R

N O

N OH

O
je

NH (R)

je

N N
a

 :
a, , a, ,

NH2

1 a

NH2

N
H

H
R

ea

H2N

2-pa
2-a

NH2

NH2
2
3

3--2-a

NH2

HO
1

NH2

1,3- 2-ae

Ko 2 a a

N H
H

NHCH3

..

NH CH3

CH2CH3

N-e
N-a
N-e

N
H

N
H

3 a

NCH3
C2H5
N--N-


HO

NH2

NH2

NH2

OH

MeO

OH

OMe
OMe

OH

NH2

NH2

sp3 N

Me

Et

Et

HO

(S)-2-

HO

H
R

R1

R # R1 # H #

Me

(R)-2-

4
sp3

a

Et
H
Me

Et

Et
N

N
H
Me

Me

o
( e
o 5 7 Kcal/mol)

Et

Et
H
Me

N
H
Me

Me


o

K-
1. : RNH2 (pKa ~ 35) << ROH (pKa ~ 15)
2. K
(BuLi Na)

(CH3)2HC

CH(CH3)2

n-C4H9Li

(CH3)2HC

C4H10

Li

CH(CH3)2

2 NH3 + 2 Na

NaNH2
-a

H2

-
(LDA)

NaOH pKb ~ 1.7

(+I)

NH3 < CH3

pKb = 4.76

(+I)

NH2

pKb = 3.38

< CH3

(+I)

N
CH3
H pKb = 3.27

Me
N
Me

Me
pKb ~ 4.21

N
H

 BH+ ( )
B B.

1. (+I) (+R) e

1, 2 i 3 a (pKb 3 -4) > NH3 (pKb 4.7) >> ArNH2 (pKb

8.8 -13)

NH 2

NH 2

NH 2

NH 2

NH 2

N
-

..
N
H

 a
1.

NH2
G (+R) e
(NH2, OR..) - (+I) e
(CH3, R),

G
NH2
E- (-I) (-R) e (-NO2, CHO,
CO2R, CN) , (-I )>> (+R) X (-I) e
NH3+, -CF3

G
2. O : o-
a , a

3.

NH2

NH2

NH2

NH2

NO 2

NO2

- (-I)

: m- > p- > o-
1. +I e
2. +M (+R) e ,

 :
3. -
: sp3 < sp2 < sp ,
a ; .

R C NR

HCl

R C NR
H

R C NR
H

:
) N-; N,N-, ;
b) 1-N,N-

C2H5CONMe2

NH
O


1. A

H3N + CH3 Cl

H3N CH3 Cl

NH3

H2N CH3 + NH4Cl

-

CH3Cl, OH (CH ) NH CH3Cl, OH

3 2

(CH3)3N

CH3Cl

(CH3)4N Cl

Br

2 NH3

CO2H

NH2
CO2NH4

H+

NH2
CO2H

2. - () a-
(a) 1C-a

ROH + SOCl2

RCl

CN

RC N i LiAlH+4/Et2O
ii H3O

RCH2NH2

3. a :

NO2
HNO 3
H2SO4

NH2

CH3NH

Cl
NO 2

Fe/HCl

NO 2
CH2NH2

CH2Cl
2 NH3
NH4Cl

NO 2

CH3NH2

-
SN

NO 2

4. A

CH3

-H2O

CH3

NH3
NH

NaBH3CN
EtOH

5. a

RCONH2

NH2

1--2-

CH3

i LiAlH4/THF

RCH2NH2

ii H3O

Br2 /NaOH, H2O

RNH2

CO2


1.

2.
( ):
a, a, N-e

3. 1, 2 3

1. :

R3NH OH

HOH

HCl
R3N

R3NH Cl

CH3COOH

CH3COO NR3
H

je HCl:
a) , b) c) d) e)
b) f) p-a

2.

A. A ( )

R1NH2

CH3

O
C
Cl

O
CH3 C

HCl
NHR1

O
CH3 C
C6H5NH2

O
O

CH3

NHC6H5

C
O

R3N

CH3 C

N-
(a)

CH3CO2H

B. A
1

R NH2

i CH3

Cl

ii OH

R1NHCH3

Cl

HOH

1 a 2 a

CH3

CH3

2 CH3I

N
H
3-
2 a

N
H3C

CH3

 -:
, b) c) d) ki ) pa ,
f) 3- ()

( )

NaNO2 + HCl

HO N O

HCl
H2O

N O

N O

RNH2 NaNO2, HCl

N2

HOH

a + a

1 a NaNO2

H
N

H
H

N O

N O

H
N

H2O

CH2

HOH

N2

HOH
CH2OH

OH
C

N OH
H

N OH
H

CH2

 1 a 0 5 C

NH2
NaNO 2/H

N O

2 NaNO2 N-

CH3 N H

CH3 N N O
HO N O
HOH

N-

NaNO2/ HCl

R3N

NaNO2/ HCl

N--N-

3. 1, 2 i 3 a
1, 2 i 3

O
C6H5

RNH2

Cl

HCl

C6H5

NR

KOH

O H

N-
ja

C6H5

R2NH

C6H5

S
O

R3N

PhCO2Cl

Cl

HCl

C6H5

S
O

NR K

NR2
N,N-

1 a ( )

CHCl3

KOH

CCl2 + KCl + H2O

H
RN
H

H
CCl2

RN C Cl
H Cl

3
N-o

2 KOH

RN C

RN C

2 KCl

R3N

CH3CO 2H
H2O2

2 HOH

R3N O

-N-o

R NH2 I

NHCOCH3

RI

NH2

C6H5NMe3 Br

(CH3CO)2O
ili CH3COCl
N C

3 CH3Br
O
C6H5C
H
N C

C6H5

CHCl3/KOH
CCl2

H
K ()
Schiff-o

+R, -I NH2

NH2
3 Br2

Br

Br

3HBr

Fe
Br

NH2

NH3 HSO4

H2SO4
180 C

NH2

NHSO3H

H2O

180 C
SO3H

OH
HOH

Br
NH2
NaNO2/HCl

N Cl CuBr(Cl)

0 - 5 C

CN

H3PO2

CuCN
KI

: e

E ArN2+

Cl

H
N

H3O

pH 3 - 5

NMe2 NMe2: OH, O-, OR

ao

N
HCl

NMe2

4-a

NMe2
Cl

N
Me2N

SO3 Na

N
OH

Cl

N
N
OH