CARBOXYLIC ACIDS

Introduction
Carboxylic acids are organic compounds that contain carbonyl and hydroxyl groups on the same
carbon atom. They under go unique reactions due to interaction of the two groups.

There are three features that can be noted of the carboxylic group; that it is planar, polar and has
increased number of lone pairs when compared with aldehydes and ketones.

O
R C
O H
Carboxylic acids are important biologically and commercially. A few examples are mentioned.

Aspirin, the all round painkiller contains both carboxyl group and an ester group.

O
O C CH3
CH3(CH2)7CH=CH(CH2)7CO2H
C OH
O
Aspirin Oleic acid

Oleic acid is a fatty acid, a component of fats and oils. Base hydrolysis of fats, a process known
as saponification, leads to formation of soap and the fatty acid moiety is one involved.

Nomenclature of carboxylic acids

In naming of carboxylic acids by IUPAC system, the suffix ‘e’ in alkane is replaced with ‘oic acid’
to lead alkanoic acid and is derived from the name of the longest carbon chain that contains the
carboxyl group. However, the ‘e’ is retained in dicarboxylic acids.

HCO2H CH3CO2H CH3CH2CO2H

Methanoic acid Ethanoic acid Propanoic acid
The chain is numbered, beginning with the carbon atom of the carboxylic group. If the carboxylic
acid contains a carbon-carbon double or triple bond, change of infix from ‘an’ to ‘en’ and ‘yn’ to
indicate the presence of multiple bond. The location of the multiple bond is indicated by a number
with reference to the carboxyl group.

CH3CH=CHCO2H CH2=CHCH2CO2H
2-Butenoic acid 3-Butenoic acid

In IUPAC system, a carboxyl group takes precedence over most other functional groups. For that
the other groups are indicated by prefixes.

HO O
H2NCH2CH2CO2H CO2H
CO2H
4-Hydroxypentanoic acid 3-Aminopropanoic acid 5-Oxohexanoic acid

In dicarboxylic acids the ‘e’ in alkane is retained and the suffix ‘-dioic’ acid added to the name of
the longest carbon chain that contains both carboxylic groups. The numbers for the position of the
carboxyl groups are not indicated because they can only be at the ends of the parent chain

O O O O O O
HO C C OH HO CCH2C OH HO CCH2CH2C OH
Ethanedioic acid Propanedioic acid Butanedioic acid
(Oxalic acid) (Malonic acid) (Succinic acid)

Carboxylic acid containing carboxyl group attached to a cycloalkane or cycloalkene ring is named
by giving the name of the ring and adding the suffix ‘carboxylic acid’. The atoms are numbered
beginning with the carbon with carbon bearing the carboxyl group.
Physical Properties of carboxylic acids
Carboxylic acids with one to four carbon atoms are colourless liquids with sharp pungent
(unpleasant) smell. Acids with five to nine carbon atoms may be liquids or solids depending on
the isomeric forms. Those with more than ten carbon atoms are usually no-volatile solids and the
odor diminishes due to low volatility.

Carboxylic acids interact with water molecules by hydrogen bonding through both hydroxyl and
carbonyl groups. The solubility diminishes as the number of carbon atoms increases. This is
because of increasing of the hydrophobic (‘water fearing’) hydrocarbon group. Thus lower
members are highly miscible with water.

O H
CH3C O
O H H
Ethanoic acid Water

Normally carboxylic acids have high boiling points than other types of organic compounds of
comparable molecular weight such as alcohols, aldehydes and ketones. In their liquid and solid
states, carboxylic acids are associated by hydrogen bonding into dimeric structures as illustrated
with acetic acid in liquid state.

O H O
CH3C CCH3
O H O
Dimer of acetic acid

Carboxylic acids can be detected due to their odor. Hexanoic acid (caproic acid), for example,
smells like goat (Goat sweat contains it). Dogs differentiate the odors of individual humans
because of differing proportions of carboxylic acids in human sweat. Pentanoic acid (valeric acid)
is a sex attractant of the sugar beet wireworm.
Preparation of Carboxylic Acids
Three main types of reactions are involved in preparation of carboxylic acids. They are: oxidation
reactions, Grignard reactions and hydrolysis reactions of carboxylic acids derivatives.

Oxidation Reactions
Oxidation reactions of primary alcohols and aldehydes lead to formation of carboxylic acids.
Various common oxidizing agents can be used. They include potassium permanganate (KMnO4),
potassium dichromate (K2Cr2O7), chromic acid (H2CrO4), manganese dioxide (MnO2) and even
hydrogen peroxide (H2O2).

RCH2OH
10 Alcohols [O]
RCO2H
Carboxylic acid
RCHO
Aldehydes

When alkenes react with strong oxidizing agent oxidative cleavage leads to formation of oxidized
products like carboxylic acid through fragmentation. This depends on the structural feature of the
alkene. When the carbon atoms of the double bond are bonded to hydrogen atoms carboxylic acids
are formed through aldehydes. However, if they are substituted ketones are formed.

[O]
RCH=CR'2 [RCHO] + R'2C=O (R' not Hydrogen)
Substituted Aldehyde Ketone
Alkene

RCO2H
Carboxylic acid

Grignard Reactions
When the Grignard reagent is reacted with carbon dioxide followed by acid hydrolysis, carboxylic
acid is formed. The acid that is formed is one carbon atom more that the starting alkyl halide.

(1) Mg, ether

RX RCO2H R = Alkyl or Aryl group
(2) CO2 X = Cl, Br, I
(3) H2O/H+
Hydrolysis of Acid Derivatives
(a) Esters
Esters differ from acids by replacement of the hydrogen of the hydroxyl group of acid with an
alkyl or aryl group. Hydrolysis of ester can be performed under acidic or basic conditions. Both
methods lead to formation of carboxylic acids.

H2O/H+
RCO2R' RCO2H + R'OH
Ester acid alcohol

OH-
RCO2R' RCO2- + R'OH
Ester Carboxylate ion alcohol

(b) Amides
Amides are organic compounds where the hydroxyl group of the carboxylic acid is replaced with
an amino group. That is, a nitrogen atom is directly bonded to the carbon of the carbonyl. When
the nitrogen has two hydrogens, the amide is termed as primary (10) amide. When the nitrogen has
one hydrogen atom and an alkyl (or aryl) group it is termed as a secondary (20) amide. If both
hydrogens have been replaced with alkyl (or aryl) groups, the amide is termed as a tertiary amide.

O O O
R C NH2 R C NHR' R C NR'2 (Where R' is not Hydrogen)
10 amide 0
2 amide 0
3 amide

Amides undergo hydrolysis in hot aqueous acid to give a carboxylic acid and ammonium ion.

H2O/H+
CH3CH2CH2CONH2 CH3CH2CH2CO2H + NH4+
Heat Ammonium
Butanamide Butanoic acid
ion
(c) Acid (acyl) halides
Acyl or acid halides are derivatives of carboxylic acids in which the hydroxyl group of the acid is
replaced by a halogen. The most common ones are the acid chlorides.
Low-molecular-weight acid chlorides react very rapidly with water to form carboxylic acid and
hydrogen chloride (HCl). Higher-molecular-weight acid halides are less soluble and consequently
react less rapidly with water.

O O
H3C C + H2O H3C C + HCl
Cl OH

(d) Acid anhydrides

These are organic compounds that have two acyl groups bonded to an oxygen atom. They are
generally less reactive than acid chlorides. But lower molecular weight anhydrides readily react
with water to form two molecules of carboxylic acids.

O O O O
H3C C O C CH3 + H2O H3C C OH + HO C CH3
Ethanoic anhydride Ethanoic acid

(e) Nitriles
Organic compounds with a cyano (C≡N) group bonded to carbon are called nitriles compounds.
The cyano group is hydrolyzed in aqueous acid to a carboxyl group and ammonium ion.

H2O/H+
N C CH2CH3 CH3CH2CO2H + NH4+
Heat
Propanenitrile Propanoic acid Ammonium
ion