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BROWN
THOMAS POON
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CHAPTER THIRTEEN
Carboxylic Acids
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13-1
Structure
13-2
Nomenclature
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13-3
Nomenclature
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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.
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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.
13-9
Physical Properties
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13-10
Physical Properties
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.
13-13
Acidity
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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
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13-16
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13-17
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.
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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.
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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.
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
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13-23
Acid Chlorides
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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.
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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.
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13-28
Carboxylic Acids
End Chapter
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13
13-29