CHAPTER 11

AMINES

LECTURER: PHAN THỊ HOÀNG ANH 1

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 I. NOMENCLATURE

 Common name: alkyl + amine

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IUPAC name: Alkanamine

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NH2 is treated as a substituent (amino-) when the compound has other functional groups
(COOH > CHO > C=O > OH)

Aromatic amines are named as derivatives of aniline.

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 II. PREPARATION
1. Alkylation of NH3:

Mixture of
products
→ Low
selectivity
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3. Reduction of nitriles

NaBH4 do not work

?
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 4. Reduction of amides
O
1. LiAlH4
C 2. H2O R CH2 N R1
R N R1
R2
R2

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5. Hofmann rearrangement of amides
Primary amide → primary amine
O
Br2, NaOH
C RNH2 + Na2CO3
R NH2 H2O

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6. Reductive amination of carbonyl compounds

65%
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 7. Synthesis of arylamines
→ Reduction of nitro group, usually with

– H2 / Pt, Pd or Ni

– Fe/HCl or Sn/HCl → do not affect C=C, C=O bonds

– Na2S, (NH4)2S

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Na2S, (NH4)2S
selectively
reduce only
one in two
NO2 groups
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 RNH2

NH3 Alkylation
RX RNR1R2

O
Amide reduction RCH2NH2
C
R NH2
O
Amide reduction
C RCH2 N R1
R N R1 R2
R2

R CH N R1
R' R2 15
 III. REACTIONS OF AMINES

Base

Nucleophile

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1. Alkylation of amines

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Quaternary ammonium salt→ Hoffman elimination
Synthesis of 1-alkene good leaving group
bad leaving group

Hofmann
D elimination

Major product
Hofmann elimination→ less substituted alkene

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2. Acylation of amines

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Acylation of arylamines

→ Protecting the NH2 group in an arylamine

→ Moderate the NH2 reactivity in an arylamine

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 ?

NH2 NH2
?

Br

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 3. Reaction with carbonyl compounds
Primary amine → imine

imine
Secondary amine → enamine

enamine 24
 4. Reaction with HNO2
HNO2 / H+→ NO+

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Primary alkyl amine → diazonium ion, unstable

Unstable

Alkene, alcohol, alkylhalide

Primary arylamine b.1 → aryl diazonium ions

NO+
ArNH2 ArN≡N+
0-5oC
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Secondary arylamines, alkylamines → Nitrozoamine

N-Nitrozoamine
Tertiary alkylamines

R3N NO+ no reaction

Tertiary arylamines → nitrozation (SE)

NO+
R2N SE
R2N NO + H+

p-Nitrozoarylamine 28
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IV. REACTIONS OF ARYL DIAZONIUM IONS

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Nucleophilic substitution → Ar-OH và Ar-I

Phenols synthesis

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Schiemann reaction → Ar-F

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Sandmeyer reaction → Ar-Cl, Ar-Br, Ar-CN

CuX: CuCl, CuBr, CuCN X from CuX

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 Reductive deamination → Ar-H

These reductions are free-radical reactions in which ethanol or hypophosphorous

acid acts as a hydrogen atom donor: 34
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 AZO-COUPLING REACTION
SE reaction of an Aryl diazonium ion to an activated
aromatic ring

Q: strong electron donor groups

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Mechanism of Hofmann rearrangement

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