Carboxylic acids and their

Derivatives
(chapter 36)
 Structure

Two functional groups

adjacent to each other
O -I effect
R C O-H C=O and –OH groups
modify each other and
shows different properties.
 Formation of RCOOH

• Halides → nitriles → acids

• Oxidation of 1o R-OH and R-CHO
• Oxidation of Alkylbenzene
• Iodoform reaction
Possible reactions
Carbonyl group property

Acidic property
O
R C
O H Alkanolic property

Decarboxylation
 Acidity

Greater polarization of
this bond
O
R C
O H
extra
+ve
Polarization of this bond is
increased, O-H bond is
weakened. (Acidic)
 Acidity

..
O O- -ve charge is spreaded
over the –C=O group
R C .. - R C and stabilize the anion
O O RCOO-
 Acid strength
RCOOH  RCOO- + H+

Acid pKa
HCOOH 3.8
CH3COOH 4.8
CH3CH2COOH 4.9
CH3CH3CH2COOH 4.8

All are weak acids,

<1% ionized in water
 Question

Explain the following order of acid strength

a. RCOOH > C6H5OH > R-OH

b. CCl3COOH > CHCl2COOH > CH2ClCOOH

> CH3COOH
 Formation of salts

Formation of salts by reacting with

2. Metals
3. Carbonates
4. Hydroxides
 Reaction of the C=O group

1. LiAlH4/ether 2. H3O+
RCOOH RCH2OH
NaBH4 H2/Ni

No reaction No reaction
 Reduction mechanism

O H
H
R C R C O-
O H R C
O H
H:- H:-
H
H+
R C OH
H
 Nucleophilic substitution

Nucleophilic substitution
• C-OH bond as attractor of Nu: (HBr, PBr3, SOCl2)
• C=O play background role in enhancing the
reactivity of C-OH bond by attracting Nu:
 Acid Derivatives
O O
R C NH2 R C
O R’
Amide O Ester

R C
O H
O
O O
R C
R C O C R Cl
Acid Anhydride Acid Chloride
Conversion to Acid Derivatives

1. To Acyl chlorides

PCl5/SOCl2
RCOOH → RCOCl

1. To Ester
H+
R’COOH + ROH  R’COOR + H2O
Conversion to Acid Derivatives
1. To acid anhydride

RCOOH + R’COCl →RCOOCOR’ + HCl

1. To amide

RCOOH + NH3 → RCOO-NH4+

excess RCOOH
→ RCONH2 + H2O
reflux
(excess RCOOH is used to repress the hydrolysis of amide)
Reactions of acyl halides and
acid anhydrides
O O O

R C R C O C R
σ+ σ-
σ+ Cl
σ-

C=O provides extra polarity to activate the

C-X, C-O bonds
Reactions of acyl halides and
acid anhydrides
O O:-
R C R C BH+
Z
HB: Z
-Z-

O -H+
O pKa
R C BH+ HCl -2.2
R C B RCOOH 4~5
Reactivity: -Cl > -OCOR > -OR > -NH2 ROH 16~19
NH3 34
(base strength: NH2->OR->OCOR->Cl-)
 Reaction with water

O
H2O: RCOOH + HCl
R C
Cl

O O
R C O C R 2 RCOOH
H2O:
 Reaction with R-OH

CH3COCl + R-OH → CH3COOR + HCl

COOH
OH + (CH3CO)2O

COOH
OCOCH3 + CH3COOH
(Aspirin)
 Reaction with ammonia and
amine
CH3COCl + 2NH3 → CH3CONH2 + NH4Cl

CH3COCl + NH(CH3)2 → CH3CON(CH3)2 + HCl

(CH3CO)2O + 2NH3 → CH3CONH2 +

NH4+CH3COO-

(CH3CO)2O + 2RNH2 → CH3CONHR +

RNH3+CH3COO-
 Reactions of esters
1. Hydrolysis
H3O+, reflux
RCOOR’ + H2O  RCOOH + R’OH
OH-
RCOOR’ + H2O  RCOO- + R’OH

• Reduction with LiAlH4

1. LiAlH4/ether
RCOOR’ → RCH2OH + R’OH
2. H3O+
 Mechanism of reduction
AlH3-
O
O AlH 4
-

R C OR’
R C OR’
H

O
R C H + R’O-AlH3-
LiAlH4 H3O+
RCH2O-AlH3- R’OH
H3O+
RCH2OH
 Reactions of amides
1. Hydrolysis
reflux
RCONH2 + H3O+  RCOOH + NH4+
reflux
RCONH2 + OH-  RCOO- + NH3

1. Dehydration
P2O5, heat
C6H5CONH2 → C6H5C≡N + H2O
 Reactions of amides
1. Hofmann degradation

CH3CH2CONH2 + 4KOH + Br2

→ CH3CH2NH2 + K2CO3 + 2KBr + 2H2O

(one carbon atom less)

• Reduction (LiAlH4)
LiAlH4 H3O+
RCONH2 → → RCH2NH2
 Mechanism (Hofmann)
O O
R C NH2 + OH- + Br2 R C NH + Br- + H2O
Br
O O
OH
-
-Br-
R C N Br R C N- Br R-N=C=O
H
O
R-N=C=O + H2O R-NH-C-OH RNH2 + CO2
Mechanism (reduction)

O O- Li+
R C NH2 R C NH2
H :H-
:H-
LiAlH4

RCH2NH2 + Li2O