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WILLIAM H.

BROWN
THOMAS POON
www.wiley.com/college/brown

CHAPTER THIRTEEN

Carboxylic Acids

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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.
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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-.

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13-3

Nomenclature

The carboxyl group takes precedence over


most other functional groups.

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13-4

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.

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13-5

Nomenclature
If the carboxyl group is bonded to a ring, name
the ring compound and add the suffix -carboxylic
acid.

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13-6

Nomenclature
Benzoic acid is the simplest aromatic carboxylic
acid.
Use numbers to show the location of
substituents.

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13-7

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.

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13-8

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?
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13-9

Physical Properties

In the liquid and solid states, carboxylic acids


are associated by hydrogen bonding into
dimeric structures.

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13-10

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.
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13-11

Physical Properties
Water solubility decreases as the relative size of
the hydrophobic portion of the molecule
increases.

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13-12

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.
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13-13

Acidity

Electron-withdrawing substituents near the


carboxyl group increase acidity through their
inductive effect.

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13-14

Acidity
The acid-strengthening effect of a halogen
substituent falls off rapidly with increasing
distance from the carboxyl group.

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13-15

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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13-16

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.

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13-17

Reaction with Bases

Figure 13.1
Flowchart for
separation of
benzoic acid from
benzyl alcohol.

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13-18

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.

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13-19

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.

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13-20

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.
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13-21

Fischer Esterification
A key intermediate in Fischer esterification is a
tetrahedral carbonyl addition intermediate formed
by addition of ROH to the C=O group.
O
R C OH + HOCH3

H+

O
R C OCH3
O
H

H+

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O
R C OCH3 + HOH

13-22

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.

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13-23

Acid Chlorides

Acid chlorides are most often prepared by


treating a carboxylic acid with thionyl
chloride.

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13-24

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.

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13-25

Decarboxylation
Thermal decarboxylation of a -ketoacid
involves rearrangement of six electrons in a
cyclic six-membered transition state.

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13-26

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

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13-27

Decarboxylation
Problem: Draw the product of decarboxylation.

Problem: Draw the -ketoacid that undergoes


decarboxylation to give this ketone.

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13-28

Carboxylic Acids

End Chapter
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