1. Chapter 15 Amine and Nitriles
I Classification and nomenclature of amines
II physical properties
III Basicity of amines
IV Preparation of amines
V Reactions with inorganic acids

2. I. Classification and nomenclature of amines
Amine: derived fromNH3
Primary amines: RNH2
Secondary amines: RNHR〞
Tertiary amines: 　　　RNR′R 〞
（氨） 伯胺 仲胺 叔胺
Quaternary ammonium compounds:
季铵盐

3. Examples: CH3NH2 CH3CH2NH2 methylamine ethylamine tert-butylamine
aniline
methyethylamine
diethylamine
(CH3CH2)3NH
Triethylamine
methylethylpopylamine

4. 2-methyl-4-aminohexane
(CH3)4N+Cl-
Tetramethyl
ammonium chloride
2-methyl-4-aminohexane
p-minobengoic acid
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5. II physical properties
Polarity: moderately polar
Hydrogen bond:
Primary and secondary amines can form strong hydrogen bonds to each other and to water.
Tertiary amines cannot form hydrogen bonds to each other but they can form hydrogen bonds to water.

6. III Basicity of amines 1.Structure feature of amines. CH3NH2 NH3
similar to NH3 ，sp3 hybtidized.
NH3
CH3NH2
(CH3)3N

7. (2) Compairison of basicity.
(1) Lone pair of electrons.
(2) Compairison of basicity.
a. Arimary amines
Secondary amines
Tertiary amines
CH3CH2NH2
(CH3CH2)2NH
(CH3CH2)3N
and ammonia
NH3

8. Conclusion? Consider (F3C)3N?
b. Aliphatic amines
Aromatic amines
Consider from:
a. Inductive effect
b. Conjugative effect
c. Steric effect
Conclusion? Consider (F3C)3N?

9. IV Preparation of amines
1.Alkylation of ammonia.

10. 3.Reduction of nitriles and amides.
H2/Ni
NC-CH2CH2CH2CH2-CN H2N-CH2 (CH2)4CH2NH2
hexadiamine
LiAlH4
H2O
RCONH2
RCH2NH2
LiAlH4
H2O
LiAlH4
H2O
Specially suitable for preparing secondary and tertiary amine.

11. 4. Reduction of nitro compounds
Specially suitable for preparing aromatic amines.
Discuss different reductants used in reduction.

12. 5.Hofmann degradation(降级)
NaOX / 2NaOH　　
+Na2CO3　　
RCONH2
RNH2　　
+NaX+H2O
Producing amines with one less carbon.

13. V. Reactions with inorganic acids
CH3CH2NH CH3CH2 N+H3Cl-
(CH3CH2) 2 NH (CH3CH2) 2 N+H2Cl-
(CH3CH2) 2 N (CH3CH2) 3N+H2Cl-

14. Applications: 1.Distinguish from 1.Distinguishing amines from nonbasic
compounds that are water insoluble.
2.Separating amines from nonbasic compounds
that are water insoluble.
Examples:
1.Distinguish
from

15. 2. Separate CH3 (CH2)10 CH3(b.p.221。C) with CH3 (CH2)9NH2 (b.p.216。C)
Organic Layer
dilHCl
CH3 (CH2)10 CH3
CH3 (CH2)9NH2
Water Layer
CH3 (CH2)9NH2·HCl
Organic Layer
CH3 (CH2)9NH2
NaOH
Water Layer
Water Layer
(NaCl)

16. 2.Acylation (with acid chloride or anhydride)
no reaction

17. (1) Prepare one amine form another amine.
Applications:
(1) Prepare one amine form another amine.
(2) Protect-NH2 from oxidation
Example:

19. (Similar to alylation)
4.Sulfonylation
(Similar to alylation)
soluble
unchanged (oil-like makerial)
Separating and distinguishing three types of amine.

20. a. Primary aliphatic amines
5.Nitrosation
(1)With primary amines
a. Primary aliphatic amines
0~5℃
Alkene,alkyl halide
or alcohol etc.

21. b.Primary aromatic amines.
(stable if keept below 5℃)
Diazonium salt