Amines

‫ مي محمد جواد المظفر‬.‫د‬

Lecture 5
Reference Text Book
John McMurry "Organic Chemistry“
8th Edition
 Amines; Introduction
• Amines are organic derivatives of ammonia in the same way that
alcohols and ethers are organic derivatives of water. Like ammonia,
amines contain a nitrogen atom with a lone pair of electrons, making
amines both basic and nucleophilic.
• Amines occur widely in all living organisms. Trimethylamine, for
instance, occurs in animal tissues and is partially responsible for the
distinctive odor of fish; nicotine is found in tobacco. In addition, amino
acids are the building blocks from which all proteins are made, and
cyclic amine bases are constituents of nucleic acids.

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 Naming Amines

• Amines can be either alkyl-substituted (alkylamines) or

aryl-substituted (arylamines). Although much of the
chemistry of the two classes is similar, there are also
substantial differences. Amines are classified as primary
(RNH2), secondary (R2NH), or tertiary (R3N),
depending on the number of organic substituents attached
to nitrogen.
• Thus, methylamine (CH3NH2) is a primary amine,
dimethylamine [(CH3)2NH] is a secondary amine, and
trimethylamine [(CH3)3N] is a tertiary amine.
• Note: that this usage of the terms primary, secondary,
and tertiary differs from our previous usage in other
types of organic compounds.
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 Types of amines
• When we speak of a tertiary alcohol or alkyl halide, we refer
to the degree of substitution at the alkyl carbon atom, but
when we speak of a tertiary amine, we refer to the degree of
substitution at the nitrogen atom.

• Compounds containing a nitrogen atom with four attached groups

also exist, but the nitrogen atom must carry a formal positive charge.
Such compounds are called quaternary ammonium salts.

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 IUPAC NAMES of amines
• Primary amines are named in the IUPAC
system in several ways. For simple amines, the
suffix -amine is added to the name of the
alkyl substituent. Phenylamine, C6H5NH2, has
the common name aniline.

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 IUPAC NAMES of aliphatic amines
• In aliphatic amine the IUPAC System, apply
the following rules to name amines:
1- Pick out the longest continuous chain of carbon atoms.
The parent name comes from the alkane of the same
number of carbons.
2- Change the -e of the alkane to “amine.”

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 IUPAC names and Common names
• The IUPAC names are listed first and coloured blue. This system
names amine functions as substituents on the largest alkyl group.
The simple -NH substituent found in 1°-amines is called an amino
group.
• While, a common system for simple amines names each alkyl
substituent on nitrogen in alphabetical order, followed by the suffix -
amine. These are the names given in the last row (coloured black).

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 Names of amines
• Symmetrical secondary and tertiary amines are named
by adding the prefix di- or tri- to the alkyl group.

• Many aromatic and heterocyclic amines are known by

unique common names:

o-toluidine
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 Names of amines
• Unsymmetrically substituted secondary and tertiary
amines are referred to as N-substituted primary
amines. The largest alkyl group takes the parent
name, and the other alkyl groups are considered N-
substituents on the parent (N because they’re attached
to nitrogen).

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 Structure and Bonding in Amines
• Bonding to N is similar to that in ammonia
 N is spᴣ -hybridized
 C–N–C bond angles are close to 109°tetrahedral
value

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 Physical Properties of Amines
• Boiling Point:
• It is instructive to compare the boiling points and water solubility of
amines with those of corresponding alcohols and ethers. The dominant
factor here is hydrogen bonding, and the table below shows the powerful
intermolecular attraction that results from -O-H----O- hydrogen bonding
in alcohols (light blue columns).
• Corresponding -N-H----N- hydrogen bonding is weaker, as the lower boiling
points of similarly sized amines (light green columns) demonstrate. Alkanes
provide reference compounds in which hydrogen bonding is not possible.

Compound CH3CH3 CH3OH CH3NH2 CH3CH2CH3 CH3CH2OH CH3CH2NH2

Mol.Wt. 30 32 31 44 46 45

Boiling -88.6º 65º -6.0º -42º 78.5º 16.6º

Point ºC

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 Boiling point comparison

• The table below illustrates differences associated with

isomeric 1ͦ, 2ͦ & 3ͦ-amines. Since 1ͦ-amines have two
hydrogens available for hydrogen bonding, we expect
them to have higher boiling points than isomeric 2ͦ -
amines, which in turn should boil higher than isomeric
3ͦ-amines (no hydrogen bonding).

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 Water Solubility and Odor

• Amines Form H-Bonds

• Like alcohols, Amines with fewer than five carbons are water-
soluble, with borderline solubility being reached at about six
carbon atoms. Amines are soluble in less polar solvents like ether,
alcohol, benzene.
• Primary and secondary amines form hydrogen bonds, increasing
their boiling points.

• Low-molecular-weight amines such as trimethylamine have a

distinctive fishlike aroma. 13
 Sources of Amines
• Simple methylated amines from reaction of
NH3 with CH3OH and alumina catalyst.
Yields a mixture of monomethylated,
dimethylated, and trimethylated products that
are easily separated by distillation.

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 Basicity of Amines
• The lone pair of electrons on nitrogen makes
amines basic and nucleophilic.
• They react with acids to form acid–base salts and
they react with electrophiles.

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 Basicity of Amines
• The base strength of an amine can be measured by
defining an analogous basicity constant Kb. The
larger the value of Kb and the smaller the value of
pKb, the more favourable the proton-transfer
equilibrium and the stronger the base. For the
reaction:

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 General Patterns of Basicity

• Most simple alkylammmonium ions have pK a's

of 10 to 11.
• Arylamines and heterocyclic aromatic amines
are considerably less basic than alkylamines
(conjugate acid pKa 5 or less)

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 Basicity of Substituted Arylamines
• The N lone-pair electrons in arylamines are delocalized
by interaction(resonance) with the aromatic ring π
electron system and are less able to accept H⁺ than are
alkylamines.

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 Substituted Arylamines

• Can be more basic or less basic than aniline

 Electron-donating substituents (such as -CH3, -NH2, -OCH3)
increase the basicity of the corresponding arylamine.
 Electron-withdrawing substituents (such as -Cl, -NO2, -CN)
decrease arylamine basicity.

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 Basicity of arylamines

Ex. 1:

Ex. 2:

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 Synthesis of Amines
1. Reduction of nitro compounds:
a. Catalytic hydrogenation using hydrogen
b. Chemical reduction by a metal and acid
Ar NO2 Ar NH2
m e ta l, H +
or or
R NO2 o r H 2 , c a t.
R NH2

Examples:

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Other Examples

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