STRUCTURE
The carboxyl functional group is unusual in that it is composed of two functional groups,
i.e., carboxyl group is made up of a hydroxyl group bonded to a carbonyl group.
Hybridization state of C in the carboxyl group is sp2.
In carboxylic acids, the bonds to the carbonyl carbon lie in one plane and are separated by
120º.
The carboxylic carbon is less electrophilic than carbonyl carbon because of resonance
structures.
As a result, Nu addition reactions which are characteristic reactions of aldehydes &
ketones do not take place with carboxylic acids.
However, like carbonyl group, carboxyl group is also polar due to the resonance structures.
PREPARATION
1. From Primary Alcohols and Aldehydes
(a) Primary alcohols are readily oxidized to corresponding carboxylic acids with common
oxidizing agents such as KMnO4 in neutral, acidic or alkaline medium or by K2Cr2O7
and CrO3 (chromium trioxide) in acidic medium (Jones reagent).
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PREPARATION OF CABOXYLIC ACIDS 2 CLASS - XII
Oxidation with K2Cr2O7 or CrO3 in acidic media often gives some amount of esters
also. Therefore, oxidation with KMnO4 in neutral of alkaline medium is preferred.
(b) Aldehyde are easily oxidized to carboxylic acids having same number of carbon atoms
than the parent aldehyde.
Oxidizing agents:
Strong oxidizing agents : Nitric acid, potassium permanganate, potassium dichromate
Mild oxidizing agents : Tollens’ reagent and Fehlings’ reagent
2. From Alkylbenzenes
Aromatic carboxylic acids can be prepared by vigorous oxidation of alkylbenzenes with
a number of oxidizing agents such as acidic or alkaline KMnO4, acidified K2Cr2O7
(chromic acid) or even dil. HNO3.
The entire side chain is oxidized to the carboxyl group (because of higher reactivity of
the benzylic hydrogens as compared to other hydrogens on the alkyl chain, oxidation
occurs at this carbon) irrespective of length of the carbon chain.
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PREPARATION OF CABOXYLIC ACIDS 3 CLASS - XII
Methyl group, primary and secondary alkyl group which contain the reactive benzylic
hydrogens are oxidized to the carboxyl group in this manner while tertiary alkyl group
which do not contain the benzylic hydrogens are not oxidized.
3. From Cyanide (Nitriles) and Amides
Nitriles are first hydrolysed to amides and then to acids in the presence of H + or ̅
as catalyst.
This reaction used for ascending the series.
For e.g., CH4 TO CH3COOH
Mild conditions are used to stop the reaction at the amide stage. For example, amides
are produced by shaking the nitriles with cold conc. HCl.
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PREPARATION OF CABOXYLIC ACIDS 4 CLASS - XII
4. From Grignard Reagents
Grignard reagents react with dry ice (CO2) in ethereal solution to produce salts of
carboxylic acids, which on acidification with mineral acids give corresponding carboxylic
acids.
This reaction used for ascending the series.
For e.g., C2H6 TO C2H5COOH
5. From Acyl Halides and Acid Anhydrides
(a) Acid chlorides when hydrolysed with water give carboxylic acids or more readily
hydrolysed with aqueous base to give carboxylate ions which on acidification provide
corresponding carboxylic acids.
(b) Anhydrides on the other hand are hydrolysed to corresponding acids with water.
Formic acid cannot be prepared by these two methods (a) and (b) because its
corresponding formyl chloride and formic anhydride are unstable compound.
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PREPARATION OF CABOXYLIC ACIDS 5 CLASS - XII
6. From Esters
Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis gives
carboxylates, which on acidification give corresponding carboxylic acids.
Acid hydrolysis CH3COOCH3 + H2O → CH3COOH + CH3OH
Base hydrolysis CH3COOCH3 + NaOH → CH3COONa + CH3OH
CH3COONa + HCl → CH3COOH + NaCl
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