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Aminesphenols

This document discusses the nomenclature, properties, preparation reactions, and characteristic reactions of amines. It covers several methods for preparing amines, including reduction of nitro compounds, nitriles, amides, imines/enamines, and reductive amination of carbonyl compounds. It also discusses amine reactions such as those involving bases, amide formation, alkylation, and reaction with nitrous acid to form diazonium salts, nitrosamines, or C-nitroso compounds depending on the amine. Characteristic reactions of phenols such as ether formation, ester formation, Friedel-Crafts acylation, halogenation, and coupling with diazonium salts

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Sivakumar Ponnusamy
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31 views15 pages

Aminesphenols

This document discusses the nomenclature, properties, preparation reactions, and characteristic reactions of amines. It covers several methods for preparing amines, including reduction of nitro compounds, nitriles, amides, imines/enamines, and reductive amination of carbonyl compounds. It also discusses amine reactions such as those involving bases, amide formation, alkylation, and reaction with nitrous acid to form diazonium salts, nitrosamines, or C-nitroso compounds depending on the amine. Characteristic reactions of phenols such as ether formation, ester formation, Friedel-Crafts acylation, halogenation, and coupling with diazonium salts

Uploaded by

Sivakumar Ponnusamy
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Amines

Nomenclature Properties Preparation reactions Characteristic reactions Spectroscopy

Nomenclature and Properties of Amines

Preparation Reactions of Amines


Reduction reactions Rearrangements Nucleophilic substitution reactions

Amines via Reduction


Reduction

of nitro compounds Reduction of nitriles Reduction of amides Reduction of imines/enamines Reductive amination of aldehydes/ketones

Amines via Reduction: A Summary


R NO R CN R C NH O R C NHR' O R C NR' O R' C R'' R' C R'' C CH NR NH
H 2 / Pt or LiAlH 4
2

H 2 / Pt or LiAlH
2

or Sn / H

R NH

H 2 / Pt or LiAlH
2

RCH 2 NH RCH 2 NH

LiAlH

LiAlH

RCH 2 NHR' RCH 2 NR'


NH 3
2

LiAlH

H R' C NH R'' H R' C NHR R'' C


4

R'

C R''

H 2 / Pt

H 2 / Pt or LiAlH 4

RNH

R'

C R''

H 2 / Pt

NR

2 H / Pt or LiAlH 2

CH 2 NR

Amines via Rearrangement


Hofmann rearrangement (degradation) Curtius rearrangement


R C NH O
Primary amide X2
2

OH /H 2O

RNH

+ CO 2

+ R C N N N O
Acyl azide

H 2O

RNH

+ CO 2

+ N2

Amines via Bimolecular Nucleophilic Substitution


O C N H C O KOH C O O C N C O CH 2 R OH /H 2 O
-

O C N K+ RCH 2 X

O C N CH 2 R C O O C O RCH 2 NH 2 + C O O

Gabriel Synthesis

RCH 2 X + NH 3 RCH 2 NH 2 RCH 2 X RCH 2 X

RCH 2 NH 2 RCH 2 NHCH 2 R (RCH 2 )3 N + X

Alkylation
(RCH 2 )3 N

RCH 2 NHCH 2 R

RCH 2 X

(RCH 2 )4 N

Amine Reactions
Reaction

as Bases: Salt Formation Amide Formation Alkylation Reaction with Nitrous Acid

Amine Reactions with Nitrous Acid

Primary amines: Diazotization Secondary Amines: Nitrosamine formation Tertiary Amines: C-nitroso compounds
HONO o 0 C

RNH

+ R N N
alkyl diazonium salt unstable

N2

+ R

ArNH

HONO o 0 C

Ar

+ N N

Nu

N2

+ Ar Nu

aryl diazonium salt stable at low temp.

R 2NH
or

R
HONO o 0 C

R N N O
or

Ar N N

ArNHR

O
Nitrosamines

NR 2

HONO o 0 C

N O

NR 2

Aromatic C-nitroso compound

Mechanism of Diazonium salt formation


H H H O N
+

O O

+ H

H H H 2O +

O N
+

O N

N O nitrosonium ion H R N
+

NH

H N-nitros oammonium ion H R N


+

H 2O

O + H 3O

H N-nitros amine N O R tautomerization a diazenol N OH + H +


+

N H

OH

H H

H H

H 2O

a diazonium ion

Diazonium Salt Reactions


HO N N an azo dye I KI H 2O heat
+

OH

Phenol N N

Cl CuCl

CN CuCN 1. HBF 4 2. heat F

CuBr Br

H 3 PO2 H

Reactions of Phenols
formation via strong base or active metal Williamson ether synthesis Ester formation Friedel-Crafts acylation: Fries rearrangement Halogenation Coupling with diazonium salts Kolbe-Schmitt Carboxylation Reimer-Tiemann reaction
Salt

Phenol Reactions: A Summary


OR O- Na + NaOH CO2 4-7 atm heat OH C O Na O
+

1. NaOH 2. RX (primary) RCOCl OH or (RCO) 2 O ArN


+ 2

R C O

or Na

AlCl

OH R OH C O

CHCl 3 NaOH O Na C O H
+

N N Ar

Halogenation of Phenols
OH Cl 2 no solvent high temp. Cl major product OH Cl Cl Cl 2 H 2O Cl No Lew is acid is required OH Br 2 CS2 low temp. Br major product OH Br 2 H 2O Br Br Br OH

OH

No Lew is acid is required

Reimer-Tiemann Reaction Mechanism


O CHCl 3 OH NaOH/H heat
2O

C OH

H salicylaldehyde

Overall:

CHCl 3 + OH CCl 3
-

CCl 3 - + H 2 O
CCl 2 + Cl a carbene

OH + OH -

O H

O H + OCHCl 2 H 2O heat

O CCl 2 CCl 2 H O C H

CHCl 2

OH

2 HCl

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