Chapter 20:

Carboxylic Acids and Nitriles

The Importance of Carboxylic Acids
(RCO2H)

 Readily available in nature;

◦ Acetic acid, CH3CO2H, - vinegar
◦ Long-chain aliphatic acids from the breakdown of
vegetable oils and fats

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The Importance of Carboxylic Acids
(RCO2H)
 They are the starting materials for other acyl
derivatives;
 20.1 Naming Carboxylic Acids & Nitriles
 Carboxylic Acids, RCO2H
 If derived from open-chain alkanes, replace the terminal -e
of the alkane name with -oic acid
 The carboxyl carbon atom is C #1

Propanoic acid 4-Methylpentanoic acid 3-Ethyl-6-methyloctanedioic acid

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 Alternative Names
 Compounds with ⎯CO2H bonded to a ring are named
using the suffix -carboxylic acid
 The CO2H carbon is not itself numbered in this system

trans-4-Hydroxycyclohexanecarboxylic acid 1-cyclopentenecarboxylic acid

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  Some common or trivial names
Common Names: are also used for carboxylic acids.

Names
accepted
by IUPAC
 Nitriles, RCN
 Named by adding -nitrile as a suffix to the alkane name;
 nitrile carbon numbered C #1.

4-Methylpentanenitrile

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 Nitriles, RCN
 Complex nitriles are named as derivatives of carboxylic
acids.
◦ Replace -ic acid or -oic acid ending with -onitrile

Acetonitrile
(From acetic acid) Benzonitrile
(From benzoic acid)

2,2-Dimethylcyclohexanecarbonitrile
(From 2,2-dimethylcyclohexanecarboxylic acid)

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 20.2 Structure & Properties:
 Carboxylic acids form hydrogen bonds,
 exist as cyclic dimers held together by 2 hydrogen bonds

 Strong hydrogen bonding causes much higher boiling points

than the corresponding alcohols
1-Propanal 1-Propanol Ethanoic Acid (Acetic acid)
(MW = 58) (MW = 60) MW = 60
O O
CH3CH2C H CH3CH2CH2-OH
CH3C OH
Boiling
Point 49oC 97oC 118oC
 Reaction with bases
 Carboxylic acids react with bases to produce metal
carboxylate salts, RCO2− +M.

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 Acidity Constant and pKa

 The acidity constant, Ka,, is about 10-5 for a typical

carboxylic acid (pKa ~ 5); a weak acid.
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 Substituent Effects on Acidity
Electron withdrawing (electronegative) substituents (like F, Cl, Br, I) promote
formation of the carboxylate ion so raise the Ka (lower the pKa)

CH3OH 15.5
H2O 15.7

CH3CH2OH 15.9
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 Resonance Effects on Acidity

Phenols
Carboxylic acid
Alcohols
Inorganic acids

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Resonance Effects on Acidity

Alcohols are weaker acids since O- is not stabilized by resonance.

C=O Bond length
(120 pm)
Negative charge spread over O-C-O
C-O Bond length
(134 pm) C-O Bond
lengths same
(127 pm)

Carboxylic acids are more acidic since O- is stabilized by resonance.

 20.4 Substituent Effects on Acidity

Electron withdrawing (electronegative) substituents (like F, Cl, Br, I) promote

formation of the carboxylate ion so raise the Ka (lower the pKa).
They stabilize the carboxylate anion by induction.

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 Aromatic Substituent Effects

electron-donating
(activating) group (like OCH3)
decreases acidity by
destabilizing the
carboxylate anion
electron-withdrawing
(deactivating) groups (like -
NO2)increase acidity by
stabilizing the
carboxylate anion
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Aromatic Substituent Effects

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 Learning Check:
Rank the following in order of increasing acidity:
(#1 is least acidic) (Don’t look at a table of pKa data to help you.)
A. O O O O
C C C C
OH OH OH OH

H3C Cl HO

B. O O O
C C C
OH OH CH3 OH

O2N
 Solution:
Rank the following in order of increasing acidity:
(#1 is least acidic) (Don’t look at a table of pKa data to help you.)
A. O O O O
C C C C
OH OH OH OH

H3C Cl HO
3 2 4 1

B. O O O
C C C
OH OH CH3 OH

O2N

2 3 1
20.5 Preparation of Carboxylic Acids:
From Oxidation of Benzylic Carbons
 Oxidation of a substituted alkylbenzene with KMnO4 or
Na2Cr2O7 gives a substituted benzoic acid

 1° and 2° alkyl groups can be oxidized, but 3° are not

1o O
CH2CH3 C OH
KMnO4
H3C H3C
H3C
C CH CH3 C C OH
CH3 CH3 2o H3C
3o CH3 O
3o
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 From Oxidative Cleavage of Alkenes
 Oxidative cleavage of an alkene with KMnO4 gives a
carboxylic acid if the alkene has at least one vinylic hydrogen

CH3CH2 H KMnO4 CH3CH2 OH

C C C O + O C
CH3 CH3 H3O+ CH3 CH3

CH3CH2 H KMnO4 CH3CH2 OH

C C C O + O C
H H H3O+ HO OH

CO2
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From Oxidation of 1o Alcohols & Aldehydes
 Oxidation of a 1o alcohols or aldehydes with CrO3 in
aqueous acid

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Hydrolysis of Nitriles

 Hot acid or base yields carboxylic acids

+
O
H3O
CH3 CH2 CH2 C N CH3 CH2 CH2 C OH
or
1) NaOH
2) H3O+

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Halides → Nitriles → Carboxylic Acids
 Conversion of an alkyl halide to a nitrile (by an SN2 with
cyanide ion) followed by hydrolysis produces a carboxylic
acid with one more carbon (RBr → RCN → RCO2H)

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 Carboxylation of Grignard Reagents
 Grignard reagents react with dry CO2 to yield a metal
carboxylate

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 Halides → Nitriles → Carboxylic Acids

Halides → Grignard → Carboxylic Acids

20.6 Reactions of Carboxylic Acids:
An Overview

NaOH 1) LiAlH4
2) H3O+

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 20.7 Chemistry of Nitriles
 C’s of nitriles and carboxylic acids are electrophilic.

d-

d+ d- d+

d- d+

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Preparation of Nitriles:
Dehydration of Amides
 Reaction of primary amides RCONH2 with SOCl2 or
POCl3 (or other dehydrating agents).

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Mechanism:
Dehydration of Amides
 Nucleophilic amide oxygen atom attacks SOCl2 followed
by deprotonation and elimination

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 Reactions of Nitriles
 RCN is strongly polarized;
 Attacked by nucleophiles to yield sp2-hybridized imine anions

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Hydrolysis: Nitriles → Carboxylic Acids

 Hydrolyzed in with acid or base catalysis to a carboxylic

acid and ammonia or an amine

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Mechanism:
Hydrolysis of Nitriles

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Mechanism:
Step 4: Hydrolysis of Amides
Reduction: Nitriles → 1o Amines
◦Reduction of a nitrile with LiAlH4 gives a primary amine

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Reaction of Nitriles with Organometallic
Reagents
 Grignard reagents add to give an intermediate imine anion
that is hydrolyzed by addition of water to yield a ketone

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Reactions of Nitriles: Overview
Learning Check:
Prepare 2-methyl-3-pentanone from a nitrile.
Solution:
Prepare 2-methyl-3-pentanone from a nitrile.
A couple of possibilities:

THE END