CHEM 222 LECTURE NOTE

TOPIC: CARBOXYLIC ACIDS AND DERIVATIVES

Carboxylic acids have the functional group;

Basic
O O O-

O H Acidic hydrogen O- O
Carboxylate ion

It is made up of carbonyl (C=O) and hydroxy (O-H) functional groups. When it loses the
acidic hydrogen to form carboxylate ion, then it is no longer acidic but basic.

NOMENCLATURE
Carboxylic acids are named according to the number carbon atoms:
HCOOH Methanoic acid CH3COOH Ethanoic acid

CH3CH2COOH Propanoin acid CH3CH2CH2COOH Butanoic acid

CH3CH2CH2CH2COOH Pentanoic acid CH3CH2CH2CH2CH2COOH Hexanoic acid

COOH
COOH

Cyclohexane carboxylic acid

Benzoic acid

CH3CHCH2CH2COOH 4-Bromopentanoic acid H2C CHCOOH Propenoic acid

O
Br

H2C CHCH2CH2COOH 4-Pentenoic acid CH3CCH2CH2CH2COOH

5-Oxohexanoic acid
Cl
Br

COOH
O
COOH

1-Bromo-2-chlorocyclopentane carboxylic acid 4-Oxocyclohexane carboxylic acid

CARBOXYLIC ACID DERIVATIVES
When the hydroxy group of carboxylic acid is being replaced by another group in the process
of chemical reaction to give a new product, the new product is called carboxylic acid
derivative. Some of these derivatives are:
O O O O
O
O
R
R R R OR R
X
NHR
Acid halide Anhydride Ester Amide

Carboxylic acid has the following resonance structures:

.. .. ..
:O :O : : O:
R R (+).. R
OH OH ..
.. OH
(+)

Two molecules of carboxylic acids can form dimmer through hydrogen bonding

Hydrogen bond

O H O

R R Dimmerization (dimmer)
O H O

Hydrogen bond

ACIDITY AND BASICITY OF CARBOXYLIC ACIDS

Acidic nature: carboxylic acid is not a strong acid but in presence of water, it deprotonates
its acidic hydrogen to form a carboxylate ion.
O O
H

R + :O R + H3O
O
O H H

Basic nature: carboxylic acid being a weak acid protonated when treated with mineral acids.

..
O OH

R + HCl R + Cl

OH OH
Electro withdrawing substituents increase the acidic strength of carboxylic acids:

Acids PKa
H3C COOH 4.74
Cl CH2COOH 2.86
Cl2CHCOOH 1.26
Cl3CCOOH 0.64
F3CCOOH 0.23
CH3CH2CHClCOOH 3.8
CH3CHClCH2COOH 4.1
CH2ClCH2CH2COOH 4.5

SALT FORMATION: When carboxylic acids react with base, they form salt of carboxylic
acid;
CH3 CH3
NaOEt
H3C CH2CH2COOH H3C CH2CH2COONa
H2O
CH3 CH3
4,4-Dimethylpentanoic acid Sodium-4,4-dimethylpentanoate

METHODS OF PREPARATION OF CARBOXYLIC ACIDS

1. Hydrolysis of acid derivatives; when acid halides are treat with water, it gives carboxylic
acids

O O

+ H2O + HX
R R
X OH

2. Oxidation of alcohols; alcohols are oxidized by oxidizing reagents to carboxylic acids

KMnO4 KMnO4
CH3 CH2 CH2OH CH3 CH2 CHO CH3 CH2 COOH
H2O /NaOH H2O /NaOH

3. Oxidation of side chain of aromatic compounds

When alkyl benzene is treated with an oxidising agent such KMnO4 in alkaline medium,
benzoic acid is produced.
 CH3 COOH
KMnO4
NaOH

H2
C COOH
CH3
KMnO4
NaOH

4. Kolbe reaction; when phenol is treated with dry carbon dioxide in alkaline medium and
followed by treatment with aqueous acid, hydroxybenzoic acid obtained.
OH OH

COOH
(i) KOH
+ CO2
(ii) H /H2O

5. From Grignard reagent and carbon dioxide; when Grignard reagent reacts with carbon
dioxide and then followed by neutralization with aqueous acid, carboxylic acid is produced.

H
CH3CH2MgX + CO2 CH3CH2COOMgX CH3CH2COOH
H2O
MgX COOMgX COOH

+ CO2 H
H2O

6. Hydrolysis of cyanide or nitrile; when alkyl cyanide or nitrile is hydrolysed in alkaline

medium and then acidified with aqueous acid, carboxylic acid obtained:

NaOH H
CH3CH2CN CH3CH2COONa CH3CH2COOH + NH3
H2O H2O
CN COONa COOH
NaOH
H
H2O + NH3
H2O
7. Oxidation of aldehyde with nitric acid or any other oxidizing agent gives carboxylic acid;

K2Cr2O7 /H
CH3CH2CHO CH3CH2COOH

CHO COOH

K2Cr2O7 /H

REACTIONS OF CARBOXYLIC ACIDS

The carbonyl group in carboxylic acid is attacked by a Nucleophile to eliminate the hydroxyl
group.

.. O - O
O Nu - OH
R OH R
R elimination
OH addition Nu Nu

The addition – elimination can be catalyzed by acid or base:

(i) Acid catalyzed by protonation;
O OH OH OH
..
H Nu-H
R R R OH R OH2
OH OH
Nu-H Nu
O-H O
- H2O -H
R R
Nu Nu

Base catalyzed by deprotonation;

Nu H + :B Nu + BH

O O O
Nu - OH
R R OH R
OH Nu
Nu
TRANSFORMATION OF CARBOXYLIC ACIDS TO ITS DERIVATIVES
1. FORMATION OF ESTER;
Carboxylic acid reacts with alcohols in the presence of mineral acids as catalyst to give an
ester (sweet smelling liquid);
O

R Ester structure

OR
H2SO4
CH3CH2CH2COOH + CH3OH CH3CH2CH2COOCH3 + H2O

2. FORMATION OF AMIDE
Carboxylic acid when treated with concentrate ammonia gives amide;
O

R Amide structure

NHR
CH3CH2CH2COOH + NH3 CH3CH2CH2CONH2 + H2O

CH3CH2CH2COOH + CH3NH2 CH3CH2CH2CONHCH3 + H2O

3. FORMATION OF ACID HALIDE

Carboxylic acid reacts with sulphonyl chloride or phosphorus pentachloride to give acid
chloride;
O

R Acid chloride structure

Cl
RCH2CH2COOH + SOCl2 RCH2CH2COCl + SO2 + HCl

RCH2CH2COOH + PCl5 RCH2CH2COCl + OPCl3 + HCl

4. FORMATION OF ACID ANHYDRIDE

When two molecules of carboxylic acids are heated, a molecule of water is lost and acid
anhydride is obtained;
O

O Structure of acid anhydride

O
 O

H3C
heat
2 CH3COOOH O
- H2O
H3C

HYDROLYSIS OF ACID DERIVATIVES

1. HYDROLYSIS
When acid derivates are hydrolysed, a carboxylic acid is obtained as the main product:
O O
H2O
R + HX
R
20 oC
OH
X

H2O
R O R R COOH + RCOOH
H
O O
O
H2O
R
H R COOH + R'OH
OR'

O O
H2O
R R + RNH2
H
NHR OH

REACTIONS OF INDIVIDUAL ACID DERIVATIVES

1. SOME REACTIONS OF ACID CHLORIDE:
(i). When acid halide, example acid chloride is hydrolysed with water, a carboxylic acid is
obtained as the main product;
O
H2O
R RCOOH + HCl

Cl

(ii). When acid chloride is treated with a carboxylic salt, it forms an anhydride

O O O
O

R + R' O
R R' + NaCl
Cl ONa
(iii). When acid chloride reacts with an alcohol, carboxylic ester is obtained
O O

R + R'OH R OR' + HCl

Cl

(iv). When treated with an amine, it forms an amide

O O

R + R'NH2 R NHR' + HCl

Cl

(v). Acid chloride reacts with Grignard reagent to give ketone

O O

R + RMgBr ClMgBr
R R +
Cl

2. SOME REACTS OF CARBOXYLIC ESTERS

(i). Hydrolysis of carboxylic ester gives carboxylic acid and alcohol
H2O
CH3CH2COOCH3 + CH3OH
CH3CH2COOH
(i). Carboxylic ester forms an amide and an alcohol when it reacts with amine

CH3CH2COOCH3 + RNH2 CH3CH2CONHR + CH3OH

(iii). Ester reacts with two moles of Grignard reagent to form a tertiary alcohol as the main
product and a primary alcohol
R

CH3CH2COOCH3 + 2RMgBr CH3CH2C R + CH3OH

OH

(iv). Ester are reduced by reducing reagent to alcohols

O
LiAlH4
R R CH2OH + ROH
OR O

LiAlH4
N CHCH2OH + CH3CH2CH2OH
N CH
OCH2CH2CH3 H /H2O
CH3
CH3
3. SOME REACTIONS OF ACID ANHYDRIDES
(i). Anhydrides are hydrolysed by water to carboxylic acids;
O
O O
H2O HOCCH2CH2COH

O O
Butanedioic anhydride
O O
O
H2O O
H3C O R H3C + R

OH OH

(ii). Anhydrides react with alcohols to form esters and carboxylic acids:
O O O O
CH3OH
R O R R + R
H
OCH3 OH
Ester Acid
O O O O
CH3OH
CH3CH2 O CH3 CH3CH2 + H3C
H
OCH3 OH

Cyclic anhydrides react with alcohol to give half acid-half ester

O
O O
CH3OH
HOOCCH2CH2COOCH3
100 oC

(iii). Anhydride reacts with amine to give amide and carboxylic acid
O O O O
RNH2
R O R R + R
H
NHR OH
Ester Acid
O O O O
RNH2
CH3CH2 O CH3 CH3CH2 + H3C
H
NHR OH
 O
O O O

O
NHR O
RNH2
H
+

REACTIONS AMIDES
(i). Amides are hydrolysed by aqueous sulphuric acid and heating for 3 hours to give
carboxylic acid and ammonium sulphate

CH3 O CH3 O
H2SO4 /H2O
CH3CH2CHCH2C NH2 CH3CH2CHCH2C + (NH4)2SO4
heat, 3hours OH

Then hydrolysed with aqueous base and heated, a carboxylic salt is formed, which when
neutralized with acid gives carboxylic acid
CH3 O CH3 O
KOH /H2O
CH3CH2CHCH2C NHCH3 CH3CH2CHCH2C + CH3NH2
heat, 3hours OK

H /H2O

CH3 O

CH3CH2CHCH2C
OH

(ii). Amides react with alcohols to give carboxylic esters and amines
O O

NHCH3 CH3CH2CH2OH OCH2CH2CH3

+ CH3NH2
H

N-Methylcyclohexane carboxyamide
(iii). Amides are reduced to amines by reducing reagents
O

(i)LiAlH4 /Ac2O
NH (ii)H /H O NH
2

H3C
H3C CH3
CH3
5,5-Dimethylpyrrolidin-2-one 2,2-Dimethylpyrrolidine