Amines

Definition of Amines

"Amine is a derivative of ammonia (NH3) with one or more hydrogen atoms replaced by alkyl or aryl
groups."

Types of Amines

• Primary Amines: Those with one alkyl or aryl group attached to the nitrogen atom.

• Secondary Amines: Those with two alkyl or aryl groups attached to the nitrogen atom.

• Tertiary Amines: Those with three alkyl or aryl groups attached to the nitrogen atom.

Nomenclature of Amines

Amine Nomenclature

CH3CH2NH2 Ethylamine

C2H5NH2 Propylamine

C6H5NH2 Aniline

Preparation of Amines

Reduction of Alcohols

• Reduction of alcohols with LiAlH4 or NaBH4 to form primary amines.

• RX → RNH2

Reduction of Nitro Compounds

• Reduction of nitro compounds with SnCl2 or FeCl2 to form primary amines.

• RNO2 → RNH2

Reduction of Amides

• Reduction of amides with LiAlH4 to form primary amines.

• RC(O)NH2 → RNH2

Reactions of Amines

Hofmann Rearrangement

• A reaction of primary amides with Br2 and KOH to form primary amines.

• RC(O)NH2 → RNH2

Hoffman Bromamide Reaction

• RNH2 → R-Br

Conclusion

Amines are an important class of organic compounds with various applications in biology, medicine,
and industry. Understanding their structure, nomenclature, preparation, and reactions is crucial for
any chemistry student. ## Gabriel Thalamites and Amine Reactions

Gabriel Thalamites Reaction

The Gabriel Thalamites reaction is a multi-step reaction in which a primary amine is synthesized
through the reaction of a halogenated alkane with potassium phthalimide.

Gabriel Thalamites Reaction: A multi-step reaction to synthesize primary amines from halogenated
alkanes and potassium phthalimide.

The reaction involves the following steps:

• Reacting the halogenated alkane with potassium phthalimide to form an intermediate • Reacting
the intermediate with a base to form the primary amine

Amine Properties

Physical Properties

Property Characteristics

Physical State Lower aliphatic amines are gases, primary amines with 3 or more carbon atoms are liquids, and

Colour Amines are colourless, but may develop colour on exposure to air

Solubility Lower amines are soluble in water, while higher amines are less soluble due to decreased hydro

Boiling Point Boiling point increases with increasing branching and molecular weight

Basic Character

The basic character of an amine depends on three factors:

• Inductive Effect: Electron-releasing groups increase the basic character of an amine • Steric
Hindrance: Steric hindrance decreases the basic character of an amine

• Solution Effect: Hydrogen bonding in solution affects the basic character of an amine

Basic Character: The ability of an amine to donate an electron pair to form a bond.

The basic character of an amine can be calculated by considering these three factors.

Chemical Properties

Alkylation Reaction
The alkylation reaction of an amine involves the reaction of an amine with a halogenated alkane to
form a new amine.

Alkylation Reaction: A reaction in which an amine reacts with a halogenated alkane to form a new
amine.

The reaction is carried out in the presence of a strong base, such as potassium hydroxide.

Reaction with Acid Chloride

Amines can react with acid chlorides to form a new amine.

Reaction with Acid Chloride: A reaction in which an amine reacts with an acid chloride to form a new
amine.

The reaction involves the following steps:

• Reacting the amine with the acid chloride to form an intermediate • Reacting the intermediate
with a base to form the new amine## Carbonyl Amine Reaction

The carbonyl amine reaction is a famous reaction in organic chemistry. It involves the reaction of an
amine with a carbonyl compound, resulting in the formation of a carbonyl amine.

Primary Amines

Primary amines are amines that have one alkyl or aryl group attached to the nitrogen atom. They are
represented by the general formula RNH2.

Carbonyl Compounds

Carbonyl compounds are compounds that contain a carbonyl group (C=O). They are represented by
the general formula RCOX, where X is a leaving group.

Reaction Mechanism

The reaction mechanism of the carbonyl amine reaction involves the following steps:

• The amine (RNH2) reacts with the carbonyl compound (RCOX) to form an intermediate.

• The intermediate then reacts with a base to form the carbonyl amine.

• The carbonyl amine is then treated with water to form the final product.

Examples

• Benzylamine (C6H5CH2NH2) reacts with benzaldehyde (C6H5CHO) to form N-benzylidene

• Aniline (C6H5NH2) reacts with acetone (CH3COCH3) to form N-phenylacetamide.

Nitrous Acid Reaction

Nitrous acid (HNO2) is a strong oxidizing agent that reacts with amines to form nitro compounds.

Reaction Mechanism

The reaction mechanism of the nitrous acid reaction involves the following steps:

• The amine (RNH2) reacts with nitrous acid (HNO2) to form a diazonium salt.
 • The diazonium salt is then treated with a base to form the nitro compound.

Examples

• Aniline (C6H5NH2) reacts with nitrous acid (HNO2) to form phenyl diazonium chloride.

• Ethylamine (C2H5NH2) reacts with nitrous acid (HNO2) to form ethyl nitrite.

Diazotization Reaction

Diazotization is a reaction that involves the conversion of an amine into a diazonium salt.

Reaction Mechanism

The reaction mechanism of the diazotization reaction involves the following steps:

• The amine (RNH2) reacts with nitrous acid (HNO2) to form a diazonium salt.

• The diazonium salt is then treated with a base to form the final product.

Examples

• Aniline (C6H5NH2) reacts with nitrous acid (HNO2) to form benzene diazonium chloride.

• Toluidine (CH3C6H4NH2) reacts with nitrous acid (HNO2) to form toluidine diazonium
chloride.

Sandmeyer Reaction

The Sandmeyer reaction is a reaction that involves the conversion of a diazonium salt into a halide or
pseudohalide.

Reaction Mechanism

The reaction mechanism of the Sandmeyer reaction involves the following steps:

• The diazonium salt reacts with a copper(I) halide or pseudohalide to form the final product.

Examples

• Benzene diazonium chloride reacts with copper(I) chloride to form chlorobenzene.

• Toluidine diazonium chloride reacts with copper(I) bromide to form Bromo toluene.

Physical Properties of Diazonium Salts

Diazonium salts have the following physical properties:

Property Description

Appearance Colorless or yellowish solid

Solubility Soluble in water, but unstable in water

Stability Unstable in water, but stable in dry state

Temperature Stable up to 5°C

Note: The physical properties may vary depending on the specific diazonium salt.## Organic
Chemistry Reactions

Benzoate Reaction

• The benzoate reaction involves the reaction of a negative ion with a benzene ring

• This reaction is also known as the Bulky reaction

Effect of HBF4 on the Reaction

• When HBF4 is added to the reaction, it helps to remove the negative ion from the benzene
ring

• The negative ion is replaced by F-, resulting in the formation of a new compound

Reaction with H2O

• When the reaction mixture is treated with H2O, the negative ion is removed and replaced by
OH-

• This results in the formation of a final product with a hydroxyl group attached to the benzene
ring

Coupling Reaction

• A coupling reaction is a type of reaction that involves the combination of two molecules to
form a new compound

• In this reaction, the didymium cation acts as the "bridegroom" and the benzene ring acts as
the "bride"

• The didymium cation is fixed and cannot change, while the benzene ring can change its
structure

Products of the Coupling Reaction

Product Description

Benzene Aromatic ring with a nitrogen atom attached

Par amino benzene A compound with an amino group attached to the benzene ring

Identification of the Products

• The final product can be identified by its orange colour and its ability to form a clear solution

• The presence of a benzene ring and an amino group can be confirmed through various
chemical tests