CHAPTER

FOUR

CARBONYL
COMPOUNDS
PART 2 :
CARBOXYLIC ACIDS &
ESTER

Copyright © 2014 McGraw-Hill Education. All rights reserved.

SYLLABUS CONTENT

4.1 Structure
4.2 Nomenclature
4.3 Physical Properties
4.4 Synthesis
4.5 Reactions
1.0 STRUCTURE
CARBOXYLIC
ACIDS
Carboxylic acids, , constitute one of the
most
frequently encountered classes of organic
compounds.
2.0 NOMENCLATURE
IUPAC – replacing the -e from the parent alkane and add
the suffix -oic for the acid
-When substituents are present, their locations
are identified by numbering begining at the
carboxyl group.

CH3CH2CH2COOH
butanoic acid
 IUPAC Common Names
C1 methanoic acid formic acid
C2 ethanoic acid acetic acid
C3 propanoic acid propionic acid
C4 butanoic acid butyric acid
C5 pentanoic acid valeric acid
C6 hexanoic acid caproic acid
C7 heptanoic acid
C8 octanoic acid
C9 nonanoic acid
C10 decanoic acid
 If the compound contains a carbon-carbon double bond,
change the infix -an- to -en- (enoic acid), plus E or Z
stereochemistry

(E)-3-phenyl-2-butenoic acid
 Carboxyl group takes precedence over most
other functional groups.

OH O O O

OH OH

(R)-5-hydroxyhexanoic acid 5-oxohexanoic acid

O
H2 N
OH

4-aminobutanoic acid
 Cyclic Carboxylic Acid

- name the ring compound and add the suffix –carboxylic acid
Nomenclature – of Dicarboxylic Acids and Common Names
O
O O
HO
OH
HO OH
O
Ethanedioic acid Propanedioic acid
(Oxalic acid) (Malonic acid)

O O O O
HO HO
OH HO OH OH
O O
Butanedioic acid Pentanedioic acid Hexanedioic acid
(Succinic acid) (Glutaric acid) (Adipic acid)
3.0 PHYSICAL
PROPERTIES
 3.1 Boiling point
High boiling point:

In a pure carboxylic acid, hydrogen bonding can occur

between two molecules of acid to produce a dimer.
Increased size of the molecule increases van der Waals
dispersion forces - resulting in a high boiling point.
 15

3.2 Solubility

• Carboxylic acids with up to four carbon atoms are solubl

e in water in any proportion.
• Reason:
Hydrogen bond can form between RCOOH and water
molecules.

• Solubility decreases as no of carbon atoms in the chain l

ength increases
• Reason:
Chain is hydrophobic
Less hydrogen bond
4.0 SYNTHESIS
4.1 Oxidation of alcohols
4.2 Oxidation of aldehydes
4.3 Hydrolysis of nitriles
 17

4.1 Oxidation of 1alcohols

Reagents : Potassium dichromate (VI) + dilute

sulfuric acid
Conditions : Heat under reflux
Observation : Orange to green
Equation:

Ethanol Ethanoic acid

 18

4.2 Oxidation of aldehydes

Reagents : Potassium dichromate (VI) + dilute

sulfuric acid
Conditions : Heat under reflux
Equation:

CH3CH2CHO + [O] → CH3CH2COOH

 19

4.3 Hydrolysis of nitriles

Reagents : dilute acid or dilute alkaline
Conditions : Heat under reflux
Equation: l
H C
u t e
Carboxylic acid
Dil

Dil
ute
Na
OH

Salt of carboxylic acid

 20

Carboxylic acid

Dilute HCl

R-COOH + NaCl
 SUMMARY OF CARBOXYLIC ACID SYNTHESIS
CH2OH

KMnO4

CH3

KMnO4, heat
CO2H

Br MgBr
Mg
CO2; then H+

C N

H2O, H+, heat

5.0 CHEMICAL REACTIONS
5.1 Reduction reaction
5.2 Neutralization reaction
5.3 Reaction with PCl5
5.4 Esterification reaction
 23

5.1 Reduction

Reagent : lithium tetrahydridoaluminate (III)

LiAlH4 (lithium aluminium hydride)
Conditions : Dry ether
Equation :

CH3CH2COOH + 4[H] → CH3CH2CH2OH + H2O

Carboxylic acid Primary Alcohol
 24

5.2 Neutralization
TEST
CARB
OXYL
Reagent : Na2CO3 or NaHCO3 ACID IC

Conditions : Room temperature

Equation :

2CH3COOH + Na2CO3 → 2CH3COO-Na+ + H2O + CO2

CH3COOH + NaHCO3 → CH3COO-Na+ + H2O + CO2

Products: Salt of carboxylic acid + carbon dioxide +
water
 25

5.3 Reaction with PCl5 TEST

- OH G
RO UP

Reagent : phosphorus(V) chloride (p

hosphorus pentachloride)
Conditions : Dry
Equation :
Steamy fumes

CH3COOH + PCl5 → CH3COCl + HCl + POCl3

Carboxylic acid Acid Chloride

Products : Acid chloride + Hydrogen chloride

+ Phosphorusoxytrichloride
 26

5.4 Esterification Reaction

Reagent : alcohol
Conditions : concentrated sulfuric acid
heat under reflux
Equation :
 27

Example:
CH3COOH + CH3CH2CH2OH → CH3COOCH2CH2CH3+ H2O

Products : Ester + Water

Observation: Sweet/ pleasent smell

 28

Reagent : alcohol
Conditions : Room temperature
Equation :

Products: Ester + Hydrogen chloride