CH 13

9/18/2018
WILLIAM H. BROWN
THOMAS POON
www.wiley.com/college/brown
CHAPTER THIRTEEN
Carboxylic
Acids
Copyright © 2017 John Wiley & Sons, Inc. All rights reserved.
13-1
Structure
• The functional group of a carboxylic acid is a

carboxyl group.
– The general formula of an aliphatic carboxylic

acid is RCOOH.
– That of an aromatic carboxylic acid is ArCOOH.
Copyright © 2017 John Wiley & Sons, Inc. All rights reserved. 13-2
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Nomenclature
• IUPAC names: drop the -e from the parent

alkane and add the suffix -oic acid.
– If the compound contains a carbon-carbon
double bond, change the infix -an- to -en-.
Nomenclature
• The carboxyl group takes precedence over

most other functional groups.
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Nomenclature
– Dicarboxylic acids: add -dioic acid to the name of the
parent alkane containing both carboxyl groups.
– There is no need to use numbers to locate the carboxyl
groups; they can only be on the ends of a chain.
Nomenclature
– If the carboxyl group is bonded to a ring, name

the ring compound and add the suffix -carboxylic
acid.
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Nomenclature
– Benzoic acid is the simplest aromatic carboxylic

acid.
– Use numbers to show the location of
substituents.
Nomenclature
– When common names are used, the letters α, β, γ etc.
are often used to locate substituents.
– In common nomenclature, keto indicates the presence of

a ketone, and a CH3CO— group is named an aceto
group.
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Nomenclature
– Problem: In omega-3 fatty acids, the last carbon

of the last double bond of a hydrocarbon chain
ends three carbons from the methyl terminal of
the chain. The last carbon of the chain is called
the omega carbon, hence the designation
omega-3. Eicosapentaenoic acid is a common
polyunsaturated fatty acid found in cold water
fatty fish and health food supplements.
– How many cis-trans isomers are possible for this

polyunsaturated fatty acid?
Physical Properties
• In the liquid and solid states, carboxylic acids

are associated by hydrogen bonding into
dimeric structures.
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Physical Properties
• Carboxylic acids have significantly higher

boiling points than other types of organic
compounds with comparable molecular
weight.
– They are polar compounds and form very strong
intermolecular hydrogen bonds.
• Carboxylic acids are more soluble in water
than are alcohols, ethers, aldehydes, and
ketones with comparable molecular weight.
– They form hydrogen bonds with water molecules
through their C=O and OH groups.
Physical Properties
– Water solubility decreases as the relative size of

the hydrophobic portion of the molecule
increases.
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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 of which contain an OH group, is
due to resonance stabilization of the carboxylate
anion.
Acidity
• Electron-withdrawing substituents near the

carboxyl group increase acidity through their
inductive effect.
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Acidity
– The acid-strengthening effect of a halogen

substituent falls off rapidly with increasing
distance from the carboxyl group.
Reaction with Bases
• Carboxylic acids, whether soluble or insoluble in

water, react with NaOH, KOH, and other strong
bases to give water-soluble salts.
• They also form water-soluble salts with ammonia

and amines.
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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.
Reaction with Bases
• Figure 13.1
Flowchart for the
separation of
benzoic acid from
benzyl alcohol.
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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 alkenes and alkynes to alkanes.
– Carboxyl groups are not 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 solvents.
Selective Reduction
• Catalytic hydrogenation does not reduce a COOH

group.
– We can use H2/M to reduce an C=C in the presence of a
COOH group.
– We can use NaBH4 to reduce an aldehyde or ketone in

the presence of a COOH group.
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Fischer Esterification
• Esters can be prepared by treating a carboxylic acid with
an alcohol in the presence of an acid catalyst, commonly
H2SO4 or gaseous HCl.
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.
Fischer Esterification
– A key intermediate in Fischer esterification is a

tetrahedral carbonyl addition intermediate formed
by addition of an alcohol to the C=O group.
H
O + O + O
H H
R C OH + HOCH3 R C OCH3 R C OCH3 + HOH
O
H
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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.
Acid Chlorides
• Acid chlorides are most often prepared by

treating a carboxylic acid with thionyl chloride.
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Decarboxylation
• Decarboxylation: loss of CO2 from a carboxyl group.
– Most carboxylic acids, if heated to a very high temperature, undergo
thermal decarboxylation.
– Most, however, are quite resistant to decarboxylation.

– Exceptions are carboxylic acids that have a carbonyl group beta to
the carboxyl group.
– -ketoacids undergo decarboxylation on mild heating.
Decarboxylation
– Thermal decarboxylation of a β-ketoacid involves

rearrangement of six electrons in a cyclic six-
membered transition state.
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Decarboxylation
– Thermal decarboxylation of malonic acids also

involves rearrangement of six electrons in a
cyclic six-membered transition state.
Decarboxylation
– Problem: Draw the product of decarboxylation.
– Problem: Draw the -ketoacid that undergoes

decarboxylation to give this ketone.
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Carboxylic Acids
End Chapter 13
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9/18/2018

• The functional group of a carboxylic acid is a

– The general formula of an aliphatic carboxylic

• IUPAC names: drop the -e from the parent

• The carboxyl group takes precedence over

– If the carboxyl group is bonded to a ring, name

– Benzoic acid is the simplest aromatic carboxylic

– In common nomenclature, keto indicates the presence of

– Problem: In omega-3 fatty acids, the last carbon

– How many cis-trans isomers are possible for this

• In the liquid and solid states, carboxylic acids

• Carboxylic acids have significantly higher

– Water solubility decreases as the relative size of

• Carboxylic acids are weak acids.

– The greater acidity of carboxylic acids relative to

• Electron-withdrawing substituents near the

– The acid-strengthening effect of a halogen

Reaction with Bases

• Carboxylic acids, whether soluble or insoluble in

• They also form water-soluble salts with ammonia

Reaction with Bases

• Carboxylic acids react with sodium

Reaction with Bases

• The carboxyl group is very resistant to reduction.

• Catalytic hydrogenation does not reduce a COOH

– We can use NaBH4 to reduce an aldehyde or ketone in

Fischer esterification is an equilibrium reaction. By careful

– A key intermediate in Fischer esterification is a

• The functional group of an acid halide is a

• Acid chlorides are most often prepared by

– Most, however, are quite resistant to decarboxylation.

– Thermal decarboxylation of a β-ketoacid involves

– Thermal decarboxylation of malonic acids also

– Problem: Draw the product of decarboxylation.

– Problem: Draw the -ketoacid that undergoes

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