????? 9 Amines

1
????? 9Amines
2
Amines
2
1
3
2
3
IUPAC Name ????????

1. ??????????????????????????? parent chain
   ?????????????????????????????? amino(-NH2
   )?????????????? ???? aminoethane
2. ?????????????????? -NH2 ??????????????????
3. ?????????? R ??????? N (?????? H)
   ????????????????? R ????????? N-
   ???? N-methylaminoethane

3
4
CH3CH2CHNH2
2-aminobutane

(Sec-butylamine)
CH3
1
1
CH3CH2CHNHCH3

CH2CH3
3-(N-methylamino)pentane
(methyl-sec-pentylamine)
????????common name ??? aliphatic amines
???????????????? R ????????????????
?????????????? amine
4
5
1
CH3 - CH2 - N - CH2 - CH3
CH3  
1-(N-ethyl-N-methylamino)ethane
(methyldiethylamine)
1
CH3 - CH2 - N - CH2 - CH3
H
1-(N-ethylamino)ethane
(diethylamine)
5
6
CH3 - CH2 - CH - CH2 - CH3
  CH3 - N - CH3 
1
3-(N,N-dimethylamino)pentane
(dimethyl-sec-pentylamine)
1
CH3 - N - CH2 - CH2 - CH2 - CH3    
              CH3 - CH - CH3                 
1-(N-isopropyl-N-methylamino)butane
(methylisopropylbutylamine)
6
7
??????????? -NH2 ?????????????????????????
? ???????????? ??? parent chain
????????????????????
1
NH2- CH2 - CH2- OH
2-aminoethanol
O


1
NH2- CH2 - CH2- C - CH2- CHO

5-amino-3-oxopentanal
7
8
Aromatic Amines
Aniline
8
9
3-bromoaniline
2,4,5-trichloroaniline
9
10
???????????????????????

• Polar molecule
• ? ?????????????????????? ??????????? lone
• pair electron ???????????????? (N)
• ????????????
• 2. Basicity
• ? ???????????????????? (organic base)
  ????????????????? (NH3)???????? weak inorganic
  base

..
10
11

• 3. High boiling point
• 1? amines (RNH2) ??? 2? amines (R2NH)
• ?? H ??????????? N ?????????????? H-Bond
  ???
• ????????????????????????
  ????????????????????
• ?????????????????????????????????????????
  ?

11
12

• 4. Solubility
• ? ?????????????????? (1?, 2?, 3?) ??????????
• ????????????????? ?????????????????????????
  
• ?????? ???????????????????????????????????

13
???????????????

• Reduction of Nitriles ? ?????? 1?amine
  ????????????????????? 1 ?????
• R C N
  RCH2NH2
• Reduction of Amides ? ?????????????????????
• RCONH2 RCH2NH2

13
14

• Reduction of Nitro compounds
• ? ?????? aromatic amine arylamine
• ArNO2 ArNH2
• Hofmann degradation of Amides
• ? ?????? 1?amine ????? C ???? 1 ?????
• RCONH2 RNH2

14
15
Reduction of Nitriles
1
NaCN
RCH2Br
RCH2CN
1) LiAlH4
RCH2CH2NH2
RCH2CN
2) H2O
1) LiAlH4
NaCN
CH3CH2Br
CH3CH2CH2NH2
2) H2O
????????????? primary amine ?????????????????????
1 ?????
15
16
Reduction of Amides ( 1?, 2?, 3? amines)
2
O
1) LiAlH4
RCNH2
RCH2NH2
2) H2O
O
1) LiAlH4
CH3CNH2
CH3CH2NH2
2) H2O
??????????????????????????
16
17
Preparation of Arylamines
3
17
18
Hofmann degradation
4
O
RCNH2
RNH2
KOBr
ArNH2
ArCONH2
O
KOBr
CH3CNH2
CH3NH2
?????????????????????? 1 ?????
18
19
?????????????????

• Reaction of amines and alkyl halides
• 2. Reaction of amines and acid chlorides
• (Acylation of amines)
• 3. Diazonium salts from arylamines
• 4. Hinsberg Test

19
20
Reaction of Amines Alkyl halides
I
RX
RX
NH3
NH2R
NaOH
NaOH
(1?)
NHR2
(2?)
NR3
RX
(3?)
NaOH
CH3CH2Cl
CH3CH2NHCH3
CH3CH2NCH3
NaOH
CH2CH3
21
Reaction of Amines and Acid chlorides
(Acylation of Amines)
II
Amides
21
22
Diazonium Salts from Arylamines
III
Benzenediazonium ion
22
23
23
24
Hinsberg Test
IV

Amines Benzene sulfonyl chloride
Sulfonamides
???????????????????????? pri, sec ???
tert-amines
24
25
Benzene sulfonyl chloride
Sulfonamide
25
26
Primary sulfonamide Base soluble
Secondary sulfonamide Base insoluble
26
27
Tert-Amines
27
28
Hinsberg Test

• Pri-amine Benezenesulfonyl chloride

KOH
??????????
HCl
????????????
28
29
Hinsberg Test

• Sec-amine Benezenesulfonyl chloride

KOH
????????????
HCl
????????????
29
30
Hinsberg Test

• Tert-amine Benezenesulfonyl chloride

KOH
???????????? (??????????????)
HCl
?????????? (amine ??????????)
30