AMINES

AMINES
An amine is generally a functional group
with a nitrogen atom having a lone pair.
Amines resemble ammonia with one or
more alkyl or aryl groups bonded to the
nitrogen atom.

The general structure of an amine can be

represented as R-NH2, R2NH, or R3N,
where R represents an alkyl or aryl group.
 CLASSIFICATION

PRIMARY AMINE SECONDARY AMINE TERTIARY AMINE

Only one of the hydrogen Two of the hydrogens in All of the hydrogens in
atoms in the ammonia an ammonia molecule an ammonia molecule
molecule has been have been replaced by have been replaced by
replaced. hydrocarbon groups. hydrocarbon groups

Methylamine Dimethylamine Trimethylamine

(CH3NH2) (CH3)2NH) (CH3)3N)
 HOW DO WE NAME AMINES?
RULE #1: IDENTIFY THE LONGEST CONTINUOUS CARBON CHAIN

RULE #2: REPLACE THE -E OF THE ALKANE WITH -AMINE

RULE #3: NUMBER THE CHAIN SO THAT THE -NH₂ (AMINO

GROUP) GETS THE LOWEST NUMBER

RULE #4: NAME AND NUMBER RULE #5: USE THE PREFIX N- RULE #6: USE MULTIPLE N’S IF
ANY OTHER SUBSTITUENTS ON FOR GROUPS ATTACHED MORE THAN ONE GROUP IS
THE CARBON CHAIN DIRECTLY TO THE NITROGEN ATTACHED TO THE NITROGEN
 COMMON NAMES
Common names for the most aliphatic The prefixes di-, tri-, and
amines list the groups bonded to nitrogen tetra- are used to describe
in alphabetical order in one word ending in two, three or four identical
the suffix -amine. substituents.

For primary amines (one alkyl group attached), this is The common name is
straightforward: formatted by
CH₃NH₂: Methylamine identifying the alkyl
CH₃CH₂NH₂: Ethylamine​ group attached to the
N atom and adding the
For secondary and tertiary amines (two or three alkyl groups term amine.
attached), the alkyl groups are listed in alphabetical order, followed Methanamine is also
by "amine":​ known as
(CH₃)₂NH: Dimethylamine methylamine;
CH₃CH₂NHCH₃: Ethylmethylamine ethanamine is
ethylamine, etc.
 PHYSICAL PROPERTIES OF AMINES
Amines are polar compounds due to the electronegativity difference between nitrogen
(N) and hydrogen (H). This polarity makes them capable of intermolecular interactions,
such as hydrogen bonding—a significant factor affecting their physical properties like boiling
point and solubility.

GENERAL PROPERTIES
Primary amines (R-NH₂) -
Amines are derivatives of ammonia (NH₃) where one or
Forms strong hydrogen
more hydrogen atoms are replaced by alkyl or aryl
bonds
groups.
Secondary amines (R₂NH) -
They are classified into:
Capable of hydrogen
Primary (1°) amines – one hydrogen replaced (RNH₂)
b o n d i n g , b u t l e s s e f f ic ie n t
Secondary (2°) amines – two hydrogens replaced
Tertiary amines (R₂N) - No
(R₂NH)
hydrogen is attached to
Tertiary (3°) amines – all three hydrogens replaced
nitrogen
(R₃N)
BOILING POINTS
The boiling points of amines
increase with increasing relative
molecular mass
The lower aliphatic amines are
gases or low-boiling liquids
Amines are polar compounds
and both primary and
secondary amines associate by
intermolecular hydrogen
bonding
THE BOILING POINTS OF 1°, 2° , AN D 3° AMIN ES
For isomeric amines, the boiling points decreases in the order, 1° amines > 2°
amine > 3° amine
Reason: decreases in intermolecular hydrogen bonding
 COMPARING WITH OTHER ORGANIC
COMPOUND
The boiling points of aliphatic amines are higher than those of alkanes or
haloalkanes of similar relative molecular mass due to intermolecular hydrogen
bonding
The N-H bond is more polar than the C-H bond but less polar than O-H bond.
Hydrogen bonding in amines are weaker than that of alcohols or carboxylic acids
Boiling points of amines are lower than those corresponding alcohols or carboxylic
acids.
 SOLUBILITIES OF 1°, 2°, AND 3°
All three classes of aliphatic amines Lower aliphatic amines: usually colorless
are capable of forming hydrogen gases or liquids at room temperature
bonds with water molecules. Higher amines: generally colorless oily
The lower amines (with chain length liquids or even solids as the molecular
up to four carbon atoms per weight increases
molecule) are very soluble in water Most are clear and don’t have any color
because they can form hydrogen unless they are part of a more complex
bonds with water molecules compound.
The solubilities of amines decrease
with increasing number of carbon Fishy
atoms in the chain. Especially strong in lower amines
Amines are soluble in organic Higher or aromatic amines have less
solvents. noticeable odor but many still carry a
chemical-like scent
CHEMICAL PROPERTIES OF AMINES
The Basicity of Amines
Amines act as bases by using their lone pair of electrons to form bonds
with electrophiles (Lewis base) or accept protons from acids (Brønsted-
Lowry base).

Amines are fairly strong base and their aqueous solutions are basics.
An amine can abstract a proton from water, giving an ammonium ion
and a hydroxide ion.
The equilibrium constant for this reaction is called base-dissociation
constant, symbolized by Kb.
CHEMICAL PROPERTIES OF AMINES
 FACTORS THAT AFFECT THE
BASICITY OF AMINES:
1. Substitution by Alkyl Groups
The presence of alkyl groups (electron-donating group) such as (CH3-)
and (CH3CH2-) will make the amine become more basic.

Example: methylamine is more basic than ammonia

2. Substitution by Electron-withdrawing Groups

The presence of electron-withdrawing groups or atom will decrease the
basicity.

Example: nitroaniline is less basic than aniline

BASICITY OF AROMATIC AMINES:
Aromatic amines is less basic than aliphatic amines and ammonia.

The lone pair of electrons on the nitrogen atom is delocalised into the
benzene ring. As a result, the lone pair of electrons is less available
for donation to an acid.

The reaction is shifted toward the left and makes aniline a weaker
base than ammonia or aliphatic amines.
REACTION OF
AMINES
 SALT FORMATION

Amines exhibit basic characteristics because of a lone pair of electrons on the nitrogen
atom, permitting them to accept a hydrogen ion (H⁺) from an acidic substance.

Composed of 2 types of ions, the Ammonium ion and an anion derived from the acids.
 REACTION WITH NITROUS ACID
Nitrous Acid (HNO2) is usually prepared in situ because of its reactivity

Formation of Nitrous Acid and Nitrosonium Ion

Primary Aliphatic Amine (One alkyl group and two hydrogen)
Formation of diazonium salt
and production of alcohol,
water, and nitrogen gas
Example: Ethylamine
(CH2H5NH2) reacts with
HNO2 (Nitrous Acid)

Secondary Aliphatic and Aromatic (two alkyl or aryl group and one hydrogen)

Characterized by two organic groups attached to nitrogen atom, with one

hydrogen left. It has a general formula of R2NH.

R = Alkyl or Aryl Group

 Example: Dimethylamine
reacts with nitrous acid

Nitrosoamine are often biologically active, and some are known to be carcinogenic.

Tertiary Aliphatic Amines (Three organic groups with no hydrogen)

A tertiary aliphatic amines react with HNO2 will produced ammonium salts which
is dissolve readily in water as a clear solution.
Primary Aromatic Amines
It reacts with cold HNO2, and dissolved in dilute HCL at 0-5°C will produced diazonium
salt. When this cold salts heated at room temperature, nitrogen gas will evolved.

Diazotization Reaction Warmed to Room Temperature

Tertiary Aromatic Amines
Reacts with nitrous acid HNO2 below 5°C to undergo electrophilic aromatic substitution
RELATED VIDEO
 AMIDE FORMATION
Reaction of acyl chlorides

Amides are commonly synthesized by the reaction of acyl chlorides (also referred to as acid
chlorides) with ammonia or amines in a process known as nucleophilic acyl substitution .

EXAMPLES: 2. Aniline (C6H5NH2) reacts

1.Methylamine (CH3NH2) with ethanoyl chloride, where
reacts with ethanoyl chloride the nitrogen attacks the
(CH3COCl) to form N- carbonyl carbon to form N-
methylethanamide phenylbenzamide
(CH3CONHCH3) and (C6H5NHCOCH3) and release
hydrochloric acid (HCl) as a HCl. This shows that both
side product. The nitrogen of aliphatic and aromatic amines
the amine attacks the can form amides with acid
carbonyl carbon, replacing the chlorides.
chlorine atom.
 AMIDE FORMATION
Reaction of acid anhydrides

Are widely used as

acylating agents and can be
reacted with ammonia or
amines to yield amides

EXAMPLE:
For example, reacting acetic anhydride (CH₃CO)₂O) with ammonia produces ethanamide
and acetic acid in the initial step . However, in the presence of excess ammonia, the acetic
acid readily forms ammonium ethanoate (ammonium acetate), leading to the combined
overall reaction:

(Ethanamide) (Ammonium ethanoate)

 RING HALOGENATION OF
PHENYLAMINE
When aniline is treated with bromine water under room temperature conditions, it reacts
rapidly and without catalyst to produce 2,4,6-tribromoaniline, a white precipitate (C6H4Br3N).

The reaction can be summarized as:

C6H5NH2 + 3Br2—>C6H2Br3NH2 + 3HBr
 USES OF AMINES
Uses of Amines in Daily Life Uses of Amines in Pharmacy

Gas treatment: Amines remove CO₂ from Amines are frequently used in morphine
combustion gases. and Demerol which are popular pain
Dye production: Used in making dyes, killers.
especially azo dyes for textiles like leather Amines are also used as solvents for
and nylon. antihistamine diphenhydramine which are
Agriculture: Help solubilize herbicides and act used in Benadryl syrups.
as emulsifiers. Novocaine is one drug used as an
Industrial use: Serve as corrosion inhibitors in anaesthetic which is hugely dependent on
boilers and lubricants. amines.
Photography: Used as developing agents for Amines are important sources of amino
photographs. acids which regulate the vitamin levels in
our bodies.
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