Chapter 9: Amines

The content includes:

9.1. Structure, Classification

9.2. Nomenclature

9.3. Preparation of Amine

9.3.1. Alkylation of Amines

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9.3.2. Reduction of Nitro Compounds

9.4. Physical Properties

9.5. Reactions of Amines

9.5.1. Basicity of Amines

9.5.2. Electrophilic Aromatic Substitution of Arylamine

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9.5.3. Alkylation of Amine

9.5.4. Acylation of Amine

9.5.5. Reactions of amine with nitrous acid

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9.6. Reactions of Arenediazonium Salt

9.6.1. Replacement of the Diazonium Group

9.6.2. Diazo Coupling

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 Chapter 9: Amines

9.1. Structure, Classification

Bonding to N is similar to that in ammonia N is sp3-

hybridized

C–N–C bond angles are close to 109° tetrahedral value

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 Chapter 9: Amines

Amines are classified as primary (1°), secondary (2°), or

tertiary (3°), corresponding to one, two, or three alkyl or
aryl groups bonded to nitrogen.

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 Chapter 9: Amines

Quaternary ammonium salts

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9.2. Nomenclature

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 Chapter 9: Amines

9.3. Preparation of amine

9.3.1. Alkylation of amines: Using an excess of ammonia

helps to minimize multiple alkylations

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9.3.2. Reduction of Nitro Compounds

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 Chapter 9: Amines

9.4. Physical Properties

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 Chapter 9: Amines

9.5. Reactions of Amines

9.5.1. Basicity of Amines

- Amines are weak bases

- Primary alkyl amines are more basic than ammonia

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In the gas phase, basicity in the family of methylamines

increases with increasing methyl substitution

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In aqueous solution, trimethylamine is less basic than

dimethyl- or methylamine

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 Chapter 9: Amines

9.5.2. Electrophilic Aromatic Substitution of Arylamine

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 Chapter 9: Amines

9.5.3. Alkylation of Amines

Using an excess of ammonia helps to minimize multiple alkylations

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9.5.4. Acylation of Amines

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 Chapter 9: Amines

9.5.5. Reactions of amines with nitrous acid

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Secondary amine

N- nitroso amine

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 Chapter 9: Amines

Primary amine

diazonium

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 Chapter 9: Amines

Predict the major product of the following reactions

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 Chapter 9: Amines

9.6. Reactions of Arenediazonium Salts

9.6.1. Replacement of the Diazonium Group

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 Chapter 9: Amines

9.6.2. Diazo Coupling

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 Chapter 9: Amines

Exercises

1) Maximum pKb value is of

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2) pKb of amines is in order when X is

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 Chapter 9: Amines

3) Arrange the compounds shown below in order of

decreasing basicity (most basic first).

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