CHAPTER 10

CARBOXYLIC ACIDS
AND ITS DERIVATIVES
 10.1 Write the
general
formula

10 : 10.5
10.2 CARBOXYLIC ACIDS
AND ITS DERIVATIVES
Chemical
Nomenclature
Properties

10.3 Physical 10.4

Properties Preparation
 Learning Outcomes:
At the end of the lesson the students should be able to :

10.1 Write the general formula of carboxylic acids.

O O

R C OH and Ar C OH

10.2 Nomenclature of Carboxylic Acids

a) Draw the structures and name the carboxyl compounds

(parent chain ≤ C10) according to the IUPAC nomenclature.
b) Give common name with parent chain ≤ C5

3
 10.1 Introduction to Carboxylic Acids

What is carboxylic acid?

Is an organic acid
Contain one or more carboxyl group as functional group
General formula:

O O

R C OH C OH
RCOOH or RCO2H Functional group: Carboxyl

(R ≡ alkyl, aryl or H) 4
 10.2 Nomenclature to Carboxylic Acids

Naming Aliphatic Carboxylic Acids

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)

5
 IUPAC & Common Name For Some Carboxylic Acids

STRUCTURAL IUPAC NAME COMMON NAME

FORMULA

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

Naming Aliphatic Carboxylic Acids

When a compound contains a carboxyl group and other

functional group (s), the priority is given to the carboxylic
acid as the parent name.
Example:

Br CH3 O
CH3 CHCHCH2 C OH
5 4 3 2 1

4-bromo-3-methylpentanoic acid
NOT
4-bromo-3-methyl-1-pentanoic acid
7
Naming Aliphatic Carboxylic Acids

Carboxylic acid with double bonding are named as

x – alkenoic acid [x = position of double bond]
Example:
O CH3

HO C CH2 CH CH CH CH3
5-methyl-3-hexenoic acid
Exercise:

HOOC COOH

C C

H H 8

cis-2-butenedioic acid
Naming Aliphatic Dicarboxylic Acids

Two COOH groups, the compound will be named as

alkanedioic acid

9
Naming Aliphatic Cyclic carboxylic Acids
A cyclic carboxylic acid is named as:
(i) cycloalkanecarboxylic acid
(ii) cycloalkenecarboxylic acid

The C atom which is attached to –COOH is numbered as C1

Example:
Exercise:
COOH COOH
1
6 2
cyclopentanecarboxylic acid
3
5
CH3
4
3-methyl-2-cyclohexenecarboxylic
10 acid
Naming Aliphatic Cyclic Dicarboxylic Acids

A cyclic dicarboxylic acid is named as:

(i) 1,x – cycloalkanedicarboxylic acid
(ii) 1,x – cycloalkenedicarboxylic acid
Example:
6
COOH
5
1
1,2-cyclohexanedicarboxylic acid
4
2
COOH
3

Exercise:
6
1 COOH
5
4-chloro-1,2-cyclohex-1-enedicarboxylic acid

Cl 4 2 COOH 11
3
Naming Aromatic Carboxylic Acids

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

Example:

3 2

Cl 4 1
COOH

5 6

4-chlorobenzoic acid @
p-chlorobenzoic acid

12
 Naming Aromatic Dicarboxylic Acids

An aromatic dicarboxylic acid is named as

1,x-benzenedicarboxylic acid

Exercise:
Example:
HOOC HOOC
3 2
4 3
CH3
2 4 1
5 CH CH3 COOH

6 1 6
5
COOH 1,3-benzenedicarboxylic acid
2-isopropyl-1,4-benzenedicarboxylic acid

13
 Learning Outcomes:
At the end of the lesson the students should be able to:
10.3 Physical Properties of Carboxylic Acids

a) Explain the physical properties:

i. boiling point
ii. solubility in water
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
14
c) Compare the acidity between carboxylic acids.
 10.3 Physical Properties of Carboxylic Acids

Physical Properties of Carboxylic Acids

(i) Boiling Point

The boiling point of carboxylic acid is higher than an alcohol, a ketone
or an aldehyde (with similar molecular mass) because:

i. it exists as stable dimers that form intermolecular 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 hydrogen bonds,
 boiling point increase
15
 Hydrogen bond
O H O

R C C R

O H O
Hydrogen bond

Dimerisation of carboxylic acids

16
Example
Arrange the compounds in each set in order of increasing boiling
point and explain.

(a) CH3(CH2)5COOH, CH3(CH2)6CHO, CH3(CH2)6CH2OH

Answer
CH3(CH2)6CHO < CH3(CH2)6CH2OH < CH3(CH2)5COOH
octanal 1–octanol heptanoic acid
increasing boiling point
• Octanal has the lowest boiling point because it only has
weak van der Waals forces between their molecules.
• 1-octanol and heptanoic acid have strong hydrogen bond
between their molecules.
• Boiling point of heptanoic acid is higher than 1-octanol
because it exists as stable dimers through hydrogen bonds .
• the hydrogen bond of heptanoic acid is stronger than 1-
octanol.
 10.3 Physical properties of Carboxylic Acids

(ii) Solubility in water

(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
19

Hydrogen bonds
(a) Solubility in water

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

alcohol.

• Simple carboxylic acids (C1 – C5) are completely soluble in

water.

• Carboxylic acids with C > 5 are insoluble in water due to:

– Size of alkyl group (R) bigger, hydrophobic area
larger, hydrogen bonding with water molecule
hardly formed
– Thus solubility of carboxylic acid in water decrease

O
hydrophilic
hydrophobic R C OH 20
(a) Solubility in water

• Aromatic carboxylic acids are slightly soluble in water due to

the huge aromatic ring Bigger hydrophobic area
-reduce solubility
Cl COOH

• Dicarboxylic acids are relatively more soluble since more

hydrogen bonds are formed.

21
 Example : Descending order of solubility in water

COOH COOH COOH

> >
CH3 CH CH2 CH2 CH3 CH2 CH2

COOH
> COOH
CH3 CH2 CH2 CH2

Descending order of solubility

22
(b) (i) Solubility in nonpolar organic 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
(only exist between molecules)
23
(b) (i) Solubility in polar organic solvent

• Carboxylic acids are soluble in polar solvent such as ether

and alcohol through to the formation of: van der Waals forces
between the ether and alkyl group of carboxylic acids .
 Hydrogen bond between hydroxyl group of alcohol and
carboxyl group of carboxylic acids

van der Waals forces

H O
R
C R R–O
R–O
H O

Hydrogen bond 24
 10.3 Physical properties of Carboxylic Acids

Acidity of Carboxylic Acids

• The acidity of carboxylic acid is influenced by:

i. Resonance effect
- the stabilization by delocalisation of pi electrons

ii. Inductive effect

- the shift of electron density from one atom to another

to form polar bond

25
 COMPARISION ACIDITY OF CARBOXYLIC ACID,
PHENOL AND ALCOHOL

Acidity of carboxylic acids – Resonance Effect

Carboxylic acids are more acidic than phenol and alcohol.

• Carboxylic acid dissociate in water to form carboxylate ion.

• The negative charge in carboxylate ion are delocalised between

two electronegative oxygen atoms which stabilises the carboxylate
ion and promotes the release of H+

• Due to the resonance stabilization of the carboxylate ion, carboxylic

acid is more acidic than phenol and alcohol.
-
O O O

R C R C R C

OH
+ H2O ⇌ O
-
O
+ H 3O+

carboxylic acid carboxylate ion 26

(resonance structure)
Acidity of phenol
• Phenol dissociate in water to form phenoxide ion.
• The negative charge in phenoxide ion are delocalised in the
benzene ring.
• The resonance structure of carboxylate ion is more stable than
the phenoxide ion.
• Therefore carboxylic acid are more acidic than phenol.

-
OH + H2O ⇌ O + H 3O+

phenol phenoxide ion

27
Acidity of alcohol

• Alcohol dissociate in water to form alkoxide ion

• Alcohol is the least acidic compare to carboxylic acid and phenol due
to the electrons are localized at oxygen atom in alkoxide ion.

R—O—H + H2O ⇌ R—O– + H3O

alcohol alkoxide ion

28
In conclusion;

• Carboxylic acid is relatively a weak acid, however it is

stronger acid than phenol & alcohol

OH

> H2O
R C OH > > R OH

29
Acidity of carboxylic acids – Inductive Effect

• Substituent group that attached to the carbon of the carboxyl plays

major role in determining the acidity of a carboxylic acid.
• It can be divided into:
Electron withdrawing group
eg: NO2, -F, -Cl, -Br, -I
Electron donating group
eg:-NH2, -NHR,-NR2,-OH,-OR,-NHCOR,-R

30
Electron withdrawing group Electron donating group

O O

EWG C EDG C
- -
O O
An electron withdrawing An electron donating
group, EWG that attached to group, EDG will
a carboxylate ion will destabilise the carboxylate
stabilises the carboxylate ion ion and decreases acidity.
and increases acidity.

31
Inductive Effect - The effect of electron-withdrawing group towards
acidity

How electron withdrawing group increases the acidity ?

• Electron withdrawing groups reduce the electron density of

–O-H bond.
• Thus the –O-H bond becomes weaker and H+ can be easily
released and form stable carboxylate ion.
• The compound is said to be more acidic.

32
Example
CH3CH(Cl)COOH and CH3CH2COOH

• The inductive effect of Cl is an electron-withdrawing groups,

reduce the electron density of O-H bond.
• Thus the O-H bond becomes weaker and H+ can be easily
released.
• Acidity : CH3CH(Cl)COOH > CH3CH2COOH
• Electron-withdrawing groups increase the acidity.
Inductive Effect
(a) (i) Number of electron-withdrawing group
in the compound.
• Example:

CH3C(Cl)2COOH and CH3CH(Cl)COOH

• CH3C(Cl)2COOH contains 2 Cl atoms(electron withdrawing

group) which creates a greater inductive effect and makes the
bond of –OH weaker than CH3CHCl-COOH (with only one Cl
atom).

• Thus, H+ is easily donated.

• Acidity : CH3C(Cl)2COOH > CH3CH(Cl)COOH

34
Inductive Effect
(a) (ii) The position of electron-withdrawing group

• Example:

CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH

• The distance between Cl atom and carboxyl group in

CH3CH2CH(Cl)COOH is nearer compare to in
CH2(Cl)CH2CH2COOH, which will gives a greater inductive effect of
withdrawing electron.

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

CH2(Cl)CH2CH2COOH, so H+ is easily donated.

• Acidity: CH3CH2CH(Cl)COOH > CH2(Cl)CH2CH2COOH

35
(b) The inductive effect of electron donating group
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 EDG than CH3-.
• The electron density of O-H in CH3CH2COOH increases and H+ is
difficult to be donated.
 EDG reduce the acidity of a carboxylic acid.

36
 SUMMARY

Electron Withdrawing Electron Donating Group

Group (EWG) (EDG)

• Presence EWG (More • Presence of EDG (More

electronegative/More no alkyl groups)
of EWG/Distance of
EWG near to -COOH • Stronger EDG, greater
group) inductive effect
• Stronger EWG, greater • Increase electron density
inductive effect of O-H,make O-H bond
• Reduce electron density stronger.
of O-H bond, make O-H • Decrease acidity
bond weaker
• Increase acidity
37
Exercise:
Arrange acetic acid, ethanol and phenol in order of increasing
acidity. Explain in term of stability of their conjugate bases.
Answer:
Ethanol < Phenol < Acetic acid
Increasing acidity
CH3CH2O- is the least stable anion since ethyl is an electron
donating group (inductive), no resonance.
-
O

is moderately stable anion because the phenyl is an

electron withdrawing group, negative charge in phenoxide ion is
delocalised into the benzene ring by forming resonance structure.

CH3COO- is the most stable anion since carbonyl is an electron

withdrawing group @ resonance of the carboxyl anion @
delocalisation of negative charge at both electronegative oxygen
atoms of carboxylate ion by forming resonance structure.
Exercise:

The structural formulae of three carboxylic acids D, E and F

are shown below:

O O O
C OH Cl C OH H3C C OH

D E F
Arrange the above carboxylic acids in order of increasing acidity.
Explain.
Answer:

CH3 COOH < COOH < Cl COOH

F D E
increasing acidity

F : -CH3 substituent is an electron donating group(EDG), strengthen

the O-H bond.
D : no electron donating or withdrawing group
E: -Cl substituent is an electron withdrawing group(EWG), weaken the
OH bond

Structure E is the most acidic compared to structure D and F because

Cl is an EWG which will stabilize R-COO- and increase acidity.
CH3 an alkyl group is a good EDG which will destabilize R-COO-
and weaker the acid.
 Learning Outcomes:
At the end of the lesson the students should be able to :

10.4 Synthesis Of Carboxylic Acids

Explain the preparation (synthesis) of carboxylic acid through:

i. oxidation of alkylbenzene, alcohol and aldehyde
ii. hydrolysis of nitrile compound
iii. carbonation of Grignard reagent

41
i. oxidation of alkyl benzene, primary alcohol and aldehyde
Oxidation of alkyl benzene
General equation :

oxidizing
R COOH
agent

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

+ 2CO2 + 3H2O
42
i. oxidation of alkyl benzene, primary alcohol and aldehyde

Oxidation of primary alcohol and aldehyde

General equation :
R R
H
PCC / CH2Cl2 oxidizing
C O agent C O
R C OH
H HO
H
1o alcohol aldehyde carboxylic acid

Strong oxidizing agent

Strong oxidizing agent = KMnO4/H+, or K2Cr2O7/H+,

or Na2Cr2O7/H+
43
Example:
O
O

PCC / CH2Cl2 KMnO4 / H+

CH3CH2OH CH3C H CH3C OH
Δ
ethanol ethanal ethanoic acid

KMnO4 / H+
Δ

44
ii. formation and Hydrolysis of nitrile

General equation :
H2O / H+
R COOH

NaCN / alcohol
R–X reflux
R CN

H2O / OH- H+
R- COO- R COOH

45
Example:
CH2COOH

H2O / H+

CH2Br CH2CN

NaCN / alcohol
reflux

CH2COO- CH2COOH

H2O / OH- H+

46
iii. carbonation of Grignard reagents

General equation :
R—MgX i) CO2 R—COOH + Mg(OH)X
ii) H2O/H+

Example:
CH2 MgBr CH2 COOH

i) CO2
ii) H2O/H+ + Mg(OH)Br

47
 Learning Outcomes:
At the end of the lesson the students should be able to :

10.5 Chemical Properties of Carboxylic Acids

a) Explain the chemical properties with reference to :

i. neutralisation with a base
ii. reaction with electropositive metals such as Na, K, Mg or Ca.
iii. reduction with LiAlH4 followed by H3O+
iv. acyl chloride formation
v. anhydride formation
vi. esterification
vii.amide formation

48
b) Predict the products of reactions of carboxylic acids with reagents in (a).
c) Explain the reducing property of methanoic acid with:
i. KMnO4/H3O+
ii.Tollens’ reagent
d) Outline the synthesis of compounds related to reactions of carboxylic
acids.
(A) CHEMICAL PROPERTIES OF CARBOXYLIC ACIDS

Main reactions of carboxylic acid:

 The reaction that involves the donation of H+ from –OH group.

 The reaction that involves the substitution of OH group
 The reaction that involves the reduction with LiAlH4 to primary
alcohol

50
 a. The reaction that involves O-H cleavage

1. Neutralisation with a base

Carboxylic acids are acidic, it can react with base such as NaOH(aq)
to give metal carboxylate salts,

General equation :
O O

R C + NaOH R C + H2 O
-
OH O Na+

OR
O
O
+ NaHCO3 R C + CO2 + H2O
R C
@ -
OH
O Na+
Na2CO3 51
Exercise:

COO-Na+
COOH

i. + NaOH + H2O

Sodium benzoate

O O
ii.

CH3CH2-C-OH + NaHCO3 CH3CH2-C-O-Na+

+ CO2 + H2O
52
2. Reaction with electropositive metals such as Na, K, Ca, Mg

General equation :

O O

R-C-OH + M R-C-O-M+ + H2 ↑
(metal)

2 CH3COOH + Ca (CH3COO-)2Ca2+ + H2 53
a. The reaction of carboxylic acid (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

General equation :
O
SOCl2 + SO2 + HCl ↑
R C Cl
white fume
O O
PCl5
R C OH R C Cl + POCl3 + HCl ↑
white fume
O
PCl3
R C Cl + H3PO3 54
Exercise:

O
SOCl2 CH3 CH C Cl + SO2 + HCl

O CH3
PCl5 O
CH3 CH C OH + POCl3 + HCl
CH3 CH C Cl
CH3
CH3
PCl3 O
+ H3PO3
CH3 CH C Cl

CH3
55
2. Esterification

Carboxylic acids react with alcohols in the presence of mineral acid

catalyst to produce esters.

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

Example:
O O

CH3 CH2 C OH + HOCH2CH3 H+ CH3 CH2 C OCH2 CH3

⇌Δ
propanoic acid ethanol ethyl propanoate
+ H2 O 56
3. Acid anhydride formation

i. Using phosphorous pentoxide, P2O5

- a strong dehydrating agent
General equation :
O O O O
R-C-OH + R'-C-OH P2O5 R-C-O-C-R' + H2O
heat
carboxylic carboxylic acid
acid acid anhydride

57
3. Acid anhydride formation

i. Carboxylic acids react with acyl chlorides in the presence of

pyridine to form acid anhydride.
General equation :
O O O O
pyridine
R-C-OH + R'-C-Cl R-C-O-C-R' + HCl
carboxylic acid acid
acid chloride anhydride

58
4. Amides formation

Reaction of carboxylic acids with an ammonia or amine give amide.

General equation : O
NH3
Δ R C NH2 + H2O
(1o amide)
O O
RNH2 R C NHR + H2O
R C OH Δ
(1o amine) (2o amide)
O
R2NH
R C NR2 + H2O
Δ
(2o amine) (3o amide) 59
 Exercise:

O
H 3C
CH C OH
H 3C Δ

Δ
60
 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 .

General equation :
O
i.LiAlH4
R C OH ii.H3O+ R CH2 OH
1o alcohol
Example:
COOH CH2OH

i.LiAlH4
ii. H3O+
61
 (B) REDUCING PROPERTY OF METHANOIC ACID
O

• Methanoic acid molecule, H C OH has both

O O
C OH and H C
carboxyl 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.

O KMnO4 / H+
Δ
CO2 + H2O
H C OH

[Ag(NH3)2]+/OH- 62
Ag + CO2 + H2O
Silver mirror
Exercise:
Based on the following reaction scheme, draw the structure of
P, Q, R and S.
OH
LiAlH 4 / H
i.LiAlH
+
C CH3CH(OH)CH3 / H+
4
S P
ii.H3O+ O ∆

SOCl2

CH3CH2NH2

R
:

O CH3
C CH
P
O CH3

Cl
C
Q
O

NH CH3
C CH2
R
O

CH2OH
S