William H.

Brown
Christopher S. Foote
Brent L. Iverson
Eric Anslyn
http://academic.cengage.com/chemistry/brown

Chapter 17
Carboxylic Acids

William H. Brown • Beloit College

17-1
식초제조공정

17-2
롯데이네오스화학
17-3
Structure
 The functional group of a carboxylic acid is a
carboxyl group.
O O
C COOH CO2 H
O H O H
Alternative representations for a carboxyl group

• The general formula for an aliphatic carboxylic acid is

RCOOH; that for an aromatic carboxylic acid is
ArCOOH.

17-4
Nomenclature - IUPAC
 IUPAC names: drop the -e from the parent alkane
and add the suffix -oic acid.
O
HCOOH CH3 COOH
OH
M ethanoic acid Ethanoic acid 3-M ethylbutanoic acid
(Formic acid) (Acetic acid) (I sovaleric acid)

• If the compound contains a carbon-carbon double

bond, change the infix -an- to -en-.
O
O O
OH
OH OH

Propenoic acid trans-2-Butenoic acid trans-3-Phenylpropenoic acid

(A crylic acid) (Crotonic acid) (Cinnamic acid)
17-5
Common names

17-6
Nomenclature - IUPAC
 The carboxyl group takes precedence over most
other functional groups.
OH O O O O
H2 N
OH OH OH
(R)-5-H ydroxyhexanoic 5-Oxohexanoic acid 4-Aminobutanoic acid
acid

17-7
Nomenclature - IUPAC
• Dicarboxylic acids: add the suffix -dioic acid to the
name of the parent alkane containing both carboxyl
groups.
O
O O
HO
OH
HO OH
O
Ethanedioic acid Propanedioic acid
(Oxalic acid) (Malonic acid)

O O O O
HO HO
OH HO OH OH
O O
Butanedioic acid Pentanedioic acid Hexanedioic acid
(Succinic acid) (Glutaric acid) (Adipic acid)

17-8
Nomenclature - IUPAC
• If the carboxyl group is bonded to a ring, name the ring
compound and add the suffix -carboxylic acid.
2
1 COOH
3
HOOC COOH

2-Cyclohexenecarboxylic trans-1,3-Cyclopentanedicarboxylic
acid acid

• Benzoic acid is the simplest aromatic carboxylic acid.

• Use numbers to show the location of substituents.
COOH
COOH COOH COOH
OH COOH

COOH
Benzoic 2-H ydroxybenzoic 1,2-Benzenedicarboxylic 1,4-Benzenedicarboxylic
acid acid acid acid
(Salicylic acid) (Phthalic acid) 17-9
(Terephthalic acid)
Nomenclature-Common
• When common names are used, the letters
α, β, γ, δ, etc. are often used to locate substituents.
O
O O
δ γ β
α H2 N OH
5 3 1 OH OH
4 2 NH2
4-A minobutanoic acid (S)-2-Aminopropanoic acid
(γ-A minobutyric acid, GABA) [(S)-α-Aminopropionic acid;
L-alanine]

17-10
Example 17.1

17-11
Physical Properties
 In the liquid and solid states, carboxylic acids are
associated by hydrogen bonding into dimeric
structures.

17-12
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.

17-13
Physical Properties
 Table 17.2
M olecular Boiling
Weight Point Solubility
Structure Name (g/mol) (°C) (g/100 g H 2 O)
CH3 COOH Acetic acid 60.1 118 I nfinite
CH3 CH2 CH2 OH 1-Propanol 60.1 97 I nfinite
CH3 CH2 CHO Propanal 58.1 48 16

CH3 ( CH2 ) 2 COOH Butanoic acid 88.1 163 I nfinite

CH3 (CH2 ) 3 CH2 OH 1-Pentanol 88.1 137 2.3
CH3 ( CH2 ) 3 CHO Pentanal 86.1 103 Slight

CH3 ( CH2 ) 4 COOH Hexanoic acid 116.2 205 1.0

CH3 (CH2 ) 5 CH2 OH 1-H eptanol 116.2 176 0.2
CH3 ( CH2 ) 5 CHO Heptanal 114.1 153 0.1
17-14
Physical Properties
• Water solubility decreases as the relative size of the
hydrophobic portion of the molecule increases.

17-15
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.
븬 븬
O O
븬

븬
븬
CH3 C CH3 C
O O
븬
븬

븬
븬 븬
These contributing structures are equivalent;
the carboxylate anion is stabilized
by delocalization of the negative charge 17-16
Acidity
• Electron-withdrawing substituents near the carboxyl
group increase acidity through their inductive effect.

Formula: CH3 COOH ClCH2 COOH Cl2 CHCOOH Cl3 CCOOH

Name: Acetic Chloroacetic D ichloroacetic Trichloroacetic
acid acid acid acid
pKa : 4.76 2.86 1.48 0.70
I ncreasing acid strength

17-17
Acidity
• The form of a carboxylic acid present in aqueous
solution depends on the pH of the solution.
O O O O
OH - OH-
R- C-OH R- C-OH + R- C-O - + R- C-O -
H+ H
predominant present in equal predominant
species when the concentrations when species when
pH of the the pH of the the pH of the
solution is solution is equal to solution is 7.0
2.0 or less the p Ka of the acid or greater

17-18
Example 17.2

17-19
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 + N aOH COO Na + H2 O
H2 O
Benzoic acid Sodium benzoate
(slightly soluble (60 g/100 mL water)
in water)

 They also form water-soluble salts with ammonia

and amines.
- +
COOH + N H3 COO NH4
H2 O
Benzoic acid A mmonium benzoate
(slightly soluble (20 g/100 mL water)
in water)
17-20
*SOAP

17-21
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.
- +
CH3 COOH + NaHCO3 CH3 COO Na + H2 CO3
H2 CO3 CO2 + H2 O
- + +
CH3 COOH + NaHCO3 CH3 COO Na CO2 + H2 O

17-22
Example 17.3

17-23
 Reaction with bases
• The acid-base
properties of
carboxylic acids
allow an easy
separation of
carboxylic acids
from water-insoluble
nonacidic
compounds.

17-24
Preparation
 Carbonation of Grignard reagents
• Treatment of a Grignard reagent with carbon dioxide
followed by acidification gives a carboxylic acid.

O
Mg Cl + C
O
Carbon dioxide

O O
- HCl
C-O [ Mg Cl] + C-OH + Mg 2 +
H2 O
A magnesium carboxylate Cyclopentane-
carboxylic acid

17-25
Methanol to Acetic Acid
 Acetic acid is synthesized by carbonylation of
methanol.
• The carbonylation is exothermic.
O
CH3 OH + CO CH3 COH ∆H?= -138 kJ(33 kcal)/mol

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

and HI to catalyze the reaction.

17-26
롯데비피화학
17-27
Methanol to Acetic Acid
• Steps 1 and 2: Preparation of the catalyst.
CH3 OH + HI CH3 I + H2 O

CH3 I + Rh( CO) I2 [CH3 -Rh(CO)I3 ] -

A methyl-rhodium
carbonyl complex
• Steps 3 and 4: The catalytic cycle.
O [ CH3 - Rh( CO) I 3 ] -
CH3 COH CO

catalytic
(4) cycle (3)

CH3 OH O
[ CH3 C- Rh( CO) I 3 ] -
An acyl-rhodium
carbonyl complex 17-28
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 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
1 . LiAlH4
COH CH2 OH + LiOH + Al(OH) 3
2 . H2 O
4-H ydroxymethyl-
cyclopentene
17-29
Selective Reduction
• Carboxyl groups are not affected by catalytic reduction
under conditions that reduce aldehydes and ketones.
O O OH O
Pt
OH + H2 OH
25캜, 2 atm
5-Oxohexanoic acid 5-Hydroxyhexanoic acid
(racemic)

• Nor are carboxyl groups reduced by NaBH4.

O O OH O
1 . Na BH 4
C6 H5 OH C6 H5 OH
2 . H2 O
5-Oxo-5-phenylpentanoic acid 5-Hydroxy-5-phenylpentanoic acid
(racemic)

17-30
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.
O O
H2 SO 4
OH + HO O + H2 O
Ethanoic acid Ethanol Ethyl ethanoate
(Acetic acid) (Ethyl alcohol) (Ethyl acetate)

17-31
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).

17-32
Fischer Esterification
• A key intermediate in Fischer esterification is the
tetrahedral carbonyl addition intermediate (TCAI)
formed by addition of ROH to the C=O group.
H TCAI
O
R C OCH3
O
H
H+ H+
O O
R C OH + HOCH3 R C OCH3 + HOH

17-33
Example 17.4

17-34
Diazomethane
 Diazomethane, CH2N2
• A potentially explosive, toxic, yellow gas is best
represented as a hybrid of two contributing structures.
+ +
:

:
H C N N: H C N N:
H H

• Treating a carboxylic acid with diazomethane gives a

methyl ester.
O O
ether
RCOH + CH2 N 2 RCOCH3 + N 2
Diazomethane A methyl ester

17-35
Diazomethane
 Esterification occurs in two steps.
Step 1: Proton transfer to diazomethane.
O O
+ – +
R C O H + CH2 N N R C O: + CH3 N N
A carboxylate M ethyldiazonium
anion cation

Step 2: Nucleophilic displacement of N2.

O O
– + SN 2
R C O: + CH3 N N R C O CH3 + N N

17-36
Esters as Flavoring Agents

17-37
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.
O O O
- C- X CH3 CCl C-Cl

Functional group A cetyl Benzoyl

of an acid halide chloride chloride

17-38
Acid Chlorides
• Acid chlorides are most often prepared by treating a
carboxylic acid with thionyl chloride.
O O
OH + SOCl2 Cl + SO2 + HCl
Butanoic acid Thionyl chloride Butanoyl chloride

17-39
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 O O O
R- C-O- H + Cl-S- Cl R C O S Cl + H- Cl
A chlorosulfite
group

17-40
Acid Halides
Step 2: Attack of chloride ion gives a tetrahedral
carbonyl addition intermediate, which collapses to
give the acid chloride.
O O

R C O S Cl + Cl -

-
O O O

R C O S Cl R- C- Cl + SO2 + Cl -

Cl

A tetrahedral carbonyl
addition intermediate

17-41
Example 17.5

17-42
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 R-H + CO2
heat

• Most carboxylic acids, however, are quite resistant to

moderate heat and melt or even boil without
decarboxylation.

17-43
Decarboxylation
 Exceptions are carboxylic acids that have a
carbonyl group beta to the carboxyl group
• This type of carboxylic acid undergoes
decarboxylation on mild heating.
O O O
warm
β α OH + CO2
3-Oxobutanoic acid Acetone
(Acetoacetic acid)

17-44
Decarboxylation
• Thermal decarboxylation of a β-ketoacid involves
rearrangement of six electrons in a cyclic six-
membered transition state.
H H
O O O O
O
(1) + (2)
C + CO2
O
O

(A cyclic six-membered Enol of A ketone

transition state) a ketone

• Only one of the carboxyl groups in oxalosuccinic acid,

an intermediate in the TCA cycle, has a carbonyl group
beta to it. HO O
O O
only this carboxyl O
has a C=O beta to it. O α OH + CO2
β OH
HO O HO O
Oxalosuccinic acid α-Ketoglutaric acid 17-45
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 O
140-150°C
HOCCH2 COH CH3 COH + CO2
Propanedioic acid
(M alonic acid)

17-46
Decarboxylation
• Thermal decarboxylation of malonic acids also
involves rearrangement of six electrons in a cyclic six-
membered transition state.
H H
O O O O O
(1) (2)
+ C + CO2
HO O HO HO
O
A cyclic six-membered Enol of a A carboxylic
transition state carboxylic acid acid

17-47
Example 17.6

17-48
Carboxylic
Acids

End Chapter 17
17-49