Chapter 20

Carboxylic Acids and Nitriles

Contents
(20.1) Naming carboxylic acids and nitriles
(20.2) Structure and properties of carboxylic acids
(20.4) Substituent effects on acidity
(20.5) Preparing carboxylic acids
(20.6) Reactions of carboxylic acids: An overview
(20.7) Chemistry of nitriles

Carboxylic Acids (RCO2H)

▪ Abundant in nature from oxidation of aldehydes and alcohols in metabolism
▪ Acetic acid, CH3CO2H
▪ Butanoic acid, CH3CH2CH2CO2H
▪ Long-chain aliphatic acids
▪ Starting materials for acyl derivatives

20-1: Naming Carboxylic Acids and Nitriles

▪ Carboxylic Acids, RCO2H
▪ Derived from open-chain alkanes, the terminal -e of the alkane is replaced with -oic
acid
▪ The carboxyl carbon atom becomes C1

▪ Compounds with –CO2H bonded to a ring are named using the suffix –carboxylic acid
▪ The CO2H carbon is not numbered in this system
▪ As a substituent, the CO2H group is called a carboxyl group

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1
Common Names of Some Carboxylic Acids and Acyl Groups

▪ Nitriles, RC≡N
▪ Compounds containing the –C≡N functional group
▪ Simple open chain nitriles are named by adding nitrile as a suffix to the alkane name
▪ Nitrile carbon numbered C1
▪ Also named as derivatives of carboxylic acids
▪ Replacing the -ic acid or -oic acid
ending with –onitrile
▪ Replacing the –carboxylic acid
ending with -carbonitrile
'

Problem 20-2 ¥9
Draw structures corresponding to the following IUPAC names:
(a) 2,3-Dimethylhexanoic acid
(b) 4-Methylpentanoic acid
(c) trans-1,2-Cyclobutanedicarboxylic acid
e)
(d) o-Hydroxybenzoic acid
Ho
(e) (9Z,12Z)-9,12-Octadecadienoic acid - -

(f) 2-Pentenenitrile It! 2

3 a 5 6 7 89 to 1119 15 16 12 18

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20-2: Structure and Properties of Carboxylic Acids
▪ Carboxyl carbon sp2 hybridized
▪ Groups are planar with C–C=O and O=C–O bond angles of approximately 120°
▪ Forms hydrogen bonds, existing as cyclic dimers held together by two hydrogen bonds
▪ Causes higher boiling points than the corresponding alcohols

→ 118°C

fgrc
Dissociation of Carboxylic Acids
▪ Carboxylic acids are proton donors toward weak and strong bases
▪ Produces metal carboxylate salts, RCO2– M+
▪ Carboxylic acids with more than six carbons are slightly soluble in water
▪ Conjugate base salts are water-soluble

Acidity Constant and pKa

▪ Carboxylic acids transfer a proton to water to give H3O+ and carboxylate anions, RCO2−
▪ Acidity constant, Ka, is about 10-4 to 10-5 for a typical carboxylic acid
▪ Gives the extent of acidity dissociation

[RCO 2 - ][H3O + ]
Ka = and pK a = - log K a
[RCO2 H]

3
 ▪ Carboxylic acids are more acidic than alcohols and phenols

▪ Carboxylic acid dissociate to give carboxylate ion

▪ Carboxylic ion is a stabilized resonance hybrid of two equivalent structures

Inductive
20-4: Substituent Effects on Acidity
▪ Factors that stabilize the carboxylate anion relative
effect
to the undissociated carboxylic acid will drive the
equilibrium toward increased dissociation and result
in increased acidity

▪ Inductive effects operate through σ bonds and are dependent on distance

▪ Substituent moves farther from the carboxyl causing the effect of halogen substitution
to decrease

Aromatic Substituent Effects

▪ An electron-withdrawing group increases acidity
by stabilizing the carboxylate anion
▪ Electron-donating group decreases
acidity by destabilizing the carboxylate
anion
▪ By finding the acidity of the corresponding benzoic acid reactivity can be predicted

4
Problem 20-6
Which would you expect to be a stronger acid, the lactic acid found in tired muscle or acetic acid?
Explain.
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Lactic acid jÉ a-
hydroxy
acid ?

stronger to
( inductive
gut )

Problem 20-8 ← 4.19 stronger

0
The pKa of p-cyclopropylbenzoic acid is 4.45. Is cyclopropylbenzene likely to be more reactive or less
reactive than benzene toward electrophilic bromination? Explain.

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Problem 20-9
Rank the following compounds in order of increasing acidity.
@ ③ ①
(a) Benzoic acid, p-methylbenzoic acid, p-chlorobenzoic acid
(b) p-Nitrobenzoic acid, acetic acid, benzoic acid

① ① ②

5
20-5: Preparing Carboxylic Acids
▪ Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic
acid
▪ 1°and 2°alkyl groups can be oxidized
▪ Tertiary groups cannot

Problem 16-18
What aromatic products would you obtain from the KMnO4 oxidation of the following substances?
a) b)
0
t t stable
Coo

d
KOOC

▪ Oxidation of a primary alcohol or an aldehyde yields a carboxylic acid

▪ 1°alcohols and aldehydes are often oxidized with CrO3

▪ Hydrolysis of nitriles
▪ Nitriles on heating with acid or base yields carboxylic acids
▪ Conversion of an alkyl halide to a nitrile followed by hydrolysis produces a carboxylic acid
with one more carbon (RBr → RC≡N → RCO2H)

6
 ▪ Carboxylation of Grignard Reagents
▪ Grignard reagents react with dry CO2 to yield a metal carboxylate
▪ The organomagnesium halide adds to C=O of carbon dioxide
▪ Protonation by addition of aqueous HCl in a separate step gives the free carboxylic
acid

Worked Example 20-2, problem 20-10

① %%+f ②
→
Hyo
-1

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How would you prepare the following carboxylic acids?
ekes
tÉÉ a) PhCH2COOH from PhCH2Br - ① Mg
-
,

(b) PhCOOH from PhBr game poor

②

(
It Ot
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c) PhCOOH from PhMe kmnoq , Hzoy to
d) PhCH2COOH from PhCH2CH2OH
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20-6: Reactions of Carboxylic Acids: An Overview
▪ Carboxylic acids transfer a proton to a base to give anions, which are good nucleophiles in
SN2 reactions
▪ Undergo addition of nucleophiles to the carbonyl group
▪ Undergo other reactions characteristic of neither alcohols nor ketones

1) LiAlH4
2) H3O+

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① NY
,

ether
a. ② Cor , Chapter 22
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Chapter 21

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Problem 20-11
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How might you prepare 2-phenylethanol from benzyl bromide? More than one step is needed.

ar
① %
@ ,
it

③ liAlHz
Problem 20-12
How might you carry out the following transformation? More than one step is needed.

8
20-7: Chemistry of Nitriles
▪ Has a carbon atom with three bonds to an
electronegative atom, and contain a bond
▪ Are electrophiles and undergo nucleophilic
addition reactions
▪ Rare occurrence in living organisms

Preparation of Nitriles oxhioa amide

▪ SN2 reaction of –CN with 1°or 2°alkyl halide
▪ Also prepared by dehydration of primary amides RCONH2 → nitrile

▪ Nucleophilic amide oxygen atom attacks SOCl2 followed by deprotonation and elimination

Problem 20-22
Predict the products and provide the mechanism for each reaction below.
(a) (b)

9
Reaction of nitriles
▪ Strongly polarized and has an electrophilic carbon atom
▪ Attacked by nucleophiles to yield sp2-hybridized imine anions

▪ Hydrolysis - Conversion of nitriles into carboxylic acids

▪ Nitriles are hydrolyzed with acid or base catalysis to a carboxylic acid and ammonia

10
▪ Reduction - Conversion of nitriles into amines
▪ Reduction of a nitrile with LiAlH4 gives a primary amine
▪ Nucleophilic addition of hydride ion to the polar C N bond, yields an imine anion
▪ The C=N bond undergoes a second nucleophilic addition of hydride to give a dianion,
which is protonated by water

▪ Reaction of nitriles with Grignard reagents

▪ Add to give an intermediate imine anion that is hydrolyzed by addition of water to
yield a ketone

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 Worked Example 20-3, problem 20-13

0
How would you prepare the following compounds from a nitrile? Provide the mechanism for each
reaction.
(a) (b) better
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-
,

① It

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cHgUhMgBr ①
@ 110
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g. ,
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→
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or
~ Mgbr+ CH > are
~c-=W
prÑg€ TÉ
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Problem 20-14 +α
How would you prepare the following compounds? Provide the mechanism for each reaction.

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(a) + -

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13
From entrance examination, Exercises 20-30
Provide the mechanism for each reaction. (Ritter reaction)
a)

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④
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-

→ An c- me

b)

14