Chemistry of Amines

By:
Prof. I. O. Otemuyiwa
Dept of Chemistry
Obafemi Awolowo University, Ile-Ife, Nigeria

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Amines are organic compounds which contain and are often actually based on one or more atoms of nitrogen.
Structurally amines resemble ammonia in that the nitrogen can bond up to three hydrogens, but amines also have
additional properties based on their carbon connectivity. In an amine, one or more of the hydrogen atoms from
ammonia are replaced by organic substituents like alkyl (alkane chain) and aryl (aromatic ring) groups.

Amine Primary Amine Secondary Amine Tertiary Amine

Types of amines
Amines can be either primary, secondary or tertiary, depending on the number of carbon-containing groups that are
attached to them.
If there is only one carbon-containing group (such as in the molecule CH NH ) then that amine is considered
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primary. Two carbon-containing groups makes an amine secondary, and three groups makes it tertiary.

Utilizing the lone electron pair of nitrogen, it is sometimes energetically favored to use the nitrogen as a nucleophile
and thus bind a fourth carbon-containing group to the amine. In this case, it could be called a quaternary ammonium
ion.
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General properties

Hydrogen bonding significantly influences the properties of primary and secondary amines as well as the
protonated derivatives of all amines. Thus the boiling point of amines is higher than those for the corresponding
phosphines (compounds containing phosphorus), but generally lower than the corresponding alcohols. Alcohols,
or alkanols, resemble amines but feature an -OH group in place of NR . Since oxygen is more electronegative
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than nitrogen, RO-H is typically more acidic than the related R N-H compound.
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Methyl, dimethyl, trimethyl, and ethyl amines are gases under standard conditions. Most common alkyl amines
are liquids, and high molecular weight amines are, quite naturally, solids at standard temperatures. Additionally,
gaseous amines possess a characteristic ammonia smell, while liquid amines have a distinctive “fishy” smell.
Most aliphatic amines display some solubility in water, reflecting their ability to form hydrogen bonds. Solubility
decreases relatively proportionally with the increase in the number of carbon atoms in the molecule – especially
when the carbon atom number is greater than six. Aliphatic amines also display significant solubility in organic
solvents, especially in polar organic solvents. Primary amines react readily with ketone compounds (such
as acetone), however, and most amines are incompatible with chloroform and also with carbon tetrachloride as
solvent solutions. 3
Properties as bases

When evaluating the basicity of a nitrogen-containing organic functional group, the central question we need to
ask ourselves is: how reactive (and thus how basic) is the lone pair on the nitrogen? In other words, how much
does that lone pair want to break away from the nitrogen nucleus and form a new bond with a hydrogen?

Like ammonia, amines act as bases and are reasonably strong (see the provided table for some examples of
conjugate acid K values). The basicity of amines varies by molecule, and it largely depends on:
a

 The availability of the lone pair of electrons from nitrogen

 The electronic properties of the attached substituent groups (e.g., alkyl groups enhance the basicity, aryl groups diminish
it, etc.)

 The degree of solvation of the protonated amine, which depends mostly on the solvent used in the reaction
The nitrogen atom of a typical amine features a lone electron pair which can bind a hydrogen ion (H ) in order +

to form an ammonium ion — R NH . The water solubility of simple amines is largely due to the capability for
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+

hydrogen bonding that can occur between protons on the water molecules and these lone pairs of electrons. 4
Comparing the basicity of alkyl amines to ammonia
Because alkyl groups donate electrons to the more electronegative nitrogen. The inductive effect makes the
electron density on the alkylamine’s nitrogen greater than the nitrogen of ammonium. Correspondingly, primary,
secondary, and tertiary alkyl amines are more basic than ammonia.

Comparing the basicity of alkylamines to amides

With an alkyl amine the lone pair electron is localized on the nitrogen. However, the lone pair electron on an amide
are delocalized between the nitrogen and the oxygen through resonance. This makes amides much less basic
compared to alkylamines.

In fact, when and amide is reacted with an acid, the protonation occurs at the carbonyl oxygen and not the
nitrogen. This is because the cation resulting from oxygen protonation is resonance stabilized. The cation
resulting for the protonation of nitrogen is not resonance stabilized.

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Reactions of Amines
Due to the unshared electron pair, amines can act as both bases and nucleophiles.
Reaction with acids
When reacted with acids, amines donate electrons to form ammonium salts.

Reaction with acid halides

Acid halides react with amines to form substituted amides.

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Aldehydes and ketones react with primary amines to give a reaction product (a
carbinolamine) that dehydrates to yield aldimines and ketimines (Schiff bases).

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Reaction with nitrous acid

Nitrous acid is unstable and must be prepared in the reaction solution by mixing sodium
nitrite with acid.

Primary amines react with nitrous acid to yield a diazonium salt, which is highly unstable
and degradates into a carbocation that is capable of reaction with any nucleophile in
solution. Therefore, reacting primary amines with nitrous acid leads to a mixture of alcohol,
alkenes, and alkyl halides.