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CARBOXYLIC ACIDS
Saturated monocarboxylic acids have general formula of CnH2nO2.

PREPARATION OF CARBOXYLIC ACIDS

(1) By Oxidation of Alcohol:

R  CH 2OH 
 O
 RCOOH
1 alcohol Carboxylic acids
G.R. with same number
of carbon atom
Oxidation ofalkene also gives carboxylic acids
O 
RCH  CH  R  
 RCOOH  RCOOR 
(2) Using Grignard reagent (carbonation)

(a) H3O+
X
R — MgX + CO2 RCOOMgX RCOOH + Mg
(i) CO2 X
aryl grignard
(b) MgBr reagent +
COOH
(ii) HO
3

(3) By the hydrolysis of cyanides

alc.KCN 3  R  COOH H O
R  X  R  C  N 
The acid formed contain one carbon more than the parent alkyl halide.
(4) By heating gem. dicarboxylic acids

R — CH — COOH 
 R — CH 2COOH
| CO 2
COOH
(5) Preparation of aromatic carboxylic acids
Benzoic acid is obtained by the oxidation of the alkyl benzene provided the carbon bonded directly to
benzene contains at least one hydrogen atom.
CH3 COOH
+
KMnO 4/H

PROPERTIES OF CARBOXYLIC ACIDS

(1) Carboxylic acids have a higher boiling point than the corresponding alcohol. This is due to their ability
to associate via intermolecular hydrogen bonding and exists as dimer. The dimer exists even in the
vapour phase.
O — H --- O
R—C C—R
O --- H — O
 B.P. of carboxylic acids increases regularly down the homologous series.
ACIDIC STRENGTH OF CARBOXYLIC ACIDS
(1) Carboxylic acids give H3O+ ion in water and thus acts as acid.
 ˆˆ† R  COO  H3O
R COOH  H 2O ‡ˆˆ
and
carboxylateion

 RCOO   H3O 
Ka    
 R COOH 
 The strength of carboxylic acid depends on its ability to lose proton.
..
O O–
..
R — C — O– R—C—O
Note: The presence of electron donating group (EDG) decreases the acidic strength and electron with
drawing group (EWG) increases the acidic strength.
The decreasing acidic strength order, of few common carboxylic acids are given below,
(i) HCOOH > CH3COOH > C2H5COOH
(ii) FCH2 COOH > ClCH2COOH > BrCH2COOH
(iii) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
(iv) RCOOH > H2O > ROH > HC  CH > NH3
Ortho Effect :
All ortho-substituted benzoic acids are stronger than benzoic acid. This is due to (a) steric factor (b) I-effect
(c) chelation by H bonding. In other positions, we have to see both resonance and the inductive effect.
(i) Nitrobenzoic acid : o > p > m > benzoic acid
(ii) Hydroxybenzoic acid : o > m > p > benzoic acid
(iii) Chlorobenzoic acid : o > m > p (iv) Methyl benzoic acid : o > m > p
Chemical Reactions:

HELL-VOLHARD-ZELINSKY REACTION :
The reaction involving substitution of   hydrogen by halogen in pesence of red P is called HVZ reaction.

2 X / red P
R — CH 2 — COOH 
 R — C H — COOH
X  Cl, Br |
X

H
 RCOOR  H 2 O
Esterification : R  COOH  R OH 
Ester

Esterification is an SN2 reaction. Therefore, as the size of R group in carboxylic acid increases, the rate
of esterification decreases.

HCOOH > CH3COOH > COOH

REACTIONS OF BENZOIC ACID
–COOH groups is deactivating and meta directing.
(..) .. .. ..
O O O O
C–O–H C–O–H C–O–H C–O–H

+ +

(+)

H O–C=O
Resonance
hybrid:

COOH
Br2
FeBr3
Br

COOH COOH
HNO3/H2SO4

NO2

COOH
H2SO4/SO3

SO3H
Test for carboxylic acid:
1. Acids turns blue litmus red.
2. Formic acid (It is only the carboxylic acid) gives positive Tollen’s reagent test and Fehling solution test.
3. Carboxylic acid gives brisk effervesence with NaHCO3 or Na2CO3.
ACID DERIVATIVES
O
1. Acid chlorides (Acyl halides) ||
R — C— Cl
O
2. Esters ||
R — C— OR 
O O
3. Acid anhydrides || ||
R — C— O — C— R
O
4. Amides ||
R — C— NH 2

(1) ACYL HALIDES

Preparation :

PCl5
RCOCl + POCl3 + HCl

O
PCl3
(i) R — C — OH RCOCl + H3PO3

SOCl2
RCOCl + SO2 + HCl

PCl5
(ii)  RCO 2 O   2RCOCl  POCl3
Acid chlorides have lower b.p. than carboxylic acid as there is no association via intermolecular hydrogen
bonding. Due to weak C–Cl bond, acid chlorides are more reactive than carboxylic acids towards nucleophilic
substitution reaction.
H2 O
RCOOH + HCl
white fumes

R'OH
O RCOOR' + HCl
Base ester

R — C — Cl
NH3/
Acid chlorides RCONH2 + HCl
Base amide

R'COONa
RCOOCOR' + NaCl
acid anhydride
 (2) ACID ANHDYRIDES

O O
Acid anhdyrides function Group : || ||
C  O  C 
Preparation

(1) Acid anhydrides are prepared by the dehydration of carboxylic acid using P2O5 / .
P O
4 10  RCO O  H O
R  COOH   
2 2
(2) Acetic anhydride is prepared commercially by heating acetic acid to 1073 K.
1073K
  CH3CO 2 O  H 2O
2CH 3COOH 
Acid anhydrides have higher b.p. than acid chlorides and are less reactive than acid chlorides.
Reactions :
Chemcial reactions of acid anhydride are shown below,
NH3
RCONH2 + RCOOH

R'OH
RCOOR' + RCOOH

O O
C6H6 / AlCl3
R — C — O— C—R COR + RCOOH
Base
Acid
anhydride LiAlH4
RCH2OH
Reduction

C6H5OH
O – COR

(3) ESTERS

O
||
Ester functional group is: R — C— O — R '.

Preparation

H2SO4
ˆˆˆˆˆˆ
(1) Esterification reaction: RCOOH  R OH ‡ˆˆˆˆˆ †
ˆ RCOOR   H 2O
base
(2) From acid chlorides: RCOCl  R OH   RCOOR   HCl
Esters of low molecular mass are soluble in water and solubility decreases with increasing molecular
mass. Esters are less reactive than both acid chlorides or acid anhydrides.
Chemical Reactions of esters
+
H2O/H
RCOOH + R'OH

dil NaOH
RCOONa + R'OH

O
R''OH/H2SO4
RCOOR'' +R'OH
R — C — OR' Trans-esterfication

Ester
NH3 RCONH2+ R'OH

Na/ C2H5OH
RCH2OH+R'OH
(Bouvault-Blane
reduction)
Claisen condensation: The reaction is given by ethyl ester of carboxylic acids containing alpha hydrogen.
The reaction takes place in presence of sodium ethoxide. The product obtained is  -keto ester which on
hydrolysis generates  -keto acids. The  -keto acid on heating gives carbonyl compound.
O O
C 2 H5 O Na  || ||
2CH3COOC 2H5  CH 3 — C— CH 2 — C— COOC 2H 5
Ethyl aceto acetate
(Ethyl–4–oxo pentanoate)
(4) AMIDE
O
Amide functional group is ||
R — C— NH2 .

Preparations
(1) Partial hydrolysis of nitrites:
O
||
H 2O / OH 
R —C N  R — C— NH 2

(2) Using ammonia:

RCOOH/
RCONH2

(RCO)2O
RCONH2 + RCOOH

NH3
RCOOR'
RCONH2 + R'OH

RCOCl
RCONH2 + HCl
Properties
(i) Amongst all acid derivatives, amides have the highest boiling point. This is due to extensive network of
intermolecular hydrogen bonding. The increasing b.p. order is
ROCl < RCOOR < (RCO2)2O < RCONH2
(ii) Amides are the least reactive derivatives of carboxylic acid towards nucleophilic substitution reaction due
to high bond enthalpy of C—N bond.
(iii) Amides are amphoteric in nature:
(a) As base:
O
|| 
RCONH 2  HCl ƒ R — C— N H3Cl
base
(b) As acid:

 R COONa   NH 3
RCONH2  NaOH 
acid
1. Hydrolysis:
H SO
2 4  RCOOH  NH HSO
R CONH 2  H 2 O  4 4

NaOH
R CONH2  H 2O 
 R COONa  NH3
2. Dehydration:
P O
4 10  R — CN  H O
R CONH2  2
Heat
nitriles

P4O10
CONH2 CN + H2O
Heat
benzamide benzonitrile

3. Reduction:
(i)LiAlH
4  RCH NH
RCONH2 
 2 2
(ii)H3O 1 amine

4. Hydrolysis using HNO2:

RCONH2 + HNO2  RCOOH + N2 + H2O
5. Hofmann bromanide reaction
Its converts amide (1°) containing  -carbon to 1° amines with one carbon less using Br2 and alkali
R CONH2 + Br2 + 4 NaOH  RNH2 + 2Na Br + Na2 CO3 + 2H2O
 In this reaction nitrene as reaction intermediate is used.