Organic Chemistry, 7th Edition

L. G. Wade, Jr.

Chapter 21
Part 1: Structure and Properties of
Carboxylic Acid Derivatives

Copyright © 2010 Pearson Education, Inc.

 Acid Derivatives

 All the derivatives can be converted to the

carboxylic acid by acidic or basic hydrolysis.
 Esters and amides are commonly found in
nature.
Chapter 21 2
 Esters from Carboxylic Acids

 Esters can be made from the carboxylic acid

through the Fischer esterification.
 Excess alcohol is used to drive the equilibrium
toward the ester.
Chapter 21 3
 Nomenclature of Esters

 Esters are named as alkyl carboxylates.

 The first word is derived from the alkyl group
of the alcohol, and the second word from the
carboxylate group of the carboxylic acid.
Chapter 21 4
 Cyclic Esters

 Reaction of —OH and —COOH on same molecule

produces a cyclic ester called lactone.
 To name, add the word lactone to the IUPAC acid
name or replace the -ic acid of common name with
-olactone.

Chapter 21 5
 Amide Structure

 Amides are the product of the reaction of a carboxylic

acid with ammonia or an amine.
 Not basic because the lone pair on nitrogen is
delocalized by resonance.
 The C—N bond has double-bond character.
Chapter 21 6
 Protonation of Amides

 Under acidic conditions, the double-bonded

oxygen will get protonated.

Chapter 21 7
 Classes of Amides

3º amide 2º amide 1º amide

 1 amide has one C—N bond (two N—H).

 2 amide or N-substituted amide has two C—N bonds
(one N—H).
 3 amide or N,N-disubstituted amide has three C—N
bonds (no N—H).
Chapter 21 8
 Nomenclature of Amides
O CH3
N-ethyl-N-methyl-2-dimethylpropanamide
CH3CHC N CH2CH3 (N-ethyl-N-methylisobutyramide)
CH3

 For 1 amide, drop -ic or -oic acid from the

carboxylic acid name, add -amide.
 Alkyl groups bonded to nitrogen are named
with N-alkyl to indicate their attachment to the
nitrogen atom. Chapter 21 9
 Cyclic Amides

 Cyclic amides are called lactams.

 To name, add the word lactam to the IUPAC
acid name or replace the -ic acid of common
name with -olactam.
Chapter 21 10
 Nitriles

 Nitriles contain the cyano group (—CN).

 They can be hydrolyzed to carboxylic acids.

Chapter 21 11
 Structures of Acetonitrile and
Propyne

 In both compounds, the atoms at the ends of the triple bonds

are sp hybridized, and the bond angles are 180°.
 In place of the acetylenic hydrogen atom, the nitrile has a lone
pair of electrons in the sp orbital of nitrogen.
 The nonbonding electrons on the nitrogen are not basic.
Chapter 21 12
 Naming Nitriles

 For IUPAC names, add -nitrile to the alkane name.

 The Ethyl Octanoate group can also be named as a
substituent, the cyano group.
 Common names come from the carboxylic acid.
Replace -ic acid with -onitrile.
Chapter 21 13
 Acid Halides

 Also called acyl halides.

 These are more reactive than carboxylic acids, so
they are used to synthesize other acid derivatives
such as esters and amides.
 Used in the Friedel–Crafts acylation to make
acylbenzenes.
Chapter 21 14
 Acid Halide Nomenclature

 Named by replacing -ic acid with -yl halide.

 Acyl chlorides are more common.
Chapter 21 15
 Acid Anhydrides

 Two molecules of acid combine with the loss of water

to form the anhydride.
 Anhydrides are more reactive than acids, but less
reactive than acid chlorides.
 A carboxylate ion is the leaving group in nucleophilic
acyl substitution reactions.

Chapter 21 16
 Anhydride Nomenclature

 The word acid is replaced with anhydride.

 For a mixed anhydride, name both acids.

Chapter 21 17
 Multifunctional Compounds
 The functional group with the highest priority
determines the parent name.

acid > ester > amide > nitrile > aldehyde > ketone >
alcohol > amine > alkene > alkyne
Chapter 21 18
Name the following compounds:

Chapter 21 19
Chapter 21 20
Chapter 21 23
Boiling Points of Carboxylic Acid Derivatives

Chapter 21 24
 Intermolecular Forces of Amides

The resonance picture of an amide shows its strongly polar nature.

Hydrogen bonds and dipolar attractions stabilize the liquid phase, resulting
in higher boiling points.

Chapter 21 25
 Melting Points

 Amides have very high boiling points and melting

points compared to other compounds of similar
weight.
 Melting points increase with increasing number of
N—H bonds.
 Tertiary amides cannot hydrogen bond, but still have
high boiling points.
Chapter 21 26
 Solubility
 Acid chlorides and anhydrides are too
reactive to be used with water or alcohol.
 Esters, 3 amides, and nitriles are good
polar aprotic solvents.
 Solvents commonly used in organic
reactions:
 Ethyl acetate
 Dimethylformamide (DMF)
 Acetonitrile
Chapter 21 27
Common Solvents

Chapter 21 28
• Esters, tertiary amides, and nitriles provide a polar reaction
medium without or groups that can donate protons or act as
nucleophiles.

• Ethyl acetate is a moderately polar solvent with a boiling point

of 77 °C, convenient for easy evaporation from a reaction
mixture.

• Acetonitrile, dimethylformamide (DMF), and

dimethylacetamide (DMA) are highly polar solvents that
solvate ions almost as well as water, but without the reactivity
of O-H or N-H groups.

Chapter 21 29
IR Spectroscopy

Chapter 21 30
IR Spectrum of Ethyl Octanoate

Chapter 21 31
IR Frequencies of Lactones and
Lactams

• Ring strain in lactones and lactams increases

the carbonyl stretching frequency.
Chapter 21 32
IR Spectrum of Propionic
Anhydride

Chapter 21 33
 1
Typical H–NMR Absorptions

Chapter 21 34
NMR Spectra of DMF

Chapter 21 35
 13C–NMR Spectroscopy

 The carbonyl carbons of acid derivatives appear at

shifts around 170 to 180 ppm, slightly more shielded
than the carbonyl carbons of ketones and aldehydes.
 The a-carbon atoms absorb around 30 to 40 ppm.
Chapter 21 36