CHAPTER 17

CARBOXYLIC ACIDS & ITS

DERIVATIVES

1
 17.1 Introduction to carboxylic acids
• At the end of this topic, students should be
able to:

a) Give the general formula of carboxylic acids.

GENERAL FORMULA

R C OH

RCOOH or RCO2H
(R ≡ alkyl, aryl or H)

3
 17.2 Nomenclature of carboxylic acids

• At the end of this topic, students should be

able to:

a) Draw the structures and name the carboxyl

compounds (C1-C10) according to the IUPAC
nomenclature. Give common names for C1-C5.
NOMENCLATURE

5
 IUPAC Nomenclature

•The longest chain must contain the carboxyl group.

•The carboxyl group is at the terminal, therefore the

carbon of the carboxyl group is not numbered.
One COOH – carboxyl group is at one end
Two COOH – carboxyl groups are at both ends

•Name the compound as alkane, drop ‘e’ in alkane

and add ‘oic acid’ (eg: methanoic acid).

6
 Molecular formula IUPAC name Common name

HCOOH Methanoic acid Formic acid

CH3COOH Ethanoic acid Acetic acid

CH3CH2COOH Propanoic acid Propionic acid

CH3CH2CH2COOH Butanoic acid Butyric acid

CH3CH2CH2CH2COOH Pentanoic acid Valeric acid

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 Br CH3 O

CH3 CH CH CH2 C OH

4-bromo-3-methylpentanoic acid

CH3 O

HO CH CH2 CH2 CH2 C OH

5-hydroxyhexanoic acid

8
 O CH3

HO C CH2 CH CH CH CH3

5-methyl-3-hexenoic acid

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• Two COOH groups, the compound will be
named as ‘alkanedioic acid’
(Example: ethanedioic acid, propanedioic acid)

O O

HO C CH2 CH2 CH2 C OH

pentanedioic acid

10
 O CH3 O

HO C CH2 CH CH2 CH2 C OH

3-methylhexanedioic acid

H CH2 COOH

C C

HOOC CH2 H

trans 3-hexenedioic acid

11
• When R is an aryl group, the parent name is
benzoic acid.

Cl COOH

4-chlorobenzoic acid

12
• An aromatic dicarboxylic acid is named as
1,x-benzenedicarboxylic acid.

HOOC

COOH

1,3-benzenedicarboxylic acid

13
 HOOC
CH3
CH CH3

COOH

2-isopropyl-1,4-benzenedicarboxylic acid

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• A cyclic carboxylic acid is named as
cycloalkanecarboxylic acid.

• The C atom which is attached to —COOH is

numbered as C1.

1 COOH

cyclopentanecarboxylic acid

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 1 COOH

cyclohexanecarboxylic acid

CH3

Br 1 COOH

4-bromo-2-methylcyclohexanecarboxylic acid
16
A cyclic dicarboxylic acid is named as
1,x-cycloalkanedicarboxylic acid

COOH

COOH

1,2-cyclohexanedicarboxylic acid

17
 COOH

Cl COOH

4-chloro-1,2-cyclohexanedicarboxylic acid

18
• When a compound contains a carboxyl group
and other functional group(s), the priority is
given to the carboxylic acid as the parent name.

COOH

CH3

3-methyl-2-cyclohexenecarboxylic acid

19
17.3 Physical properties of carboxylic acids

• At the end of this topic, students should be

able to:
a) Explain the physical properties:
i. boiling point
ii. solubility in water and in organic solvents
b) Explain the acidity of:
i. carboxylic acid in comparison with alcohol
and phenol
ii. halogenated carboxylic acids based on the
 number of halogens
 position of halogens
PHYSICAL PROPERTIES OF
CARBOXYLIC ACIDS

21
 Boiling Point
The boiling point of carboxylic acid is higher than
an alcohol, a ketone or an aldehyde (with Mr that
almost the same) because:
i. it exists as stable dimers that form
hydrogen bond.
ii. molecules in dimers are arranged closely
packed, therefore the hydrogen bonds are
relatively strong.
iii. high energy is needed to overcome the
intermolecular forces, boiling point is
higher. 22
 Hydrogen bond
O H O

R C C R

O H O
Hydrogen bond
The polar nature of the carboxyl groups and its stability to
form hydrogen bonds with other carboxyl groups gives
carboxylic acids relatively high boiling points.

The geometry of the carboxyl groups allow for the

formation of 2 hydrogen bonds per molecule are known to
exist predominately as dimers.
23
 Solubility
a) Solubility in water

• Carboxylic acids are soluble in water due to the

formation of hydrogen bond between the water
molecules and carboxylic acid molecules.

Hydrogen Bonds H

O H O H O

R C H C R

O H O H O

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• The solubility of carboxylic acid in water is almost
the same as alcohol.

• Aliphatic carboxylic acids with C > 5 are insoluble

in water. Size of R ↑, hydrophobic area ↑.

O
hydrophilic
hydrophobic R C OH

25
• Aromatic carboxylic acids are slightly
soluble in water due to the huge aromatic ring.

• Dicarboxylic acids are relatively more soluble

since more hydrogen bonds are formed.

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 Example : Descending order of solubility

COOH COOH COOH

> >
CH3 CH CH2 CH2 CH3 CH2 CH2

COOH COOH
>
CH3 CH2 CH2 CH2

27
b. Solubility in non polar solvent

• Carboxylic acids are soluble in non polar solvent such as

benzene due to the Van der Waals forces between the
benzene and alkyl group of carboxylic acids .

O H O

R C C R

O H O

Van der Waals forces Van der Waals forces

Hydrogen bonds

28
c. Solubility in polar solvent

• Carboxylic acids are soluble in polar solvent

such as alcohol and ether due to the formation of
hydrogen bond.

• Dimer molecule do not exist in solvent which

could form hydrogen bond with carboxylic
acid.

29
 Acidity of Carboxylic Acid
• The acidity of carboxylic acid is influenced by:
i. Resonance effect
ii.Inductive effect

30
 Resonance Effect
O
–
Carboxylate ion :R C O-

–
O-

Phenoxide ion :

31
• Carboxylic acids are more acidic due to the
resonance stabilisation of the carboxylate
ion.
-
O O O

R C + H2 O ⇌ R C R C + H3O+
-
OH O O
carboxylic acid carboxylate ion
(resonance structure)

• The electrons in carboxylate ion are

delocalised between two oxygen atoms,
32
whereas in phenoxide ion, the electrons are
delocalized in the benzene ring.

-
OH + H2O ⇌ O + H3O+

phenol phenoxide ion

(resonance structure)

33
• The C=O group in carboxylic acid is electron-
withdrawing group which reduces the electron
density of –OH, therefore the –OH bond
becomes weaker.

• Thus H+ is easily donated and carboxylic acid

is more acidic than phenol.

34
• Carboxylic acid is relatively a weak acid,
however it is stronger than phenol & alcohol.
OH

> H2O
R C OH > > R OH

R—O—H + H2O ⇌ R—O– + H3O+

alcohol alkoxide ion
(no resonance structure)

35
 Inductive Effect
O O
EWG C EDG C
- -
O O
An electron withdrawing An electron donating
group (deactivating group) group, (activating group)
that attached to a will destabilise the
carboxylate ion will carboxylate ion and
delocalise the negative decreases acidity.
charge, thereby stabilises
the carboxylate ion and
increases acidity. 36
i. The inductive effect of electron-withdrawing
group (EWG) in the compound

• electron-withdrawing groups
(e.g: –NO2, -F, -Cl, -Br, -I ) reduce the electron
density of –OH.

• Thus the O-H bond become weaker and H+ can

be easily released.

• The compound is said to be more acidic

 Electron-withdrawing group increases the
acidity.
37
 (ii ) The inductive effect of electron-donating
group (EDG) in the compound
• Example: CH3COOH and CH3CH2COOH

• -R is an electron–donating group.

• The size of –R group in CH3CH2COOH is larger than

in CH3COOH, so CH3CH2- is a stronger releasing
group than CH3-.

• The electron density of –OH in CH3CH2COOH

increases and H+ is difficult to be donated.

•  Electron-donating groups reduce the acidity of

a carboxylic acid.
38
• Example:
CH3CHCl-COOH and CH3CH2COOH

• Cl is an electron-withdrawing group, therefore reduce

the electron density of –OH.

• Thus the O-H bond become weaker and H+ can be

easily released.

• Acidity :
CH3CHCl-COOH > CH3CH2COOH

• Electron-withdrawing groups increase the acidity.

39
iii) The electronegativity of electron-
withdrawing group in the compound
• Example:
CH3CHF-COOH and CH3CHCl-COOH

• Both F and Cl are electron-withdrawing group.

• The electronegativity of F > Cl.

• The electron density of –OH in CH3CHF-COOH is

less, thus the –OH bond is weaker than in
CH3CHCl-COOH. Therefore, H+ is easily donated.

• Acidity : CH3CHF-COOH > CH3CHCl-COOH

40
 iv) Number of electron-withdrawing group in
the compound.

• Example:
CH3C(Cl)2-COOH and CH3CHCl-COOH

• CH3C(Cl)2-COOH contains 2 Cl atoms that make the

bond of –OH weaker than CH3CHCl-COOH (with only
one Cl atom). Thus, H+ is easily donated.

• Acidity : CH3C(Cl)2-COOH > CH3CHCl-COOH

41
v) The position of electron-withdrawing group

• Example:
CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH

• The distance between Cl atom and carboxyl group in

CH3CH2CHCl-COOH is nearer compare to in
CH2ClCH2CH2-COOH.

• The –OH bond in CH3CH2CH(Cl)COOH is weaker than

in CH2ClCH2CH2-COOH, so H+ is easily donated.

• Acidity :
CH3CH2CH(Cl)COOH > CH2(Cl)CH2CH2COOH
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17.4 Preparation of carboxylic acids

• At the end of this topic, students should be

able to:
a) Explain the preparation of carboxylic acid
through:
i. oxidation of alkylbenzene, alcohol and
aldehyde
ii. hydrolysis of nitrile compound
iii. carbonation of Grignard reagent
 SYNTHESIS OF
CARBOXYLIC ACIDS

44
 1. Oxidation of primary alcohol and aldehyde

H R R
oxidizing oxidizing
R C OH agent C O agent C O

H H HO
1o alcohol aldehyde carboxylic acid

Common oxidizing agents are :

•KMnO4 / H2SO4
•K2Cr2O7 @ Na2Cr2O7 /H2SO4

45
2. Oxidation of Alkyl Benzene

oxidizing
R agent COOH

Example:
Cl Cl
CH3
KMnO4 , H+
CH CH3 Δ
COOH

+ CO2 + H2O
46
 3. Hydrolysis of nitrile

NaCN H2O,H+
R CH2 X R CH2 CN R CH2 COOH
Nitrile compound

Example:
CH2 Br CH2 CN CH2 COOH

NaCN H2O,H+

47
 4. Carbonation of Grignard Reagents

R—MgX O C O R—COOH + Mg(OH)X

H2O, H+

Example:
CH2 MgBr CH2 COOH

CO2
H2O, H+ + Mg(OH)Br

48
17.5 Chemical properties of carboxylic acids

• At the end of this topic, students should be

able to:
a) Explain the chemical properties with reference
to:
i. neutralisation with a base
ii. reaction with electropositive metals such as
Na, Mg or Ca
iii. reduction with followed by LiAlH4 H3O+
17.5 Chemical properties of carboxylic acids

• At the end of this topic, students should be

able to:
a) Explain the chemical properties with reference
to:
iv. acyl chloride formation
v. anhydride formation
vi. esterification
vii. amide formation
CHEMICAL PROPERTIES OF
CARBOXYLIC ACIDS

51
• Main reactions of carboxylic acid,

a. The reaction that involves the reduction

with LiAlH4 to primary alcohol.
b. The reaction that involves the donation of
H+ from –OH group.
c. The reaction that involves the substitution
of -OH group.

52
a) The reaction that involves the reduction with
LiAlH4 to primary alcohol

Carboxylic acid are reduced to primary alcohols by

reaction with lithium aluminium hydride, LiAlH4/H+ .
O

R C LiAlH4/H+
ether
R CH2 OH
OH
1o alcohol

Example:
O
CH3 CH CH2 OH
LiAlH4 /H+
CH3 CH C O HCH2 CH3 ether
CH3
CH3 53
b) The reaction that involves the donation of H+
from –OH group
1. Neutralisation
• Carboxylic acids are acidic, it can react with base such as
NaOH (aq) or KOH to give metal carboxylate salts.
O O

R C + NaOH(aq) R C + H 2O
-
OH O Na+

RCO2H + NaHCO3(aq)  RCO2(–) Na(+) + CO2 + H2O

RCO2H + Na2CO3(aq)  RCO2(–) Na(+) + CO2 + H2O

54
 Example:
COOH COO – K+

+ KOH + H2O

Sodium benzoate

O O
NaHCO3(aq)
CH3 CH C O HCH2 CH3 CH3 CH C O -Na
CH+2 CH3

CH3 CH3

55
2. Reaction with electropositive metals such
as Na, K, Ca, Mg and Fe.
O O

R C OH + M R C O M + H2

Example:
Cl O
Cl O
C C
OH O-Mg+
OH
+ Mg
K
+ K

56
c) The reaction that involves the substitution
of –OH group (to form its derivatives)

1. Acid chloride formation

Acid chloride can be prepared from the reaction of
carboxylic acids with thionyl chloride, SOCl2; phosphorous
pentachloride,PCl5; phosphorous trichloride, PCl3.
O
SOCl2
R C Cl + SO2 + HCl
heat
O O
PCl5
R C OH heat R C Cl + POCl3 + HCl
O
PCl3
heat R C Cl + H3PO3 57
 Example:
Exercise :

SOCl2
heat
O
PCl5
CH3 CH C OH heat

CH3
PCl3
heat

58
2. Acid anhydride formation
Acid anhydrides can be prepared from carboxylic
acids by the loss of water through heating.

O O O O
, P2O5 ,
R C OH + HO C R R C O C R + H2O
heat acid anhydride
Acid chlorides react with carboxylic acids to form
mixed or symmetrical anhydrides. It is necessary to
use a base such as pyridine.

Example:

O O O O
C + C + C C +
R OH R’ Cl N
R OH R’ N+
Pyridine,
C 5H 5N
H
Cyclic anhydrides with 5- and 6-membered rings can
be synthesized by heating the appropriate diacid.
Example:
3. Esterification
Carboxylic acids react with alcohols in the presence of
mineral acid catalyst to produce esters.

O O
H+
R C OH + H—OR’ ⇌ R C O R' + H2O
carboxylic acid alcohol ester

Example:
O O

H+
CH3 CH2 C OH + HOCH2CH3
⇌ CH3 CH2 C OCH2 CH3
propanoic acid ethanol ethyl propanoate

+ H2O 62
4. Amides formation
Reaction of carboxylic acids with an ammonia or amine
give amide.
O
NH3
R C NH2 + H2O
1o amide
O
O RNH2
R C NHR + H2O
(1o amine) 2o amide
R C OH
O
R2NH
R C NR2 + H2O
(2o amine)
(3o amide)
63
Exercise :
NH3

CH3 O
CH3 NH2
CH C Cl
OH

CH3

CH3 NH
CH3

64
17.5 Chemical properties of carboxylic acids

• At the end of this topic, students should be

able to:
b) Explain the reducing property of methanoic acid
with:
i. KMnO4/H+
ii. Tollen’s reagent
 Reducing property of methanoic acid, HCOOH

• Methanoic acid molecule, H C OH has both

O O
and
C OH H C
carboxylic carbonyl

• It shows the properties of both carboxylic acid and aldehyde.

• It also shows reducing properties in reactions with acidified

KMnO4 or K2Cr2O7 and Tollens’ reagent.

66
 KMnO4 / H+
CO2 + H2O + MnO2
(brown precipitate)
O
(purple solution of KMnO4
H C OH turns to colourless)

Ag(NH3)2+
CO2 + H2O + Ag
(silver
precipitate)

67