9.1 Structure of Amines
- Amines are derivatives of ammonia (NH₃) in which one or more hydrogen atoms are replaced by alkyl or aryl groups.
- General formula: R–NH₂, R₂–NH, R₃–N
9.2 Classification
- Primary amines (1°): R–NH₂
- Secondary amines (2°): R₂–NH
- Tertiary amines (3°): R₃–N
- Aromatic amines: Amines attached to an aromatic ring (e.g., aniline)
9.3 Nomenclature
IUPAC Rules
- Identify the longest chain containing –NH₂
- Replace –e in alkane with –amine
- Number the chain so –NH₂ gets lowest number
- For aromatic amines, use aniline as parent
Examples:
- CH₃CH₂NH₂ → Ethylamine
- C₆H₅NH₂ → Aniline
9.4 Preparation of Amines
Aliphatic Amines
- From halides: RX + NH₃ → R–NH₂
- Reduction of nitro compounds: R–NO₂ + H₂ → R–NH₂
- Reductive amination of aldehydes/ketones
Aromatic Amines
- Reduction of nitroarenes: C₆H₅NO₂ + Sn/HCl → C₆H₅NH₂
- Gabriel phthalimide synthesis
9.5 Physical Properties
- Primary and secondary amines are polar → hydrogen bonding → higher boiling points
- Soluble in water (smaller molecules)
- Aromatic amines less soluble due to resonance stabilization
9.6 Chemical Reactions
- Reaction with acids: R–NH₂ + HCl → R–NH₃⁺Cl⁻
- Alkylation: R–NH₂ + RX → R₂–NH + HX
- Acylation: R–NH₂ + R’COCl → R–NH–COR’
- Diazotization (for aromatic amines):
C₆H₅NH₂ + NaNO₂ + HCl → C₆H₅N₂⁺Cl⁻
9.7 Preparation of Diazonium Salts
- Aromatic amines react with nitrous acid at 0–5°C:
C6H5NH2+HNO2+HCl→C6H5N2+Cl−+2H2O
- Important for azo coupling reactions
9.8 Physical Properties of Diazonium Salts
- Soluble in water
- Generally unstable at room temperature
- Explosive in dry form
9.9 Chemical Reactions of Diazonium Salts
- Replacement reactions:
- Sandmeyer reaction: C₆H₅N₂⁺Cl⁻ + CuCl → C₆H₅Cl
- Gattermann reaction: C₆H₅N₂⁺Cl⁻ + CuCN → C₆H₅CN
- Coupling reactions: Formation of azo dyes
9.10 Importance of Diazonium Salts in Synthesis of Aromatic Compounds
- Used to introduce halogens, CN, OH into benzene ring
- Formation of azo dyes: C₆H₅N₂⁺Cl⁻ + ArOH → Ar–N=N–Ar
📌 Important Exam Points
- Amines are basic due to lone pair on nitrogen
- Diazonium salts are key intermediates for aromatic substitution
- Aromatic amines less basic than aliphatic amines
- Sandmeyer reaction is important for halogenation