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Chemistry

Carboxylic Acids
Session - 2
Session Objectives
1. Introduction to carboxylic acids
2. Physical properties and structure
3. General method of preparation
By oxidation
Carbonation of grignard reagent
Hydrolysis of acid derivatives
From nitriles
4. Reactions of the carboxylic acids
Introduction
The functional group of carboxylic acids
consists of a C=O with -OH bonded to the
same carbon.
Carboxyl group is usually written -COOH.
Aliphatic acids have an alkyl group
bonded to -COOH.
Aromatic acids have an aryl group.
Fatty acids are long-chain aliphatic acids.
Common Names
CH
3
CH
2
CHC
Cl
OH
O
-chlorobutyric acid
CH
3
CH
2
CH
2
CHCH
2
COOH
Ph
-phenylcaproic acid
=>
Many aliphatic acids have historical
names.
Positions of substituents on the chain
are labeled with Greek letters.
IUPAC Names
CH
3
CH
2
CHC
Cl
OH
O
2-chlorobutanoic acid
Ph
C
H
C
H
COOH
trans-3-phenyl-2-propenoic acid
(cinnamic acid)
Remove -e from alkane (or alkene) name,
add -oic acid.
The carbon of the carboxyl group is #1.
Naming Cyclic Acids
COOH
CH(CH
3
)
2
2-isopropylcyclopentanecarboxylic acid
COOH
OH
o-hydroxybenzoic acid
(salicylic acid)
Cycloalkanes bonded to -COOH are named as
cycloalkanecarboxylic acids.
Aromatic acids are named as benzoic acids.
Dicarboxylic Acids
Aliphatic diacids are usually called by their
common names (to be memorized).
For IUPAC name, number the chain from the
end closest to a substituent.
Two carboxyl groups on a benzene ring
indicate a phthalic acid.
HOOCCH
2
CHCH
2
CH
2
COOH
Br
3-bromohexanedioic acid
-bromoadipic acid
Structure of Carboxyl
Carbon is sp
2
hybridized.
Bond angles are close to 120.
O-H eclipsed with C=O, to get overlap of orbital
with orbital of lone pair on oxygen.
Boiling Points
Acetic acid, b.p. 118C
Higher boiling points than similar alcohols,
due to dimer formation.
Melting Points
Aliphatic acids with more than 8 carbons are solids
at room temperature.
Double bonds (especially cis) lower the melting
point. Note these 18-C acids:
Stearic acid (saturated): 72C
Oleic acid (one cis double bond): 16C
Linoleic acid (two cis double bonds): -5C
Solubility
Water solubility decreases with the length of
the carbon chain.
Up to 4 carbons, acid is miscible in water.
More soluble in alcohol.
Also soluble in relatively nonpolar solvents like
chloroform because it dissolves as a dimer.
Acidity
Resonance Stabilization
Substituent Effects on Acidity
COOH
OCH
3
COOH COOH
NO
2
COOH
NO
2
COOH
NO
2
p-methoxy benzoic acid
m-nitro
p-nitro o-nitro
pK
a
= 4.46 pK
a
= 4.19 pK
a
= 3.47 pK
a
= 3.41 pK
a
= 2.16
Oxidation of Primary Alcohols
Oxidation of Aldehydes
Oxidation of Substituted Aromatics
Carbonation of Grignard reagents
Hydrolysis of Acid derivatives and Nitriles
Haloform reaction
Periodic acid Cleavage of Vicinal Dials/Diketones
Oxidative Cleavage of Alkenes/Alkynes
Preparation Reactions
Carboxylic Acids via Oxidation
From Primary Alcohols
From Aldehydes
From Substituted Aromatics
Oxidative Cleavage Reactions

R CH CH R' RCOOH R'COOH +
KMnO
4

R C C R' RCOOH R'COOH +


KMnO
4

ozonolysis
or
Alkene Cleavage
Hot Potassium Permanganate
Alkyne Cleavage
Hot Potassium Permanganate
Ozonolysis
Grignard Synthesis
Grignard reagent + CO
2
yields a carboxylate salt.

R

Mg
X
C
O
O

+
R C
O
OMgX
H
+
H
2
O
R C
O
OH

R C
O
G
where G = X, OR, NH
2
, NHR, NR
2
, & O C
O
R - - - - - -
H
+
H
2
O
R C
O
OH +HG
R C
O
G
H
2
O
R C
O
O
- OH
-
+ G
-
RC N
H
2
O
R C
O
NH
2
R C
O
OH R C
O
O
-
( )
H
+
OH
-
or
Hydrolysis of acid derivatives
Hydrolysis of Nitriles
Br
NaCN
CN
H
+
H
2
O
COOH
Basic or acidic hydrolysis of a nitrile produces a carboxylic acid.

C
H
OH
CH
3
R
X
2
OH
-
/H
2
O
RCOO
-
+ HCX
3
X
2
OH
-
/H
2
O
RCOO
-
+ HCX
3
CH
3
C
O
R
Haloform Reaction
Cleavage of methyl carbinols
Cleavage of methyl carbonyls

H C
O
C
O
H
HIO
4
HCOOH 2
+
HIO
3
HIO
4
C
O
C
O
H R
RCOOH
+
HCOOH
+
HIO
3
HIO
4
C
O
C
O
R R'
RCOOH
+
R'COOH
+
HIO
3
Periodic Acid Cleavage of
Vicinal Dials/Diketones
Reduction of Carboxylic Acids

RCOOH
LiAlH
4
ether
H
+
H
2
O
RCH
2
OH
RCOOH
B
2
H
6
diglyme
RCH
2
OH
(selective reduction of
carboxyl group in
preference to carbonyl
of aldehydes/ketones)
Lithium Aluminum Hydride reduction
Diborane reduction
Conversion to acid derivatives
The group bonded to the acyl carbon determines the
class of compound:
-OH, carboxylic acid
-Cl, acid chloride
-OR, ester
-NH
2
, amide
These interconvert via nucleophilic acyl substitution.
Fischer Esterification
COOH
+ CH
3
CH
2
OH
H
+
COCH
2
CH
3
O
+
HOH
Acid + alcohol yields ester + water.
Acid catalyzed for weak nucleophile.
All steps are reversible.
Reaction reaches equilibrium.
Conversion to Acid Chlorides
C
O
OH
C
O
C
O
Cl Cl
+
C
O
Cl
+
+
+ HCl CO CO
2
An activated form of the carboxylic acid.
Chloride is a good leaving group, so undergoes acyl
substitution easily.
To synthesize acid chlorides use thionyl chloride or oxalyl
chloride with the acid.
Conversion to Amides
C
O
OH
+
C
O
O
-

+
NH
3
CH
3
+
CH
3
NH
2
heat
C
O
NHCH
3
H
2
O
Amine (base) removes a proton from the
carboxylic acid to form a salt.
Heating the salt above 100C drives off
steam and forms the amide.
Reduction to 1 Alcohols
Use strong reducing agent, LiAlH
4
.
Borane, BH
3
in THF, reduces carboxylic acid to
alcohol, but does not reduce ketone.
Decarboxylation of RCOOH

C
COOH
COOH

C
COOH
H
+
CO
2
C
COOH
C
O

C
H
C
O
+
CO
2
Thermolysis of beta-diacids
Thermolysis of beta-keto acids
Substitution in the hydrocarbon part
Acids having an -hydrogen are halogenated at the -position on
treatment with chlorine or bromine in the presence of small
amount of red phosphorus to give -halocarboxylic acids.
Hell-Volhard-Zelinsky reaction

2 4 2
X /P , H O
2
RCH COOH RCH(X)COOH
Ring substitution in aromatic acids
COOH group is deactivating and meta directing.
Aromatic carboxylic acids do not undergo Friedel-Crafts reaction.
COOH
HNO (conc.)
H SO (conc.)
2
4
3
COOH
NO
2
COOH
Br /FeBr
3
COOH
2
Br
Nitration
Bromination
Some commercially important
carboxylic acids
Methanoic acid; (HCOOH)
NaOH + CO
473 K, 10 atm
HCOONa
H
+
HCOOH
It is colourles, pungent smelling liquid.
It is powerful reducing agent. It reduces Tollens reagent
and Fehling solution.
Used in rubber, textile, dyeing, leather and electroplating
industries.
Ethanoic acid(acitic acid, CH
3
COOH)
Main constituent of vinegar and is obtained by fermentation
of molasses in presence of air.
Industrially, it is obtained in pure form by oxidation of ethanal
with air in the presence of cobalt acetate catalyst or by
carbonylation of methanol in the presence of rhodium catalyst.
CH
3
CHO + CO CH
3
COOH
CH
3
OH + CO CH
3
COOH
Colourless liquid with pungent odour.
Freezes at 289 K forming ice like crystal.
Water free acetic acid, obtained by melting of the crystals is called
glacial acetic acid.
Thank you