Ch13 Carb. Acids

WILLIAM H.
BROWN
THOMAS POON
www.wiley.com/college/brown
CHAPTER THIRTEEN
Carboxylic Acids
Copyright © 2014 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. © 2014 John Wiley & Sons, Inc. All rights reserved.
13-2
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-.
© 2014 John Wiley & Sons, Inc. All rights reserved. 13-3
Nomenclature
• The carboxyl group takes precedence over

most other functional groups.
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 the
chain.
Nomenclature
– If the carboxyl group is bonded to a ring,
name the ring compound and add the suffix
-carboxylic acid.
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
etc. are often used to locate
substituents.
– In common nomenclature, keto indicates the

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

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

acids are associated by hydrogen bonding
into dimeric structures.
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 are alcohols, ethers, aldehydes, and
ketones of 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.
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.
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.
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
separation of
benzoic acid from
benzyl alcohol.
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.
– 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 alkene in the presence
of a COOH group.
– we can use NaBH4 to reduce an aldehyde or ketone

in the presence of a COOH group.
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 ROH to the C=O group.
H
O O O
H+ H+
R C OH + HOCH3 R C OCH3 R C OCH3 + HOH
O
H
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.
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.
– b-ketoacids undergo decarboxylation on mild heating.
Decarboxylation
– Thermal decarboxylation of a -ketoacid
involves rearrangement of six electrons in a
cyclic six-membered transition state.
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 b-ketoacid that undergoes

decarboxylation to give this ketone.
Carboxylic Acids
End Chapter 13

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WILLIAM H.

• The functional group of a carboxylic acid is

– The general formula of an aliphatic carboxylic

• IUPAC names: drop the -e from the parent

• The carboxyl group takes precedence over

– In common nomenclature, keto indicates the

– How many cis-trans isomers are possible for this

• In the liquid and solid states, carboxylic

• Carboxylic acids have significantly higher

– The greater acidity of carboxylic acids relative to

• Electron-withdrawing substituents near the

• They also form water-soluble salts with ammonia

• Carboxylic acids react with sodium

– we can use NaBH4 to reduce an aldehyde or ketone

Fischer esterification is an equilibrium reaction. By careful

• The functional group of an acid halide is a

• Acid chlorides are most often prepared by

– Most, however, are quite resistant to decarboxylation.

– Problem: Draw the b-ketoacid that undergoes

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