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2007

_____________________________________________________________________________

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..

-

,


2007
1

547.057
: / .. , .. ; . .
. -. , 2007. 126 .
.
.
, . .
-
.
ISBN 978-5-7964-1007-3
. 1. . 5. .: 15 .

: . . ..

ISBN 978-5-7964-1007-3

.. , .. , 2007

, 2007
2


NO2 . . , ,
-, - N-.

.
, . , (,
, ). , , .
. :

..O ..
.
+..
R .. N .
.. ..._
O.
..


(0.122 ), - 127-130. .
3

- NO
, . :
_


, :
O

O
N

N
O

1.

: 100%- (d l.51). (d l.4), 65%


HNO3, (d l.5), 94% HNO3 . ,
12% , HNO3.
. , , .
, ,
( ).
.
4

. , . . 86 .

. ,
.

,
. , ; , , , .. .

.
.

, , . , .
90%-
.
,
. , . NO2+, :
HNO3 + 2H2SO4 3+ + NO2+ + 2HSO4.

(d 1.4-1.5) (d
5

1.84) . ,
.
,
(5%- ). .
.
,
. 92-93%- ,
SO3 (10-20%
).
, .
100%- 96%- 9:1.
( IR-120).
, , :
+

NO2

HNO3 + 2 Res SO3H

+ H3O

_
+ 2 Res SO3

Res - .


, -,
- .

.

( ) :
NaNO3 + H2SO4 HNO3 + NaHSO4.
6

,
, , :
4HNO3 4NO2 + 22 + 2.

, , .
,

.

(III), (II), (II).


Al(III), Ba(II), Bi(III), Cd(II), Co(II), Hg(II),
Mn(II), Ni(II), Zn(II), Cu(II), (), :
Cu(NO3)23H2O + 5(CH3CO)2O 2CH3COONO2 +
+ Cu(CH3COO)2 + 6CH3COOH.

,
. , , , 3--4 4-, 9-
.

NO2 (II)

N2 N2O4.
. N2O4 NN:
7

N2O4 2NO2.

N2O4
NO+ NO3.
, . N2O4
, . , , ( 20-24), . N2O4
. , N2O4 - 95%. N2O4.
,
( ).
, , 5-
3--4-
4-.

N2O5 ,
; HNO3 P2O5 N2O4 ,
N2O4 HNO3. :
N2O5 2 NO2 + 1/2 O2.

, N2O5 :
O +
+ O
N O N
O
O
8

N2O5
NO2+NO3.
, , N2O5
, , , , .

,
CH3COONO2,
, .
, .
, .
HNO3 ,
, ,
, HNO3 (CH3CO)2O:
O
(CH3CO) 2O

H3C

HNO3

CH3COOH

O NO2
O

H3C

O
H 3C

O NO2

O NO 2
H

O
(CH 3CO) 2O

2 H 3C
O NO 2

NO2

N 2O5

_
NO3

N 2O5


(V) :
O
N2O5 + (CH3CO)2O

2 H3C
O NO2

CF3COONO2. - ON, .
:
O

AgNO3

AgCl

O NO2

Cl

.
, ( ).
, , , , , , .
-.
,
, . ,
. , ,
; .
10

, .
: -, -, -
, .
. .
. , , ,
, ( , .).

( )
:
C2H5

HNO3 + C2H5OH

O NO2

H2O


:
H3C

H3 C
NC

OH

NC

HNO3

O NO2

H2 O

H3C

H3 C

NO2+X, =BF4, PF6, ClO4, AsF6, HS2O7,


SO3F, SbF6 .,
.
, .

BF3
:
11

CH3NO2

HNO3 + HF + 2 BF3
NO2Cl + AgBF4

NO2BF4 + H2O BF3

NO2BF4 + AgCl

:
HNO3 + HClO4
N2O5 + HF + PF5
NO2F + SbF5

_
+
NO2 ClO4 + H2O
_
+
NO2 PF6 + HNO3
_
+
NO2 SbF6

( ) NO2OTf
in situ :
+

(CH 3)4N NO 3

CF3

S
O

O
O

S
O

CH 2Cl2
CF3

NO 2 OSO 2CF 3

(CH 3)4N OSO2CF 3

20 C, 1.5

HNO3, N2O5 NO2Cl .


, .

(NO2)4
, . . 14.2 , . . 126 , d420 1.639. ,
:
4 (CH3CO)2O + 4 HNO3 C(NO2)4 + 7 CH3COOH + CO2.

:
5 C2H2 + 38 HNO3
4 CH(NO2)3 + HNO3

3 C(NO2)4 + 24 H2O + 7 CO2 + 26 NO2


H2SO4

4 C(NO2)4 + H2O


.
12

,
, : , N2O3 (
(III) ), , HNO3, C(NO2)3C(NO2)3, N-, 1--2,6-,
VO(NO3)3, (IV) (NH4)2[Ce(NO3)6], NO2Cl, , , .
2. ,


. ,
.
, ,
( ):
R H

HNO3 (.)

110-140

R NO2

H2 O

12.5%-
(d 1.075) 110-140 .
, ,
,
.
, 2,5- c :
13

CH3

H3C

CH2
CH

CH3

CH
CH2

HNO3 (12.5%)
CH3

- H2O

CH3

O2N

CH2

CH2

H3C

CH3

CH3

NO2

CH
CH3

H3C

CH
CH

CH
CH2

CH3

CH3

83%
CH3
CH2

H3C

CH

CH
CH2

CH2 NO2

CH3

2,5--2,5-. .
HNO3

.
: , ,
, .
CH3
CH3

HNO3 (12.5%)
o

NO2

100 C

( ) 250-450
HNO3 .
, , . ,
. 2-:
H3 C

H3 C

CH
CH3

CH3

NO2

H3 C

H3C

CH
CH3

H3 C

HNO3 (12%)

4.2%

CH2NO2

37.5%

300 C

NO2
H3 C

CH
CH3

16%

14

CH3NO2
3.6%

2- , (9:1), .. . , .
. .
, . -. ,
100-108
1--1- 90%:
NO2
CH3

CH3

HNO3 (12.5%)
o

100-108 C

, 44%:
NO2
HNO3 (12.5%)

,
- -
- .
,

(SR). :
15

4 HNO3 4 NO2 + 2 H2O + O2.

NO2, ,
. R ,
:

+ .NO2

R H

. R + HNO
2 .NO + H O

HNO2 + HNO3

R NO2,
:

. R + .NO

R NO2

R O N O

, R
, :
2 HNO2 NO + NO2 + H2O

. R + . NO

R N O

:
2 HNO3 + NO

3 NO 2 + H2O

,
;
.

,
:
O
R

NO

[O]
R

H
R

H2O

NO

OH

OH
O

OH

H2O

[O]
R

16

OH

, , , .
:
+

RH + NO2 PF6

CH2Cl2 -

R NO2

HPF6


,
. ,
HNO3
:
COOC2H5
CH2
X

COOC2H5
O2N CH
X

HNO3
- H2O
X = COOC2H5, COCH3

-1,3 - :
O

O
R

HNO3

H
O

NO2

OH

COO
_

RCH2NO2

COO

3.

N2O4
1,2- 2- , 2-,
2- 2- :
17

N2O4

NO2
NO2

NO2

O N O

ROH
(R=H, Alk)

[O]

NO2

NO2

NO2
- H2O

OH

O NO2

RONO

NO2
O

, :
O

H3 C

H2C

CH
Br

NO2F

NO2
O COCH3

O NO2

NO2

- CH3COOH

OH

NO2
F
O2 N

H2 O

Br

NO2Cl
Cl

, -
:
NO2
CH3COONO2
O

CH3
O

70%

, in situ , , :

18

NO2I + AgI

AgNO2 + I2

NO2
NO2I

NO2

N(C2H5)3

N(C2H5)3 HI


:
N2O4 ,
-, - -, :
NO2

N2O4, O2

NO2

(C2H5)3N

20 C

20 C

X
X = NO2, ONO ONO2

, , ,
( in situ ), -:
OR

O
NO2

CH3COONO2

R = COCH3, Alk, Si(CH3)3


OSi(CH3)3

H3C

NO2BF4

CH2

NO2

H3C
45%


:
Si(CH3)3

NO2BF4

NO2
80%

19

N2O4 NO2Cl 1,4:

N2O4

O2N

NO2Cl

O2N

NO2

Cl


1--1,3-:
NO2
NH4NO3, (CF3CO)2O

HBF4, CH2Cl2, 20 C, 15
70%

4.
4.1.

. ,
,
,
.
,
. ,
.
. ,
, ,
. ,
0 100-110 ,
.
20

.

.
. 150 /.
(
) , :
RH + HONO2 RNO2 + 2.

, , .
10
3 .

, , .
, , , , , . ,

,
.
.
, (
) ,
. , 21

,
.
.
, ,
(
!).

.
NaCl, Na2SO4 . NaCl
( !).
. ,
, , , .
.
.
. .
. -, , -
, , :
ArH

Ar

O N O

O N O


, .
, . .
22

4.2.

, 1834 ., . NO2+.
; sp-, sp2-. - :
HNO3 + 2 H2SO4

NO2 + 2 HSO4 + H3O

NO2+
:
HNO3 , %
(.)
HNO3. NO2+, % (.)

10

20

40

60

80

90

100

100

100

62.5

28.8

16.7

9.8

5.9


, :
HNO3 + 2 HClO4
HNO3 + 2 H2SeO4

NO2 + 2 ClO4 + H3O


_

NO2 + 2 HSeO4 + H3O


NO2+ , .
, NO2+ . ,
3 HNO3

NO2 + 2 NO3 + H3O

23

( NO2+ ArH).
ArH , .. .
:
+

C2H5ONO2 + 3 H2SO4
N2O4 + 3 H2SO4
N2O5 + BF3
N2O5 + 3 H2SO4

NO2 + H3O + 2 HSO4 + C2H5OSO3H


+

NO2 + H3O + NO + 3 HSO4


_

NO2 BF3(NO3)

2 NO2 + H3O + 3 HSO4


:
C(NO2)4 <C2H5ONO2 < HNO3 < CH3COONO2 [(CH3CO)2O] <
HNO3[CH3COOH] < N2O4 < HNO3 (65%) < HNO3 + H2SO4 < KNO3 + <
< N2O4 [BF3; AlCl3] < NO2Cl [BF3; AlCl3] < NO2+ BF4, NO2+ ClO4,
(NO2)2+ SiF62, (NO2)2+ SbF62 < N2O5 [H2SO4; BF3].

NO2Y
, .
, :
H2SO4 > HNO3 > CH2Cl2 > CH3COOH > H2O


,
-.
:
H

NO2

NO2

NO2

24

NO2


- - ( ). - -
- N,
-
.
. - , sp3-,
. - , -
.
-. (), . . .
()

(. 4.1).
.
, ,
.

; , - , H 2-8
, D, 20-30 , T.

25

E
2
3
H

X
NO2
-

H
+ NO2 X

NO2
+ HX

. 4.1

, , , 2,4,6---:
CH3
(CH3)3C

C(CH3)3

CH3
+

(CH3)3C

NO2

C(CH3)3

H (D)

H (D)

NO2

C(CH3)3
kH / k D = 3.7

C(CH3)3

(- ). , (-),
(. -):
26

NO2

NO2

NO2

-
-, :
+.

.
NO
2

NO2

B
NO2

BH

4.3.


, .

: I II .
I (OH, OR, OCOR, NH2, NHR, NR2, NHCOR,
N=N, CH2Cl, Alk, Hal, SH, SR, CH2OH, CH2NH2, CH2NR2,
CH2COOH, C6H5, CH=CHR, COO) - - ( ) . .
CH3

CH3

CH3

CH3
NO2

HNO3, H2SO4

30 o C

NO2
NO2
37%
n-

59%

4%

o-

I , , ( NO), ,
.
27

, (F, Cl, Br, I), I ,


.
II (CF3, CCl3, NH3+, N+H2R, N+HR2, N+R3,
P+R3, S+R2, CH2N+R3, NO2, NO, POR2, B(OH)2, SOR, SO3H, SO2R,
SO2Hal, SO2NH2, CN, NC, COOH, CHO, COR, CONH2, COHal .)
- . II
, ,
, .
NO2

NO2

NO2

NO2
NO2

98% HNO3, H2SO4

100 C

NO2
NO2
1%
n-

6%
o-

93%
-

, (CH2F, CH2NO2, CHCl2,


CH2P+R3, CH2S+R2 .).
. 4.1 ,
, .
- - , . ,
-, -.
-/- F<Cl<Br<I, .. .
. 28

, . - .
4.1
,


F
Cl
Br
I
OH
OCH3
NHCOCH3
CH3
2H5
CH(CH3)2
C(CH3)3
CH2Cl
CHCl2
CCl3
CN
CH2NO2
CH2CN
CH2COOC2H5
COOH
COOC2H5
CH=CHNO2
CCCOOH
NO2
SO3H
(CH3)3N+

HNO3
HNO3
HNO3
HNO3
HNO3
HNO3 + (CH3CO)2O
HNO3 + H2SO4
HNO3
HNO3
HNO3
HNO3
HNO3 + (CH3CO)2O
HNO3 + (CH3CO)2O
HNO3 (CH3CO)2O
KNO3 + H2SO4
HNO3 (CH3CO)2O
HNO3 (CH3CO)2O
HNO3 (CH3CO)2O
HNO3
HNO3
HNO3
HNO3
HNO3
HNO3 + H2SO4
HNO3 + H2SO4

29

, %

12
88
30
70
38
62
41
59
59
3
38
71
1
28
8
92
59
4
37
45
7
48
30
8
62
13
10
77
41
4
55
23
34
43
7
64
29
17
81
2
22
55
23
24
20
56
54
13
33
19
80
1
28
69
3
31
2
67
27
8
65
6
93
1
26
68
6
0
89
11

, ,
, . , -, , , . -, , , , :

... O
+
_

.

.
.
1. , .
2. ,

- . ,
.
3. - - - ,
30

- - , -.
CH3

CH3
NO2

NO2

HNO3
H2SO4

Br

NO2
Br


,
:
N+R3, CF3 < NO2 < CN < SO3H < CCl3 < CHO < COR < COOH < COOR <
< CONH2 < I < Br < Cl < H < CH2COOH < C6H5 <Alk < OCOR < NHCOR <
< OR <OH < NH2 < NHR <NR2 <O

, , 27 ,
105-107 ,
.
(). (f)
-, - - C6H5X
.

fo = k(Co /100)(6/2);

f = k(C /100)(6/2);

fn = k(Cn /100)(6/1),

k
[k=k(C6H5X)/k(C6H6)], Co, C,Cn -, -
-, %.
, 30
27 , 58.1% -.
, - fo 47:

31

f o = 27 . (58.1/100) . (6/2) = 47


(6
2 - )

3.7% - 38.2% ;
f = 27(3.7 /100)(6/2) = 3; fn = 27(38.2/100)(6/1) = 62.

:
1.00

CO2C2H5

Cl

C(CH3)3
5.5

0.03

0.0026

0.0009

0.0079

75

0.0009

0.14

, , .
4.4.


, (d
1.40) (d 1.84) , 40-50.

, in situ :
NO2
(CH3)3SiCl + NaNO3
o

AlCl3, CCl4 , 0 C
97%
32

, ,
II . , (90 )

.
: 1,3,5- - 100-110 5 , ,
45%.
NO2

NO2

NO2

NO2

O2N

NO2

50-55%- (II) 50 2.4-


85%; ( ):
OH

OH
NO2

Hg(NO3)2

100 C

HNO3 , 50 oC
NO2

NO2

O2N

NO2


2,4,6--3- ; 2,4,6-3- , -.
:
33

CH3 > CH2R > CHR2 > CR3 > H.

, , - ,

+I-, ().
20-30
- n-:
CH3

CH3

CH 3
NO 2

HNO 3

H2SO 4

NO2


(60-80 ) ; 4- 2,4, 2- 2,4- 2,6-:
CH3

CH3

CH3

CH3
NO2

NO2

NO2

+
NO2

CH3
O2N

NO2

NO2

NO2


110
2,4,6 (, ):
CH3

CH3
NO2

HNO3

O2N

NO2

HNO3

O2N

NO2

H2SO4

H2SO4
NO2

CH3

NO2

, , , . ,
34

:
CH3

CH3
NO2

HNO3
o

(CH3CO)2O, - 10 C
H3C

CH3

H3C

CH3
85%

. ( -40 +80 )
, , - n-:
+

NO 2

NO 2

+
O2N

-. n-
:
HNO3
NO2

CH3COOH, 60 C

- n- ,
:
CH 2

HNO 3 + H 2SO 4

35

O 2N

CH 2

NO 2

4.5.

, : ( 63%, 80%-)
,
. ( 90-95%)
(4-5%) -:
NO2
NO2

HNO3

- -: .
( , 80-90 )
,
: 1,5- 1,8-:
NO2

NO2
HNO3
H2SO4

NO2

+
NO2

, , :
15-20 9-- 9.10:

36

O2N

HNO3
CH3COOH, (CH3CO) 2O

- CH 3COOH

CH 3
O

NO2

NO2

+
NO 2

, , ,
:
O
HNO3

, 1 ( d l.38, d 1.84
50 ), 1,5- 1,8:
O

NO2

HNO3

HNO3

H2SO4

H2SO4
O

NO2

NO2

NO2

+
NO2

9-:

HNO3 + (CH3CO)2O
NO2
37

4.6.

, I , ; ,

, .
, - n- 2 : 1:
OH

OH

OH

NO2

HNO3 , 19%

+
NO2

, HNO3

,
,
.
:
,
, NO+, .
.
:
HNO2 + 2 HNO3
OH

_
NO + H3O + 2 NO3
+

OH
NO

OH
HNO3

NO

+
NO2

38

HNO2

, . -
70%,
( );
( ) :
O

CH3

O
O

CH3
NO2

H3C

H3C COOH

O NO2


,
/ 1.8 ( ) 13.3.
, , , -:

OH

SiO2
CH3COONO 2

... H C
H
3

..SiO_
O

OH

OH
NO2

NO2

NO2
13

,
-

, , .

39

n- ( -) : n- ( , ,
, ); n :
OH

SO2C6H5

SO2C6H5

OH
+

C6H5SO2Cl

HNO3

H2O, H

- HCl

H2SO4

- C6H5SO3H
NO2

NO2

2,4-:
OH
OH

NO2
N2 O4
CH2Cl2, 0 o C
NO2

,
; n 2--4- 80%:
OH

OH

NO2

HNO3

CH3

CH3


(6-15%-) . :

40

OH

OH

+ 5-10 % (.) (C4H9)4N Br

HNO3

NO2

H2O

, 20 , 4-6

X = Cl, Br, F, CH3, Ph

85-95%


, ZrO(NO3)2xH2O,
NaNO3
La(NO3)36H2O Bi(NO3)35H2O, (II), Ni(II),
Cu(II), Mn(II) n- (
- ):
OH

OH

CHO

CHO

ZrO(NO3)2 xH2O

, 2 , 50
NO2
91%

HOCH2

OH

3 3

OH

OH

NaNO , La(NO ) . 6 H O

NO2

- (C2H5)2O

O2N
CH2OH

CH2OH
7

(80%)

OH

OH
CH3

Ni(NO3)2 6 H2O, n-CH3C6H4SO3H

O2N

CH3

97%

2,4,6-.
41

, , : 2,4-,
;
:
OH

OH

OH
SO3H

2 H2SO4

- 2 H2O

NO2

O2N

3 HNO3
- 2 H2SO4, - H2O
SO3H

NO2

4.7.

, ,
I . , - n . , , , :

. ,
, (NH3+, RNH2+, R2NH+),
II , -:
NH 2

NH2

NH 2

NH 2

HNO 3

HNO 3
H 2SO 4

H2SO4

NO2
50%

CH3

NO 2
CH3
70%

42

, - n

.
,
n, , -. . (, , ),
( ,
n-), , :

NH2

NHCOR

RCOX

- HX

R = H, COOH, CH3 ; X = OH
R = CH3, C6H5 ; X = Cl
R = CH3 ; X = CH3COO

.
3-5 n -:
NHCOCH3

NHCOCH3

NHCOCH3

HNO3, H2SO4

O2N

3-5 C
NO2
92%

43

8%

n- n-:
O2N

NHCOCH3

H2O, NaOH

O 2N

NH2

CH3COONa

-
, . 2--4-
- , n- .
2--4- ,
, :
NHCOCH3

NHCOCH3

NH2
(CH3CO)2O

HNO3

- CH3COOH

H2SO4

O2N

H2O, H

O2 N

- H2SO4, - CH3COOH
SO3H

SO3H

SO3H

NH2
+

-
- :
NHCOCH3

NHCOCH3
CH3COONO2

O2 N

CH3COOH

N,N- . 2,4--N,N-,
,
N-N--2,4,6-:

44

H3C

N(CH3)2

N(CH3)2
O2N

HNO3 (d 1.49)

COOH
NHCH3

O2N

O2N

H2 SO4 (d 1.84)

- CO2
NO2

H3C
HNO3

NO2

NO2
NO2

O2N

H2SO4

NO2

NO2

N,N- n- (IV):
C2H5
N
C2H5

CH3CN

(NH4)2[Ce(NO3)6]

25 C, 1

C2H5
O2N

N
C2H5
65%

,
-, :
2-

2-

[Ce(NO3)6]

2-

(NO3)5Ce

(NO3)5Ce

N O

N O
H

NR2

NO2

NR2

[Ce(OH)(NO3)5]

2-

NR2


--
:

45

X
NO2

Ph3P/Br2/AgNO3

CH3CN
X = NH2, NHR, NR2

Br

NO2

Ph3P/Br2/AgNO3

NHCH3

Br

CH3CN

NHCH3
NO2
91%


:
_
Ph3PBr Br
+

Ph3P + Br2

AgNO3

Ph3P

- AgBr

ONO2

_
Br

ArH
- HBr, - Ph3P=O

ArNO2

4.8.


- n-, n . I , , ,
. , , - n-
(d 1.42) (d l.84) ; , .
Br

Br

Br

NO2

HNO3

H2SO4
NO2

46

n- 0
(d 1.50) (d 1.84):
F

F
HNO3
H2SO4

NO2

2,4-.
(III)-.
4.9.
(, ,
)

II ,

, . - :
COOH

COOH
KNO3
H2SO4

NO2

; , 3,5- , :

47

COOH

COOH
HNO3 (d 1.51)
H2SO4 (d 1.84)

O2N

NO2
60%


, -, , , :
COOH
HO

COOH
HO

NaNO3
. H2SO4

NO2
64%



N2O5 :
CO2CH3

N2O5, SO2

O2N

CO2CH3

- 78 C
CO2CH3

CO2CH3
90%


II ,
- . -
, II ,
;
0-5

100 ,

-
- ( 20%) :
48

CHO

CHO
HNO3
- H2O

NO2

n- () .
n- , (79%)
n-,
n-:
CHO

CH(OCOCH3)2

CH(OCOCH3)2
(CH3CO)2O

CHO
+

Cu(NO3)2

H2O, H

CH3COOH

- 2 CH3COOH
NO2

NO2

( d 1.42, d 1.84 0 ) -. :
-10 -15, , - -:
COCH3

COCH3

COCH3
O2N

HNO3 (d 1.5)

- H2O

NO2
55%

34%

4.10. -

-

(,
49

, )
0 . , :
ArH + 2 NO2 + O3

ArNO2 + HNO3 + O2
NO2

NO2 + O3
o

CH2Cl2 , 0 C
89%

, , - , -
. ( (III), CH3SO3H, BF3O(C2H5)2) :
NO2

NO2

NO2

NO2

NO2

NO2 + O3, CH3SO3H

CH2Cl2 , -10 C

NO2
NO2
91

(98%)

-
(. 4.2).

50

4.2
, -

(, ,
, )


, %

CH3

CH2Cl2. 3 , -10C

99

57

41

COCH3

CH2Cl2. 4 , -10C

99

52

48

COC(CH3)3

CH2Cl2. 3 , -10C

99

68

18

14

COCH2Cl

CH2Cl2. 4 , -10C

100

44

56

CHO

CH2Cl2. 3 , -10C,
CH3SO3H

99

32

64

COPh

CH2Cl2. 2 , -10C

99

42

36

22

COOH

(CH2Cl)2. 2 , 0C

94

27

72

COOCH3

(CH2Cl)2. 3 , 0C

88

31

66

COCl

CH2Cl2. 3 , -10C

99

99

CN

CH3NO2. 6 , 0C

85

15

82

NHCOCH3

CHCl3. 2.5 , -10C

99

81

19

OCOCH3

CH2Cl2. 2 , 0C

80

60

40

CH2CO2CH3

CH2Cl2. 3 , 0C

85

88

- , NO3
. ,
. NO3 - -
.
51

NO2 + O3

NO3 + O2
R

.
NO

.
H

R
2

H
ONO2

O2NO

- HNO3
NO2

NO2

- HNO2

R
R

NO3

NO2

_
NO3

NO2
ONO2
H

OH

- HNO3

NO2
NO2

-H

NO2
R

+
H

- H+
NO2

NO2

- ,

.

52

5.

5.1.

,
, , ,
:

N
H

, .. , ;

, .

- .
- .
.
-10 2 5
2--5-, ,
2-:

53

HNO3
O

(CH3CO)2O

CH3COO

H
O

NO2

NO2

_
+

N CH COO3
H

, ,
(CHO, COOH .) ,

:
H 2O

HNO 3 (d 1.42) + 5-7% H 2SO 4 (d 1.84)


o

(CH 3CO)2O, - 10 C

CHO

O 2N

CH(OCOCH 3)2 - 2 CH 3COOH O 2N

CHO

90%

.
,
. ,
10 +5
50% 2- 7% 3-:
NO2
HNO3 (100%)
N
H

(CH3CO)2O

N
H

NO2

N
H

3-
; - 3-,
3-:
O
C2H5ONO2
N
H

+
N O Na

NO2

C2H5ONa

N
H

54

. ( )
2 5. 2.5-. 2 - ,
,
:
CH3COONO2
- CH3COOH

NO2

80%

- ,
, ,
3, 2.
3

3
2

2
1

N
H

NO2
PhCOONO2
N
H

- PhCOOH

N
H

5.2.

, , .
3. 330 ,
(18% SO3), ..
, -

55

,
3- 15%:
NO2

HNO3, KNO3,

330


N2O5 3- 68%. N-. , in situ
, N-

NHSO3 3- 64%; -4- :
NO2

_
O3 S
_
HSO3

NO2, O3
N

H
_
O 3S
H

NO2

NO2
N

NO2
_
HSO3

_
NO3

NO2

_
HSO3

_
SO3

_
SO3
- HNO2

NO2

, N- , 4-:
NO2
HNO3 , 89%
+

H2SO4 , 94%, 130 o C

O-

N
O-

N- 4-:
56

NO2

NO2

Ph3P

Ph3PO

O-


,
5-- 8-. ,
, 24 :
NO2
2

SO4

H2SO4

N
H

HNO3
N

NO2

,
-
, .. 5,7- (I) , , 6,8- (II):
O2N

NO2

N
O2N

NO2

N
I

II

6.


- :

57

RCH2

2 LiN[CH(CH3)2]2

CH3

RCH

OLi

OH

Li

1. C3H7ONO2

OLi

2. H3O

RCH

CH3

HN

H3C

CH3

O
RCH

RCH2NO2
OH

Li

CO2

45-65%

NO2

().

,-.
-
. ,-:
K+

N O
O

1) KNH2 / . NH3

H3O

2) 2 RONO2
+

O2N(CH2)5NO2

- CO2

90%

N O
_

_ +

O
OC2H5

C2H5O N

C2H5OK

O
_

OC2H5
O OC2H5
_

C2H5O
O

C2H5O

K _
O O
+
N OC2H5
H

K
+

N O
- C2H5OH

58

O
+

H3O

N O

:
+
_

C2H5OK

CH2
CN

C2H5O N

N OC H
2 5

K
+

CN
HO

N O

KOH / H2O

CN
+

N O

CH
CN

- C2H5OH

- C2H5OH

H3O
+

COO K

N O

- CO2

N O

,
2 :
COOC2H5
R

H3C

CN

H3C

ONO2

COOC2H5

NaH

R
NO2

X = COOC2H5, COCH3


- :
NO2
R

2 C5H11ONO2

1. (CH3)3COK
+

2. H3O

NO2

2 C 5H11OH

( ):
CH3O
CH3O

-C4H9Li
- -C4H10

CH3O

N2O4 , -78 o C
- LiNO2

CH3O
Li

CH3O
CH3O
NO2
67%

59

NO2

Br
1) -C4H9Li
o
2) N2O4, -78 C

S
77%

, ,
.

- - . KNH2 :
CH3

CH2NO2
1) KNH2, NH3
2) C3H7ONO2

CN

CN
47%

CH3

CH2NO2
1) KNH2, NH3
2) C3H7ONO2

N
66%

:
_

NO2 K

C2H5ONO2

C2H5OK

70%

60

7.
7.1.

-
, NaNO2 -,

( ):
2 ClCH2COOH + Na2CO3 2 ClCH2COONa + H2O + CO2;
ClCH2COONa + NaNO2 O2NCH2COONa + NaCl;
O2NCH2COONa + H2O CH3NO2 + NaHCO3.


, , 0-20 ( ):

RCH2Br + AgNO2

, 0-20

RCH2NO2 + RCH2ONO + AgBr


20-25%

75-80%

RCHCOOC2H5 + AgNO2

, 20

RCHCOOC2H5 + AgI
NO2

75-85%

80 AgNO3:
2 AgNO2 AgNO3 + Ag + NO.


,
.
N- - (/) . 75-85%,
61

15-18% 5% ( ). , , AgNO2.

, (, ) (
).
, (, ).
60%, .. , . :
CH3CH(CH2)nCH3 + NaNO2

25

CH3CH(CH 2)nCH3

Br

55-60%

NaNO2

NaBr

ONO

NO2

Br

CH3CH(CH2)nCH3

25-30%

NO2

- NaBr
57%


- . - 60-80%
.
,
:
CH2Br

COOH

CH2NO2
NaNO2

NaNO2

, -16

, 25

62

- NaNO2 KNO2
( ):
Cl

NO2

H3C

NO2

K2CO3, NaNO2
H3C

NO2

:
Cl

H3C

Cl

Cl

NO2

H3C

NO2

NO2

HNO2
H3C

+
N OH

NO2

O
NO2
H3C

+
N OH

Cl

-
:
RCH2NO2 + Cl2 + NaOH RCHClNO2 + NaCl + H2O.
7.2. -

,
, . , , , , ,

, 2,4--1- .:

63

OH

OH

OH

SO3H

2 H2SO4

NO2

- 2 H2SO4

OH

OH

O2N

3 HNO3

OH
NO2

SO3H


OH

OH

OH
SO3H

2 H2SO4

NO2

2 HNO3
- 2 H2SO4

SO3H

NO2

- - , - , -
- . , , :
CH(CH3)2

CH(CH3)2
HNO3
H2SO4

CH(CH3)2

O2N

CH(CH3)2

NO2

+
CH(CH3)2

CH(CH3)2

CH(CH3)2

NO2

NO2

+
CH(CH3)2

+
CH(CH3)2

CH(CH3)2

H2C CH + H
CH3

- ,
, , :
64

CH3O

Br

(CH3CO)2O

HNO3

CH3O

Br

CH3O

NO2

O 2N
30%

70%

, - -, -- ,
. , - 1,2-,
NO2+ -.
X

NO2

NO2

NO2

- H+

-
X+,
, :
X

NO2

NO2

Y
+

H
CH3

H3C

H3C

NO2

HNO3
(CH3CO)2O
CH3

_
+

H2C

CH3

NO2
ROH

- NO2, - H
CH2

OR
R = H, COCH3, NO2

65

7.3.

, , , 2-, 1,4- .
(I) (Cu2O, Cu2SO4):
_

NH 2

N 2 HSO 4
NaNO 2 / H2SO 4

NO 2
NaNO2 / Cu2SO 4

0 C

- N2

NO2

NO 2

NO 2
60%

:
NO2

NO2

NO2
Cu . - NaNO2

1) NaNO2 + HCl

- N2, - BF3, - CuF

2) NaBF4
NH2

N2 BF4

NO2
80%

7.4.

, , . ,
, , ,
(2KHSO5KHSO4K2SO4):

66

O2 N

CF3CO3H

NH2

O2 N

CH2Cl2 , 50 o C

NO2
86%

H3C

CH3

CH3
CH
NH2 3

H3C

KMnO4

H3C

e-, 50 o

H3 C

CH3

CH3
CH3
NO2

82%
CH3CO3H

NH2

NO2

CH2Cl2
70%

NO2

NH 2
O3 / SiO2,
o

-78 C
70%

R NH2

H3C

CH3

R NO2

3
O O

H3C

CH3

H2O

80-90%

, NaBO3
,
:
NOH

(CF3CO)2O , H2O2

NO2

CH3CN
60%


H2SO5, in situ , ,
:
NH2

NO2

NO2

NO
K2S2O8

K2Cr2O7

H2SO4

H2SO4
NO2
67

NO2

N- (NBS)
( ),

, , HNO3 H2O2 .:
NOH

NO

Br
NBS
_

NO2

Br

HNO3
H2O2

H
N

72%


:
NO2

Br

NO2

H
NaBH4
76%

:
NO2

HNO3

N
OH

NO2

H2O2 + HNO3

NO2

NO

N2O4.
- ( -):
_

R
R

+ O
N
Ag+
_
O

AgNO2

NO2

NO2

2 Ag

- , .

:
68

O + O
N
H3C

H3C
H3C
O2N

2-

S2O8

CH3

CH3
CH3
NO2

2-

2 SO4

60%


:
H3C
R N

CH3

R NO2

O O


:
Ph3P

R N3

- N2

R N

PPh3

O3
- Ph3PO

R NO2

8. N-
,
, - ,
. , . ,
:
CH3NH2

NH3
H3C

Cl
H
N

O
O

NO2

H3C

C2H5

. NH

HCl
3

- NH4Cl

H3C

N
H
H
N

69

C2H5

HNO3

H3C

N
NO2

NO2

C2H5

CH3NH2

Cl
H
N

NH3
H3C

O
O

NO2

H3C

C2H5

. NH

HCl
3

H3C

- NH4Cl

N
H
H
N

HNO3

C2H5

H3C

C2H5

NO2
NO2

:
O

Cl

Cl

CH3NH

2 CH3NH2

2 HNO3

NCH3 - (CONH2)2

CH3N

NHCH3

NO2
2
H3C

H
N

NO2

. NH

HCl
3

- NH4Cl

H3C

H
N

NH3

NO2

NO2

,
:
C2H5NH2

H3 C

H3C

CN

OH

C2H5

ONO2

H
N

NO2

H3 C

CN

H3C

OH

N,N-
N-,
:
HOCl

RNH2

RNCl2

Cl

HNO3

NaHSO3

R N

(CH3CO)2O

NO2

H
N

NO2


N,N- :
O
H 3C

NH 2

2 HNO3

(CH 3CO)2O

H 3C

H 3C

NO 2

CO2

NH 4NO 3

CH3

CH 3

H 3C

S
O

HNO 3

(CF 3CO)2O
o

0C

70

H 3C

NO 2

CH3

C6H5SO 3H

:
R

(CH3)3SiCl

N H

(C 2H5)3N

N2O5

Si(CH3)3

N NO2

(CH3)3Si

ONO2

N2O5 CCl4
-30 0 N2O4 -80 , ,
( ) :
HNO3 + (CH3CO)2O

(CH3)2NH

(CH3)2NNO2

ZnCl2

:
H3C

CH3

CH3

Cl

CH3CN

AgNO3

H3C

CH3

ONO2

H 3C

NO2

CO2


:
NO2

N
N
N

HNO3

N
O2N

NO2

, (, , ) ( ):
_

R2NH + C4H9Li
_

R2N Li +

NH2

R2N Li + C4H10
_

R2NNO2

C2H5ONO2
C2H5OK

C2H5O Li

N + _
+
N O K
_
O

C2H5ONO2

71

2 C2H5OH

,
:
_

NH2

HNO2

1) K3[Fe(CN)6]

2 OH
- H2O

N N

N N _
O

2) H

NO2
N
H
80%

9. -
.
(0-10 ) , , :
CH3OH + HNO3

H2SO4

CH3ONO2

H2O

80%

, :
OH

HO

3 HNO3

H2SO4

ONO2

O2NO

OH

ONO2


()
OH
HO

4 HNO3

H2SO4

O2NO

OH
O2NO

HO

ONO2

4 H2O

ONO2

()

72

3 H2O

OH
OH
O

6n HNO3

O
O

CH2ONO2

ONO2

ONO2
O

H2SO4

OH

CH2OH

CH2ONO2

ONO2

CH2OH
O
O
OH

ONO2

- :

..
..

R OH

.. NO

NO2 HSO4

R O

.. +
.. NO

R O

HSO4

H2SO4


, N2O5:
C2H5OH + NO2 BF4

C2H5ONO2 + HBF4
CH3ONO2 + CH3COOH

CH3OH + CH3COONO2
C3H7OH + N2O5

C3H7ONO2 + HNO3

- :

R OH

[(CH3)3Si]2NH

R O

(CH3)3SiCl

N2O5

Si(CH3)3

CH2Cl2

R O NO2

(CH3)3Si

ONO2

.
:
H3C

H3C
Br

AgNO3
H3C

H3C

73

ONO2

AgBr

CH2Cl

AgNO3

CH2 ONO2

AgCl


. ,
:

Cl

AgNO3

ONO2

RONO2

CO2


, ,

(I) 1,2-:
2

CH2Br

Hg2(NO3)2

CH2ONO2

Hg2Br2


98%- .
, BrNO3 INO3
:
H3C

CH2

HNO3

- 20 C

H3C

H3C
H3C
H3C

ONO2

(III)
20 1,2- 1,3- :
C8H17CH CH2

Tl(NO3)3

C8 H17

ONO2
ONO2

85%
74

(AdH)
HNO3 (CH3CO)2O
. :
ONO2

3 HNO3

+
+

NO2

AdH

Ad

_
NO3

Ad

- HNO2

2 NO2

2 H2O

ONO2

10.
. . ,
:
RNO2 + 6 [H] RNH2 + 2 H2O.

. 1-2
30%- NaOH,
.

.
.
, - :
R

NO2

HNO2

NO2

H2O

H2O

NOH
R

NO2

NaOH

NOH

NO2
NONa

75

. 1.5 1
NaOH.
0.5-1 10%- NaNO2
5%- - .
.
HNO2 , :
R

CH

NO2

HNO2

C
N

NO2

H2O

. 0.5 2- 3 2.5%-
- KOH 0.5 NaNO2,
.
HNO2 .
. - .
.
,
-:
HO
ArNO2

ArNH2

ArN2Cl

Ar

N N

11.

, ( 2,4-),
, (
76

).
. :
O2 N

CH3

CH3

CH3

CH3

O2N

NO2

O2 N

NO2

O2 N

NO2

C(CH3)3

H3 C

C(CH3)3

H3 C

C(CH3)3

NO2

NO2

NO2

CH3O

COCH3

C(CH3)3

(, ,
). , ,
, , , .

: , ,
; ( ); ..
. (2-), ,
:
HOOC

O2N

COCHCl2

H NH

CH2OH
OH H

NO2

N
H

NO2

OCH3

O
O

77

, : (, ),
(, ), (), , (, ,
) .
N
O

NH2
O2 N

N
O

N
H

O2 N

N
O

H3C

NO2

O
OH

Cl
O

OH

N
H

NO2

H3C

N
N
H

NO2

Cl

,
.
12.


,
. , ,
. (),
, , . , , . 78

, ,
. .
, , , ,
, .
13.
-
NO2

(d 1.84)
(d 1.4)

H2SO4
- H2O

HNO3


12.8 200 (2 .)
13
7.2

7
13 (24 , 0.23 ) , 7.2 (10
, 0.103 ) 65%- .
50 12.8 (0.1
) .
50 .

, ( ). , -
1,5- 1,8-.
79


, , 1
60 .
, -
, . , - 15 100 .
.
, .
- 200 ,
- .
,
. .
15 (87%).
-
, , , ; . . 61.5 , . . 304 .

OH

OH

SO3H

2 H2SO4

- 2H2O
SO3H
OH

OH
O2N

SO3H

3 HNO3

- 2 H2SO4, - H2O
NO2

SO3H

(d 1.4)
(d 1.84)

NO2


100
200

5
14
13.6

80

5 (0.053 ) 13.6 (25 , 0.245 ) ,


. ,

2,4 20 .
14 (19.6
, 0.20 ) 65%- . , , . ,
.

1.5 . -,
- . , 100 ,
2,4,6- .
6.1 (50%).
- . . 122 .
( 100 ): 1.4 (20 ), 6.8 (100 C);
.
2- 4-
OH

OH

OH
NO2
+ NaNO3 + H2SO4

(d 1.84)

, 10%-
-
, 10%
, 2%

- H2 O
- NaHSO4

+
NO2


100
50

5
5.5
8
40
40
30

81

8 (0.094
) 20 .
5.5 (10.1 , 0.1 ) . 20 .
5 (0.053 ) , 2 ,
, 20 ( 2,4-).
2 ,
. . () .
,
2-.
,
; 2 .
2- .
3 (40%).
4-
.
20 10%- , 0.2 , 510 .
,
. 4-
. 10%-
. 482

10%- , 10-15 .
4- ,
. , 4- 2%- .
. 0.8 (11%).
2- , . . 45 ; , ,
, (0.21 100 20 ).
4- . . 114 ; , , , (1.6 100 25 ).
4- ( 4-)
OH

ONa

NaOH

ONa

H2 O

H2 O

OH

NaNO2

2 H2SO4

2 NaHSO4

NO
OH

OH

2 NO

H2 O

NO2

NO



, 25%
, 23%
, 18%

2 HNO3


1000

21
9
18
50
250

83

21 (0.22 ) , 9 (0.225 ) NaOH 18


(0.25 ) 500 , 0 ,
42.5 (50 , 0.128 ) 25%-

( ). 2 4-
, .
4 220 (250 , 0.91
) 23%- , 40 . 2-3 . () - ,
18%- .
18.4 (60%), . . 114 .
2--4-
OH

OH
+

HNO3

NO2

10 % (.) (C4H9)4N Br

H2 O

, 20 , 6

Cl

4-

, 6%

Cl


100



50


1.29
0.32
20
20

100 1.29 (0.01 ) 4-, 0.32


(0.001 ) , 20 20
6%- HNO3 84

6 . , (3 25 ), .
, .
1.41 (81%), . . 86-87 .
N-(4--2-)
H3C

H3C

O
H3C

NH

HNO3

- H2O

H3 C

NH
NO2

N--n-
, 80%



100




50

5.67
22.5

N--n- (5.67 , 0.038 ) 30


20 ( )
22.5 (32.7 , 0.415 ) 80%- .
20 10-15 .
140
, . 5 ,
. 10
5.31 (72%) .
N-(4--2-) -
. . 91-92 .
85

3--4-
CH3O

C CH3

H2SO4

HNO3

- H2O

CH3O

C CH3
O

O2N

4-
(d 1.84)
(d 1.4)


250

( )

100
500

20
50
25
90

250 , , ( !), 20 (0.133 ) 4 25


(46 , 0.45 ) H2SO4 . 0 2
25
(46 , 0.45 ) 25 (35
, 0.36 ) 65%- . 15 .

, 250 . 1
, , , (3 30
). 20 (73%); . . 97-98 .
86

10-
O

HNO3

H2O

NO2

(d 1.5)

20
7
400




250

1 , , ,
20 (0.1 ) 300 .
60 1
7 (10.5 , 0.16 ) 50
.
10 15
- , ,
. 100
,
- (1:1). 16.5 (67%), . . 140 .

87

1,5--9,10-
O

2 HNO3

(d 1.84)
(d 1.5)

- 2 H2O
NO2

NO2


100 (2 .)
100

15
37
10
60

300 37 (68 ,
0.667 ) (d 1.84), 0 15 (0.072 ) .
10 (15 , 0.224 ) (d 1.5), 0
. 4 . 1,5-
.
, .
, , 60

.
1,5- ; .
14-15 (65-70%).
1,5- -
( ) . . 420-422 .
,
.
88

3-
O

OH

OH

OH

OH

HNO3

- H 2O

NO2

HNO3, 65%

10
6
90


250

, , 10 (0.0416 ) 90 . , , 6 (8.4 , 0.087 ) 65%- .


. 12-15
, . 3- ,
.
11 (93%); . . 244 ( ).
3-
CHO

CHO

KNO3

H2SO4

+ KHSO4 + H2O
NO2

(d 1.84)


100 (2 .)





( )

10
40
11
1

89

100 , , 11 (0.11 ) 40 (73.6 , 0.72


) . , 0 , 9.6
(10 , 0.094 ) , 0 5. 1.5 , ,

100 , 20 . , 20 5% , . .
11.8 (83%); . . 58-60 .
5-
O

HNO3

CH3COOH

CH3O

+
CH3O

OH

(d 1.5)

H2O

NO2
OH



100

15
6
150

90

100 , , , 15.2 (0.1 ) 150


30
15 6 (9 , 0.136 ) (d 1.5). 15 1
. , .
13 (66%)
- , . . 171 .
1,3-
NO2

NO2
+ NaNO3 + H2SO4

+ NaHSO4 + H2O
NO2

(d 1.84)




50

150


50

4.1
12.5
6.3
15
50

50 , , 4.1 (4.9 , 0.04


) 12.5 (23 , 0.225 )
,
80-90 . 6.3 (0.074
) ,
130 . ,
91

, ;
1,3- . , .
70 60-70
, 1,3- .
, 25 , (1,3 ), . ,
, 2 ( 25 ), .
, ,
( !).
1,3- 6.3 (94%).

5.3 (79%) .
1,3- ( ), . . 89-90 ; . . 291 .
, .
1,5- 1,8-
NO2

NO2
HNO3
- H2O

92

NO2
NO2

NO2


1-
(d 1.84)
(d 1.4)

4.3
15.5
2.5


50
50


100



50 11.7 (21.5
, 0.21 ) (d l,84) 4.3 (0.025
) 1-.
0
, 2.5 (3.5 , 0.036 )
(d 1.4) 3.8 (7.0 , 0.069 )
(d 1.84), 0 . .
, , .
1,5- 1,8- .
. 1,5 , .
1,5- , ,
2/3 . , 1,8-, , .
93

1,5- 1.2 (22%), 1,8 3.5 (64%). 1,5- . . 216 ; . 1,8- . . 170 ; .
3-
COOH

COOH

KNO3

H2SO4

+ KHSO4 + H2O
NO2


(d 1.84)


, 10%

6
15.6
12
10
20


100

100 , , 15.6 (28.7 ,


0.28 ) 70 .
6 (0.049 ) 12 (0.12 ) ,
80 . . 8090 ,
3- , . ,
94

,
.
3- , . 3 20- ( )
( ). 250 . 3- .
3-
10%- ;
3-
, .
3- ( ), . . 141 ; ,
, , .
3-
COOH

O
O

H2SO4

+ HNO3

NO2


(d 1.84)
(d 1.4)

COOH

9
8.1
10.1

95


100


50

100 9 (0.061 )
( 10 ), 8.1 (14.9 ,
0.146 ) 10.1 (14.1 ,
0.146 ) 65%- . 2 ; . 3-
. 50 . 3 , . 4- .
5 (40%).
3- . . 219.5 C;
, .
(4-)
CN

CN

H2SO4
- H2O

HNO3

NO2

HNO3, 65%
H2SO4, 96%

50
140
140


500



140 (196 , 2.02 ) 65%- 140


(258 , 2.52 ) 10 .
96

1 50.0 (0.427 ) ,
20 .
1 .
600 , ,
250 . 37.4 (54%) (4-).
(4-) - . .
115-116 .
4- 4-
O
HN

O
CH3

HN

NH2

CH3

HNO3 , H2SO4

H2SO4 , 25%

- H2O

- CH3COOH
NO2

(d 1.84)
(d 1.4)
, 25%
, 10%

5
14
2.4
26
50

NO2


100
500 50



100

5 (0.037 ) 10 (18.4 , 0.18 ) 40 .


5
4 (7.36 , 0.072 ) 2.4 (3.36 , 0.035 ) , , 15 . 97

45
250-300 . 4 .
4- , 26 25%-
. 10% ( ). 4 , .
4 (78%).
4- - , , . . 206-207 .
4- . . 147-147.5 . , , ,
(0.08 100 20 , 2.2 100 ).
2-
NH

C CH3

HNO3

(CH3CO)2O

NH

C CH3

2 CH3COOH

O
NO2

5
150

25 150
(d 1.4) 6

150 ( ), , ,
5 (0.037 ) 25 (27 , 0.265 )
98

. 5 ( ) , ( , ), 2 6 (8.4 , 0.087 ) 5 65%- . 1


(50 50 ). .
6 (95%); . . 91-94 . .
3--N,N-
N(CH3)2

N(CH3)2

HNO3

H2SO4

H2O

NO2

N,N-
12.1
(d 1.84)
49
( d 1.42)
6.67
(d
0.90)
120



100


( )

500


50

100 , , , 42.3 (0.767 ) 99

. 12.1 (0.3 ) N,N 25 .


5 ,
1.5 , 6.67 (12.2 , 0.12 ) 6.67 (9.53 , 0.105 ) (d 1.42).
. 5
10 . 510 1 200 .

(d 0.90) ,
-, 6368 . 25 , . 4--N,N , 7 .
25 , 3, 50-55 . , 20 .
3--N,N- 13 95% , 3 .
9.3-10.5 (56-63%). 3--N,N- - , . . 59-60 .
4--N,N-
. 2.5-3.1
(14-18%) 4--N,N- - . . 163-164 .
100

2,4-
Cl

Cl

NO2

2 HNO3

NO2

, 8%-
(d 1.5)


15
250
25
16
300
100

500


250

250 , , , 16
(24 , 0.358 ) 25 8%- ( ;
), 50 13.6
(15 , 0.133 ) . 50-55 ,
. 2 ,

250-300
. ,
, ( ).
25 (90%); . . 52 .
101

6--2,3--1,4-
O

HNO3

- H2O

2,3--1,4
(d 1.4)

7
4.75

NO2



100

100 , , ,
10 7 (0.051 ) 2,3--1,4,
.
80-90 ( ) ,
,
4 (5.6 , 0.058 ) 65%- HNO3. ,
, .
1 , , 0.75 (1.05 , 0.011 ) 65%- HNO3 30 .
40 ,
2,3-1,4- ( 20 ). , .
8 (90%); . . 119-120 .
102

4-

HNO3

, 77% (d 1.45)

CH3COOH

NO2

- H2O


50


5
4
10

50 5 (0.0324
) , 10 2.75 (4 ,
0.049 ) 77%- HNO3, , ,
( ,
), 1 . ,
, (), .
4.5 (70%); . . 110 .
9-
NO2

HNO3

HCl

CH3COOH

+
Cl

NO2

NO2

NaOH

Cl

103

NaCl

H2O

H2O


(d 1.42)
(d 1.19)
NaOH, 10%

20
400
8
50
220



500




500

500 , , , 20 (0.112 ) 80
.
20 8 (11.36 , 0.126 ) 70%-
, . , 30 .
30 ,
, 30 .
50
(0.60 ) 37%- 50
. - 9--10--9,10 , (2 25 )
.
9--10--9,10-
60 (60-70 ) 10%- NaOH
20 . 9 , 10% NaOH (4 40 ) 1.5-2
. 104

( 1
10 ).
, 9- .
15-17 (60-68%).
9- - , . . 145-146 .
2-

(d 1.42)

HNO3

6
8
120
0.05

CH3COOH

NO2

H2O


100

100 , , , 6 (0.036 )
50 .
50 15 8
(0.13 ) (d 1.42).
, . 6065 ; , .
80 (
!). 5 , , 105

. , 25 ,
50 .
. 6 (79%) . . 155-156 .
2- 20
; . . 157 .
4(5)-
O2N
N

- H2O

N
H

(d 1.42)
(d 1.84)

15
30
25

H2SO4

HNO3

N
H


100



100 , , 30 (42.6 , 0.487 ) 72%- HNO3


0-5 15
(0.22 ) .
25 (46 , 0.45 ) H2SO4.
2 100 , . ,
, , . 16.2
(65%).
4(5)-
, . . 307-308 .

106

5(6)-
N

HNO3

N
H

(d 1.84)
(d 1.4)
, 35%

H2SO 4

O 2N

NH

- H2O

N
H

_
NO3

NH3

O2N

- NH4NO3

N
N
H


100


250



100

5.9
26
4
16

100 , , ,
20 H2SO4 5.9 (0.05 )
.
25-30 , 4
(5.6 , 0.0578 ) 65%- 6 (11 , 0.108
) . 15-20

(100 ) 16
35%- .
5(6)- ,
, 2-3
100 .
5(6)-, .
.
7-7.4 (86-90%); . . 205-206 .
107

4-
NO2
N

N
N

KNO3

H2SO4

N
H

KHSO4

H2O

N
H

2
100
(d 1.84) 70

3.44
( )

100 , , 100 2
(16.8 ) 70 (129 , 1.26 ) . 0 3.44 (34 ) 30 . 60
3 , .
,
. 2.39 (87%) 4-
, . . 218 ( .).
5-
O

O
NH

N
H

O2N


(d 1.52)

NH

HNO3
O

10
14.3

N
H

H2O


100




150
108

100 , , 14.3 (21.7 ,


0.345 ) 10 (0.061 )
40 ( ).
1 ,
43
10 . , 60-80 . 90
, . , , 110-115 3-4 . 9-9.4 (85-90%), . . 176 ( .).
2-
S

HNO3

(CH3CO)2O + CH3COOH
S

84
(d 1.51)
53

600
(30-40 )

NO2

: 84 (1 )
340 53 (80 , 1.2 )
(d 1.51) 600
. . 2-
, ,
, 10 .
109

,
20 .
.
,
10 ,
. - . - , . 2 ,
( )
. 2-
- . 24 .
,
, .
(. . 30-40 ) .
90 (70%).
2- , , . . 44-45 .
(2--1-)
I
CH CH CH3

I2

AgNO2

- AgI

NO2
H3 C

N(C2H5)3

NO2

NO2

H3C

H3 C

110

(C2H5)3N HI

NaHSO3, 5%
, 5%
. NaHCO3

0.236
1.016
0.616
0.632
1.5


100




100
1.016 (4 ) I2, 0.616 (4 ) AgNO2, 20
45 . 0.236 (2 ) - 0.632 (8 )
3.5 . , 0.5
. 1 1 CH2Cl2 1 . ,
CH2Cl2. 5%- NaHSO3, 5%- HCl, NaHCO3 , Na2SO4 . , - ,
, 8%- .
0.249 (76%).

111


CH2(COOC2H5)2

O2N CH(COOC2H5)2

HNO3


(d 1.5)

, 5%
, 10%
(d 1.19)

20
46

H2O



100

(20 , 0.125 )
100 , , , ,
. 12
1 46 (69 , 1.095 )
, , 15 20 . 3.5 15 . 250 , , 50 .
, 5%- 50
.
10%-
, , ,
.
50 . , .
112

, 50 . 50 , 5%- ,
, .

. 23 (90%) .
, . . 81-83 (
0.3 . .), nD20 1.4274.
1,4-
+

NH2

NaNO2

2 H2SO4

NO2
+

_
HSO
N
4
NaHSO4

2 H2 O

NO2

_
N HSO4

NO2
NaNO2

Cu

NO2

n-

()
(d 1.84)
, 65%

NaHSO4

N2

NO2


500

3.5
11.5
7
6

500 11.5 (0.167 )


NaNO2 30 . 7 .
60 .
113

3.5 (0.0254 ) 4- 30 , 6 (11 , 0.113 ) .


4- .
2.5-3 ,
60-70 . 4, ,
. . , 1.4- .
2.5 (59%).
1,4- - ,
, , ; . . 174 , . . 299
(760 . .).
2--2-
NO2

NOH

3 NaOH

40
20
25

Br

2 Br 2

3 NaBr

2 H2O


500

0.5 , , , , 40 (1 ) NaOH 200 114

10
20 (62 , 0.388 ) . 25 (0.152 ) . 5
. ,
, 50 .
, . 2--2- 20
(50%), . . 181-184 .

2 ClCH2COOH + Na2CO3 2 ClCH2COONa + H2O + CO2


ClCH2COONa + NaNO2 O2NCH2COONa + NaCl
O2NCH2COONa + H2O CH3NO2 + NaHCO3


250

250



25

37.8
21.2
28

250 37.8 (0.4 ) 80 .


21.2 (0.2 ) . 28 (0.406 )
50 .
1/3 250 . , ,
. CO2.
115

80-89 . , .
, .
, 85 . , , 110 .

( ) .
() (
10 30 ) ( ).
. .
, , 98-102 .
9 (37%).
,
; 100 10 ; . . -28.6 ; . . 101.18 ; d4 20 1.1381; nD20 1.3819.
1,4-(2-)
O

O
+ 2 CH3NO2


(4 )

10.7
60
10
12.8
160

- 2 H2O

O2NCH CH

CH CHNO2


500


250



116

, ,
10.7 (0.08 ) , 60 8.8 (10 , 0.164 )
-5 10-15 12.8 (0.32 ) 20
; 40-45 .
5 10 , 120
.
,
160 4 . , , , ,
. 9 . . 231-232 ( .) 2.8
. . 229-231 ( .). 11.8 (67%).
14.

1. C7H7NO2. .
2. ?
NO2

CH3
H 3C

CH3

OH
CHO

COOH
OH

CH3

3.
HNO3 ( )
. .
117

4. n- 4--2?
5.
?
OH

Cl
O2N

Br
NO2

OC2H5

)
H2N
NO2
SO3H
O2N

NH2

CH3

O2N

NO2

NO2

NO2

CH3

6. C7H6O2NCl, C7H7O3N,
C7H5NO4.
.
7. 2-? .
8. : ) 2-, 3-, 4;
) 1--2,5-;
)
5--2; ) 2--4-.
9. .
10. .
11. , , ,
, , , kH/kT ( D), , 1 3. ,
?

118

12. , ( NaNO3)
.
13.
?
14. -, ?
15. :
R

R = OCH3, Cl, C2H5, N(CH3)3, As(CH3)3, P(CH3)3

?
16. , :
CH3
HNO3
O
H3C

CH3

H2SO4

C8H8N2O5

CH3

17. :
C6H5NO2 C6H5CH2CH2NO2.

18. 3-
: ?
19.
I II:

119

O
H3C

H3C

NH

O
H3C

O
II

?

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

15.

.. : : 2- . .: , 2004.
.., .., .. . 4- . .:
- . , 2004.
.., .., .. :
. : , 2002. 624 .
.. : 3- ., . .: , 2000.
. : 2- . .: , 1981.
: : 2- . / . . .:
, 1979.
.., . / . .
.: , 1999. 704 .
. : 4- . / . . .: , 1987. . 4.
470 .
: . . .: , 1959.
.. . . III. .:
- , 1961. 252 .
.. . .: - , 1956. 488 .
.. . . .: , 1965. 410 .
. - . 2- . .: , 1973.
.., .., .., ..
. .: ,
1974. 416 .
. . 12. / . . .: , 1965. 550 .

120

, -1
*
920-830
. .
1565-1545
.
1385-1360
.
1380
.

1545-1530
1360-1340
,- 1530-1510

1360-1335
-
1580-1570
1355-1340
,1600-1575

1340-1325
- 1550-1510

1365-1335
860-840
~750
*

.
.
.
.
.
.
.
.
.
.
.
.

. , . , .. .

121

as NO2
s NO2
. CH2
CH2NO2
as NO2
s NO2
as NO2
s NO2
as NO2
s NO2
as NO2
s NO2
as NO2
s NO2

2
20

(), /3
1.000
1.005
1.010
1.015
1.020
1.025
1.030
1.035
1.040
1.045
1.050
1.055
1.060
1.065
1.070
1.075
1.080
1.085
1.090
1.095
1.100
1.105
1.110
1.115
1.120
1.125
1.130
1.135
1.140
1.145
1.150
1.155
1.160
1.165
1.170
1.175
1.180

% ()
0.3296
1.255
2.164
3.073
3.982
4.883
5.784
6.661
7.530
8.398
9.259
10.12
10.97
11.81
12.65
13.48
14.31
15.13
15.95
16.76
17.58
18.39
19.19
20.00
20.79
21.59
22.38
23.16
23.94
24.71
25.48
26.24
27.00
27.76
28.51
29.25
30.00

(), /3

0.0523
0.2001
0.3468
0.4950
0.6445
0.7943
0.9454
1.094
1.243
1.393
1.543
1.694
1.845
1.997
2.148
2.301
2.453
2.605
2.759
3.913
3.068
3.224
3.381
3.539
3.696
3.854
4.012
4.171
4.330
4.489
4.649
4.810
4.970
5.132
5.293
5.455
5.618

1.185
1.190
1.195
1.200
1.205
1.210
1.215
1.220
1.225
1.230
1.235
1.240
1.245
1.250
1.255
1.260
1.265
1.270
1.275
1.280
1.285
1.290
1.295
1.300
1.305
1.310
1.315
1.320
1.325
1.330
1.335
1.340
1.345
1.350
1.355
1.360
1.365
122

% ()
30.74
31.47
32.21
32.94
33.68
34.41
35.16
35.93
36.70
35.48
38.25
39.02
39.80
40.58
41.36
42.14
42.92
43.70
44.48
45.27
46.06
46.85
47.63
48.42
49.21
50.00
50.85
51.71
52.56
53.41
54.27
55.13
56.04
56.95
57.87
58.78
59.69

/
5.780
5.943
6.110
6.273
6.440
6.607
6.778
6.956
7.135
7.315
7.497
7.679
7.861
8.049
8.237
8.426
8.616
8.808
9.001
9.195
9.394
9.590
9.789
9.990
10.19
10.39
10.61
10.83
11.05
11.27
11.49
11.72
11.96
12.20
12.44
12.68
12.93

. 2

(), /3
1.370
1.375
1.380
1.385
1.390
1.395
1.400
1.405
1.410
1.415
1.420
1.425
1.430
1.435
1.440
1.445
1.450
1.455
1.460
1.465

/
% ()
60.67
13.19
61.69
13.46
62.70
13.73
63.72
14.01
64.74
14.29
65.84
14.57
66.97
14.88
68.10
15.18
69.23
15.49
70.34
15.81
71.63
16.14
72.86
16.47
74.09
16.81
75.35
17.16
76.71
17.53
78.07
17.90
79.43
18.28
80.88
18.68
82.39
19.09
83.91
19.51

(), /3
1.470
1.475
1.480
1.485
1.490
1.495
1.500
1.501
1.502
1.503
1.504
1.505
1.506
1.507
1.508
1.509
1.510
1.511
1.512
1.513

/
% ()
85.50
19.95
87.29
20.43
89.07
20.92
91.13
21.48
93.49
22.11
95.46
22.65
96.73
23.02
96.98
23.10
97.23
23.18
97.49
23.25
97.74
23.33
97.99
23.40
98.25
23.48
98.50
23.56
98.76
23.63
99.01
23.71
99.26
23.79
99.52
23.86
99.77
23.94
100
24.01

3
c 20

(), /3
1.005
1.012
1.025
1.038
1.052
1.066
1.080
1.095
1.109
1.124
1.139
1.155
1.170
1.186
1.202
1.219
1.235
1.252
1.268
1.286
1.303
1.321
1.338
1.357
1.376
1.395

% ()

1
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
42
44
46
48
50

10.05
20.24
41.00
62.31
84.18
106.6
129.6
153.3
177.5
202.3
227.9
254.1
280.9
308.4
336.6
365.6
395.2
425.5
456.6
488.5
521.1
554.6
588.9
624.2
660.5
697.5

(), /3
1.415
1.435
1.456
1.477
1.498
1.520
1.542
1.565
1.587
1.611
1.634
1.657
1.681
1.704
1.727
1.749
1.769
1.787
1.802
1.814
1.824
1.8312
1.8355
1.8365
1.8305

%
()
52
54
56
58
60
62
64
66
68
70
72
74
76
78
80
82
84
86
88
90
92
94
96
98
100

/
735.8
774.9
815.2
856.7
898.8
942.4
986.9
1033
1079
1127
1176
1226
1278
1329
1382
1434
1486
1537
1586
1633
1678
1721
1762
1799
1831

V3 3
3 2 2
1 1,
:
V1 = V3(3/1)[(2 3)/(2 1)]; V2 = V3(3/2)[(3 1)/(2 1)].
(1=0, 1=1),
:
V = V33[(2 3)/2]; V2 = V3(3/2)(3/2).
124


............................................................................................................... 3
1. .......................................................................................... 4
2. , ......... 13
3. ................... 17
4. ....................................................... 20
4.1. ............................................... 21
4.2. .................................................................................... 23
4.3.
................................................................................. 27
4.4.
................................................................................ 32
4.5. ........ 36
4.6. ............................................................ 38
4.7. ......................................................... 42
4.8. ....................................................................... 46
4.9.
(, , )............................................ 47
4.10. -................................................................................. 49
5. ...... 53
5.1.
..................................................................................... 53
5.2. ........................................................... 55
6. ............................................................................... 57
7. ..................................................................... 61
7.1. ........................... 61
7.2. -........................................................................................ 63
7.3. .......................................... 66
7.4. ................................................ 66
8. N-.................................................................................................. 69
9. -.................................................................................................. 72
10. .............................................................. 75
11. .................................................................... 76
12. ............... 78
13. ............................................................................ 79
14. .............................................. 117
.......................................................................... 120
................................................................................................... 121

125

. .
. .
. .
. 04.09.07.
6084 1/16. . .
. .. 7,44. . .-. 7,44. .-. . 7,21.
100 . . 278.
__________________________________________________________________



443100. . , . , 244.


443100. . , . , 244. 8
126