Chapter 14A Carboxylic Acids and

Esters
14.1
Carboxylic Acids

0
 Carboxylic Acids
A carboxylic acid
● Contains a carboxyl group, which is a carbonyl group
(C=O) attached to a hydroxyl group (—OH).
● Has the carboxyl group on carbon 1.
carbonyl group
O

CH3 — C—OH hydroxyl group or CH3COOH

carboxyl group

0
 Models of Carboxylic Acids
● The three-dimensional models show the geometry
of atoms in carboxylic acid molecules.

0
 IUPAC Names
The IUPAC names of carboxylic acids
● Replace the -e in the alkane name with -oic acid.
CH4 methane HCOOH methanoic acid
CH3—CH3 ethane CH3—COOH ethanoic acid
● Number substituents from the carboxyl carbon 1.
CH3 O
| ║
CH3—CH—CH2—C—OH
4 3 2 1

3-methylbutanoic acid

0
 Common Names

The common names of simple carboxylic acids

● Are formic acid (1C), acetic acid (2C), propionic acid
(3C), and butyric acid (4C).
HCOOH formic acid
CH3—COOH acetic acid
● Locate substituents using , , γ for the carbon
atoms adjacent to the carboxyl carbon.
CH3
γ |
CH3—CH—CH2—COOH
3-methylbutanoic acid ( -methylbutryic acid)
0
 Alpha Hydroxy Acids
Alpha hydroxy acids
(AHAs)
● Occur naturally in
fruit, milk, and
sugarcane.
● Are used in skin
care products.

0
Names and Sources of Some
Carboxylic Acids
TABLE 16.1

0
Common Carboxylic Acids

Methanoic acid (formic acid)

O
║
H─C─OH

ethanoic acid (acetic acid)

O
║
CH3─C─OH

0
 Aromatic Carboxylic Acids

Benzoic acid
● Is the aromatic carboxylic acid.
● Locates substituents by assigning 1 to the carbon
attached to the carboxyl group.
● Has common names that assign prefixes ortho,
meta, and para for 2 substituents.
ortho 1, 2 location
meta 1, 3 location
para 1, 4 location

0
Aromatic Carboxylic Acids

benzoic acid 3-chlorobenzoic acid 4-aminobenzoic acid

m-chlorobenzoic acid p-aminobenzoic acid

0
Learning Check

Give the IUPAC and common names:

A. CH3—COOH

CH3
|
B. CH3—CH—COOH

C.

0
Solution

A. CH3—COOH ethanoic acid (acetic acid)

CH3
|
B. CH3—CH—COOH 2-methylpropanoic acid
( -methylpropionic acid)

C. 2-bromobenzoic acid
(o-bromobenzoic acid)

0
Learning Check
Give the IUPAC and common names for the following:
A. CH3─CH2─COOH
CH3
|
B. CH3─CH─CH2─COOH
C.

0
Solution
A. CH3─CH2─COOH propanoic acid
(propionic acid)
CH3
|
B. CH3─CH─CH2─COOH 3-methylbutanoic acid
(β-methylbutyric acid)

C. 3-bromobenzoic acid
(m-bromobenzoic acid)

0
 Preparation of Carboxylic Acids
● Carboxylic acids can be prepared by oxidizing
primary alcohols or aldehydes.
● The oxidation of ethanol produces ethanoic acid
(acetic acid).

OH O O
| [O] || [O] ||
CH3—CH2 CH3—C—H CH3—C—OH

ethanol ethanal ethanoic acid

(ethyl alcohol) (acetaldehyde) (acetic acid)

0
Learning Check
What alcohol could be used to prepare the following:

1. butanoic acid

2. propanoic acid

0
Solution
What alcohol could be used to prepare the following:
[O] [O]
1. butanol butanal butanoic acid

[O] [O]
2. 1-propanol propanal propanoic acid

0
 14.2
Properties of Carboxylic Acids

0
 Polarity of Carboxylic Acids
Carboxylic acids
● Are strongly polar.
● Have two polar groups:
hydroxyl (−OH) and carbonyl (C=O).

δ-
O
║δ+ δ- δ+
CH3 C O H

0
 Boiling Points of Carboxylic Acids

The boiling points of carboxylic acids

● Are higher than alcohols, ketones, and aldehydes of
similar mass.

● Are high because they form dimers in which

hydrogen bonds form between the polar groups in the
two carboxyl groups.

O H—O
|| |
CH3—C C—CH3
| ||
O—H O
A dimer of acetic acid 0
Comparison of Boiling Points
Compound Molar Mass Boiling Point
O
║
CH3−CH2−C−H 58 49°C

CH3−CH2−CH2−OH 60 97°C

O
║
CH3−C−OH 60 118°C

0
 Solubility in Water
Carboxylic acids Water molecules
● Form hydrogen
bonds with many
water molecules.

● With 1-4 carbon

atoms are very
soluble in water.

0
Boiling Points and Solubility

TABLE 16.2

0
 Acidity of Carboxylic Acids
Carboxylic acids
● Are weak acids.
● Ionize in water to produce carboxylate ions
and hydronium ions.
O O
║ ║
CH3−C−OH + H2O CH3−C−O– + H3O+

0
 Neutralization of Carboxylic Acids
Carboxylic acid salts
● Are a product of the neutralization of a carboxylic acid
with a strong base.
CH3—COOH + NaOH CH3—COO– Na+ + H2O
acetic acid sodium acetate
(carboxylic acid salt)
● Are used as preservatives and flavor enhancers.

0
Learning Check

Write the equation for the reaction of propanoic acid with

A. water

B. KOH

0
Solution
Write the equation for the reaction of propanoic acid with
A. water
CH3—CH2—COOH + H2O CH3—CH2—COO– + H3O+

B. KOH
CH3—CH2—COOH + KOH CH3—CH2—COO– K+ +
H2O

0
14.3 Esters

0
 Esters
In an ester,
● The H in the carboxyl group is replaced
with an alkyl group.

CH3 — C—O—CH3
ester group

0
 Esterification

Esterification is
● The reaction of a carboxylic acid and alcohol in the
presence of an acid catalyst to produce an ester.
O
H+
CH3—C—OH + H—O—CH2—CH3

CH3—C—O—CH2—CH3 + H2O
ethyl acetate (an ester)

0
Learning Check
Write the equation for the reaction of propanoic acid and
methanol in the presence of an acid catalyst.

0
Solution
Write the equation for the reaction of propanoic acid
and methanol in the presence of an acid catalyst.
O
H+
CH3—CH2—C—OH + H—O—CH3
propanoic acid methanol
O

CH3—CH2—C—O—CH3 + H2O

0
 Naming Esters
The name of an ester contains the names of
● The alkyl group from the alcohol.
● The carbon chain from the acid with –ate ending.
from alcohol from acid
O
methyl
CH3— O—C —CH3
ethanoate (acetate)
IUPAC: methyl ethanoate
common: methyl acetate

0
 Ester Products
Aspirin
● Is used to relieve pain and
reduce inflammation.
● Is an ester of salicylic acid
and acetic acid.

Oil of wintergreen
● Is used to soothe sore
muscles.
● Is an ester of salicylic acid
and methanol.

0
 Esters in Plants
TABLE 16.4
Esters give flowers
and
fruits their
pleasant
fragrances and
flavors.

0
Learning Check

Give the IUPAC and common names of the following

compound, which is responsible for the flavor and odor
of pears.

CH3—C—O—CH2—CH2—CH3

0
 Solution
Give the IUPAC and common names of the following
compound, which is responsible for the flavor and odor
of pears.
from 1-propanol
O

CH3—C—O—CH2—CH2—CH3

Propyl ethanoate (IUPAC)

Propyl acetate (common)

0
Learning Check

Name the following esters:

O
║
A. CH3—CH2—CH2—C—O—CH3

B. CH3—CH2 —C—O—CH2—CH3

0
Solution

A. Methyl butanoate (methyl butyrate)

B. Ethyl propanoate (methyl propionate)

0
Learning Check

Write the structure of the following esters:

A. Ethyl pentanoate

B. Propyl butyrate

0
Solution

A. Ethyl pentanoate
O
║
CH3—CH2—CH2—CH2—C—O—CH2—CH3

B. Propyl butyrate
O
║
CH3—CH2—CH2—C—O—CH2—CH2—CH3

0
Properties of Esters

0
 Acid Hydrolysis of Esters

In acid hydrolysis
● An ester reacts with water to produce a carboxylic
acid and an alcohol.
● An acid catalyst is required.
O
H+
H—C—O—CH2—CH3 + H2O

H—C—OH + H—O—CH2—CH3

0
 Base Hydrolysis (Saponification)
Base hydrolysis (also called saponification)
● Is the reaction of an ester with a strong base.
● Produces the salt of the carboxylic acid and an
alcohol.
O
||
CH3—C—O—CH2—CH3 + NaOH
O
CH3—C—O– Na+ + HO—CH2—CH3
salt of carboxylic acid alcohol

0
“Soaps”
The base hydrolysis of long chain fatty acids
produces acid salts called “soaps”.

0
 Cleaning Action of Soap
A soap
● Contains a nonpolar
end that dissolves in
nonpolar fats and
oils, and a polar end
that dissolves in
water.
● Forms groups of
soap molecules
called micelles that
dissolve in water
and are washed
away.
0
Learning Check

Write the organic products when methyl acetate reacts

with
A. Water and an acid catalyst

B. KOH

0
Solution
Write the organic products when methyl acetate reacts
with:
A. Water and an acid catalyst
O

CH3—C—OH + HO—CH3

B. KOH
O

CH3—C—O– K+ + HO—CH3

0
Chapter 14B Amines and Amides
14.4
Amines

0
 Amines
Amines
● Are derivatives of ammonia NH3.
● Contain N attached to one or more alkyl or aromatic
groups.

CH3 CH3

CH3—NH2 CH3—NH CH3—N—CH3

0
 Classification of Amines
Amines are classified as primary, secondary, or tertiary.
● In a primary (1°) amine, one carbon group is bonded
to the nitrogen atom.
● A secondary (2°) amine has two carbon groups.
● A tertiary (3°) amine has three carbon groups.
H CH3 CH3

| | |
CH3—N—H CH3—N—H CH3—N—CH3
1° 2° 3°

0
Models of Amines
The three-dimensional models show the shapes of
amine molecules with one or more alkyl groups
bonded to the nitrogen atom.

0
 Naming Amines: Common
Simple amines
● Are named as alkylamines.
● List the names of the alkyl groups bonded to the N
atom in alphabetical order in front of amine.

CH3—CH2—NH2 ethylamine
CH3—NH—CH3 dimethylamine

CH3
|
CH3—N—CH2—CH3 ethyldimethylamine
0
 Naming Amines: IUPAC

In the IUPAC system,

● Amines are named as alkanamines.
● The ​e in the alkane name of the longest chain is
changed to ​amine.
● The chain is numbered to locate the amine group
and substituents.
NH2
|
CH3—CH2—NH2 CH3—CH—CH3
Ethanamine 2-Propanamine

0
 Naming Amines: IUPAC
2o or 3o amines
● Number longest alkane chain
● Alkyl grps bonded to N are named as N-alkyl grp

CH3—CH2—CH2—NH HN—CH3
—CH3 |
CH3—CH—CH2—CH3
3 2 1
1 2 3
N-Methyl-1-propanamine
4
N-Methyl-2-butanamine

0
 Learning Check
Give the common and IUPAC names, and classify as
primary, secondary, or tertiary:
A. CH3—CH2—CH2—NH2

CH3
|
B. CH3—CH2—N—CH3

0
 Solution
Give the common and IUPAC names, and classify as
primary, secondary, or tertiary:
A. CH3—CH2—CH2—NH2

n-propylamine, 1-propanamine, 1°

CH3
|
B. CH3—CH2—N—CH3

ethyldimethylamine,
N,N-dimethylethanamine, 3°

0
Learning Check
Write a structural formula for
A. 2-pentanamine

B. N-methyl-1-butanamine

0
Solution

A. 2-pentanamine
NH2
|
CH3—CH—CH2—CH2—CH3

B. N-methyl-1-butanamine

CH3—CH2—CH2—CH2—NH—CH3

0
 Aromatic Amines
● The amine of benzene is aniline.
● Alkyl groups on the N use the prefix N- and the alkyl
name.

Aniline 3-chloroaniline N-methylaniline

0
Learning Check
Give a name for each:
A. CH3—NH—CH2—CH3

CH3
|
B. CH3—CH2—N—CH2—CH2—CH2—CH3

C.

0
Solution
A. CH3—NH—CH2—CH3
ethylmethylamine; N-methylethanamine

CH3
|
B. CH3—CH2—N—CH2—CH2—CH2—CH3
N-ethyl-N-methyl-1-butanamine

C. aniline

0
Properties of Amines

0
 Boiling Points:
Alcohols > Amines >Alkanes of similar mass.

0
 Hydrogen Bonding for Amines
The polar N-H bond
● Provides hydrogen bonding in 1°and 2° amines, but not 3°.
● In amines is not as polar as the O-H bonds in alcohols.

0
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
 Solubility in Water
Amines are soluble in water
● If they have 1-5 carbon atoms.
● Because the N atom in smaller amines forms
hydrogen bonds with the polar O-H bond in water.

0
Learning Check

Consider the following compounds:

1. CH3—CH2—CH2—NH2
2. CH3—CH2—NH—CH3
3. CH3—CH2—CH2—CH3

A. Which compound has the highest boiling point?

B. Which compound(s) is(are) soluble in water?

0
Solution
Consider the following compounds:
1. CH3—CH2—CH2—NH2
2. CH3—CH2—NH—CH3
3. CH3—CH2—CH2—CH3

A. Which compound has the highest boiling point?

1. CH3—CH2—CH2—NH2

B. Which compound(s) is(are) soluble in water?

1. CH3—CH2—CH2—NH2
2. CH3—CH2—NH—CH3

0
 Amines React as Bases
Amines are
● Bronsted-Lowry bases that attract a H+ from H2O
to the N atom.
● Weak bases in water.

NH3 + H2O NH4+ + OH–

ammonium hydroxide

CH3—NH2 + H2O CH3—NH3+ + OH–

methylammonium hydroxide

0
 Neutralization forms Amine Salts
An amine salt
● Forms when an amine is
neutralized by acid.
● Is named by replacing the amine
part of the name with ammonium
followed by the name of the
negative ion.
CH3—NH2 + HCl CH3—NH3+Cl–
methylamine methylammonium
chloride

0
 Properties of Amine Salts
Amine salts are
● Solids at room temperature.
● Soluble in water and body fluids.
● The form used for drugs.

0
 Learning Check
Write the equation for ethylamine when it reacts with
each of the following:

1. + H2O

2. + HCl

0
Solution
Write the equation for ethylamine when it reacts with
each of the following:

1. CH3—CH2—NH2 + H2O CH3—CH2—NH3+

OH–

2. CH3—CH2—NH2 + HCl CH3—CH2—NH3+ Cl–

0
Heterocyclic Amines and Alkaloids

0
 Heterocyclic Amines
A heterocyclic amine
● Is a cyclic organic compound.
● Has a five- or six-atom ring.
● Contains one or more nitrogen atoms.

0
Examples of Heterocyclic Amines

0
Learning Check
Identify the following heterocyclic amines:
1. 2. 3.

0
Solution
Identify the following heterocyclic amines:
1. 2. 3.

1. piperidine 2. pyrrole 3. imidazole

0
 Alkaloids

Alkaloids are
● Physiologically active nitrogen-containing
compounds.
● Produced by plants.
● Used as stimulants, anesthetics, and
antidepressants.
● Often habit forming.

0
 Caffeine
Caffeine
● Is a stimulant of the
central nervous
system.
● Is found in coffee
beans, tea, chocolate,
and soft drinks.
● Contains an
imidazole ring.

0
 Nicotine
Nicotine
● Increases the adrenaline level in the blood.
● Causes addiction to tobacco.
● Contains a pyrrolidine ring.

0
 Alkaloids Related to Morphine
Alkaloids
● Such as morphine and codeine are
produced by the poppy.
● Have been used for centuries as
painkillers.

0
Morphine and Codeine

0
 Pharmacology
An area of research in pharmacology
● Is to design drugs such as procaine, lidocaine, and
demerol that retain some of the characteristics of
alkaloids.
● Is to modify the structures of cocaine and morphine to
produce anesthesia, but without the addictive side
effects.

0
Learning Check
Identify the heterocyclic amine in serotonin.

serotonin

0
Solution
Identify the heterocyclic amine in serotonin.

pyrrole

0
Amides

0
 Preparation of Amides
Amides are prepared
● By reacting a carboxylic acid with ammonia or
an amine (1° or 2°).
● Using heat.
O O
Heat
CH3—C—OH + NH3 CH3—C—NH2 + H2O

O O
Heat
CH3—C—OH + CH3—NH2 CH3—C—NH—CH3 +
H2O
0
Amides
In amides, an amino group(–NH2) replaces the –OH
group of carboxylic acids.
O O
|| ||
CH3—C—OH CH3—C—NH2

0
 Naming Amides
Amides are named as alkanamides.
● IUPAC replaces –oic acid ending with –amide.
● Common names replace -ic acid ending with –amide.
O
Methanamide (IUPAC)
H—C—NH2 Formamide (common)

O
Propanamide (IUPAC)
CH3—CH2—C—NH2 Propionamide (common)

0
 Naming Amides with N Groups
● An alkyl group bonded to the N atom is named as
N-alkyl in front of the amide name.
O H
│
CH3 —C—N—CH3 N-methylethanamide (IUPAC)
N-methylacetamide (common)
O H
│
CH3—CH2 —C—N—CH2—CH3
N-ethylpropanamide (IUPAC)
N-ethylpropionamide (common)

0
 Aromatic Amides

● The amide of benzene is named benzamide.

0
 Learning Check
Give the IUPAC and common names for the following:

A. CH3–CH2–CH2–C–NH2

O H
│
B. CH3–C–N–CH2–CH3

0
Solution
O

A. CH3–CH2–CH2–C–NH2
butanamide; butryamide

OH
│
B. CH3–C–N–CH2–CH3

N-ethylethanamide; N-ethylacetamide

0
Learning Check

Draw the structures of

A. pentanamide
B. N-methylbutyramide

0
Solution
A. pentanamide
O

CH3–CH2–CH2–CH2–C–NH2

B. N-methylbutyramide
O

CH3–CH2–CH2–C–NH–CH3

0
 Classification of Amides
● Amides are classified according to the number of
carbon atoms bonded to the nitrogen atom.
O H
|| |
CH3—C—N—H Primary (1°) amide

O H
|| |
CH3—C—N—CH3 Secondary (2°) amide

O CH3
|| |
CH3 —C—N—CH3 Tertiary (3°) amide

0
 Learning Check
Give the common and IUPAC names for the following
amides and classify as primary, secondary, or tertiary:

O
||
A. CH3—CH2—CH2—C—NH2

O CH3
|| |
B. CH3—C—N—CH2—CH3

0
Solution

O
||
A. CH3—CH2—CH2—C—NH2
butryamide (common);
butanamide (IUPAC) primary(1°) amide

O CH3
|| |
B. CH3—C—N—CH2—CH3
N-ethyl-N-methylacetamide (common);
N-ethyl-N-methylethanamide (IUPAC)
tertiary (3°) amide 0
 Some Amides in Health and
Medicine
● Urea is the end product of
protein metabolism.
● Saccharin is an artificial
sweetener.
● Acetaminophen is used to
reduce fever and pain.

0
Some Amides in Health and Medicine

0
 Physical Properties of Amides
Amides
● That are primary (−NH2) or secondary (−NH−) form
hydrogen bonds.
● That are primary have higher melting points than
secondary.
● That are tertiary (no H on N) do not form hydrogen
bonds and have lower melting points.
● All form hydrogen bonds with water.
● With 1-5 carbon atoms are soluble in water.

0
Hydrogen Bonding of Amides
O
||
CH3—C—N—H
|
H Hydrogen bonding occurs
between primary amides.
O
||
CH3—C—N—H
|
H

0
Hydrolysis of Amides

0
Hydrolysis of Amides

Amides undergo

acid hydrolysis base hydrolysis

carboxylic acid salt of carboxylic acid

ammonium salt and an amine or ammonia

0
 Hydrolysis Reactions
acid hydrolysis
O
||
O CH3—C—OH + NH4+Cl–
|| HCl + H2O
CH3—C—NH2

NaOH O
||
CH3—C—O– Na+ + NH3

base hydrolysis

0
 Learning Check

Write the equation for the hydrolysis of

N-ethylpropanamide with NaOH.

0
Solution

Write the products of the hydrolysis of

N-ethylpropanamide with NaOH.

CH3—CH2—C—N—CH2—CH3 + NaOH
N-ethylpropanamide

CH3—CH2—C—O– Na+ + CH3—CH2—NH2

0