Carboxylic

Acids
Chapter 17

17-1

Structure

The functional group of a carboxylic acid is a

carboxyl group.
O
C
O H

O
O H

COOH

CO2H

Alternative representations for a carboxyl group

17-2

Common Carboxylic Acids

Acetic Acid

Salicylic Acid

Butanoic Acid

17-3

Nomenclature - IUPAC

IUPAC names: drop the -e from the parent alkane

and add the suffix -oic acid.
acid
O
HCOOH

CH3COOH

Methanoic acid
(Formic acid)

Ethanoic acid
(Acetic acid)

OH
3-Methylbutanoic acid
(Isovaleric acid)

If the compound contains a carbon-carbon double bond,

O
changeOthe infix -anan toO-en-.
en
OH

OH

Propenoic acid trans-2-Butenoic acid

(Acrylic acid)
(Crotonic acid)

OH
trans-3-Phenylpropenoic acid
(Cinnamic acid)
17-4

Nomenclature - IUPAC

The carboxyl group takes precedence over most

other functional groups.
OH

OH
(R)-5-Hydroxyhexanoic
acid

OH
5-Oxohexanoic acid

O
H2 N

OH
4-Aminobutanoic acid

17-5

Nomenclature - IUPAC
Dicarboxylic acids: add the suffix -dioic acid to the name
of the parent alkane containing both carboxyl groups.
O
HO

O
OH

O
Ethanedioic acid
(Oxalic acid)
O
HO

O
OH HO

O
Butanedioic acid
(Succinic acid)

HO

O
OH

Propanedioic acid
(Malonic acid)
O

O
OH

HO

OH
O

Pentanedioic acid
(Glutaric acid)

Hexanedioic acid
(Adipic acid)

17-6

Nomenclature - IUPAC
If the carboxyl group is bonded to a ring, name the ring
compound and add the suffix -carboxylic acid.
acid
2

COOH

2-Cyclohexenecarboxylic
acid

HOOC

COOH

trans-1,3-Cyclopentanedicarboxylic
acid

Benzoic acid is the simplest aromatic carboxylic acid.

Use numbers to show the location of substituents.
COOH

COOH
OH

COOH
COOH

COOH

COOH
Benzoic 2-Hydroxybenzoic 1,2-Benzenedicarboxylic 1,4-Benzenedicarboxylic
acid
acid
acid
acid
(Salicylic acid)
(Phthalic acid)
(Terephthalic acid)
17-7

Physical Properties

In the liquid and solid states, carboxylic acids are

associated by hydrogen bonding into dimeric
structures.

17-8

Physical Properties

Carboxylic acids have significantly higher boiling

points than other types of organic compounds of
comparable molecular weight.
They are polar compounds and form very strong
intermolecular hydrogen bonds.

Carboxylic acids are more soluble in water than

alcohols, ethers, aldehydes, and ketones of
comparable molecular weight.
They form hydrogen bonds with water molecules
through both their C=O and OH groups.
17-9

Physical Properties
Water solubility decreases as the relative size of the
hydrophobic portion of the molecule increases.

17-10

Acidity

Carboxylic acids are weak acids.

Values of pKa for most aliphatic and aromatic carboxylic
acids fall within the range 4 to 5.

The greater acidity of carboxylic acids relative to

alcohols (both compounds that contain an OH
group) is due to resonance stabilization of the
carboxylate anion.

17-11

Acidity
Electron-withdrawing substituents near the carboxyl
group increase acidity by their inductive effect.
Formula: CH3COOH ClCH2COOH
Name:
pKa :

Acetic
acid
4.76

Cl2CHCOOH

Chloroacetic Dichloroacetic
acid
acid
2.86
1.48

Cl3CCOOH
Trichloroacetic
acid
0.70

Increasing acid strength

17-12

Acidity
The form of a carboxylic acid present in aqueous
solution depends on the pH of the solution.

17-13

Reaction with Bases

Carboxylic acids, whether soluble or insoluble in

water, react with NaOH, KOH, and other strong
bases to give water-soluble salts.
COOH + NaOH
Benzoic acid
(slightly soluble
in water)

H2 O

COO Na

+ H2 O

Sodium benzoate
(60 g/100 mL water)

They also form water-soluble salts with ammonia

and amines.
COOH + NH3
Benzoic acid
(slightly soluble
in water)

H2 O

COO NH4

Ammonium benzoate
(20 g/100 mL water)
17-14

Reaction with Bases

Carboxylic acids react with sodium bicarbonate

and sodium carbonate to form water-soluble salts
and carbonic acid.
Carbonic acid, in turn, breaks down to carbon dioxide
and water.
CH3COOH + NaHCO3
H2 CO3
CH3COOH + NaHCO3

CH3COO Na + H2 CO3
CO2 + H2O
- +
CH3COO Na + CO2 + H2O

17-15

Carboxylic Acid Synthesis

Methods We Have Already Learned

17-16

Preparation

Carbonation of Grignard reagents

Treating a Grignard reagent with carbon dioxide
followed by acidification gives a carboxylic acid.

17-17

Methanol to Acetic Acid

Acetic acid is synthesized by carbonylation of

methanol.
The carbonylation is exothermic.
CH3 OH + CO

O
CH3 COH H = -138 kJ(33 kcal)/mol

The Monsanto process uses a soluble rhodium(III) salt,

HI, and H2O to catalyze the reaction.

17-18

Reduction

The carboxyl group is very resistant to reduction.

It is not affected by catalytic hydrogenation under
conditions that easily reduce aldehydes and ketones to
alcohols, and easily reduce alkenes and alkynes to
alkanes. Nor is it reduced by NaBH4.

Lithium aluminum hydride reduces a carboxyl

group to a 1 alcohol.
Reduction is carried out in diethyl ether, THF, or other
nonreactive, aprotic solvent.
O
COH

1. LiAlH4
2. H2O

CH2 OH + LiOH + Al(OH) 3

4-Hydroxymethylcyclopentene
17-19

Selective Reduction
Carboxyl groups are not affected by catalytic reduction
under conditions that reduce aldehydes and ketones.
O

OH + H2
5-Oxohexanoic acid

OH
Pt
25C, 2 atm

OH
5-Hydroxyhexanoic acid
(racemic)

groups reduced by OH
NaBH4. O
Nor are
O carboxyl
O

1. NaBH4
C6 H5
OH
C6 H5
OH
2. H2 O
5-Oxo-5-phenylpentanoic acid
5-Hydroxy-5-phenylpentanoic acid
(racemic)

17-20

Fischer Esterification

Esters can be prepared by treating a carboxylic

acid with an alcohol in the presence of an acid
catalyst, commonly H2SO4, ArSO3H, or gaseous
HCl.
Preparation of an ester in this way is called Fischer
esterification.
O
OH
Ethanoic acid
(Acetic acid)

HO
Ethanol
(Ethyl alcohol)

H2 SO4

O
+ H2 O
O
Ethyl ethanoate
(Ethyl acetate)

17-21

Fischer Esterification

Fischer esterification is an equilibrium reaction.

By careful control of experimental conditions, it is
possible to prepare esters in high yield.
If the alcohol is inexpensive relative to the carboxylic
acid, it can be used in excess to drive the equilibrium to
the right.
Alternatively, water can be removed by azeotropic
distillation and a Dean-Stark trap (Figure 16.1).

17-22

Fischer Esterification Mechanism

17-23

Fischer Esterification Mechanism

17-24

Diazomethane

Diazomethane, CH2N2
This potentially explosive, toxic, yellow gas is best
represented as a hybrid of two contributing structures.
H C N N:

H C N N:

Treating a carboxylic acid with diazomethane gives a

methyl ester.
O
RCOH + CH2 N2

ether

Diazomethane

O
RCOCH3 + N2
A methyl ester

17-25

Diazomethane

Esterification occurs in two steps.

Step 1: Take a proton away. Proton transfer to
diazomethane gives the methyldiazonium cation.
O
R C O H

CH2 N N

R C O:

A carboxylate
anion

CH3 N N

Methyldiazonium
cation

Step 2: Make a bond between a nucleophile and an

electrophile. Nucleophilic displacement of N2 gives the
ester.
O

R C O: + CH3 N N

SN2

O
R C O CH3 + N N
17-26

Acid Chlorides

The functional group of an acid halide is a

carbonyl group bonded to a halogen atom.
Among the acid halides, acid chlorides are by far the
most common and the most widely used because of
their lower cost and ready availability.
O
-C-X

O
CH3 CCl

Functional group
of an acid halide

Acetyl
chloride

O
C-Cl
Benzoyl
chloride

17-27

Acid Chlorides
Acid chlorides are most often prepared by treating a
carboxylic acid with thionyl chloride.
O

+ SOCl2
OH
Cl + SO2 + HCl
Butanoic acid Thionyl chloride Butanoyl chloride

17-28

Acid Chlorides

The mechanism for this reaction is divided into two

steps.
Step 1: Reaction with SOCl2 transforms OH, a poor
leaving group, into a chlorosulfite group, a good leaving
group.
O

R-C-O-H + Cl-S-Cl

R C O S Cl + H-Cl
A chlorosulfite
group

17-29

Acid Halides
Step 2: Attack of chloride ion gives a tetrahedral carbonyl
addition intermediate, which collapses to give the acid
chloride.
O
R

O
O

Cl

Cl

O
R

O
O

O
Cl

R-C-Cl

SO2

Cl

Cl

A tetrahedral carbonyl
addition intermediate
17-30

Decarboxylation

Decarboxylation: The loss of CO2 from a carboxyl

group.
Most carboxylic acids, if heated to a very high
temperature, undergo thermal decarboxylation.
O
decarboxylation
R-C-OH
heat

R-H + CO2

Most carboxylic acids, however, are quite resistant to

moderate heat and melt or even boil without
decarboxylation.

17-31

Decarboxylation

Exceptions are carboxylic acids that have a

carbonyl group beta to the carboxyl group
This type of carboxylic acid undergoes decarboxylation
guite readily on mild heating.
O

warm

OH
3-Oxobutanoic acid
(Acetoacetic acid)

O
Acetone

+ CO
2

17-32

Decarboxylation
Thermal decarboxylation of a -ketoacid involves
rearrangement of six electrons in a cyclic six-membered
transition state.
H
O

(1)

(2)

CO2

(A cyclic six-membered
transition state)

Enol of
a ketone

A ketone

Only one of the carboxyl groups in oxalosuccinic acid,

an intermediate
in the
group
HO
O TCA cycle, has a carbonyl
O
O
beta
to
it.
only this carboxyl
has a C=O beta to it.

OH

HO
O
Oxalosuccinic acid

OH + CO2

HO
O
-Ketoglutaric acid

17-33

Decarboxylation
Decarboxylation occurs if there is any carbonyl group
beta to the carboxyl.
Malonic acid and substituted malonic acids, for
example, also undergo thermal decarboxylation.
O
O
140-150C
HOCCH2 COH
Propanedioic acid
(Malonic acid)

O
CH3COH + CO2

17-34

Decarboxylation
Thermal decarboxylation of malonic acids also involves
rearrangement of six electrons in a cyclic six-membered
transition state.
Step 1: Redistribution of six electrons in a cyclic sixmembered transition state gives carbon dioxide and the
enol form of a carboxyl group.
Step 2: Keto-enol tautomerism of the enol gives the
more stable keto form of the carboxyl group.
O
HO

(1)
O

HO

O
+ C
O

A cyclic six-membered
Enol of a
transition state
carboxylic acid

(2)

O
HO
A carboxylic
acid

+ CO2

17-35