(Amine)
01403221
(Amine)
)/0.12*
& 3456
*78#
*(( +9 *(
-NH2 )/=>$
R-NH2 , Ar-NH2
!"
#$
%&'()'" *(&#
'" +#
(
, '" -*.*"
1
2
$97
$2
1.
Primary amine
Secondary amine
Tertiary amine
(92
RNH2
R2NH
R3N
R4N+X-
CH3NH2 methylamine
(CH3)2NH dimethylamine
(CH3)3N trimethylamine
(CH3)3N+HCltrimethylammonium chloride
$97"R
+6S*((+9*(S *(8# 8#
-#S
amine
CH3NH2
methylamine
CH3CH2NH2
ethylamine
CH3CH2CH2NH2
propylamine
CH3CH2CH2CH2NH2 UUUU.
3
2. $97*XX IUPAC
)/0.1234X [NH2
#S amino -+8$9734X .8*"
-*+S2 [NH2 8#
#(2
CH3CH2NHCH3 ethylmethylamine
C6H5-NH-C6H5
diphenylamine
C6H5-NH2
aniline
C6H5-N-(CH3)2
N,N-dimethylaniline
4
NH2
CH3CH2CHCH3
NHCH3
CH3CH2CHCH3
H2NCH2CH2OH
H2NCH2CH2COOH
5
2-aminobutane
2-(N-methylamino) butane
2-aminoethanol
3-aminopropanoic acid
6
1
Aromatic amine
$97(92 aniline
$97*XX"R )/0.1 aniline
58+6S*(( SX3 ^+8^$8, N
X -*+S2+6S*((
NH2
NHCH3
NH2
CH3
anilne
N(CH3)2
o-toluidine
"S#^+RS
$97"R*XX*((
* S)(7
-(8
amine )/ ammonium
+9 aniline )/ anilinium
*(8#
$97*3 +(
N-methylaniline
"6 #7 3)2(9 R4N+X- +9 R3N+HX-
N,N-dimethylaniline
7
8
"X _.
$97(92 aniline
(CH3)3N+HNO3-
)/(0(72!#
(&(
!-38.&"5.1&34X!-
- primary amine *(& secondary amine "5.1&34
&+#S(0(38 primary amine .1&34#S
secondary amine
- tertiary amine 3S.1&34&+#S(0(
trimethylammonium nitrate
-
+
-
NH3Cl
CH3
N−
−CH3Cl
CH3
anilinium chloride
+
N,N,N-trimethylanilinium chloride
H
CH3−N−
−H
H
N−
−H
CH3
H
N−
−H
CH3
9
10
)
X
X092
- 092 "6#S"*( * S 7-#S
".#*(4(7!-+(0(^(8
- 092 primary amine *(& secondary amine
"6#S tertiary amine
11
"
CH3NH2
CH3CH3
CH3CH2NH2
CH3NHCH3
CH3CH3CH3
$97
methylamine
ethane
ethylamine
dimethylamine
propane
MW
31
30
45
45
44
09,°°C
-7.5
-89
17
7.5
-42
12
2
Kb 2 aliphatic amine &"6#S Kb 2 NH3
#)/X"2"
97k(2 inductive effect no7+6S*(()/+6S
7^+8(f releasing group
)/"7(f 6S7
#7& 3 -^+8*"#)/X"
+
RNH2 + H2O
R-NH3 + OHKb
"_.#)/X""5
(-X38!
NH3 < NR3 < RNH2 < R2NH
NR3 )/X"8
97 steric effect -^+8& 9728^$8(f 6S3S"&#
+
[R-NH3 ][OH-]
[RNH2]
=
13
Aromatic amine S Kb 7-#S aliphatic amine o
)/X"7S#S97 resonance effect
NH
+
2
* S97X) +
NH2
+
NH2
NH2
14
"
1. Alkylation of Ammonia and Amine
*((*43(-)t
X*
38
*(&58*
.-)t
X
*((*43( S&38"$+o7
+
NH3
NH2
H+
destabilization
R-X + NH3
R-NH2 + R-X
R2NH + R-X
R3N + R-X
15
16
(3)t
R-NH2
primary amine
R2NH
secondary amine
R 3N
tertiary amine
R4N+ Xquaternary ammonium salt
R-X + NH3
H
R-N-H2 + NH3
+
$S
C2H5Cl + NH3
C2H5NH2 + CH3Cl
17
+
R-NH
3+X
R-NH2 + NH4+
C2H5NH2
primary amine
C2H5NHCH3
secondary amine
18
3
2. Reduction
2.1 Reduction of Nitro Compound
& "5 38
#"")&X3 8#
reducing agent $S
+(f "&" +9 X0 X
)v
!38"+(
$)
CH3(CH2)6CH2Br + NH3
CH3(CH2)6CH2NH2 + [CH3(CH2)6CH2]2NH + [CH3(CH2)6CH2]3N
+
[CH3(CH2)6CH2]3N+Br-
Ar-H
HNO3 , H2SO4
Ar-NO2
Zn, HCl
Ar-NH2
19
$S
20
2.2 Reduction of Nitrile
NO2
NH2
[H]
R-C≡
R-CH2NH2
≡N
Nitriles
primary amine
Reducing agent 7^$8
- H2/Ni , Pt , Pd
- NaBH3CN (Sodium cyanoborohydride)
- LiBH3CN (Lithium cyanoborohydride)
- LiAlH4 (Lithium aluminium hydride)
1. Sn,HCl, ∆
2. OH-
CH3
NO2
CH3
1. Sn,HCl, ∆
2. OH-
NH2
21
)v
72o!)/ nucleophilic addition hydride 7& 2X*(&3 H
H
O
2
R-C≡
≡N + LiAlH4
R-C=NH
#
S
CH3CH2C≡
≡N
Propanenitrile
LiAlH4
R-CH2-NH2
H2O
22
LiAlH4
H2O
C=N
LiAlH4
H2O
H
R-C-N--H
H
23
CH3CH2CH2NH2
Propylamine
CH2NH2
24
4
3. The Gabriel synthesis
)v
!
^$8 primary amine ^$8
phthalimide + KOH
potassium phthalimide
OH- /H2O
potassium phthalimide + RX
amine
O
C NH
C
O
potassium phthalimide
R−
−NH2 + Na2CO3
+ 2H2O + 2NaBr
CH3−NH2+ Na2CO3
+ 2H2O + 2NaBr
)v
!&38 primary amine 7X"01~
27
)v
2
R2−NH + H+
R−
−NH3+
R2NH2+
R3−N + H+
R3NH+
O
R−
−C−
−Cl
+ NaN3
O
CH3-C-Cl + NaN3
O
R−
−C−
− N3
R−
−N=
=C=
=O
H2O
R−
−NH2 + CO2
H2O , ∆ CH -NH + CO + N
3
2
2
2
4.3 Schmidt reaction
H SO
RCOOH + NaN3 2 4
CHCl3
R−
−NH2
H2SO4
CHCl3
CH3−NH2
CH3COOH + NaN3
28
"5*
"
-
-)v
X&38(9 *(8#*
"S#7)/
"(&(
-^+8)/S&38"
N+H3Cl-
NH2
+ NaOH
N+H3Cl-
NH2
OH- /H2O
26
4.2 Curtius reaction
38}.& Amide 7 2 & 2 H SX N
O
1. )v
X
R−
−NH2 + H+
potassium phthalimide
25
O
acetamide
RX
DMF
O
C O
+ RNH2
C O
amine
O
4. +90.12
4.1 Hofmann Rearrangement
CH3−C−
−NH2 + Br2+ 4NaOH
O
C NR
C
O
O
− +
C NK
C
O
KOH
C2H5OH
R−
−C−
−NH2 + Br2 + 4NaOH
O
− +
C NK
C
O
+ H2O + NaCl
+ HCl
29
30
5
3. )v
amide
2. Alkylation
R−
−NH2
R−
−X
R−
−X
R2−NH
R3−N
(CH3CH2)3−N + CH3I
R−
−X
R4
-N+X-
primary amine *(& secondary amine -)v
X
Xn(*(&0.138 amide
O
(CH3CH2)3N+CH3I-
CH3CH2NH2 + CH3I
excess
CH3CH2N+(CH3)3I-
O
R−
−C−
−OH
R−
−NH−
−C−
−R
O
O
R-NH2
R−
−NH−
−C−
−R
R−
−C−
−Cl
O
O
O
R−
−C−
−O−
−C−
−R′
R−
−NH−
−C−
−R
$S
O
O
+
CH3CH2−NH2 CH3C−
−Cl
CH3C−
−NHCH2CH3
+ HCl
O
32
4. )v
X Sulfonyl chloride
)v
!#S Hinsberg test
Primary amine
CH3−NH2 + CH3C−
−OH
O
O
S Cl NaOH
R-NH2 +
CH3−NH2 + CH3C−
−Cl
O
O
+ R′−C−
−OH
31
O
O
(CH3)3N + CH3−C−
−O−
−C−
−CH3
H O
R-N S
+ NaCl + H2O
O
N-alkyl sulfonamide
(&(
^X"
33
Secondary amine
O
R2-NH +
S Cl
O
34
5. )v
X3 " (HNO2)
NaOH
O
R2-N S
+ NaCl
O
+ H2O
N,N-dialkyl sulfonamide
3S(&(
^X"
Primary aliphatic amine
)v
72o!
#S Diazotization ^+8"
diazonium salt 73S"5
*(&&"(
#^+8
*(4( "*( *(&*€"3 R-NH2
Tertiary amine
3S)v
XXnn(=((3
HNO2
[RN2+] H2O N2 + ROH + C=
=C
diazonium salt
35
36
6
Primary aromatic amines
Ar−
−NH2
$S
HNO2
[Ar−
−N2
+]
(CH3)2NH + HCl + NaNO2
dimethyl aniline
arene diazonium salt
Secondary amines
! *(( *(&*( 97-)v
X3 "
&38 nitrosamines )/2+(#"+(9
R-NH2
HNO2
(CH3)2N−
−N=
=O
nitrosodimethyl aniline
N H + HCl + NaNO2
N
CH3
N=O
CH3
N-nitroso-N-methyl aniline
[R2N−
−N = O]
nitrosamine
37
tertiary *( 97-)v
X3 "
& nitrosoaromatic compound 7 -*+S para* S58 -*+S para +6S&*(8#&28 -*+S orthoH3C
N
H3C
)v
2 aromatic diazonium salt
1. )v
X!-
Ar-N2+Cl- + H2O
NH2
H3C
N
H3C
+ HCl + NaNO2
38
N=O
CH3
OH
p-nitroso-N,N-dimethyl aniline
*7+6S diazonium 8#
& 34
^$8 H3PO2
Ar-N+ ≡NCl- + H3PO2 →
Br
NH2
CH3
Br NaNO2 Br
H2SO4
N+2
CH3
CH3
N2
CH3
H2O, H+
40
Br
CuBr
Cl
N≡N+Cl-
Br
CH3
HNO2
3. Sandmeyer reaction
*78#
-Cl -Br -CN
Ar-H + N2
Br H3PO4
N2+
O-cresol
39
2. )v
X34)="="
Ar-OH + N2 + HCl
+ N2
Br
+
CuCl
CN
CuCN
41
42
7
4. )v
coupling reaction
)v
& azo compound
OH
N≡N+Cl+
OH
N=N
Orange solid
43
8