Chapter 11

Amines

Asst. Prof. Bilgesu Onur SUCU

Based on
McMurry’s Organic Chemistry, 6th edition
 Naming Amines
 Alkyl-substituted (alkylamines) or aryl-substituted (arylamines)

 Classified: 1° (RNH2), methyl (CH3NH2), 2° (R2NH), 3° (R3N)

2
 Quaternary Ammonium Iions
 A nitrogen atom with four attached groups is positively charged

 Compounds are quaternary ammonium salts

3
 IUPAC Names – Simple Amines
 For simple amines, the suffix -amine is added to the name of the alkyl

substituent

4
IUPAC Names – Amines With More Than One Functional Group

 Consider the NH2 as an amino substituent on the parent molecule

5
 IUPAC Names – Multiple Alkyl Groups

 Symmetrical secondary and tertiary amines are named by adding the

prefix di- or tri- to the alkyl group

6
 IUPAC Names – Multiple, Different Alkyl Groups

 Named as N-substituted primary amines

 Largest alkyl group is the parent name, and other alkyl groups are considered N-

substituents

7
Common Names

8
 Structure and Bonding in Amines
 Bonding to N is similar to that in ammonia

 N is sp3-hybridized
 C–N–C bond angles are close to 109° tetrahedral value

9
 Basicity of Amines
 The lone pair of electrons on nitrogen makes amines basic and nucleophilic

 They react with acids to form acid–base salts and they react with electrophiles

10
 Amides
 Amides (RCONH2) in general are not proton acceptors except in very strong acid

 The C=O group is strongly electron-withdrawing, making the N a very weak base

 Addition of a proton occurs on O but this destroys the double bond character of

C=O as a requirement of stabilization by N

11
 Amines as Acids
 Loss of the N–H proton requires a very strong base

12
 Basicity of Substituted Arylamines
 The N lone-pair electrons in arylamines are delocalized by interaction

with the aromatic ring  electron system and are less able to accept H+
than are alkylamines

13
 Substituted Arylamines
 Can be more basic or less basic than aniline

 Electron-donating substituents (such as CH3, NH2, OCH3) increase the

 Electron-withdrawing substituents (such as Cl, NO2, CN) decrease

14
 Synthesis of Amines
 Reduction of nitriles and amides

15
 Reduction Aryl Nitro Compounds
 Arylamines are prepared from nitration of an aromatic compound and reduction of the nitro

group
 Reduction by catalytic hydrogenation over platinum is suitable if no other groups can be

reduced
 Iron, zinc, tin, and tin(II) chloride are effective in acidic solution

16
 Nucleophilic Substitution Reactions of
Alkyl Halides
 Ammonia and other amines are good nucleophiles

17
Reductive Amination of Aldehydes and Ketones

 Treatment of an aldehyde or ketone with ammonia or an amine in the

presence of a reducing agent

18
 Reductive Amination Is Versatile
 Ammonia, primary amines, and secondary amines yield primary,

secondary, and tertiary amines, respectively

19
 Reactions of Amines
 Alkylation and acylation have already been presented

20
Diazonium Salts: The Sandmeyer Reaction
 Primary arylamines react with HNO2, yielding stable arenediazonium

salts
 Alkylamines react with HNO2 but the alkanediazonium products of these

reactions lose N2 rapidly, leaving carbocations

 The N2 group can be replaced by a nucleophile

21
 Diverse Reactions of
Arenediazonium Salts
 Sequence of (1) nitration, (2) reduction, (3) diazotization, and (4)

nucleophilic substitution leads to many different products

22
 Preparation of Aryl Halides
 Reaction of an arenediazonium salt with CuCl or CuBr gives aryl halides

(Sandmeyer Reaction)
 Aryl iodides form from reaction with NaI without a copper(I) salt

23
 Aryl Nitriles and Carboxylic Acids
 An arenediazonium salt and CuCN yield the nitrile, ArCN, which can be hydrolyzed to

ArCOOH

24
 Formation of Penols (ArOH)
 From reaction of the arenediazonium salt with copper(I) oxide in an

aqueous solution of copper(II) nitrate

25
 Reduction to a Hydrocarbon
 By treatment of a diazonium salt with hypophosphorous acid, H 3PO2

26