General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,

by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.

 Lecture 20

Chapter 12

Carboxylic Acids
Carboxylic Acid Nomenclature
 systematic IUPAC names replace "-e"
ending of alkane with "oic acid"
Systematic Name
O

HCOH methanoic acid

O
CH3COH ethanoic acid
O

CH3(CH2)16COH octadecanoic acid

 common names are based on natural origin
rather than structure
Systematic Name Common Name
O

HCOH methanoic acid formic acid

O
CH3COH ethanoic acid acetic acid
O

CH3(CH2)16COH octadecanoic acid stearic acid

 O Systematic Name Common Name

CH3CHCOH 2-hydroxypropanoic lactic acid

acid
OH O
CH3(CH2)7 (CH2)7COH

C C
H H
(Z)-9-octadecenoic oleic acid
acid
Structure and Bonding
Formic
Formicacid
acidisisplanar
planar
 Formic
Formicacid
acidisisplanar
planar

O H

120 pm C O

H
134 pm
 Electron
ElectronDelocalization
Delocalization

•• • •• •–
R O• R + O•
C C ••

• O •• • O ••
• •
H H
 Electron
ElectronDelocalization
Delocalization

•• • •• •– •• •–
R O• R + O• R O•
C C •• C ••

• O •• • O •• + O ••
• •
H H H

stabilizes carbonyl group

Physical Properties
 Boiling
BoilingPoints
Points

O OH O

OH
bp 31°C 80°C 99°C 141°C

Intermolecular forces, especially hydrogen

bonding, are stronger in carboxylic acids than
in other compounds of similar shape and
molecular weight
 Hydrogen-bonded
Hydrogen-bondedDimers
Dimers

O H O
H3CC CCH3
O H O

Acetic acid exists as a hydrogen-bonded

dimer in the gas phase. The hydroxyl group
of each molecule is hydrogen-bonded to the
carbonyl oxygen of the other.
 Solubility
SolubilityininWater
Water

carboxylic acids are similar to alcohols in respect

to their solubility in water
form hydrogen bonds to water

H
O H O
H3CC H
O H O
H
 Acidity of Carboxylic Acids

Most carboxylic acids have a pKa close to 5.

 Carboxylic
Carboxylicacids
acidsare
areweak
weakacids
acids

but carboxylic acids are far more acidic than alcohols

O
CH3COH CH3CH2OH

Ka = 1.8 x 10-5 Ka = 10-16

pKa = 4.7 pKa = 16
 Free
FreeEnergies
Energiesof
ofIonization
Ionization

CH3CH2O– + H+

G°= 64 kJ/mol O
G°= 91 kJ/mol
CH3CO– + H+

G°= 27 kJ/mol
O
CH3CH2OH CH3COH
Salts of Carboxylic Acids
Carboxylic
Carboxylicacids
acidsare
areneutralized
neutralizedby
bystrong
strongbases
bases

O O

RCOH + HO– RCO– + H2O

stronger weaker
acid acid

equilibrium lies far to the right; K is ~ 1011

as long as the molecular weight of the acid is
not too high, sodium and potassium
carboxylate salts are soluble in water
 Micelles
Micelles

unbranched carboxylic acids with 12-18 carbons

give carboxylate salts that form micelles in
water
O

ONa
sodium stearate
(sodium octadecanoate)
O
–
CH3(CH2)16CO Na+
 Micelles
Micelles
O

ONa

nonpolar polar
sodium stearate has a polar end (the carboxylate end)
and a nonpolar "tail"
the polar end is "water-loving" or hydrophilic
the nonpolar tail is "water-hating" or hydrophobic
in water, many stearate ions cluster together to form
spherical aggregates; carboxylate ions on the outside
and nonpolar tails on the inside
AAmicelle
micelle
 Micelles
Micelles

The interior of the micelle is nonpolar and

has the capacity to dissolve nonpolar
substances.
Soaps clean because they form micelles,
which are dispersed in water.
Grease (not ordinarily soluble in water)
dissolves in the interior of the micelle and is
washed away with the dispersed micelle.
Substituents and Acid
Strength
 Substituent
Substituent Effects
Effects on
on Acidity
Acidity
standard of comparison is acetic acid (X = H)

X CH2COH

Ka = 1.8 x 10-5
pKa = 4.7
Substituent
Substituent Effects
Effects on
on Acidity
Acidity
O

X CH2COH

X Ka pKa

H 1.8 x 10-5 4.7

CH3 1.3 x 10-5 4.9
CH3(CH2)5 1.3 x 10-5 4.9

alkyl substituents have negligible effect

Substituent
Substituent Effects
Effects on
on Acidity
Acidity
O

X CH2COH

X Ka pKa

H 1.8 x 10-5 4.7

F 2.5 x 10-3 2.6

Cl 1.4 x 10-3 2.9

electronegative substituents increase acidity

Substituent
Substituent Effects
Effects on
on Acidity
Acidity

X CH2COH

electronegative substituents withdraw

electrons from carboxyl group; increase K for
loss of H+
 Substituent
Substituent Effects
Effects on
on Acidity
Acidity
O

X CH2COH
X Ka pKa

H 1.8 x 10-5 4.7

Cl 1.4 x 10-3 2.9
ClCH2 1.0 x 10-4 4.0
ClCH2CH2 3.0 x 10-5 4.5
effect of substituent decreases as number of bonds
between X and carboxyl group increases
 Ionization of
Substituted Benzoic Acids
 Hybridization
Hybridization Effect
Effect
O Ka pKa

COH 6.3 x 10-5 4.2

O
H2C CH COH 5.5 x 10-5 4.3
O

HC C COH 1.4 x 10-2 1.8

sp2-hybridized carbon is more electron-
withdrawing than sp3, and sp is more electron-
withdrawing than sp2
Ionization
Ionizationof
ofSubstituted
SubstitutedBenzoic
BenzoicAcids
Acids
O
X effect is small unless X is
COH electronegative; effect is
largest for ortho substituent
pKa
Substituent ortho meta para
H 4.2 4.2 4.2
CH3 3.9 4.3 4.4
F 3.3 3.9 4.1
Cl 2.9 3.8 4.0
CH3O 4.1 4.1 4.5
NO2 2.2 3.5 3.4
Sources of Carboxylic
Acids
 Synthesis
Synthesis of
of Carboxylic
Carboxylic Acids:
Acids:
Review
Review

side-chain oxidation of alkylbenzenes

oxidation of primary alcohols

oxidation of aldehydes
Synthesis of Carboxylic Acids
by the Carboxylation of
Grignard Reagents
 Carboxylation
Carboxylation of
of
Grignard
Grignard Reagents
Reagents
O
Mg CO2
RX RMgX RCOMgX
diethyl
ether H3O+

converts an alkyl (or O

aryl) halide to a
carboxylic acid having RCOH
one more carbon atom
than the starting halide
 Example:
Example: Alkyl
Alkyl Halide
Halide

1. Mg,
CH3CHCH2CH3 diethyl ether CH3CHCH2CH3
2. CO2
Cl CO2H
3. H3O+
(76-86%)
Example:
Example: Aryl
Aryl Halide
Halide
1. Mg,
diethyl
ether
2. CO2
CH3 3. H3O+ CH3

Br CO2H

(82%)
Synthesis of Carboxylic Acids
by the
Preparation and Hydrolysis of
Nitriles
 Preparation
Preparation and
and Hydrolysis
Hydrolysis
of
of Nitriles
Nitriles
O
•• –
C N •• H3O+
RX RC N •• RCOH
SN2 heat + NH4+
converts an alkyl halide to a carboxylic acid having
one more carbon atom than the starting halide

limitation is that the halide must be reactive toward

substitution by SN2 mechanism, i.e. best with primary,
then secondary…… tertiary gives elimination
Example
Example
NaCN
CH2Cl CH2CN
DMSO
(92%)
H2O
H2SO4
O heat
CH2COH

(77%)
Reactions of Carboxylic Acids:
A Review and a Preview
 Reactions
Reactionsof
ofCarboxylic
CarboxylicAcids
Acids

Acidity Reduction with LiAlH4

Esterification

Reaction with Thionyl Chloride

Acid-Catalyzed Esterification
Acid-catalyzed
Acid-catalyzed Esterification
Esterification
(also called Fischer esterification)

O
H+
COH + CH3OH

O
COCH3 + H2O

Important fact: the oxygen of the alcohol is

incorporated into the ester as shown.