Академический Документы
Профессиональный Документы
Культура Документы
..
2007
_____________________________________________________________________________
..
..
-
,
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.
. , . . 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
+ H3O
_
+ 2 Res SO3
Res - .
, -,
- .
.
( ) :
NaNO3 + H2SO4 HNO3 + NaHSO4.
6
,
, , :
4HNO3 4NO2 + 22 + 2.
, , .
,
.
,
. , , , 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
CH3NO2
HNO3 + HF + 2 BF3
NO2Cl + AgBF4
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
20 C, 1.5
(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
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
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
H3C
NO2BF4
CH2
NO2
H3C
45%
:
Si(CH3)3
NO2BF4
NO2
80%
19
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+
:
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+ , .
, NO2+ . ,
3 HNO3
23
( NO2+ ArH).
ArH , .. .
:
+
C2H5ONO2 + 3 H2SO4
N2O4 + 3 H2SO4
N2O5 + BF3
N2O5 + 3 H2SO4
NO2 BF3(NO3)
:
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
NO2
NO2
NO2
NO2
100 C
NO2
NO2
1%
n-
6%
o-
93%
-
, . - .
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
OH
NO2
Hg(NO3)2
100 C
HNO3 , 50 oC
NO2
NO2
O2N
NO2
2,4,6--3- ; 2,4,6-3- , -.
:
33
, , - ,
+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
HNO3
NO2
H2O
, 20 , 4-6
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
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
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
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
(CH 3CO)2O, - 10 C
CHO
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%
+
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
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
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
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
OH
+
HNO3
NO2
10 % (.) (C4H9)4N Br
H2 O
, 20 , 6
Cl
4-
, 6%
Cl
100
50
1.29
0.32
20
20
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
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
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
CHO
KNO3
H2SO4
+ KHSO4 + H2O
NO2
(d 1.84)
100 (2 .)
( )
10
40
11
1
89
HNO3
CH3COOH
CH3O
+
CH3O
OH
(d 1.5)
H2O
NO2
OH
100
15
6
150
90
NO2
+ NaNO3 + H2SO4
+ NaHSO4 + H2O
NO2
(d 1.84)
50
150
50
4.1
12.5
6.3
15
50
, ;
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
,
.
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
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
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
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
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
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
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
NOH
3 NaOH
40
20
25
Br
2 Br 2
3 NaBr
2 H2O
500
10
20 (62 , 0.388 ) . 25 (0.152 ) . 5
. ,
, 50 .
, . 2--2- 20
(50%), . . 181-184 .
250
250
25
37.8
21.2
28
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
?
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