Amines

Key Questions
8.1 What Are amines?
8.2 How Do We Name Amines?
8.3 What Are the Physical Properties of Amines?
8.4 How Do We Describe the Basicity of Amines?
8.5 What Are the Characteristic Reactions of
Amines?
8.1 What Are Amines?
• Amines are classified as primary (1°),
secondary (2°), or tertiary (3°), depending on
the number of carbon groups bonded to
nitrogen.
Aliphatic amine
• An amine in which nitrogen is bonded only to
alkyl groups or hydrogens.

Aromatic amine
• An amine in which nitrogen is bonded to one
or more aromatic rings
Heterocyclic amine
• An amine in which nitrogen is one of the
atoms of a ring

Heterocyclic aromatic amine

• An amine in which nitrogen is one of the
atoms of an aromatic ring
Example 8.1 Structure of Amines
• How many hydrogen atoms does piperidine
have? How many hydrogen atoms does pyridine
have? Write the molecular formula of each
amine.
Solution
• Piperidine has 11 hydrogen atoms, and its
molecular formula is C5H11N.
• Pyridine has 5 hydrogen atoms, and its molecular
formula is C5H5N.
Problem 8.1
• How many hydrogen atoms does pyrrolidine
have? How many does purine have?
• Write the molecular formula of each amine.
 8.2 How Do We Name Amines?
• A. IUPAC Names
• IUPAC names for aliphatic amines are derived
just as they are for alcohols. The final -e of the
parent alkane is dropped and replaced by
-amine. Indicate the location of the amino
group on the parent chain by a number.
• IUPAC nomenclature retains the common name
aniline for C6H5NH2, the simplest aromatic amine.
• Its simple derivatives are named using numbers
to locate substituents or, alternatively, using the
locators ortho (o), meta (m), and para (p).
• Several derivatives of aniline have common
names that remain in use. Among them is
toluidine for a methyl-substituted aniline.
• Unsymmetrical secondary and tertiary amines
are commonly named as N-substituted
primary amines.
• The largest group bonded to nitrogen is taken
as the parent amine; the smaller groups
bonded to nitrogen are named, and their
locations are indicated by the prefix N
(indicating that they are bonded to nitrogen).
 Example 8.2 IUPAC Names of Amines

• Write the IUPAC name for each amine. Try to

specify the configuration of the stereocenter
in (c).
Problem 8.2
• Write a structural formula for each amine.
(a) 2-Methyl-1-propanamine
(b) Cyclopentanamine
(c) 1,4-Butanediamine
B. Common Names
• Common names for most aliphatic amines list
the groups bonded to nitrogen in alphabetical
order in one word ending in the suffix -amine.
 Example 8.3 Common Names of Amines
• Write a structural formula for each amine.
(a) Isopropylamine
(b) Cyclohexylmethylamine
(c) Triethylamine
Problem 8.3
• Write a structural formula for each amine.
(a) 2-Aminoethanol
(b) Diphenylamine
(c) Diisopropylamine
• When four atoms or groups of atoms are
bonded to a nitrogen atom—as, for example,
in NH4+ and CH3NH3+—nitrogen bears a
positive charge and is associated with an
anion as a salt.
• The compound is named as a salt of the
corresponding amine. The ending -amine (or
aniline, pyridine, or the like) is replaced by
-ammonium (or anilinium, pyridinium, or the
like) and the name of the anion (chloride,
acetate, and so on) is added.
• Several over-the-counter mouthwashes contain an
N-alkylpyridinium chloride as an antibacterial agent.
 8.3 What Are the Physical Properties
of Amines?
• Like ammonia, low-molecular-weight amines
have very sharp, penetrating odors.
Trimethylamine, for
example, is the pungent
principle in the smell of
rotting fish. Two other
particularly pungent
amines are 1,4-
butanediamine
(putrescine) and 1,5-
pentanediamine
(cadaverine).
http://www.sptimes.com/2007/12/20/Pasco/Storm_als
o_brings_fis.shtml
• Amines are polar compounds because of the
difference in electronegativity between
nitrogen and hydrogen 3.0 - 2.1 = 0.9.
• Both primary and secondary amines have N-H
bonds, and can form hydrogen bonds with one
another.

• Tertiary amines do not have a hydrogen bonded

to nitrogen and, therefore, do not form
hydrogen bonds with one another.
• An N-H---N hydrogen bond is weaker than an
O-H--O hydrogen bond, because the
difference in electronegativity between
nitrogen and hydrogen 3.0 - 2.1 = 0.9 is less
than that between oxygen and hydrogen 3.5 -
2.1 = 1.4.
 8.4 How Do We Describe the Basicity
of Amines?
• Like ammonia, amines are weak bases, and
aqueous solutions of amines are basic.
• Assume that the amine, RNH2, has a pKb of 3.50
and that it is dissolved in blood, pH 7.40. We first
write the base dissociation constant for the amine
and then solve for the ratio of RNH3+ to RNH2.
• As this calculation demonstrates, an aliphatic
amine present in blood is more than 99.9% in
the protonated form.

• Performing the same type of calculation for an

aromatic amine, ArNH2, with pKb of
approximately 10, we find that the aromatic
amine is more than 99.0% in its unprotonated
(ArNH2) form.
 Basicity of Amines
• Select the stronger base in each pair of amines.

Solution
(a) Morpholine (B), a 2° aliphatic amine, is the stronger base. Pyridine (A),a
heterocyclic aromatic amine, is the weaker base.
(b) Benzylamine (D), a 1° aliphatic amine, is the stronger base. Even though it
contains an aromatic ring, it is not an aromatic amine because the amine
nitrogen is not bonded to the aromatic ring. o-Toluidine (C), a 1° aromatic
amine, is the weaker base.
Problem 8.4
• Select the stronger base from each pair of
amines.
 8.5 What Are the Characteristic
Reactions of Amines?
• Amines, whether soluble or insoluble in water,
react quantitatively with strong acids to form
water-soluble salts, as illustrated by the
reaction of (R)-norepinephrine(noradrenaline)
with aqueous HCl to form a hydrochloride salt.
 Example 8.5 Basicity of Amines
• Complete the equation for each acid–base
reaction, and name the salt formed.

• Solution
 Problem 8.5
• Complete the equation for each acid–base
reaction and name the salt formed.
• The basicity of amines and the solubility of amine salts
in water gives us a way to separate water-insoluble
amines from water-insoluble nonbasic compounds.
Summary of Key Reactions
END OF CHAPTER