ORGANIC CHEMISTRY –II

4. CARBOXYLIC ACIDS

• Saturated mono carboxylic acids are called fatty acids.

• Functional group is – COOH which is made up of carbonyl and hydroxy groups.
• General molecular formula is CnH2nO2 or CnH2n+1COOH.
• General representation is R – COOH
• Most of these fatty acids are derived from fats.
NAMING OF CARBOXYLIC ACIDS :

COMMON NAME IUPAC NAME

STRUCTURE
HCOOH Formic acid Methanoic acid
CH3COOH Aceticacid Ethanoic acid
CH3CH2COOH Propionic acid (or) Methyl acetic Propanoic acid
acid
CH3CH2CH2COOH Butyric acid (or) Ethyl acetic acid Butanoic acid
β α β − chloro--α - methyl butyric 3-chloro – 2-methyl Butanoic
CH 3 − CH− CH − COOH acid acid
| |
Cl CH 3

HOOC – COOH Oxalic acid Ethanedioic acid

HOOC – CH2 - CH2 - COOH Succinic acid Butanedioic acid

HOOC – CH2 – COOH Malonic acid Propanedioic acid

HOOC – CH = CH – COOH Maleic acid (or) Fumaric acid But – 2 – ene – dioicacid
CH3 − CH− COOH α - Hydroxy propionic acid (or) 2 – Hydroxy propanoic acid
|
Lactic acid
OH

ISOMERISM IN FATTY ACIDS :

• The molecule formula CnH2nO2 permits the existence of chain, functional , and metamerism.
• Mono carboxylic acids will exhibit chain and functional isomerism. They don’t exhibit position
isomerism as
– COOH group is at chain terminal position.
• Carboxylic acids and esters having same molecular formula are functional isomers.
Example :
1) C2H4O2 : CH3COOH Functional
HCOOCH3
2) C3H6O2 : CH3CH2COOH
Functional
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 Organic Chemistry – II
CH3COOCH3
3) C4H8O2 : CH3CH2CH2–COOH
CH3 − CH − COOH Chain isomers
|
CH3
CH3CH2CH2COOH Functional
CH3CH2COOCH3
CH3COOC2H5
C2H5COOCH3 Metamers

Acetic acid (or) Ethanoic acid (CH3COOH)

Methods of preparation of Acetic acid :

CH3CHO
CH3 - CH2 - OH
½ O2 CH3CN
KM r K 2
o
nO Cr 2

Mn(CH3COO)2

O
4

2
,H-
O7

H
O
CH3 - CHO CH3COCH2
KM r K 2
o
nO Cr 2

3
H
-N
2O
4

H
7
O

Co or Rh Micoderma aceti
CH3OH + CO CH3COOH CH3CH2OH + air
Pressure, Δ
H2O, H+

CH3COOMgBr

CH3MgBr + CO2

• Primary alcohols on oxidation give aldehydes which are easily oxidised to carboxylic acids in
presence of acidified K2Cr2O7 or KMnO4.
• CH3MgBr on addition of CO2 gives an intermediate which on hydrolysis gives acetic acid.
• Alkyl cyanides on hydrolysis give carboxylic acids. Methyl cyanide or Acetonitrile on hydrolysis
gives acetic acid and NH3. The intermediate is acetamide.
• Acetic acid is mostly prepared from CH3OH and CO in presence of Co or Rh catalyst.
• Commercially , acetic acid is prepared by the oxidation of ethanal with air in presence of Mn2+
catalyst.

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 Organic Chemistry – II
• Biochemical oxidation of ethylalcohol inpresence of Micoderma aceti bacteria yield 6 to 10%
acetic acid, called vinegar.
Physical properties :
• It is colorless liquid with pungent smell.
• It is corrosive liquid
• It’s boiling point is higher than even H2O due to formation of stronger hydrogen bonds [118°C].
It’s b.p. is higher than the b.p of corresponding alcohols, ethers, alkylhalides, alkanes, alkenes,
alkynes.
• It is miscible with H2O, alcohol, ether.
• Due to hydrogen bonding it exists as dimer in vapour state or in aqueous solution and polymer in
liquid state.
CHEMICAL PROPERTIES :

CH3CN+H2O
3
CO

H2 O
Cl
+H

NaH

O+
P2O5,Δ

2
Cl 3
Cl

+C
+
PO
+H

ONa
2

Cl+

a
SO

CH3CONH2+H2O
ON
l+

3 CO
O

3 CO
C

O
Δ
CO

CH 3

H2
CH

+
CH
3

a
CH

CH CH3COONH4
OON
3 -C C
3
3

CO

H
2 O

CH
3
l5
Cl 2

Na C
NH3

3
HI
aH
PC
SO

+ OH
2N

Re
dP Na
H2+Ni PCl3
CH3-CH3 CH3COOH CH3COCl + H3PO3
C2 H
P 4O 1
0
5 OH
O
Red P
Cl2

Ox

-H 2 H+
LiA
Na

ida

)O CH
CO 2
lH 4

tio

H 3C
(C 3
OO
n

CH
2
5 +H
O
CO

2
C 2H
Red P
Cl2

2
+H
5
-O

2
O
H
Red P
Cl2

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 Organic Chemistry – II

• Reactions of salts of acetic acid :

1) De carboxylation : CH3COONa+NaOH ⎯⎯ ⎯→ CH4 + Na2CO3
CaO

2) Kolbe’s electrolysis : 2CH3 COONa + 2H – OH ⎯⎯ ⎯ ⎯⎯→ C2H6+ 2CO2 + 2NaOH + H2

electrolys is

(anode) (cathode)
3) Dry distillation of calcium acetate :
Δ
i) (CH3COO)2Ca ⎯⎯→ CH3COCH3 + CaCO3
Δ
ii) (CH3COO)2Ca+ (HCOO)2Ca ⎯⎯→ 2CH 3 CHO + 2CaCO 3
• With any active metal like Na, K, Zn it liberates H2 gas.
• It neutrlises bases basic salts NaOH, Na2CO3, NaHCO3.
• With ethyl alcohol, it forms fruity smelling ester.
• With chlorinating agents like PCl3, PCl5, SOCl2 it gives ethanoyl chloride.
• With ammonia it first gives ammonium acetate and on heating it gives acetamide.
• With excess of Cl2 and in presence of red P it gives trichloro acetic acid. It is α - chlorination and
is called HVZ reaction.
• In the reaction of CH3COOH with metals, bases, metal carbonates and bicarbonates and NH3 , O–
H bond is cleaved.
• In the reaction of CH3COOH with alcohol, PCl3, PCl5, SOCl2 C – OH bond is cleaved.

PREPARATION OF BENZOIC ACID

• FROM AMIDES :

Benzamide Benzoic acid

• FROM ESTERS :

Ethyl benzoate Benzoic acid

FROM CO2 AND GRIGANARD REAGENT :

FROM ALKYL BENZENE :

• Aromatic carboxylic acids can be prepared by vigorous oxidation of alkyl benzenes with chromic
acid (or) acidic (or) alkaline potassium permaganate. The entire side chain is oxidised to the
carbonyl group irrespecitve of length of the side chain.
• Primary (or) secondary alkyl groups are oxidised in this manner tertiary group is not effected.

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 Organic Chemistry – II

a)
Toluene Benzoic acid

b)
Propylbenzene Benzoic acid

Uses of acetic acid :

• As solvent in industry
• For curing meat and fish
• As vinegar in food stuffs
• In the Preparation of perfumes , dyes and drugs.
• In the preparation of acetone, ester, acetic anhydride, acetamide etc