27

.

Usus magister egregious

 ,
-.


. .
, , .

,
,
.

. . ,
, . -.

O
+

O
R

CH3NO2
H

OH

NaOMe

OH
R

NO2

Ac2O

NO2

pyridine
(85 %)

CHO

CH3NO2
NaOMe, MeOH

NO2
(85 %)

Me
Me
CHO +

MeO

NO2

BuNH2

NO2

MeO
H

88 %
Cl H

Cl
CHO + Me-NO2

NO2

KOH
MeOH

74 %

Cl

Cl

H
H
H
HO

H
MeNO2

H
H

O
H2NCH2CH2NH2

H
HO

NO2

H
H

95 %

O
+
H

H2O

OH2

HO

H O

HO

HO

OH

H
O
H

OH

1,1-

H2O

HO

HO

OH

O
0,001

+
R

H2O

O
H

Cl

H
Cl

1,06

2000

Cl

O
2280

O
sp2 C 120 ,
60

1 200 000

H2O

HO

OH

sp3 C 109.5 ,
60

>
H

Alk

>
Ar

Ar

>
Alk

Alk

>
Ar

Alk
O

H
<
MeO

>

>
H
O

Ar
O

H
<
O2N


EtOH

O
R

EtO

OH

Et-OH
R

Et
H

HOEt

EtO

O
HO

O
H

OH

OH
H

OH
O

HOEt

O
H


HO
OH
HO
OH

HO
HO
HO

HO

HO

OH

OH

HO
HO

OH
OH

> 99%

OH

OH

HO

O
OH

HO
H

OH

HO
HO

HO

OH

HO

OH


EtO

OEt

O
EtOH +

EtO

OH

EtO

EtO

OH
+

O
Et-O

R
H
R
H
- ,

EtO

O
R

+ EtOH

EtO

OH

O
R

Et-OH

H
Et

OH

-

,
H

H
OH

O
2

OR
R

2 OR

+ H

R2

R1

HO

O R

HO

H
O R3

R1

R2

R1

R2

H2O

O R3

R1

R2

OH

H
3

R O
1

O R3
2

R3
R2

OH


OH

HO
HO

HO

OH

HO

HO
O

OH
OH

n CH2O

HO-(-CH2-O-)n-H
CH3

OH

OH

OH
OH

OH

HO
HO

OH

OH

OH

HO

OH

H3C

OH

O
O

O
O

O
CH3

Bu

+
H

Me

OH 12 .,

CHO
Me

MeOH

Me

MeO

HCl
2 , 30

Me

O O

. TsOH

0 , 2 .

OMe
OMe
H

OMe

O
+

Bu

50 %

OMe
60 %

iPrOH

TsOH

Bu

MeOH, H+ .
20 C, 15 .

62 %

OMe
O
OMe
+ MeO
H

 ()

3 % HCl, H2O

O
Me

30

MeO
Me

OMe
R

Me

O
+ 2 BuOH
H

CHO

2 M H2SO4
Me

-
H
H

OH

HO

HO

O
OH

OH

OH

HO

H2O

- H+

OH

OH

O H

MeO

CF3CO2H, H2O

MeO
O

CHCl3, 0 C, 1 .

OHC

O
O

(96 %)


CH3

SH

HS

BF3*Et2O

0-20

CH3
S
S
(99 %)

O
CH3

HS

SH

ZnCl2

25

S
S
CH3
(95 %)


CH2-
1

O +
2

HS

SH

BF3*Et2O

R1 S

CH2Cl2

R2 S

Ni + H2
EtOH

HH
1 C
R
R2

CH3

CH3

Ni + H2

H
S

20-40

(60 %)

 .
S

1) BuLi
2) CH3(CH2)4Br

HgCl2

MeOH-H2O

1) BuLi

2) Cl(CH2)3Br

S
S

1) BuLi
2) CH3(CH2)4Br

(87 %)
H

Cl

HgCl2
HO-CH2-CH2-OH - H2O

1) BuLi

O (50 %)

Nu

OH

R1

Nu

R2

Nu
O
H2N

H+

+ H2O
H

Me
H+ .

Me

O
+
Ph

Me

H2N

Ph

N
Ph

Ph
Me

(72 %)

 pH
pH 4

O
Ph

- pH 6

Ph

H2N

Ph

Ph
Ph

H H
Ph

OH2

OH
N
H

Ph

Ph

N
H

Ph

Ph

N
H

Ph

Ph

log
O
R

RNH2
R

R
+

H2O

pH
pH

Me

N
N

Me

Me

OH
- H2O

H2N

R
R

OH

Me

Me
CO2H

OH + H2O

R

N

N
O

Me

CO2H

Me

OH
O
NH2

CO2H

Me

CO2H

,
CHO

NH

+ NH3

+ H2O

H
O + NH3
H

N + H2O

N
N

Ph

Ph

NH

O CH OH; H+
3

+
NH
Ph

N
CHR + H2O
N
Ph

OH
()

NH2OH
()

NH2

O
Ph
N

NH

PhNHNH2
()

H2N NH O
()

NH2
NH

NH2

NO2

O2N

. 143

NH

NH

. 157
NO2

NO2

O2N

O2N
N

NH

. 139

NH2

NH2

NH

. 112

. 106

. 102

. 102

NH

. 156

NH

. 125

 -
1) NH2NH2*H2O
O

CHO

2) KOH; HOCH2CH2OCH2CH2OH; 200 C

CH3

(60 %)

1) NH2NH2*H2O

2) KOH; HOCH2CH2OCH2CH2OH; 240 C

HOOC

COOH
O

N2H4
KOH

(90 %)

HOOC

COOH
9

(93 %)

OH

N
2

NH2

R1

R1
R2

R1
H

H
2

R1 H

OH

R2

H2O

H2O

NH

H2O

R2

NH

R1
N2 + H
R

- N2

NH

H2O

OH

R1
H
R2

N
N


OH
O

OH
Zn(Hg)/HCl

65%
O
Zn(Hg)/HCl
83%


Ph

NH3

CHO

Ph

NH2

70 C
90 H2, Ni

89 %
Me

O
NaCNBH3
pH 6

Me

Me

Me

NaCNBH3

pH 6
90 %

NH3

O
Ph

Me

pH 6

NH2
Ph

Me

NaCNBH3

H
Ph

NH2
Me

CH2=O
Me
Me
NaCNBH3
N
pH 6

Ph

Me
81 %

O
H2N
H
N
BnO

O
OBn

H
N
BnO

O
OBn

O
N
H
CONH2

N
BnO

N
H

N
HN

CHO

O
BnO

NHR
O

OBn

NaCNBH3
20 C, 2 .

O
N
H
CONH2

NH

O
N
H

N
BnO

N
H
O

NH
N

HN

O
BnO
OBn

NHR
O

O
H

TsOH ()

C6H6, - H2O

( -)

, 94-95 %

H
H

OH2
N

OH
H

H
N

H2N

R1

H+ ()
- H2O

CHO

H2N

R2

H+ ()
- H2O

R1

R2

HN

. TsOH
O +

HN

O + H2O

110 C; ; 1

(75 %)

H
O

. TsOH

+ H2O

110 C; ; 1
(90 %)

2 R2NH

Me3SiCl

R2N-SiMe3 + R2NH2Cl

O
Si

NR2

R3

CH2Cl2

R1

R3
NR2

Si

Si