WILLIAM H.

BROWN

THOMAS POON

www.wiley.com/college/brown

CHAPTER TEN

Amines

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Structure & Classification

• Classification
– 1°, 2°, or , 3° amines: Amines in which 1, 2,
or 3 hydrogens of NH3 are replaced by alkyl or
aryl groups.

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Structure & Classification

• Amines are further divided into aliphatic,

aromatic, and heterocyclic amines.
– Aliphatic amine: An amine in which nitrogen
is bonded only to alkyl groups.
– Aromatic amine: An amine in which nitrogen
is bonded to one or more aryl groups.

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Structure & Classification

– Heterocyclic amine: An amine in which

nitrogen is one of the atoms of a ring.

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Structure & Classification

• Example: Classify each amino group by

type.

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Nomenclature

• Aliphatic amines: replace the suffix -e of

the parent alkane by -amine.

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Nomenclature

• The IUPAC system retains the common

name aniline.

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Nomenclature

• Among the various functional groups

discussed in the text, -NH2 has one of the
lowest priorities.

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Nomenclature

• Common names for most aliphatic amines

are derived by listing the alkyl groups
bonded to nitrogen in one word ending with
the suffix -amine.

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Nomenclature

• When four groups are bonded to the

nitrogen atom, we name the compound as
a salt of the corresponding amine.

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Physical Properties

• Amines are polar compounds, and both 1°

and 2° amines form intermolecular
hydrogen bonds.
– N-H- - - -N hydrogen bonds are weaker than O-H-
- - -O hydrogen bonds because the difference in
electronegativity between N and H (3.0 - 2.1 =
0.9) is less than that between O and H (3.5 - 2.1
= 1.4).

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Basicity

• All amines are weak bases, and aqueous

solutions of amines are basic.

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Basicity

• It is also common to discuss the basicity of

amines by reference to the acid ionization
constant of its corresponding conjugate
acid.

– For any acid-conjugate base pair.

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Basicity

• Using values of pKa, we can predict the

position of equilibrium in acid-base
reactions.

– Acetic acid is the stronger acid and, therefore,

the position of this equilibrium lies to the right.
10-14
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Basicity

– Aliphatic amines have about the same base

strength, pKb 3.0 – 4.0 and are slightly
stronger bases than NH3.

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Basicity

– Aromatic amines are considerably weaker

bases than aliphatic amines.

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Basicity

Aromatic amines are weaker bases than

aliphatic amines because the resonance
stabilization of the free base is lost on
protonation.

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Basicity

• Electron-withdrawing groups, such as

halogen, nitro, and carbonyl, decrease the
basicity of aromatic amines by decreasing
the availability of the electron pair on
nitrogen.

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Basicity

• Example: Select the stronger base in

each pair of amines.

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Guanidine

• Guanidine (pKb 0.4) is the strongest base among

neutral organic compounds.

– Its basicity is due to the resonance delocalization of

the positive charge over the three nitrogen atoms.

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Reaction with Acids

• All amines, whether soluble or insoluble in

water, react quantitatively with strong
acids to form water-soluble salts.

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Synthesis of 1°

• Most 1° aromatic amines are synthesized

by nitration of an aromatic ring followed by
catalytic reduction of the nitro group to an
amino group.

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Amines as Nucleophiles

• Reaction of an amine with an alkyl halide can be

used to form a new covalent bond.

• Step 1: Reaction of a nucleophile with an

electrophile to form a new covalent bond.

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Amines as Nucleophiles

• Reaction of an amine with an alkyl halide can be

used to form a new covalent bond.

• Step 2: Take a proton away. Converts the amine

salt to a free amine.

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Amines as Nucleophiles

• In Step 2, a new 2° amine was produced,

which can then act as a nucleophile with the
result that the final reaction mixture will
consist of varying ratios of RNH2, R2NH, R3N,
and R4N+Cl–. These ratios are difficult to
control and, therefore, we avoid using amines
as nucleophiles in nucleophilic substitutions
reactions.

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Amines

End Chapter 10
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