ORGANIC CHEMISTRY
OCHE220203
Lecturer: Dat P. Nguyen, Ph.D
Email: datnp@[Link]
Department of Chemical Technology
Faculty of Chemical and Food Technology 1
CHAPTER 15
NITROGEN-CONTAINING
COMPOUNDS
2
CONTENTS
1. Amines
1.1. Preparation of Amines
1.2. Reactivity of Amines
2. Diazonium Salts
2.1. Preparation of Diazonium Salts
2.2. Reactivity of Diazonium Salts
3
1. Amines
1.1. Preparation of Amines
Aldehydes/
Ketones
Other
reductive
Nitrogen-Co
Alkyl halides amination ntaining
Compounds
alkylation reduction
Amines
4
1. Amines
1.1. Preparation of Amines
1.1. Alkylation of Ammonia (NH3)
Mechanism:
• SN2
• Can form a mixture
of 1°, 2°, 3° amines
and ammonium salt
5
1. Amines
1.1. Preparation of Amines
1.2. Gabriel Amine Synthesis
To get 1°/2° amine from alkyl halide → Gabriel amine synthesis
• Step 1
• Step 2
or
6
Amine Synthesis - Practice
7
1. Amines
1.1. Preparation of Amines
1.3. Reductive Amination
8
1. Amines
1.1. Preparation of Amines
1.3. Reductive Amination
9
Synthesis Strategy
10
Synthesis Strategy
11
Synthesis Strategy
12
Synthesis Strategy
13
Amine Synthesis - Practice
14
Amine Synthesis - Practice
15
1. Amines
1.1. Preparation of Amines
1.4. Reduction of Other Nitrogen-Containing Compounds
Reduction of Amides
Reduction of Nitriles
16
1. Amines
1.1. Preparation of Amines
1.4. Reduction of Other Nitrogen-Containing Compounds
Reduction of Imines
Reduction of Azides
SN2
17
1. Amines
1.1. Preparation of Amines
1.4. Reduction of Other Nitrogen-Containing Compounds
Reduction of Nitro Compounds
18
1. Amines
1.2. Reactivity of Amines
Nucleophilic
Substitution (SN2)
Amines as Nucleophilic Addition
Nucleophiles (AN)
Hofmann Nucleophilic Acyl
Elimination Substitution (NAS)
Amines
Reaction with
HNO2
Oxidation
19
1. Amines
1.2. Reactivity of Amines
1.2.1. Amines as Nucleophiles for SN2 Reactions
Alkylation of amines
Mechanism:
• SN2
• Can form a mixture
of 2°, 3° amines and
ammonium salt
20
1. Amines
1.2. Reactivity of Amines
1.2.2. Amines as Nucleophiles for AN Reactions
Imine/Enamine formation (review Chapter 13)
21
1. Amines
1.2. Reactivity of Amines
1.2.3. Amines as Nucleophiles for NAS Reactions
Amidation (review Chapter 14)
Reaction of amine with acid chloride/anhydride/ester
22
1. Amines
1.2. Reactivity of Amines
1.2.4. Hofmann Elimination
23
1. Amines
1.2. Reactivity of Amines
1.2.4. Hofmann Elimination
• Form less substituted C=C double bond
24
1. Amines
1.2. Reactivity of Amines
1.2.4. Hofmann Elimination
Mechanism
25
1. Amines
1.2. Reactivity of Amines
1.2.4. Hofmann Elimination
Mechanism
26
Synthesis Strategy
27
Synthesis Strategy
28
Hofmann Elimination – Practice
29
1. Amines
1.2. Reactivity of Amines
1.2.5. Reaction with HNO2
Nitrous acid and the formation of nitrosonium ion
30
1. Amines
1.2. Reactivity of Amines
1.2.5. Reaction with HNO2
1° amine → diazonium salt
Mechanism
31
1. Amines
1.2. Reactivity of Amines
1.2.5. Reaction with HNO2
Alkyl diazonium salt → unstable
Aromatic diazonium salt → stable
32
1. Amines
1.2. Reactivity of Amines
1.2.5. Reaction with HNO2
2° amine → nitrosamine
33
Reaction with HNO2 – Practice
34
1. Amines
1.2. Reactivity of Amines
1.2.6. Oxidation
Oxidation of amine can give a variety of products
35
2. Diazonium Salts
2.1. Preparation of Diazonium Salts
Reaction of 1° amine and HNO2
36
2. Diazonium Salts
2.2. Reactivity of Diazonium Salts
Reactions of aromatic diazonium salts
Sandmeyer
reaction
CuI
Schiemann
reaction
37
Diazonium Salts – Practice
38
2. Diazonium Salts
2.2. Reactivity of Diazonium Salts
Azo compound formation (Azo coupling)
Electrophile Nucleophile
+ HX
pH: acidic or mildly basic
39
2. Diazonium Salts
2.2. Reactivity of Diazonium Salts
Azo coupling – Mechanism
40
2. Diazonium Salts
2.2. Reactivity of Diazonium Salts
Azo coupling – Determine coupling partners
41
2. Diazonium Salts
2.2. Reactivity of Diazonium Salts
Azo coupling – Determine coupling partners
42
Azo Coupling – Practice
43
Azo Coupling – Practice
44