoate.
 Hydrolysis of Esters

Hydrolysis, sometimes also referred to as hydration, refers to

cleavage of any bond by the addition of a water molecule. Esters
undergo hydrolysis reactions in water, as shown in the general
reaction:

O O
R1 C H+, heat R1 C
OR2 + H2O OH + R2OH

Ester Water Carboxylic Alcohol

acid
 O O
H+, heat
CH3CH2 C OCH2CH2CH3 + H2O CH3CH2 C OH + CH3CH2CH2OH

Propyl propanoate Propanoic acid 1-Propanol

The base-catalyzed hydrolysis of an ester is called
saponification.

O O
R1 C OR2 + H2O NaOH, heat R1 C O-Na+ + R2OH
Ester Water Carboxylic Alcohol
acid salt