Chapter 20:

Carboxylic Acids

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Class I carbonyl are known as Carboxylic
Acids and Carboxylic acid Derivatives. Their
reactions follow the same pattern and it is
easy to go from one structure to the next
within the class itself by Nucleophilic Acyl
Substitution.
cannot be replaced by a nucleophile

O O

R H R R
aldehyde ketone
Class II

compounds with groups that can be replaced by a nucleophile

O O O O O O

R OH R OR R O R R X R NH2
carboxylic ester anhydride acyl halides amides
acid Class I
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• Physical Properties (20-
(20-3)

Boiling point of carbonyl usually follow this trend:

Amide > acid > nitrile >> ester > acid chloride > aldehyde >
ketone

The high boiling points of amide, acid and nitrile is

due to strong dipole interactions that exist in all
three types.

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Acidity: pKa of carboxylic acid is about 5.
They can therefore be easily deprotonated
forming the carboxylate anion.

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The acidity of carboxylic acids can be
influenced by the nature of the substituent
bonded to the carboxyl group:

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 Synthesis of Carboxylic Acids
(Review)

• Oxidation

Other reagents such as KMnO4, HNO3 etc… will also oxidize a 1o

alcohol to the corresponding carboxylic acid.

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• Oxidative cleavage
Alkenes and Alkynes can give carboxylic
acid by oxidative cleavage: either with
ozone or KMnO4.

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• Oxidation of alkyl benzene
Also provides carboxylic acids as the
product. Must have at least one benzylic
hydrogen.

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 New Synthesis of Carboxylic Acids

• Carboxylation of Grignard Reagents (20-8)

Grignard reagents react with CO2 like they do
with any other carbonyl compound. Once
protonated, the product is a carboxylic acid.

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• Hydrolysis of Nitriles (20-8)
Nitriles can be hydrolyzed to the corresponding
carboxylic acid, either under acidic or basic
conditions. (mechanisms will be discussed in
Chapter 21) We have seen that they can easily
formed by SN2 reactions with primary halides.

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Practice Questions

Complete the following reactions.

1) KMnO4
2) H3O+

CN H3O+

heat

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Provide a detailed stepwise mechanism
for the last reaction from the previous
slide.

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 Reactions of Carboxylic Acids
(Review)
• Alkylation of Acids to form Ketones (20-14)

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• Reduction of Acids to Primary Alcohols (20-13)

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Nucleophilic Acyl Substitution (20-9)
Most reactions of carboxylic acids
are classified as “acyl substitutions”
and usually produce acid derivatives.

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The hydrolysis of an ester under basic
conditions is a good example of acyl
substitution.

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The Fisher Esterification (20-10)
Reaction of a carboxylic acid with an alcohol under
acidic conditions produces an ester.
Reaction is an equilibrium, the yield of ester is not
high.
To drive the equilibrium to the formations of
products use a large excess of alcohol.

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Mechanism of Fisher Esterification

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Esterification Using Diazomethane (20-11)
One of the best way to make methyl
ester is to react the corresponding
carboxylic acid with Diazomethane. The
reaction is quantitative and very
easy…but diazomethane has a tendency
to explode….

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Mechanism of Diazomethane Esterification

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Condensation of acids with amines (20-12)
The reaction of carboxylic acids with
amines is a simple acid/base reaction
forming an ammonium salt. However,
under more extreme conditions, when
heat is applied it is possible to eliminate
water from this salt and form amide.

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Synthesis and Use of Acid Chlorides (20-15)
Acid chlorides are the most versatile acid
derivatives because they can be
transformed into all other acid derivatives
by acyl substitution. This is due to the
presence of a good leaving group, chloride
ion.

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The best reagent for converting carboxylic acids
to acid chlorides are thionyl chloride (SOCl2)
and oxalyl chloride (COCl2) because they form
gaseous by-products that do not contaminate
the product.

Thionyl chloride reaction produces SO2 while
the oxalyl chloride reaction produces HCl, CO,
and CO2 (all gaseous).

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Mechanism of Acid Chloride Formation

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As mentioned before, reactions of acid
chlorides lead to acid derivatives such as
esters, amide and others.

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