Mon Omers

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2002
2
547 + 678
24.2 + 24.7
37
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... .: : /, 2002.-696
.: .
ISBN 5-02-006396-7
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Plate N.A.
Fundamentals of Chemistry and Technology of Monomers:
Manual. N.A. Plate, E.V. Slivinskii.- M.: Nauka: MAIK
Nauka/Interperiodika, 2002. 696 p.: il.
ISBN 5-02-006396-7
The book covers various preparative and commercial methods of obtaining monomers dedicated for the synthesis of polymers by polymerization and polycondensation reactions. The theoretical and technological features of
these methods are discussed. The basic properties of the synthesized monomers are considered. A great attention is
paid to technological processes suitable for the production of monomer raw materials (petroleum refining, as well as
coal and natural and associate gases processing).
The book is intended for senior students of the chemical faculties of universities and technological institutes
specializing in the chemistry and technology of polymers, organic chemistry, and related fields. This book presents a
valuable resource for post- graduate students, teachers, academic and industrial researchers, as well as engineers
engaged in organic synthesis and various fields related to the manufacture and processing of polymers (plastics,
chemical fibers, films, rubbers, lacquers, coatings, etc.).
ISBN 5-02-006396-7
.., .. , 2002
.................................................................................................... 19
........................................................................................................... 22

1. ......................................................
26
1.1. ..............................................................
1.1.1. - ..................................
1.1.2. ....................................................................................
1.1.3. ..................................................................
1.1.4. .........................................................
1.1.5. ...........................................................
................................
..............................
.......................................................
1.1.6. ....................................................................................
1.2. ..............................................................
1.2.1. ..............................................................
...................................................
........................................
1.2.2. ........................................................
..................................................
.......................
..........................
.
...
1.2.3. ..............................................................................
1.2.4. .......................................................
..............................
1.2.4. .............................................................................
1.2.5. .................................................................
1.3.
27
27
28
28
30
30
30
32
34
34
35
35
39
39
41
43
43
44
46
47
49
49
50
54
56
56
2. ............................................
60
2.1.
2.1.1. ........................................................
2.1.2. .
............................................................................
2.1.3. ....................................................................
2.2. ......
2.2.1. ...................................................
2.2.2. ...............................
2.3. ..........................................
2.3.1.
2.3.2. ..............................
2.3.3. ................
60
63
66
68
71
71
73
74
74
77
78

,

3. ................................................................
81
3.1. .......................................................................................
3.1.1. ..............................
3.1.2.
...........................
............................................................
........................................................
..................................................................
3.1.3. ..................................................................

-................................................. ............................

- ( )
....

( )
3.1.4. -1 ....................................................................
-1 4 ..
.......................................
3.1.5. ...............................................................
4
82
83
86
87
87
88
89
90
90
90
91
92
95
95
96
97
97
5
........................................................
-1 ................. .
..............................................
3.2. ...................................................................................
3.2.1. ........................................
............................................
.............................................
.
-
.......
- ...
-
3.2.2. ...................
3.2.3.
...........................................
...............................................
............................................

, ..........................................
3.2.4. - .........................
3.2.5. .......................................................
.................................................................
..................................................................
.....................................................................
4. ....................................................................
98
99
99
99
99
100
101
102
103
105
105
108
110
110
111
112
113
113
115
116
117
118
4.1. -1,3 ............................................................................................. 122

4.1.1. .. ................................................................ 123
4.1.2. .. ............................................... 123
4.1.3. .......................................... 124
( ).124
.......................................... 126
................... 127
.............................................. 127
4.1.4.
-1 ............................................................... 127
4-5 .................. 129
129
.. 131
............................................................... 133
4.2. .................................................................................................... 135
6
4.2.1. ................ 136
....................................................................... 137
-1,3 ..................................... 139
........................................ 139
4,4--1,3 ................... 140
4.2.2.
3--1,3 ................................................................. 143
4.2.3. ...................... 145
4.2.4. 5 ....... 146
.......... 146
........... 149

................................................................... 150
4.2.5. ............................................. 153
.............................................................. 153
2--1 2--2 ................ 155
2--2 .......................................................... 156
.................................. 159
4.2.6. .................. 159
4.2.7.
162
4.2.8. -2 - ....................... 163
4.3. --
165
4.3.1. ............................................ 166
......................................................... 166
-1,4 .................................................................. 167
-1,5 ......................................................... 167
4.3.2. ......................................... 168
...................................................... 168
......................................................... 169
....................................................... 169
5-(-2--4)--2 .................................... 170
-5---2--5-.170
5. .................................................
171
5.1. .................................................................. 171

5.1.1.
. . 171
5.1.2. ..................................................... 173
5.1.3. ...................................................................... 176
7
5.1.4. .................................................................. 176
5.1.5. ............................. 177
177
............................. 178
............................. 179
5.1.6. ............................................................ 180

............................................................................... 181

( )......................................... 185
... 186
................................................... 187
.................................................. 189
5.1.7. .................................................... 191
5.1.8. ................................................................ 193
........................... 193
.......................... 194
5.1.9. ........................................................ 197
5.2. .................................................................. 199
5.2.1. ..................... 199
5.2.2. .............................................. 200
5.2.3. ................................................. 201
......................................................... 202
.......................................................... 202
............................................ 203
5.2.4. .................................................................. 204
.................................................................... 204
................................................................................... 204
......................................................................... 205
5.2.5. ............................................................ 206
5.2.6. .................................................... 207
5.2.7. ..................... 207
............................................................ 207
........................................................ 208
............................................................... 208
5.2.8. .............. 209
....................................................... 209
- .......................................... 209
3,3,3- ................................................. 209
5.2.9. () .................................................. 210
6. ..............................................................
212
6.1. .....................................................................
6.1.1. .......................................................................
...................................
.................................
6.1.2. - .........................................................
6.2. .......................................................................................
6.2.1.
.........................................................................
6.2.2. ..............
5--2- ..............................................
2- 4- 2--5- ...
6.3. N- ...............................................................................
6.3.1. - ................
6.3.2. - ................................
6.4. N- ....................................................................................
6.4.1. N-
.....................................................................................
6.4.2. N-
6.4.3. N- ..
N-(2-) ................................
1- N-...........................
6.5. .................................................................
6.5.1. .................................................
6.5.2. ............................................................
6.5.3. ............................................................
...........................................................
...............................................
...........................................................
...........................................................
212
213
213
214
218
219
7. ................................................................
241
7.1. .........................................................................................
7.1.1.
.........................................................................
7.1.2. ......................................
7.1.3.
......
7.1.4.

7.1.5. .
7.1.6. ,
242
220
220
221
222
223
224
226
228
229
230
231
231
233
234
234
235
236
236
238
239
239
243
246
249
251
252
9
.......................................................................................
7.1.7. ............................................
7.2. ................................................................................................
7.2.1. .......................
7.2.2. ......................
................................................................................
7.3.1. .............................................................
7.3.2. ..........................................
7.3.3. ..............................................
7.3.4. .....................................................
7.3.5. - ..........................................................
7.3.6. ................................
7.4. ............................................................................
7.4.1. ...........................................
7.4.2. .............................................................
7.4.3. ....... .................................
7.5. ..................................................................................................
7.5.1.
....................................................................

...........................................................
7.5.2. .................................

........
7.5.3. .............................
7.5.4. ..............
.................................................................
...................................................
7.5.5. ..................
7.5.6. ..................................
7.6. ............................................................................................
7.6.1.
.............................................................................
( ) ...............................
.......................................
...............................................
..........
......................................
7.6.2.
- ...........................................................
252
252
252
253
253
255
255
257
257
260
260
261
261
262
262
263
263
263
260
264
265
265
265
266
266
266
267
267
267
268
268
269
269
269
270
270
271
272
273
10
- ..............
..........

7.6.3. .......................
7.6.4. ..........................
...............
.........................................
...............................

- ........................................
7.6.5. .....................................
...............................................................
............................................
7.7 .
273
273
274
274
277
277
278
279
8. ......................................................
283
8.1. ..................................................
8.2. ........................................................
8.3. ....................................................................
8.3.1.
............................................................
............
.............
8.3.2. .............
8.4. . ............................................
........

.....................................................................................
............
..
8.5. ..............
284
286
289
9. .......................................
313
9.1. ..........................................................................................
9.1.1
............... ...........................................
...........

...........................................................
9.1.2. ........................................................
316
280
281
281
281
282
290
290
292
293
294
296
298
300
304
311
316
316
321
322
323
11
...............
......................
9.2. .............................................................................................
9.2.1. ................
9.2.2. ........................................................
9.3. ........................................................................................
9.3.1.
................................................................................
....................................................................
.........
.............
..
....................................................
9.3.2.
.......................................................
9.4. ..........................................................................................
9.5. ......................................................................
9.6. ........................................................................................
9.6.1. ...............................
9.6.2. .........................
9.7. .................................................................................................
323
324
327
327
329
331
333
333
333
334
334
336
337
338
339
340
341
342
343

,

10. ....................................
346
10.1. ......................................
10.1.1. .........................................................
10.1.2. ........................................................
10.1.3. .........................................................
-...............................................

- .......................................
.....................
10.1.4. ........................................
10.1.5.

..................................................................
............................................
-
10.1.6. ...................................................
347
349
350
351
351
358
360
361
361
362
363
366
12
10.1.7. ............................. 367
10.2. ........................................................................... 368
10.2.1.
........................................................................... 368
10.2.2. ...... 370
10.2.3. - 371
10.2.4.
..................... 372
10.3. ..................................................................... 372
10.3.1. - ................. 374
10.3.2. - ............ 375
10.3.3. ..................................................................... 375
10.4. ............................................................................... 378
10.5. .. 379
10.5.1. ....... 379
10.5.2. ......... 380
10.6. -2,6- ................................................... 380
10.7. -2,5- ..................................................... 381
10.8. ............................................................................ 382
10.9. ....................................................................................................... 383
10.9.1. ........................................................ 383
........................................................ 383
............................. 384
10.9.2. -1,2 .................................................... 386
................................................... 386
-1,2............................... 388
10.9.3 -1,4........................................................ 389
-1,4 ......... 390
-1,4 ...................................... 391
-1,4
( ) ............................................ 393
-1,4
( ) ................................................ 393
-1,4
( ).............................. 394
-1,4 ( )......................... 395
10.9.4. 1,4- ..................... 398
11. .......................................................
399
11.1. , .. 400
11.1.1. .......................................................... 401
13
................................................ 401
................................ 405
............................................ 422
................................... 426
11.1.2. ....................................................... 427
11.1.3. 7- ................................ 427
11.1.4. ..................................................... 429
11.1.5. 9- ................................. 429
11.1.6. 11- ........................... 429
11.1.7. ......................................................... 432
.......................................................... 432
............................................ 433
.............................................................. 433
11.1.8. - ...................................................... 434
- ............................................. 435
- ............................. 435
... 436
- ................................. 437
11.2. , ........................................................................ 439
11.2.1 .............................................. 440
......................... 441
................ 442
................................... 442

442
11.2.2. ...................................................... 443
................... 443
...................................... 444

........................................................................................ 445
446
11.2.3. .................................. 447
......... 447
-1,6.............. 449
.......................... 449
................................................... 450
11.2.4. ...... 450
11.2.5. -............................................... 457
- ......................................................... 457
..................................................... 458
11.3. .................. 458
11.3.1.
14
1,4-......... 458
...................................................... 459
1,4-................................. 459
11.3.2.
4,4- 459
...................................... 460
4,4-............................ 460
11.4. .................... 461
11.4.1. ............. 461
...................................... 461
................................................................... 462
11.4.2.
4,4- .............. 463
11.4.3. 2,5-(-)-1,3,4- ......... 464
11.4.4. 5,5-(-)-2,2-(
1,3,4-)......... 465
11.4.5 4,4-(-)-2,2-................ 465
11.4.6. (-)(5,4-d).......... 466
11.4.7.
........................................ 466
.................................................................... 466
4,4- .......................... 467
12. ......................................................
470
12.1. ..............................................................
12.1.1. .....................................................................
12.1.2. ............................
12.2. .................................
12.2.1. -2,2,3,3-
...............................................................................
12.2.2. -2,3,5,6-
.......................................................................................
12.2.3. -2,2,6,6-
.......................................................................................
12.2.4. -3,3,4,4-
......................................................................................
12.3. ..............................
12.3.1. -1,4,5,8- .......................................................................
12.3.2. -2,3,6,7--
472
473
475
481
481
482
483
484
485
485
15
........................................................................... 486
12.4. - ....... 486
12.4.1. -3,3,4,4 ................................................................ 486
12.4.2. -3,4,9,10- ............................................. 487
12.5. ....................................................................... 488
12.5.1. - -....................................... 488
12.5.2. -................................................. 489
12.5.3. ....................................................................493
12.5.4. 4,4-................................. 493
12.5.5. 4,4-................................. 493
12.6. ............................................................................ 494
12.6.1. ..................................................... 494
12.6.2. ..................................................... 495
12.6.3. ...................................................... 495
13. ...................................................
496
13.1. ..................................................................................................
13.1.1. ............
13.1.2.
..................................................................

......

........................................................................
...................
.................
13.2. ................................................................
13.2.1. ..........................................................
13.2.2. , ..
13.2.3 ........................................
.........
.........................................
..........................................................................

13.2.4. 4,4-......................
................................
.........................................................................
13.2.5. ...........................................
13.2.6.
500
500
501
502
503
504
504
505
506
506
508
509
509
509
510
511
512
513
516
16
-
N-.............................................
N-......................................................
-..........................................
13.3. ....................................
13.3.1. - .................................................................
13.3.2. ...............................................................
13.3.3. .................................
13.3.4. .....................
519
519
522
522
524
525
526
528
528
14.
531
14.1. ....................................................................................
14.1.1. ..........................................................
............................................

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

........................................................................................
- ....
2--1...............
................................................
14.1.2 ........................
................................................
...............................................
14.2. ..................................................................................
14.2.1.
14.2.2.
.......................................................
14.3. S .............................................................................................
14.4. ................................................................................................
14.5. ....................................................................................
14.5.1. - ...............
14.5.2.
........................................................................................
14.5.3. ....................
14.5.4. ............
535
537
537
15. - -
544
546
548
549
550
550
551
552
553
553
555
556
558
559
564
565
566
567
569
15.1. - ............................... 569

15.1.1. .................................................................. 569
17
...........
..........
.....................
(
) ........................................................................
(
) ...............................................................
.....................................................................
...................................................................
15.1.2.
15.2. - .........................
15.2.1. ..............................................................
15.2.2. ................................................................
570
573
573
574
575
584
588
590
591
594
16. ........................................
596
574
16.1. .................... 598

16.1.1. ................................................... 598
16.1.2. .......................................................................... 598
16.1.3. ... 599
16.1.4. ... 599
16.1.5. ............................................................... 599
16.2. ............................................................................... 601
16.2.1. -
........................................................................................ 602
............................... 603
....................................................... 605
......................................................... 607
....................................................... 608
................................................... 609
...................................................... 610
16.2.2.
........................................................................ 610
.......................................... 611
............... 611
........................... 612
16.2.3.
......................................................... 612
16.2.4. ... 613
16.2.5.
....................................... 614
16.2.6. ................................................... 615
16.2.7. ........................................... 616
18
16.3. .............................................. 617
16.3.1. ....................................... 617
16.3.2.
.......................................................... 619
........ 620
621
16.3.3. ........ 623
623
624
16.4. ........... 626
16.4.1. ........................ 628
16.4.2. .......................... 629
- .......................................................... 629
N- .......................................................... 630
........................ 631
632

........ 634
,
...................... 635
,

........................................................................636
16.5. ..................................................................................... 637
17.
642
17.1. ...................................... 642
17.1.1. ..................... 642
17.1.2. 1,2- ..................................................... 643
17.1.3. n- ................................................... 644
17.2. () ................................................................ 646
17.3. ................................................................... 649
17.4. ................................................................. 653
17.4.1. ....................... 654
2,5-(-)-1,3,4- ................ 655
4,4-(-)-2,2- ..................... 656
5,5-(-)-2,2-(1,3,4-) 656
5,5-(-)-2,2-(1,3,4-) 657
17.4.2. - ............................. 657
17.4.3. ..................................................... 659
17.4.4. ........................................................ 659
17.4.5. ...................................................... 660
19
17.5. .....
17.5.1. ,
- ................................................

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

...............................................................
17.5.2.
.
17.5.3. ,
- ........................................
17.5.4. ..............
.
661
663
664
664
665
666
666
670
20
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C4H10 2 C2H5,
C4H10 CH3 + -C3H7,
C2H5 C2H4 + H,
C2H5 + C4H10 C2H6 + C4H9,

CH3 + C4H10 CH4 + C4H9,
-C3H7 C2H4 + CH3
H + C4H10 H2 + C4H9
C4H9 C2H4 + C2H5

C4H9 C3H6 + CH3
H + C3H6 CH3 + C2H4
,
, .
, ,
-1,4.
, 700 . (800-1000 ) , . , , . .
(1000-1300 ) , .
. ( 1300 )
, .

(<0,5%). :
2=2
2==2 + .
(800 ) :
32
2CH2=C=CH2
H2=CH2
H2C=H2
H2=CH2
H2C=H2
-1,4 . 1,4 900 4, :
+
~ 600 .
. , . 1000 : , . .
. ,
.
k (c-1) -
1073 :
-
18
1,5
0,001
0,003
,
, 1000-1200 ~ 0,1
, . .

:
- ( ) () ;
33
- (
).
.
. 1.1
.
,
, 1.
1113-1123 2,
;
. 423, . 673 , 3 .
. 1.1.
1-; 2- ; 3- .
: I ; II ; III ; IV ; V
; VI- ; VII ; VIII
; IX ; X
( %(.)),
1113-1143 0,25-0,40 :
- . 17,7
. 25,5
. 16,2
. 1,0
- .. 12,2
..-423 19,9
34
423-523 . 1,5
523 3,3
.. 2,7
-, 423 , 50-55% (.)

, 30-35% -, 4-8% , 2-4% .

, , , . ,
: , , ( , , ), , .
-
(1053-1063 ) ,
, .
.
1.1.6.
.
,
. . 1.2 " ".
35
. 1.2.
" "
1 - ; 2- ; 3-
; 4 - ; 5 - .
: I ; II ; III - ; IV
3-4; V ; VI - ; VII
1
, ,
- ,
3. ,
2, 753-783 . 3. -
1,
, , . , 4 5 ,
-, - , . 3 .
, . , .
1.2.
: . .
" " .
1.2.1.

: , , 3-4 .

.
1936 . - . , . 1940 . -
36
. 1941 .
" " , 1942 . - .

. 1962 . .
- ,
, , :
- ;
- ( );
- ;
- ;
-
;
- ;
- ;
- ;
- , .

, , .
, . . ,
, , . ,
.
, .

. ,
: .
37
()
.
. -
+, +-. +,
. : , -
.
. , : :
CH3
CH3
CH3CCH2CCH3 + A- ;
CH3CCH2C=CH2 + H+ACH3
CH3
CH3
CH3
CH3
+
+
CH3CCH3 + CH2=CCH3 ;
CH3CCH2CCH3
CH3
CH3
CH3
CH3
CH3
CH3
+
+
H3CCH3 + CH3CCH2C=CH2
CH3CCH2CCH3 + 2=CCH3
C
CH3
CH3
H3
CH3
CH3
CH3 ;
CH3
+
+
CH3CCH3 + CH2=CCH3 ..
CH3CCH2CCH3
CH3
CH3
CH3
CH3

:
+
CH2=CCH3 + H+AC(CH3)3 + ACH3
:
CH3
+
+
CH3CCH3 + CH2=CCH3
CH3CCH2CCH3
CH3
CH3
CH3
CH3
, :
+
H2=CHCH2CH2CH2CH2H3 + H+ACH3CHCH2CH2CH2CH2H3 + A+
CH3CHCH2CH2CH2CH2H3
CH2=CHCH3 + CH2CH2CH2H3
38
. -, , :
CH3CH2CH2CH3
CH3CH3 + CH2=CH2
, .
,
, .
:
.
:
CH2-CH2-CH3
+ CH3CH=CH2

. -
, , , , , - . .
, . , , , .
723803 . , - ,
, , , . .
0,07 . 0,4
.
39
,
. .
.
,
.
.

- (473-623 ) (623-773 ).
, ,
.
(, , , . :
- - ;
- , .
,
1 . . 1.

- , , .

, , 1940- . 1950- .
, ; . 1960 l23.
,
.
40

, .

, , .
.
, . 1980- ,
- .

"". . 1.3 - "".
.
. 1.3. - ""
1 - ; 2 - ; 3 - ; 4 - ; 5 - ;
6 - ; 7 - ; 8 -
41
; 9, 10 - ; 11 -
1 , 2.
3 . 4
5, .
6
, 7.
8 . 9 10.

.
1.2.2.
( ."reform" , ) -
,
. .
1940- ( ).
, "".
, ,
. .
,
. - , , .
-

42
. , .

Pt, Al2O3,
.
Re Ir,
,
. VIII ..
,
Al2O3 . , Ge, Sn, Pb
.
, , .
, , :
- ()
+ 3H2 ;
-
CH3
+ 3H2
- ()
-C6H14
+ 3H2 .
. -
:
-C6H14
-C6H14,
CH3
CH3
CH3
CH3
CH3
CH3
43
, .
, ,
C8H18 + H2
C5H12 + C3H8 ,
. , , ,
:
C6H5C3H7 + H2
C6H6 + C3H8 .

:
CH3
+ H2
C6H14 .

, 333-463 . , , . :
335-358 , 368-393 ,
393-413 . ,
, 8-9 - (- -) (, , 1,2,4-).

. :
C6H12
610 + 2
C6H6 + 2H2
. , , :
-
CH3
C H3
C H3
44
CH3
CH3
CH3
CH3
-
C H3
CH2CH3
CH3
.
- ,
. ( - , - ):
+
C
-H2
M
C
+
-H+
A
C H3
H2
CH3

, .
,
:
C H3
C H3
C H3
C H3
C H3
CH2CH3
C H3
CH2CH3
C H3
45
.
, :
CH2CH3
CH3
CH3
CH3
-2
CH3
CH3
. , 1,3- -, 1,2- - :
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
-
:
C
+
+
C
+
. .
-
46
. , -, 2-- 3-:
CH3

CH3CH2CH2CH2CH2CH3
(CH3)2CHCH2CH2CH3
CH3CH2CH(CH3)CH2CH3
- :
CH3
CH3
CH3
+ .
CH3
+ H+
CH3+ H .

. , ,
, .

. 6-2 :
-C6H14
C6H6 + 4H2,
:
-C6H14
C5H9CH3 + H2 .
5-3 , .
2
6 - ( , ) , , 300-310 0
(.. , .. , 1936 .).
3
5- (
.. ., 1954 .).
.
, , . :
-C5H12
Pd; [-H2]
[+H2]
-C5H10
[H+]
-C5H10
Pd; [+H2]
[-H2]
-C5H12
0,1-1,0% , -
47
. , , ,
, , ,
.
.
. ,
, .
.
.
: , , .
. , , :
- - - ;
- -
+
+
CH3CH=CHCH2CH2CH2CH3 +
CH3CH2CHCH2CH2CH2CH3;
-

+
CH3CH2CHCH2CH2CH2CH3
+
CH3CH2CH=CH2 + CH2CH2CH3
+
CH2CH2CH3
CH3CH2CH=CH2 + CH3CHCH3;
- - -
CH3CH2CH=CH2 + H+
+
CH3CH2CHCH3
CH3CH2CHCH3
CH3C(CH3)=CH2 + +

(), , , .
48
. . : ,
, :
CH3
CH3
CH3
CH3
-2
CH3
CH3
CH3
CH
3
.
.
Pt/123 :
CH3
+ H2
+ CH4 ,
CH3
CH3
+ H2
+ CH4 .
CH3
8 :
CH3
CH3
CH3
H3C
+ H2
+ CH4 ,
CH3
CH3
CH2CH3
+ H2
CH2CH3
+ CH4.
, :
CH3
CH3
+ H2
CH3
+ CH4 ,
49
CH3
CH3
CH2CH3
+ H2
+ C2H6 ,

.
1.2.3.
( . cracking ) -
: , ,
.
( , , ,
, ) , ( ) ().
: , , .
- . , " " . , ,
.
.
, , ~ 15 -
5-7 . .

- . :
4. ,
50
. 23-30% , - 40-60%.
, ,
,
. (, ) . , ,
: , , , . : 100%.
- 95-99%. : 0,56 -1
77%, 80%.
,

, . , ,
2 , -,
- : - 1,5-2.
4 (, )
- .
( ,
5).

, , . .
.
:
-
, ,
;
51
-
;
-
;
- , ;
- , ;
- , .
5 30 .
, .

15 .
.
, , , . ,
.

. .
,
678-683 :
, -1
, %
, %

+
0,7
0,56
100,0
3,3
51,0
100,0
3,4
42,7
154,3
146,1
7,4
1,8
24,0
69,1
51,0
8,4
1,8
39,9
52,3
42,7
52
,
, %

, /3
. 1.4
.
1,0
1,0
154,3
146,1

477-600
440-533
237
209
10,0
48
848
866
. 1.4.
""
1, 2 ; 3, 4, 5 - .
: I ; II ; III ; IV ; V ; VI ""
, 1 , , ,
-
, 2, . , , 3-5 .
, .
, Ni(Co) - Mo(W)-.
VIII - ,
.
53
Ni-, Pt-, Pd- ,
- .

, , IV,VI VII (Sn, Re, Ge, Ti).
-
0,5-0,8%. VIII .
Co, Ni, Mo W. ,
,
, Mo
W, , , Ni (Co)/Mo (W).
-:
( ,
);
, , ;
,
.

: ( ) . ,
Ni(Co) Mo(W).
- ,
.
.
.
, , ,
. , . , . ,
, -
54
10-1000 / .
-
.
, , , , .
25%
.
1.2.4.
.
, -, , .
:
C6H6
RCH=CH2
C65CHRCH3,
, , .
1877 . . . . 1878 . . 113.
. 1.5.
55
. 1.5.
1 - ; 2 - ; 3 - ;
4 - ; 5 - ; 6 - ; 7 -
; 8 - ; 9 - .
: I ; II ; III ;
IV
; V ; VI ; VII
; VIII
1920 , . . 1936 . .. , .. , .. .. 1942 . (). .. . . . , , , , -, .

, , , , , , , , .
,
, , . :
C6H6 + CnH2n
C6H5CnH2n+1
56
:
C6H6 + CH3CH=CH2
C6H5CH(CH3)2
.
.
1.2.5.

.
.
4-6 . ,
, 45% -. ~70 .
80 . .
,
.
573673 -
.
3-4 .
50-55%.
- 96%.
1.3.

.
.
:
1. -
, .
57
, , .
.
2.
,
.
.
,
, . () , , .
, ,
. " " , "
". : % (.) 0,000150,005;
25-30%, 1%;
2,5%.

(
) , 30-40%, 25-40%. .
, , -- .

, , . ZSM, LZ-210 Y.
, 3-5.
. -
58
, , .
. 1.6. . ()
1, 2 8,8 . /; 3
; 4 ; 5 ; 6 ; 7 ; 8 ( --
2,5 . /); 9 ; 10 ; 11 5-, .;
: I ; II (
), , , .;
III 5 ; IV ; V
2; VI - ; VII (.. 616
); VIII (97,5% 2); IX ;
X ;
XI ; XII ; XIII ;
XIV ; XV - ;
XVI ; XVII ; XVIII
; XIX ; XX ; XXI .
,
: , , .

, , .
7,5% 38 87% 88 .
59
. 1.6 ,
. .
60
2

2.1 .

:
, , , . , , ,
, .
, 2 (-)
.
:
+ 0,52
,
+ 2
2 ,
+ 2
+ 2.
. , , 2, .
:
, , (), .
:
+ 2 2
4 + 2,
2,
+ 2
+ 2
2 + 2 ,
+ 32
4 + 2.
, , , . ,

, .
, ,

2.1.
61
2.1
()
(CO, H2, N2,
CH4)

(CO, H2, N2, CH4)
(

)
-,
-
(CO, H2, N2)
NH3
CH3OH,
-,
,

(H2, H4,
N2 CO2)
-
(H4,
N2 CO2)
.
, , , , ,
.
,
1950- , , .
: , , .
-, , -, , :2 2:N2,
, : .
- .
, . - - (
2.2).
62
2.2
( , ,
, )
, 2, 2 +
+

H2 + CO ( CO2, CH4 N2)
CH4 (CH4 + H2O

CO (CO + H2O
CO2
CO + H2
CO + 3H2),
CO2 + H2),

H2 (+N2)
. , " ", .
.
.

. , . , . :
-
;
- ,
;
- - , , .
63
,
, .
2.1.1.
, , " ", .

: 150 .
, , , . , , , .
1273 . .
,
,
.
. 2.3
.
, , .
(. 2.3, , ) .
5
1,3-1,8 . , , , ( 5,2 /3) ( % (.)):
27,8
2..12,4
2 3,6
N2 56,
(. 2.3, ) .
, . . , ,
, , .
. (
) 623-673
. -
64
- ~ 15000 3/, 11,8 /3. ( % (.)):
..
2
64,6
28,7
2 ..
N2
5,7
1,0
0,25 3/3
-, - 0,3 /3.
. 2.3. (, ) ()
- 1 - ; 2 - ; 3 -
;
- 1 - ; 2 - ; 3 - , ; 4 - ; 5 -

. 3 , . 5-30
,
.

. "" (. 2.4) "
"(. 2.5). -
65
. 2.5 .
2.4.

""
1 - ; 2 - ;
3 - ; 4 - ; 5 - ;
6 - ; 7 - -;
8 - ;
9 - ; 10 - ; 11-

, .
- .
"" ,
. , .
66
-, :2 . 2,0 .
. 2.5.
1 - ; 2 - ; 3 "" ; 4 -

( % ()):
58,0
2 ..25,6
2 6,3
4 . 9,1
N2 .. 1,0
2.1.2. " "

" ",
"".
-, -.
" " . , , . -
,
-, , - . 90%. ( % (.)).
. 30-50
4 . 1-2
67
2.35-46
2 .13-25
N2 ...0,5-1,5
, -, , . , , , 2, . .

:
+ 32
4 + 2.
.
-
( )
( ).
.

+ 2
2,
,
+ 2
2.

2 + 2
2
,
.
. , 65-70% .

1173-1573 .

: , , , , ,
, , ,
, .
, . , -
68
, , .
, , , ,
, , "" . ,
. .
, , 2 4, :
.

173 93 . 4 .
, -
.
: ,
"" ( "").
-
, . .
17-35 .
2
.
. , .
2.1.3.

(, ) ().
,
( ).
.
. .
.
69
, , .
- , ,
,
- .
:
,
.
- 10 Ma - .

-
. . 1-2% , . , . - - .
( 10 ) 1,5% , (90% ) 3% ,
.
,
, ,
.

, ~ 15% (, , ). , 1-4, , , , , 80-85%- .
,
, ( - ).

( 2.3).
70
2.3
1-4,
H2S

NH3, 6-8,
. .
698 K

. .
373-513
6-8
H2S
H2O
. .
593
71
12-14 / ( % (.):
2-..
3-..
...
7,7
0,8
1,2
0,8
3,1
0,9
.
2-.
4-.
5-.
2,5-..
.
30,8
12,5
21,8
2,6
5,0
10,9
, ,
: . . 513 ; ;
. . 698 ;
. . 333, 333-453, 453-573 573-673 ; ; . . 453 ; ; -.
( % .)):
6-8...

:
.
.
..

:
.
.
1,6
26,3
2,9
5,6
10,4
7,2
3,8
1,7
, 14,9% 1-2; 13,4%

3-4, 0,7% 1,6% .
2.2.

1930 . , , , -
72
.
, 70 99%. , ,
, , ,
.
2.2.1.
: ,
, , , ..
- , , .
, -
,- . .
. .
2-4 , .
.
.
. 2.1 , () 2.
- -,
,
, ( ), ( -) .
2.1
,

, ,
73
()
O2
, ,
, ,
, , ,
NH3(2)
S, 1
"

, ().
1, , I, 2-1-, -, I-,
, F
,
F-
. , , ,
S
4-
,

.
, .
HNO3
,
,
S
,
-
S
-
, O2,
. .
2.2.2.

( 243 , 7,6 ), 90-95% 5+. -
74
: 10-15% (.) 30-40% (.)
- .

, (193-213 ). : 30-50% (.) , 70-80% (.) - , 99-100%
(.) 5+.

,
, - (
), ( ).
2.3.
-
. , , , , , .
. 1990 . ~ 43
.
,
.

. :
, , , -
, ,
.
2.3.1.

.
75

.

, , :
nm + 2
2 + + 2 + 4 +
Cnm + 2
2 + C + C2 + CH4 + H2 + C
nm + 2
2 + + CH4 + 2 +
m + 2
4 + .
, ,
.
700 4 2. ( 1500 ) 2 :
nHm + nH2O
nCO + (n +m/2)H2

473
4 + 2
+ 32
= - 206 /
4,0
1033-1173 . ,
.
Ni/l23.
, , .
nm + n2
2n + m/n2.
2: .
, ; :
CH4 + CO2
2CO + 2 H2
H = 247,3 /
4CO + 3H2
H = 429,7 /
C2H6 + 2CO2
14CO + 8H2
H = 1395 /
C7H16 + 7CO2
12CO + 3H2
H = 952 /
C6H6 + 6CO2
76

- -- . :
CnHm + n O2
nCO +
CnHm + (n +
m
)O2
4
m
H2
2
nCO2 +
m
H2O
2
,
. .
, ..
.
d-, VIII .. .
:
Fe < Co < Ni < Ru < Rh < Pt < Pd
, ,

.
: ( ) , . , . .
:
BaO << SrO << CaO < Cr2O3 < BeO < MgO < Al2O3.
, .
:
NiO + H2
NiO + CO
Ni + H2O,
Ni + CO2.
, , .
, , .
77
2.3.2.
6-25% . , , , 2 . , . (623-723 ) (453-523 )
.
, . 2
2 523-723 ,
.
- -
, F34. . ,
, .
453-523 . (20-50%). , ,
, .

2 - 0,2-0,8% 2 - 0,010,5% .
2
:
+ 32
4 + 2 ,
2 + 42
4 + 22.
- .
, 2, :
, % (.).60-70
, % (.)...30-35
, % (.) .. 5
, %.60-65
, /3.1080
, 2/ 170
, 2/ .25
78

, .
2 . ,
2. 2 ,
0,0002-0,0003 3/3. , , 2.

. :
- ;
- 2 ;
- ;
- ;
- .
2 . , , .
, . , 1 3 2 . 2
.
("-"), N- (""),
(""), ("").

2. 10-15
2 .
2.3.3.

(1-7) . 95-98% , , 2, . 99% . (99,99%), -
79
, . .

..
.
95-98%- . : 1,0 4,2 .
. 2.7 . ( )
623-673 2 1. 2 - 3, .
2 . 95-98,5%- 1-5% 2.
. 2.7. 9598,5%-
1 - ; 2 ; 3 - ; 4, 5 - ; 6 - 2; 7 - ; 8 .
: I - ; II ; III - ; IV ; V 2; VI
2; VII - ; VIII -
.
.
, , ~1123 -,
.
.
, 2, 2, 4, 2 ,
,
.
. -
80
99,99%. 1,5-2,0
.
.

~ 1573 1173-1223 . : , -
. . .
.
, .
,
:
55-65 . - 1 .
.
.

.
0,7-2,3% (.) . 1 11 000-14 000 3 ,
. 90-95%.
81

, .

,
, , , .
, ,
, , , , .. .
, ,
, ,
.

- ( 4) .
, , -4--1 , ( ).
,
"".
. ,
, .
1959 . . . -1,
82
-, . . 399 . -1 ,
-1, 4-
373 513 .
-4--1
. -4--1 . . 513 .
(83 /3) , ( 65%), ( 90%). -4-1 . , 373

293 . , .
. ,
, , ( ,
, ), , , .. -4-1
, ( ,
.), (), (, ), (, , ),
( ).
.
, . ,
,
, . ,
.
, , .
3.1.
, , .
. . 3.1.
83
3.1.

(C2H4)
., ,
., .,
d, /c3
28,05 103,8 169,3 1,251 282,9 5,15
q, /
47260
(C2H6)
42,08
87,7 225,3
1,877
364,9 4,68
45880
-1 (C4H8)
56,10
87,6 266,7
2,503
419,2 4,10
45380
--2
56,10
134,1 276,7
2,503
430,0 4,22
45380
--2
56,10
167,4 273,9
2,503
428,0 4,22
45380
56,10
132,6 266,0
2,503
417,7 4,04
45380
: . , , q - .
. 1795 .
. .
. 169,3 .
50 . .
.
, .
3.1.1.
64%
, ~ 17% -
,~ 11% 8%
.
. . 3.2
.
3.2

,
%(
)
1,7-4,0
, % (.)
CH4
-
C2
3,3-11,7
C3
25-51,7
C4
24-48
C5
8,1-20,8
H2
-
84
4,0-8,0
0,8-19,5
31,3-41,1 21,3-26,1
10,0-16,0
0,4-6,4
5,8-9,2
8,0-12,0
12,3-17,4
30-36
1,9-2,8
1,1-3,2
8,0-10,0
2,0-7,0
35
30,4
22
28,5
8,2-11,1
0,8-2,5
18,4-25,6 42,7-49,8 11,9-21,4

29,5-31
5,3-14
27,4-34,6 43,2-47,4
14,5
17,5
15
10,4
0,3-3,5
4-21,0
4,8-19,1
4,6
13,5
2, , 41,1% (.).
3, ~52%, - ~ 35% - ~ 26% (.).
-
~ 50%, 47,4%% 48% (.).
, , , - ~
60%.

. 2 5% ( 45-70% ).
, ,
.
~
19% 80% , ( %(
.)):
26
38
-410
0,7
11,9
7,7
-410..
5 ..
28,5
51,2
. 3.3
12 . . /.
85
3.3

""
""

-

-

:

.
383
520
193
118
62,2
1,44
1,63
%( )
3,2
22,5
15,4
5,7
2,5
1,9
% ( )
3,2
4,3
1,6
0,99
0,52
-
36,2
43,8
0,32
44,6
14,5
0,37
31,0
57,6
232,0
34,6
1715,3
0,50
2,0
14,2
11,5
0,25
0,48
1,9
0,29
14,3
, ~ 14,3 %.

. . 3.4 .
3.4

""

713-723
11,0
2,34
22,5
37,5
25,0
, % ( )
748-753
718-723
14,7
18,5
753-758
18,5
3,5
4,0
6,1
24,0
37,0
19,0
24,0
32,0
19,5
15,5
39,9
20,0
86
4,0
100,0
5,3
100,0
6,0
100,0
6,1
100,0
,
6,1% ( ).
. 3.5 ,
.
3.5

713-723
748-753
, , ,
% ( % (
% (
) )
)
11,6
1,27
8,9
,
% (
)
1,6
718-723
753-758
, , ,
% ( % ( % (
)
) )
3,9
,
% (
)
0,7
0,9
0,1
0,9
0,17
2,5
0,4
10,4
1,14
8,7
1,6
7,8
1,2
5,3
1,0
9,5
1,04
7,5
1,4
11,3
1,6
11,5
2,1
10,7
1,17
11,3
2,1
12,0
1,8
20,6
3,8
10,2
1,12
12,4
2,3
15,9
2,3
11,8
2,2
39,7
6,3
50,3
10,3
43,0
6,0
40,4
8,3
10,8
1,19
10,6
14,8
2,2
10,2
1,8
1,96
, - 11,5% - 20,6%, - 2,1 3,8%.

3.1.2.

, .
, .
-
, -
, ,
.
87

.
1023-1173 0,3 .
~ 30%.
, . 15-25%. - 50% - :
, , . . (.
1.1.5).

~ 1173 ~0,05 .
(5%)
(95%):
26
24 + 2.
. , ,
~33% , 0,3%
.

1073-1123 . 923 , - 823 , 3:1.
, .

. , : 33% (.)
, 26% , 14% . 11,5% , 7,5% , 4,2%
, .
~80% .
.

( )
, . . .
88
:
-, .
. . , ,
, , , , . , , , .
, : , - . .
9731073 -
.
. ~
50% ( ) 8%.

, : NaMnO4/MgO-SiO2 Mn3O4/SiO2 2
1073 13-15%.
2
, 12,5% NaMnO4/g: 1073
4:N2=1:1; ~12 % .
-
.

"" (), "" ()
. 873-973 .
70-80%
30-60%.
, 1123 , 44-50% 26-36%.
-
.
89

.

CH3CH2OH
CH2=CH2 + H2O.
, .
: , , .
:
.
" " ()
- :
2CO + 4H2
CH3CH2OH + H2O.
33,5%
. (49,6%), (2,6%), (6,5%).
:
CH3OH + CO + 2H2
CH3CH2OH + H2O.

( , , , , ,
.).
, .

483-493 , - 433-453 .
, , 523-623 . , , ,
.
, 553-573 .
~ 90% .
90
3.1.3.
:
- -;
- - ;
- 2-4 .
-
. 4,5-5,5% (.) . , , ( % (.)):
N2, 2, 4,1
..6,1
39,1
..17,5
.7,3
.9,4
8,9
.2,6
...1,4
3,0
..0,6
.

( 2S 2),
. , , , .
. . .
-
( "")
-
.
, , (1)
(2):
nCO + 2nH2
2nCO + nH2
-H2O
-CO2
CnH2n
CnH2n
H2
H2
CnH2n+2 ,
(1)
CnH2n+2 .
(2)
91
(1) ,
Co-ThO2, Co-ThO2-Mgo -, 450-480 0,1-1,5
. 500-550 0,5-1,0
(2). 180
1 3 . (-).
2 -
, , , . -
n + 2n2
n2n + n2
.
-,
-. .
. 3.1
, , .
2 25-40%.
. 3.1.
,
-,

,
,
85-90%.
.
773-873 10% ,
1 8% . 3-4
54%, .
92

, (1)
, (3):
38
4 + 24
= - 67,5 /, (1)
238
26 + 36 + 4
(2)
3 6 + 2
= - 125,7 / (3)
38

, (261,9 /), (364,5 / , 359,5 / 347,8
/ ). , ,
.

. , ,
. 873 , 2,7 .
25% (.).

( "")
- : Cr2O3, MoO3, V2O5, TiO2 GeO2. Cr23 -123.
~ 873 . 75-85%
- 50-80%.
.

, , ( ). .
15-25 .
1980-
. , --
( , ). . 3.2
1990- . 70% -
93
, 28% - " ", 7%
. , , ,
.
,
.3.2. ( 1989 . 1)
94
. 3.3. ()
1- ; 2 ; 3 ;
4 .
: I ; II ; III
.
. .
1939-1940 . . .
.
10 20 .
1960- () " " .
, ,
, 1990-
t/Al2O3. 1990 . "" - ( ) t/Al2O3.
"" ,
(. 3.3).
.
250 .
/ .
,
/

323400
250000
24800
( )
,
/
37600
11
. 3.6.
3.6

"".
95
, % (.)
, m
, % (.)
, % (.)
4, 5 , m
, m
, m
, m
, m
, m
, m
, m
, m
, m
, m
99,5
20
0,5
500
1000
100
100
5
5
10
2
0,3
5
1
5
99,92
<5
0,06
52
<l
<l
<l
<l
<l
<l
<l
<0,1
<0,1
<0,03
<l
. ppm 1 .
3.1.4. -1
- 1 ( ) -1,3, , - . -1
4 ,
, -, ,
.
-1 4
-1 4 .
4 , -1 15 25%.
4 -1 , - :
- .................
2-.....
-1 .................
. .,
272,50
261,27
266,74
-1,3...............
-1 ...............
-2 ...................
. .,
268,60
281,07
299,99
96
--2...........
--2 .....
2--1
-1,2 ........
269,28
273,88
266,10
283,85
-1()
...........
............
278,00
277,50
286,08
-1 4, -. -1
2--1 -1,3. 2- -1 2-
,
2--1 -1: , . -1 4
.
-1 -2.
-1 -2
4
- -2 .
-1 98,5-99,5% . , -1,3 ( ) , NaA,
.
-1 , , ,
- ( , , , ,
, , ).

.
Pd/l2O3 313-423 .

. .
- 333-353 ,
- 373-383 .
:
AlH + C2H4
AlC2H5,.
Al(C2H4)nC2H5.
AlC2H5 + nC2H4
, -
- -
97
. -, -1 . . 373-393 ,
4,9 , :
0,01:1,0 5% (.). 200 . -1 20%, 90%. -1 .
.
-1
- .
3.1.5.
1825 . . ,
. 1875
. . . 1868 .
.. .
.
4
-

. 4
3-10, 1-2 0,4-5% (.).
4 ( % (.)) :
3-
()
-
-1
--2
--2
0,3
0,5
5,2
1,3
16,0
5,3
6,6
27,4
37,0
0,4
11,0
33,0
12,0
11,0
14,0
18,0
98
5-
()
0,5
0,5
4 65%-
( .. ) .
.
-
(3)2=2 + 2S4
(3)3S3,
.
, , - :
(3)3S3 + 2
(3)3 + 2S4 .
30%- :
(3)3
2S
(3)2=2 + 2.
.
, ,
, 65%- ,
45%. , , , .
" "
4 .
-1, .

. .
- VI .. , .
, .
Cr2O3,
.
99
, 823-893 .
-1
-1 .
- (, ), .
1980- .
-
.
, .
~0,5 % . 573 673 2,0-3,0 .

, , 673-723 .
:
O
2CH3CCH3 OH CH3COCH2 C(OH)CH3
H2O
CH3
O
H
2O
CH3CCH3 + CH3C
CH3COCH=CCH3
CH3
CH2
OH
, ,
3.2.
3.2.1.

100

.. . . 1952 .
, .

-
. , , :
+
H
+
CH CH=CH
CH CHCH
3
+
CH3CH=CH2 + CH3CHCH
3
3,
+
CH3CHCH2CHCH
3
-H+
CH3
CH3CHCH=CHCH3
CH3
..
, -- :
CH3
CH3
CH3CHCH2CH=CH2 CH3CHCH=CHCH3
+
CH3CHCH2CHCH3
+
CH3CHCHCH2CH3
CH3
CH3
+
CH3CHCHCH
2CH3
CH3
+
CH3CCH2CH2CH3
CH3
-H+
CH2=CCH2CH2CH3
CH3
CH2C=CHCH2CH3
CH3
+
CH3CHCHCH2CH3
CH3
-H+
CH3CH=CCH2CH3
CH3
CH2=CHCHCH2CH3
CH3
101
,
2- 3--1
.

, . 4-1:
23=2
2=23
3
4--1 :
2=23
3=3
3=23
3
3
3
4--1 ,
.
, :
+
CH2=CHCH3 Me+ [CH2
CH
CH2]-Me+
-H

. ,
,
, , .
4--1 :
[CH2
CH
CH2] Me + CH2=CHCH3
-
[CH2=CH-CH2-CH-CH2]++
36
CH2=CHCH2CHCH3 + [CH2
CH3
CH
CH3
CH2]- Me+
4--1 4--2 :
CH2=CHCH2CHCH3 + R-Me+
- RH
CH3
CH2
CH
CHCHCH3 Me+
CH3
RH
102
CH3CH=CHCHCH3 + R-Me+
CH3
,
, -1
~70%. -1
3,4--1 5--2.
-1 -1
- :
-C4H8
CH2=CH2 + CH2CH=CH2 - Na+
CH2=CHCHCH2CH2 - Na+
CH3
CH3
CH2=CHCHCH2CH3 + CHCH=CH2 - Na+
CH3
CH3
3--1. - 3-1, - 3,4--1 - 4-1 5--2.

. ,
:
-1 :
-(C3H7)3Al; 473 ; 20
3
2CH2=CHCH3
CH2=CCH2CH2CH3
95%
CH3
Al O ; 523 ; 0,1
CH2=CCH2CH2CH3 2 3
CH3
CH3C=CHCH2CH3 HBr; 948 ; 0,1
- CH4
CH3
CH3C=CHCH2CH3
97-99%
CH3
CH2=CCH=CH2
50%
103

1 "" .
-

.
, "in situ"( ( )) .
, , , , , ,
.

.
, VIII . -1, .

(. 3.7).
3.7
---
n+
Ni2+
Co2+
Fe3+
Co2+
Fe3+
, % (.)
-1
-2
-2

31,8
4,9
12,3
30,4
54,7
2,6
17,7
2,3
26,2
27,3
46,5
2,1
64,2
8,6
12,4
14,8
( :=2:1)
46,4
4,7
20,0
26,5
49,3
4,2
46,7
4,3
6,0
30,8
64,2
-
. : 293 ; 1,0 ; - ; 2 ;
[Al]=1,56 /; []=0,026 /.
(. 3.8)
. -
104
. , , ,
.
, , : Ni> Co > Fe > Mn.
3.8
-
n+
, 4--1
, % (.)
4--2
2--2
2-2,3---1
-1
Ni2+
13,4
0,9
16,3
48,7
8,5
23,0
2,6
Co2+
4,3
0,9
24,4
44,4
6,7
23,6
2+
Ni
Co2+
Fe3+
Mn2+
38,9
11,9
5,5
0,1
( :=2:1)
14,8
46,3
8,3
23,4
0,7
25,1
41,5
8,5
20,5
3,1
46,0
13,8
11,7
24,0
14,8
39,8
12,1
4,1
11,5
7,2
3,7
1,4
17,7

, , . . 3.9
.
3.9

, % (.)
, % - 4-- --1 2--
3-4
-2
-2
(.)
82
0,2
19,1
23,1
53,3
4,3
--
78
4,0
25,4
25,3
42,2
3,1
71
72
3,4
2,6
22,8
47,8
23,7
24,2
47,1
22,5
2,9
2,9
**
**
**
37
63
78
84
81
0,6
2,8
1,2
-
50,7
55,2
13,6
26,9
15,6
33,6
25,8
22,8
24,0
22,4
11,7
13,0
59,2
44,4
56,5
3,4
3,2
4,4
3,5
5,5
105
. : 273-283 ; 0,1-0,5 ; [Al]=2,2 /; [Ni]=0,0147 /

** ; [Al] =1,71 /.
: , , , A1:Ni, .
-
- (-1 -2)
293 .
70% -.
3-, 3,4- -
.
. -
.
-

- .

:
23=2 + 748
612 + 4714.
. 3.10 . .

4--1.
2--1. - 4--2
-2, 2,3-.
.
106
3.10
107

)
(

, - ,
)
- ,
-1
-
, - ,
-
(
)

-;
-

- -

-
(

)

-

, - -1 -2,

,
)
108
3.2.2.
1964 . " "
- ,
:
236 24 + 48 .
. 3.11.
3.11
, %
3H6, %
3H6, -1
3 + O Al2O3
436
3,2
9
43
94
3+2O3 Al2O3
433
0,7
180 ( )
36
97
3 SiO2
811
0,1
4
28
95
()6 Al2O3
344
3,5
1-2
25
97
WO3 SiO2
700
3,2
40
45
99
WO3 Al4
811
0,8
8
34
82
WS2 SiO2
811
0,l
2
18
100
Re2O7 Al2O3
298
0,1
6
30
100
Re2CO10 Al2O3
373
0,1
1600 ( )
20
100

. ,
. , 773-873 .
,
.
, . , 1:1.
- 298 , 3%.
, 700 ~
20%:
,

, %
300
400
500
600
700
800
0,001
0,002
0,004
0,009
0,015
0,022
2,8
7,2
11,7
15,9
19,7
22,6
109
2,3--2:
WO3 SiO2; 673
2CH3C=CH2
CH3C=CCH3 + CH2=CH2
CH3
H3C CH3
2,3--1,3,
. 2,3--1,3 .
(
) .

,
. ,
500 -1 648
32%- , 80% (. 3.12).

, %
,
% (.)
-1
-2
--2
50
4,79
41,1
97,8
14,5
0,8
58,3
0,9
13,6
11,2
0,7
75
3,19
40,2
98,2
13,8
0,8
59,5
0,8
13,4
11,2
0,5
100
2,39
39,8
98,5
13,3
0,8
59,8
0,6
13,8
11,3
0,4
150
1,59
38,0
98,7
13,0
0,8
61,7
0,4
13,0
10,8
0,3
300
0,798
34,2
99,3
11,3
0,7
65,4
0,3
11,5
10,7
0,1
500
0,479
32,3
99,7
11,0
0,7
67,3
0,2
10,8
10,0

, -1
3.12.
,
: 648 , 3,6 ; 4 .
, % (.)
-2 -1.
-2 -1 -
110
. , ,

. - , , .
. , , , ,
- . 0,001 % (.) - ( )
. , .
3.2.3.

,
, , .. ,
.

.

():
3C2H4
CH3CH=CCH2CH3
CH3
CH3CH=CCH2CH3 + C2H4
CH2=CCH2CH3 + C3H6
CH3
CH3
, .
3--2. 3--2 .
: , -2 -2 :
2C2H4
CH3CH=CHCH3
111
CH3CH=CHCH3 H2=CCH3
|
3
CH3CH=CHCH3 + CH2=CCH3 CH3C=CHCH3 + C3H6
CH3
CH3

. -2 .

.
:
2C3H6
CH3CHCH=CHCH3 + C3H6
CH3
CH3CHCH=CHCH3
CH3
CH3CHCH=CH2 + C4H8
CH3
50-60%,
. Ni
343-403 3,2 .
WO3/SiO2
813-853 0,15 . 5 ~ 20%, - 60%.

. 3.4.
112
. 3.4.
1 - ; 2 - ;
3-6 -

" ". :
-
WO3 SiO2; 673
2C3H6
C2H4 + C4H8,
-
2C4H8
NiCl2.P(C6H5)3 + C2H5AlCl2; 293
C8H16,
-
C8H16 + C2H4 WO3/ SiO2; 723
2C5H10.
.
,

3--1 .
4--2,
4--2 3--1 :
2C3H6
CH3CHCH=CHCH3
CH3
CH3CHCH=CHCH3 + C2H4
CH3CHCH=CH2 + C3H6.
CH3
CH3
3-1 . -
113
, -
.
3.2.4. -
- -1, -1, -1 -
.
- . 553-573 2,0-3,0
( + 2) 95 %. -
.
3.2.5.
n2n-2. , , , , , .

. ,
, -
:
n
[-CH2CH2CH=CHCH2-]n

200000, , ([2,2,1]-2).
( ) -. . ~ 153
, 40-50 .
-1,5- , . , . ,
.
114
. - 80
90% . . 208 198 .
, , . .
, .

.
, , , . , (~493 )
: , . .

.
,
.
-,
. .
: 223
.
, , ,
.
: 0,01% 24 296 . : 353-413 .
, , (, , ), .

(-). , , .

, , , .
115

,
. ,
. - .
, , , .
5 10 35% .
, , . ( 5,0 ) 323-343 9099% 93-99%.

, : , 20
1 .
() (. 3.5).
(), ,
.
. 3.5.

1 - ; 2 - ; 3 - ;
4 - ; 5, 6
- ; 7 - . .
316,8 ; 8 - .
116
: I- ; II- ; III ; IV ; V 2; VI -
:
-
(0,01%);
- ;
- ;
-
, .
5
353-383 3-4 ,
.
473-673 .

353-383
CH2
473-673
2;

- :
CH2=CHCH=CH2 + CH2=CH2
CH3
:
CH2=CHCH=CH2 + CH3CH=CH2

, (308 ):
Cl2
-HCl
Cl
-HCl
117

[2,2,1]-2 . . 317319 , . . 369 , .
( ) :
+ CH2=CH2
493-503 , 0,5-2,0 .
118
4

- , - .
100 . . ,
.
, , , , .
:
. . 4.1.
4.1.

1,4-
[-CH2C=CHCH2-]n
CH3
, ,
,
yc ;
, ,
,
,
, ,
.
, ,

1,4-
[-CH2CH=CHCH2-]n
, , ,
yc
, .
,
, ,
.
1,2
-2-=2
. ,
ac6

119

p
,
,
[- 2=2-]n-[-2--]m
65
, ,
, ,
,
,
ccop
. 4.1.
3
4
()
[-CH2C=CH-CH2-]n
Cl
[-2-C(3)2-]n

0,6-3,0% .
[-(3)2-2-]n-[-2-=-CH2-]m
3

( )
()
()
[-2CH2-]n-[-CH2CH-]m
CH3
-,
-, -,
,
,
, -, ,
, -
,

,
-, -,
-, -,
,
,
-,
-, ,
,
, ,
,

, . , ,
, , ,
, .
,

. , ,
,
.
,
,
,
, ,

120

[-CH2CH=CHCH2-]n-[-CH2CH-]m
CN
-,
-,
,

,
, -

.
. 4.1.
1
2
[-2222SS-]n
3
-,
,
, ,
, , -
4
,
R R
[-SiOSiO-]n
R R
-,
,
, -, -,
-, ,
,
,
,
,
-, -,
,
, , ,
,

()

Na
[-F2F-]n-[-F22-]m
F3
.
, ,
(2,
. NO3
.), , ,
,
,
- ,
. ,
[-2--]n-[-2--]m
-, -
121

C(O)OR
CN
, 2, 3, , ..
, ,
,
., ,
, ,
, , ,
.
. 4.1.
1
,

2
'
[-NR R-]n
O
O
3
, , ,

,
, ,
4
( . .
), , ,
,
,
~{[-(2)3l(2)2-]12-2CH-}17~
SO2Cl
, , ,
,
. ,
,
,
-,
,
, , ,

,
, ,

.

, ,
. ,
,
-, - ,

,
, , .,
[-2(3)--]n
-{-2-O-]m
2-8% (.)
H2C2=2
122

- -
-
[-2-(21)--]n
-[-H22-]m
-,
-, -,
- , ,

, (),
, -
, , , , ,
, ,
, ,
- , ,
.. 1,4-- 1,4--, 60%.
, , , .
4.1. -1,3
-1,3 () 2==2 - . . 268,59 .
-
, ,
, - , - , , .
, .

: 1,4,--, -,
-, - -, - .
,
, ( ) .
.. (). .
( ) . () (
123
, ). 4
, 4 .
4.1.1. ..
,
30- , ..
.
. :
225
46 + 22 + 2
, ,
.
. ,
:

32
3 + 2

23
3() 2
3= + 2
,
,
3= + 25
3=2 + 3
,

3=2
2==2 + 2
633-653 . : , , , .
58,7%, ,
,
.
. -
. .
124
4.1.2. ..
,
.. 1915 .,
. ..
.
:
25
3 + 2

3:1 ( ):
3 + 25
2 ==2 + 2 2
63,9% .
523-573 . , .
5 % 2% ( ).
30-40% ~ 92%. , .

, , 603-623 . :
2CH3CHO
CH3CH=CHCHO + H2O
CH3CH=CHCHO + CH3CH2OH
CH2=CHCH=CH2 + CH3CHO + H2O
~ 60% , .
1952 . , ,
- .
4.1.3.
, . :
- -
".. ";
- , , . .
( )
125
:
, ,
, .
,
, - .
( ).
:
+ H2O
3
= 142 /
.
, .
, ,
, . ~373
0,25 . 90-97% .
348-368 10-20% (.) 0,5-1,0% (.) (
Hg).
. .
, ( + d):25, 2,8. 623 .
.
673-703 .
8-12% :
23
32
= 72,2 /
~ 50% 84-88% .

32 + 2
322
328-343 30,0 . : , Ni,
Cu .

322
2==2 + 22 = -118 /
126
543-553 - . ,
. ~ 47%
97% .

.
2--1,4 ; .
- 2--1,4 ( ) 373 0,5 .
+ 22
2--2 = 231 /
, . 8%- .
80% 90%.
.
, :
-2,
+ 2
2--2.
-2 + 2
:
2222 + 252 .
2--2 + 22
423-473 30
(9% , 90% , 1% , - ).
98%.

:
CH2CH2
CH2OHCH2CH2CH2OH
CH2 CH2+ H2O.
O
( ) ~533-548 7,0 .

:
CH2CH2
CH2 CH2
CH2=CHCH=CH2 + H2O .
O
127
543-553 0,1 Na24, .
.

:
2
2=HC,
2==2.
2=HC + 2
, , - , .

.. 1916 .
, , ,
. , ,
5% (.) , 4 20 60% (.).
4.1.4.
-1
4 (- -) .

4. : , ;
.

.
, ,
. .
773-823 -
128
, . 923-973 , ..
, .
, . , , , .

.
, , .
, , ,
.
, , .

. . 4.1
.
. 4.1. - -

: .
, .
- : - - 1920- -
129
. .. , .. , .. , .. .
4-5
" " 838-853 .

(). 853-893 . - 60% (.) .
.
- 60:40 873 ~1,225 . 7-10 .
. - , .
14% (.) 54% (.) .
- (~ 30% ) 773 ,
903 30%, .
, 823 10,1 ,
1:10.
, -
.
, .
1-5%.
, Pr6O11 Nd2O3. , -123 -r23,
, r3
.

, .
130
753 .
: , ( ); .
.
-:
-C4H10 + 2I2
C4H6 + 4HI .
( ) , .
I
:
2HI + MO
2HI + M(OH)2
MI2 + H2O,
MI2 + 2H2O.
.
:
MI2 + 0,5O2
MO + I2,
MI2 + 0,5O2 + H2O
M(OH)2 +I2.

.
, . , 823
~30,3 ( 410:I2=1:2) :
, % (.)
, % (.)
-410
-48
46
28
9,5
64
63
8
27,5
, , .. HI,
,
. I2:410 :
1 4 823 13 77%.
:

.
131
- , .
.
. , :
C4H8 + 0,5O2
C4H6 + H2O.
()
2 2. , : , , , , , , , . 723-773 .
, , , , .

:
C4H10
C4H6 + 2H2

- . . 4.2
.
. 4.2.
- 0,1 ,
- 0,01 .
1 ; 2 ; 3
132
,
. ,
. , 1830% .
"" () ( ).
, . .
,
(0,015-0,020 ) ,
. 4.3.
. 4.3.
1 - ; 2 - ; 3 - ; 4 - ; 5 - ; 6 - ; 7 - ;
8 - ; 9 - ; 10 - ; 11, 12 - ;
13 - .
: I - ; II - - ;
III - ; IV - ; V - ; VI - ; VII - ; VIII - 3
; IX - 4-12; X -
- - -
1 313 2. 240 -1 4, 863-898 11,3-22,7 .
6
12 . 21 . 30 ., -
133
- 8 . 15 ., , - 2 . 35 .
6, 328 , .
~20%,
50-55% . 37-39%
, 23-25% , 12-13% .
4-5 :
,
, -1
:
,
,
, %
, %
, %
, %
873-923
130-180
1:20
873-923
0,05-0,09
40
85
33
873-923
150-220
1:20
873-923
0,04-0,09
40-43
76
32-33
59
24
45
25

, . , ,
. , .
99% (.) (% .):
0,005
..0,01-0,03
..0,001
.0,01
0,001-0,002
( )
. 4.2
, 4 .
134
4.2. ,
4 ( % (.))
- -
1033 1123
-
- - -

1-3
-1
-2
9,48
22,45
50,60
1,90
10,40
23,30
1,50
0,31
4,75
2,05
47,35
5,5
9,90
15,75
14,00
0,63
-1
0,002
0,005
0,003
0,04
0,005
0,005
0,003
0,025
0,02
9,20
2,45
0,10
0,40
14,50
7,30
1,50
8,55
2,90
18,30
7,80
29,32
63,10
32,95
0,70
0,50

0,20
0,013
0,07
0,040
0,04
0,015
0,09
0,09
0,2
0,1
0,05
0,25
8,50
4,80
16,80
68,80
0,74
1,1
2,5
9,3
29,0
14,0
10,0
32,7
0,5
0,31
23,98
6,27
7,75
50,08
0,6
0,003
0,008
0,03
0,24
0,11
0,17
0,04
0,03
0,86
-
6,68

: .
N-, .
( ) . . :
(CH3COO)2Cu2(NH3)4 + C4H6
C4H6(NH3)3Cu2(CH3COO)2 + NH3.
.

:
135
- , ;
- , ;
- ,
.
,
.

.
4.2.
130 , , 1940- .
. . . (, ,
.) -1,4-,
. 1,3 / .
:
- ;
- ;
- ;
- ;
- ;
- .
.
, , .
-
5 , 15-20% . , 15-20% . , .
136
, , , (
).
.
4.2.1.

. 1917 . . -1,3.
1932 .
. 1946 . .. ..
.
. 1964 .

.
, ,
4,4--1,3:
CH3
CH3
CH3C=CH2 + 2CH2O
CH3CCH2CH2
OCH2O
4,4--1,3
4,4--1,3
, :
CH3
CH3
CH3CCH2CH2
CH2=CCH=CH2 + CH2O + H2O.
OCH2O
. , , , , .
, , , , ( ) .
, 4, . - , :
137
CH3CH2CH=CH2 + 2CH2O
-
C2H5CHCH2CH2
O CH2 O
4--1,3
CH3CH=CHCH=CH2 + CH2O + H2O.
CH3CH=CHCH2 + 2CH2O
-
CH3
CH3CHCH2CH2
O CH2 O
4,4--1,3
CH3
CH2=CCH=CH2 + CH2O + H2O
O
C2H5CHC
+ CH2O
CH3
H

CH2=CHCH=CH2 + 2CH2O
CH2=CHCHCH2CH2
O CH2 O
4--1,3
CH
CH
CH
CH
+ CH2O + H2O.
CH 2
- () 3--1,3
CH3
CH3CCH2CH2OH
OH
, 1,3- -1,3 :
H2O
-C4H8 + CH2O
CH2O
CH3
CH3CCH2CH2OH
OH
CH3
CH3CCH2CH2
OCH2O
,
, .

138

. . :
+ O,
CH
2
1
- , 105 /, 2S4 1-10%
(.) 70-1000.
,
:
+
+
CH2O + H2C=C(CH3)2
HOCH2CH2C(CH3)2 .
+
CH2O + H
2

1,
. ,
. ,
.
2 .
:
d ( C 4 H 8 )
K CH 2 O C 4 H 8
d
k - .
,
, 1. 80-85 /.
, ,
, - , (2)3, -
2()2 (2)n.
. .
.
.
139
, - - . :
.

:
> -2, > -1
.

, , ,
.
,
. , 4- , . -1,3,
, 4,5--1,3,
,
, . - , , ,
.
-1,3

:
CH3
CH3
H+
CH3CCH2CH2
CH3CCH2CH2OH + CH2O
OCH2O
, ,
, -1,3, .

:
OH
CH2=CCH2CH2OH
CH3C=CHCH2OH CH3CCH=CH2
CH3
CH3
CH3
3--3--1
()
3--2--1
()
3--1--3
()
140
.
,
(), :
CH3
HOCH2CH2CCH3
OH
CH2=CCH2CH2OH
CH3
H2=CCH=CH2
CH3
CH3C=CHCH2OH
CH3
OH
CH3CCH=CH2
CH3
,
55-66%.
. . , . , .
- - . - (). , ,
.
4,4--1,3
- -
- 973 .
-
141
, .

,
. :
Ca3(PO4)2 + H3PO4
3CaHPO4
, 2-3 , , 773 .
. 4.4.
. 4.4.
()
1 ; 2 ; 3 - ;
4 ; 5, 10 ; 6 ; 7 ; 8, 9 -;
11
; 12 ; 13 ; 14
; 15 ; 16 .
: I ; II ; III ; IV ; V ; VI ; VII ; VIII ; IX ; X

2, 1
, 973 . 3, . ,
- - 4.
5, . 6, , ,
142
. 6 7, , . 7
- - ( 8, 9)
,
, 10.
11 12,
, ( ).
-
.
,
. , .
. ,
, - -, ().
- ,
- - .

. - (
% (.)).

..

..
0,006
0,002
0,015
0,10
0,18

99,69
.
0,0002
..0,00015
0,0001
.. 0,00033
-
, 0,5 / .
, 1 .
2% .
143
, . , ,
(453-527 ) .
, ,
. . ..
- (.
) ( .. , .., ..), .
4.2.2.
3--1,3
,
3--1,3.
CH3
CH3
CH3C=CH2 + CH2O + H2O
CH3CCH2CH2OH
OH
CH3
CH3
H2C=CCH=CH2 + H2O.
CH3CCH2CH2OH
OH
.
368 , 1,6-2,0 3-1,3 57% .
, , , .
, 2022% (.),
:
CH3
CH3
H2O
CH3CCH2CH2OH + CH2O
CH3CCH2CH2
OCH2O
OH
3--1,3. :
144
CH3
CH3
CH2O + CH3COH
CH3CCH2CH2OH
CH3
OH
3--1,3 . 4-5% (.) 373-383 .
82% . 3--1,3
473-523 , 80-90% .
:
2:2 ..................
2, % (.) ........................
2SO4 , % (.) .......................
, ..............................
48, ...............................
-48:2........
20
5-7
3-4
368
1,6-2,0
2
62-64%
96,4-96,8 %.
.
, .
. 4.3 , ,
, " ".
4.3. ,

"
( ()
"
)
()
99,0
99,0
99,0
, %
,%
1,0
1,0

0,4
0,02
0,01
0,0005
0,0001
0,0001
0,0004
0,0003
0,0010
-
0,0009
0,0003
0,0010
0,0005
0,0003

,0005
0,0003

145
4.2.3.
. , , . 2- . , ,
, , :
R
RNCH2NR, RNCH2OR, ROCH2OR, R = CH3, C2H5.
R
R
, , , :
CH3
H3
CH3
CH3
CH3
546
CH3C=CH2 +
N-2-N
CH3C=CHCH2N +
.
CH3
CH3
CH3
CH3
CH3
+ (CH3)2NH,
+ CH3CCH2CH2N
N
CH3
CH3 CH3
CH3
CH3
CH3C=CHCH2N
CH3
CH3
393
CH3
CH2=CCH=CH2 + 2(CH3)2NH.
CH3
.
CH3CCH2CH2N
N
CH3
CH3 CH3
:
CH3
CH3
H2C=CCH=CH2 + 2(CH3)2NH
CH3C=CH2 + (CH3)2NCH2N(CH3)2
, , :
146
CH3
CH3
CH3C=CH2 + CH3OCH2OCH3
H2C=CCH=CH2 + 2CH3OH.

:
2CH3OH + CH2O
CH3OCH2OCH3 + H2O.
.
4.2.4. 5
,
, .
: . ,
- . :
-C5H12
-C5H10 + H2 ,
-C5H8 + H2
-C5H10
, - .

.

.

,
, ,
.

, ,
:
CnH2n+2
CnH2n
CnH2n-2
:
H3CCH2CHCH3
CH2=CCH2CH3 + H2
CH3
CH3
2--1
147
H3CCH2CHCH3
CH3
CH2=CHCHCH2 + H2
CH3
H3CCH2CHCH3
CH3
CH3C=CHCH3 + H2
CH3
3--1
2--2
: 2--1, 3-1 2--2. () 65%.

,

. :
-
-C5H12
-C5H12;
-
2--1
3--1
2--2;
- -
H3CCH2CH2C=CH2
CH=CH
CH3CH2 CH3
--2
CH=CHCH3
CH3CH2
--2
- , ;
- , , ;
-
;
- .

1-4, 6 , , 2, .
,
,
-.
148
.
:
, " "
.

, 2. , , , . (. 4.5) " "
- (. , ).
.
4.5.
"
"
1 ;
2
; 3 ; 4
-;
5 ; 6 .
: I ; II
; III ; IV
; V
; VI
; VII ; VIII

" ":
" ", . 813- 863
" ", ...0,13-0,15
, 3/3. 100-180
, /3 .. 750

-5, % (.)28-32

-5, % (.) 68-71
149
.

-C5H10
-C5H8 + H2 +
.
: 2--2 137,830 /, 3--1 123,513 /, 2--1 131,248 /.
. 4.4
.
4.4.
,
, % (.)
-510
-58
94,2
79,6
53,2
25,2
2,9
10,2
23,4
37,4
2,9
10,2
23,4
37,4
700
800
900
1000

:
-510:,
:. 1:0

, %..
1:1
1:3
1:5
11,4 15,4 20,9
1:7
1:10
24,8 27,9
31,8
- .

, , ,
. , ( % (.)).
CrO3 - 0,5; Cr2O3 - 5-6; ZnO - 2-4; Fe2O3 - 15-17; ZnCr2O4 - 45-50; FeCr2O4 - 20-25.

, .
, - ,
150
.
.

-C5H12
C5H8 + 2H2
. : . . 773
--
1%, 873 10%.
. , 800 0,02 10% ,
873 33%.

, , . , ( 900 ) .
,
5, .
-
, .
- ; ,
5 .
""
(.).

. :
-
CnH2n+2 +X2
CnH2n-2 + 2HX, X = , I, Cl, Br
-C5H12 + I2
CH3CHCH=CH2 + 2HI,
CH3
151
-C5H12 + I2
CH3C=CHCH3+ 2HI,
3
--
=,
-C5H12 + 2
CH3CH2C=CH2 + 2H2,
CH3
-
CH3CHCH=CH2
CH3
CH3CHCH=CH2
CH3
CH3C=CHCH3,
CH3
--
CH3CH2C=CH2,
CH3
CH3C=CHCH3
CH3CH2C=CH2,
CH3
CH3
-
CH3CHCH=CH2 +2
-C5H8 + 2H,
CH3
CH3C=CHCH3 + 2
-C5H8 + 2H,
CH3
CH3CH2C=CH2 +2
-C5H8 + 2H,
CH3
, , .
4 5 .

.

1934-1935 . 60- .
: , , , . -
- 1959., 1960 .
- ( -
152
), .
, , , , , , , , , , ,
, , . 1964
. ,
, , , , , , , ,
. 65-70 % ~ 90%.
. .
, .
.
,
. :
2HI + 0,5O2
I2 + H2O.
, .
,
.
.
:
MO + 2HI
MI2 + H2O
MI2 + 2H2O
M(OH)2 + 2HI

,
- , . :
2MI2 + O2
2MO + 2I2
2MI2 + O2 + 2H2O
2M(OH)2 + 2I2
.
, .
.
.
. -
153
, , , . , - ,

. .
70-80% 80-90% ( 20-30
/ ). , , , , .
4.2.5.
1946 . . . 1960- .

.
.

. , 2--2
.
:
- 2--1
2CH3CH=CH2
CH2=CCH2CH2CH3
CH3
- 2--1 2--2
CH2=CCH2CH2CH3
CH3C=CHCH2CH3
CH3
CH3
- () 2--2
CH3C=CHCH2CH3
CH2=CCH=CH2 + CH4.
CH3
CH3

, . -
154
, 45% (.) 423-473
20,0 .
- :
+
+ AlCH2CH2CH3 + CH2=CHCH3
AlCH2CHCH2CH2CH3
CH3

2--1:
AlCH2CHCH2CH2CH3 + CH2=CHCH3
CH3
CH2=CCH2CH2CH3 + AlCH2CH2CH3.
CH3
2--1
:
AlCH2CHCH2CH2CH3
AlH + CH2=CCH2CH2CH3
CH3
CH3
AlH + CH2=CHCH3
AlCH2CH2CH3 ..
. "" :
AlCH2CH2CH3 + CH2=CHCH3
CH3CCH2CH2CH2CH3
Al
CH3CHCH2CH2CH2CH3 + CH2=CHCH3
Al
CH2=CHCH2CH2CH2CH3
AlCH2CH2CH3 +
CH3CH=CHCH2CH2CH3
2--1 :
Al
AlH + H2C=CCH2CH2CH3
H3CCCH2CH2CH3
CH3
CH3
155
H3CC=CHCH2CH3 + AlH .
CH3
2--1 2--2
2--1 . 423-473 , 0,15-0,5
/(.). 2--2 99% (.)
.
2--1
2--2
,
323-473
. . 4.6
612 .
. 4.6.
612
1 - 3,3--1, 2 4--; 3 -1; 4 - 2,3---2; 5 - 2-1; 6 -3; 7 - 2,3-1; 8 - 4- -2 (- -);
9 - 3--1; 10 -2 (-
-); 11 - 2--2;
12 - 2--1; 13 - 3--2
(- -)

:
CH3
CH3
CH2=CCH2CH2CH3 + H+
H2C=CCH2CH2CH3
CH3
CH3CCH2CH2CH3
+
H+
CH3
CH3C=CHCH2CH3 +H+

/ : , , , .
156
2--2
2--2
. 2--2 .
2--2
- . , , (, .), (), . , , , -
.
2--2, , . , , .
- :
-C6H12
CH3 + (CH3)2C=CHCH2.
,
6 11
:
CH3
CH2C=CHCH2CH3 + CH4
1
CH3
CH3
CH3-C=CH-CHCH3 + CH4
CH3 + CH3C=CH-CH2CH3
2
CH3
CH3-C=CH-CH2CH2 + CH4
3

. , 3 , -1,3:
CH3
CH3C=CHCH2CH2
CH3
CH3C
CH2CH=CH2
CH3CH=CHCH=CH2 + CH3 .
157
..
1 2:
CH3
CH2C=CHCH2CH3 + HBr
1
Br +(CH3)2C=CHCH2CH3
(CH3)2C=CHCHCH3 + HBr
2
.
2--2. :
dx
9,7 10 9 e
dV
47000
RT
P 6 12 ( 1)
6,2 10 9 e
42000
RT
P 6 12 PHBr2
(/), 2-2, V (), (), .

. 4.7 2-2.
. 4.7. 2---2 348
- ,
.
1 - ; 2-5 -
HBr : 612 , : 2 - 0,01; 3 - 0,02; 4 - 0,04; 5 - 0,05;
-
, ,
, V/ ,
, :2--2: .
158
, , . ,
,
. , 2--2
: 2-5, , , .
. 4.8
, "
" ().
. 4.8.
, " "
1 - ; 2 - ; 3 -
; 4 - ; 5 - 2--1
2--2; 6 - .
: I - ; II - ; III - ; IV - 2-1; V - 2--2; VI -
- ,
.
. 1 ,
, .
70-85% ~ 97%.
2 ,
, . () .
159
2--1
2 3 ,
. 2--1
- 4.
2--1 2--2 423-573 , 0,15-0,5
/ (.)
. 5. 2--2 , . 6 , .
, .
.
, .

: 50-60%,
45-50%.
.

,
. .
.
~473
2,0 . .
,
80-85% 2--1, .
,
.
4.2.6.

1914 .
160
. -
.
1930- , .. .
.
, .. , ,
, , , - .
.
.. .
() .
,
:
HCCH + KOH
HCCK + H2O ,
KOH + H2O
KOH H2O.
:
CH3
CH3
CH3C CCH ..
CH3C=O + HCCK
OK

.

. ,
:
2Na + 2NH3
2 NaNH2 + H2.
- :
NaNH2 + HCCH
HCCNa + NH3,
2NaNH2 + HCCH
NaCCNa + 2NH3.
:
CH3
CH3
CH3CCCH
CH3C=O + HCCNa
ONa
:
161
CH3
CH3
CH3CCCH + HCCNa.
CH3CCCH + HCCH
ONa
OH
() ():
CH3
CH3
CH3CCH=CH2
CH3CCCH + H2
OH
OH
.
0,5-1,0
303-353 . ,
, 99,099,5%.
:
CH3
CH3
CH3CCH=CH2
CH2=CCH=CH2
-
2
OH
(~ 97%) :
~ 99,8%. 98,5%-
, ,
.

. 553 :
CH3
CH3
CH2=CCCH
CH3CCCH
OH
-2
:
CH3
CH3
H2, F
CH2=CCH=CH2
CH2=CCCH
,
- , . .
162
4.2.7.

. 1960- "".
:
1.
:
CH3
CH3CHCH2CH3 + O2
CH3
CH3CCH2CH3
OOH
2. 2--2,
, 2--2:
CH3
CH3
CH3CCH2CH3 + CH3C=CHCH3
OOH
CH3
CH3
CH3CCHCH3 + CH3CCH2CH3
O
OH
-
2--2
3. 2--2 2-1--3:
CH3
CH3CCHCH3
O
CH3 OH
CH2=CCHCH3
4. :
CH3 OH
CH2=C CHCH3
-H2O
CH3
CH2=CCH=CH2
163
- ( 4.1).
4.1
2--2
--
2--2
4.2.8. -2 -

-2 - 2-. -2 - 4
, ,
. , ,
.
: () -2 2- .
1938
.( )
. , , - ,
-2 - .
-2
164
O
CH3HC=CHCH3 + CO + H2
CH3CH2CC
CH3
H
, ,
373-393 3,0-6,0 , - .
-2
- :
H2
RCHO
H2
RCORh(CO) 3
HR(CO) 3
ol
CO
RRh(CO) 3
Rh4(CO)12
ol
,
CO
H2 ,
CO
HRh(CO) 3
Rh6(CO)16
ol, CO, H 2
l .
2- (2-) 623-673 85-90%
90%:
CH3
O
CH3
CH2=CCH=CH2
CH3CH2CHC
H -2
C5H10O ,
(. 4.5).
4.5.
C5H10O

, % (.)
,
, - - H ** H O - H
1 5
5 8
2
5 8
, ,
%
-1
673
2,0
25-30 23-28
2-5
1-5
8-15
60-85
2,2-*
673
3,0
100
2-4
30-35
40-45
8-9
13-17
165
3-
783
3,0
35-40
40-45
20-25
5-8
20-25
2- 623
3,0
93,2
6,98
*
2,2- 2,2-;
**
;
3- 3-;
2- 2 .
57,6
16,1
15,4
3,96
, 2- . 3- -
, , 2-3 ,
2-. 5-
, ( ).
4.3.
--
-- . ,
,
1963 . 10
. , , , ,
-- () , . 1-10%

-
- . , .
, , :
-
;
-
, , ,
;
- , ,
;
- .
166
--
:
- - -1,4; -1,4 -1,5;
2--1,4; 2--1,5; -1,4, -1,5 1,6; 6--1,5; -1,5; 2--1,7; 3,7-1,6; 11---1,11;
- - -1,4,9; 2,6-1,5,7; -1,3,5; 3--1,4,6;
-
1,4-,
,-1,5; -, --1,5;
- - (3,2,0)-2,6; ; ;
- - 1,2-, 1,2-; 1,2,4-;
- - 4-;
- - , , 5--2,5-(-2--4)--2,
5--2,
5-2.
: , -1,4, -1,5, - .
4.3.1.

, , . , 1,5--.
- . -
:
+
, , , .
5- ~4% (.), ~ 8% (.) .
167
~2% (
1 ). .
5 . .
-1,4
. .
-1,4 -1,3 , :
CH2=CHCH=CH2 + CH2=CH2
CH2=CHCH2CH=CHCH3.
95%. " ".

-1,5
-1,5 -1,3 :
2CH2=CH-CH=CH2
-1,5,9:
3C4H6
4--1:
2C4H6
CH=CH2
, ,
--, -1,5 95%.
168
4.3.2.

. :
-1,3
:
+ CH2=CHCH=CH2
CH=CH2
,
:
CH=CH2
CH-CH3
-1,3 .. .. ( . .. ).
4 ,
.
, , ,
, , .
. 4.9.
1,
453-673 0,4-0,45 .
2, -1,3, . 3-5 . 6
7.
169
. 4.9.
1 - ; 2 - ;
3, 4, 5, 7 - ; 6 - .
: I - ; II - ; III - ; IV - ; V - ;
VI -; VII -

" " 1967 .

, ,
-, - .
"" () -:
CH2
+ CH2=C=CH2
448-498 ().
.
-
. :
+ CH2=CHCHO
CHO
H2
CH2OH
CH2
-H2O

-1,3 ,
:
+ CH2=CHCH=CH-CH3
CH=CH-H3
170
.
5'-(-2--4)--2'
5'-(-2--4)--2' -1,4:
5' 4
CH2-CH=CH-CH3
CH2=CH-CH2-CH=CH-CH3
2'
'
1'
-5---2'--5'-
,
, .
, -5--2'--5'-:
4
CH2 5
R`
CH2X
5'
R`
-MX
2'
1'
3
2
Me
- Hal, - , R = R` = 3.
-5---2'--5'- 5--2 .

, .. -5--2'--5'- .
171
5

, , - , .
. (
, .)
,
, .
.
, .
,
, .
5.1.

, .
, .. , , .
5.1.1.

-, -, -
. 1834 .:
CnH2n+2
Cl2
CnH2n+1Cl
Cl2
CnH2nCl2
Cl2
CnCl2n+2
.. .
.. , -
:
-
: > > ;
172
-

;
- , ,
;
- ,
, .
CH CCl ( /)
( = H, Cl):
A
-Cl
-H
CH3
352
436
RCH2
339
411
R2CH
339
398
R3C
331
385
CH2=CHCH2
287
369
CCl3
306
402
CH2=CH
486
, , , - .

, .
ll 500-800 :
h
l + l
l2
:
l22 + l
2 =2 + l2

:
l + RH R + l ,
R + Cl2 RCl +Cl ,
Cl + RH R + HCl ..
173

.
, :
, , , ..
:
l2,
2l
RCl.
R + l

. ,
, .
5.1.2.

, .
l .
:
4 + 4l2
l4 + 4l
23l + l
24l2

l:
- ;
- l ;
- l .
l
(, ,
) 670-770 :
2l2 + 220 +
4 l + 2
l : , 823 58%, 573 - 85%.
. - . CuCl2 KCl
174
. - .
,
. HCl
. ,
HCl - , .
: () , () -
. -
:
2=2 + l2
24l2
(CH2ClCH2Cl)
24l2
2=l + l
+ l
2=l
22=l
2=2 + + 12
:
- l
4l + 2
2l2 + 22
HR RCl + HCl
R RH + Cl2
ClR RCl + HCl
HR RCl + Cl2
-
ClR RCl + H2O
R=R + 2HCl + 0,5O2
-
R RCl + H2O
R=R + HCl + 0,5O2
- . ,
.

, . , , :
25l + l2
24l2 + l
175
24l2
2=l + l
2l + 0,52
2 + l2
25l + 0,52
2=l + 2

:
4 + l + 0,52
3l + l + 0,52
2l2 + l + 0,52
l3 + l + 0,52
3l + 2
2l2 + 2
l3 + 2
l4 + 2

4 + nHCl + 0,5nO2
CH4-nCln + nH2O
, ()
():
4HCl + O2
CH4 + nCl2
2Cl2 + 2H2O
CH4-n + nHCl
()
()
.
,
, . , .
( ), ( ):
2HCl + 0,5O2
Cl2 + H2O,
RH + Cl2
RCl + HCl,
H
H
H
H
CC + 2HCl + O2
C=C
+ 2H2O.
H
H
Cl
Cl
.
, .
176
5.1.3.
() ():
()
RCH=CH2 + HCl
RCHC1CH3
()
RCH2CH2C1
50- . .
.
393-493 . , .
99%- 98-99%.

. ,
() . ,
, . . ,
. ,
, ~40% .
5.1.4.
, , , .
100
, .
, -
177
, ,
l .
,
, , . .
ll- 84 /
l- , .
,

In
R + Cl
:
r
k k 1k 2
RCl0,5 I n 0,5 ,
k
r ; k, k1, k2, k - , , .

.

, :
r = k.[RCl]0,5[RCl]0,5 = k.[RCl]
.
50
, 113 .
5.1.5.
, .

.
:
k0
0,5Cl2 + M
Cl + M
1) 0,5Cl2 + S k0 Cl + S,
178
k1
2) Cl + RH
HCl + R,
k2 RCl + Cl ,
3) R + Cl2
, S - .
:
k4
Cl2,
Cl + Cl
k5
R +R
RR,
k6
RCl.
R + Cl
. ,
, :
Cl + Cl +
Cl2 + .

.
. 5.1.
5.1

C2H6 + Cl2 C2H5Cl + HCl

C2H5Cl + Cl2
C2H4Cl2 + HCl
CH3CHCl2 + Cl2
C2H3Cl3 + HCl
r k . PCl2
3
2
2C2H5
C2H4 + C2H6
r k . PCl 2 P 2 C2H4Cl + l C2H4Cl2
r k . PCl2
1
2
C2H3Cl2 + S
C2H3Cl3
C2H3Cl2 + l
. , .
______________________________________________________________

, Cl + S
.

: , . .
:
179
C=C + Cl2
Cl
CC
Cl

.
,
, ,
.
- .
: , . .

, :
.
:
-
32l
2=2 + l,
-
l3l3
l2=l2 + l2,
-
l3(l2)l3
l2=l2 + l4,
-
23l
2=2 + 2l
- :
l3l3 + l2
2l4
. ,
,
.
.
180
5.1.6.
( , , ) CH2=CH-Cl ; . . 114.6 , . . 259,2 , .
,
20-35% .
, . 1990- 5%. 2000 . 25
.
, , , , ,
, , . - , 20-55% . .
~ 550 . /, ~2%
.
, .
:
1. ,

CH2=CH2 + Cl2
CH2ClCH2Cl

CH2=CH2 + 2HCl + 0,5O2
CH2ClCH2Cl + H2O
1,2-
ClCH2CH2Cl
CH2=CHCl + HCl
.
2. ,

:
CH2=CH2 + Cl2
C2H4Cl2,
C2H4Cl2
CH2=CHCl + HCl.

CHCH + HCl
CH2=CHCl

181
CH2=CH2 + CHCH + Cl2
2CH2=CHCl
3. ,
.
.
4. :
CHCH + HCl
CH2=CHCl

. , 1989 . .

:
- ;
- ;
- .
.
. ,
. 1:1.
,
,
:
24 + 12
2412
= 188 /.
363-383 .
- 323343 . (, ) 313-333 100%- .

. 5.1.
182
. 5.1.
1, 3, 4 ; 2 - ; 5 .
: I ; II ; III ; IV ; V ; VI ; VII ; VIII

. . : " "
.
" ".
600-615 150 " " .
, ,
, (II), . 4-6% (.).
.
. ,
. ,
.
183

. 5.2.
. 5.2. 1,2 ()
1 - ; 2 - ; 3 - ; 4 ; 5, 6
; 7 ; 8 ; 9 - .
: I ; II ; III ; IV ; V ; VI ; VII NaOH; VIII ;
IX 1,2-; X
1 , ;
483-533 , . . 2 HCl, . 8, 2; 4, 5 6.
. 5 .
.
- () .
723-793 2 :
lCH2CH2Cl
CH2=CHCl + HCl
50-60% 96-99%.
. l
,
l 1,2-
184
. :
CH2ClCH2Cl
1 + CH2ClCH2Cl
CH2ClCHCl
CH2ClCH2 + l
CH2ClCHCl + HCl
CH2=CHCl + l
CH2ClCHCl2
1 + CH2ClCHCl
. . 5.3 .
. 5.3. .

. , 99,2% . , , ,
. . 5.2. 5.3 .
5.2

648
(
)

, % (.)
0

, %
0,8
1,0
1,0
0,1
0,1+0,1
1,0
0,5 + 0.5
2,5
2,5 + 0,1
1,8
3,6
8,4
8,5
12,4
20,5
25,0
32,0
185
+
0,5 + 0,5
0,5
1,0
1,0
1,0
1,5
55,9
56,1
63,7
66,3
67,9
71,0
5.3

773
(
)
1,1 -
1,2-
1,2,3-
, % (.)
0,0
, %
41,2
0,1
0,1
0,3
0,1
0,1
0,1
0,5
21,2
24,2
27,5
28,0
29,0
31,0
32,5

.. ( , ).
.

( "")
""
625-775 0,35-1,4 .
,
, , .
() ,
. , , ,
- , - , .
186

.
: , , , - .
, , . , (238,8 /) (71,2
/). , .
. 5.4.
. 5.4.
1 - ; 2 - -; 3 - ;
4,9 - ; 5, 10 - ; 6, 8, 14 - ; 7 - ; 11 - ; 12 - .
: I - ; II - ; III - ; IV ; V ; VI
; VII ; VIII NaOH; IX ;
X ; XI ; XII .
. 1,
, 0,4 , , 423 . 623 .
.
187
, % 54
2, %. 5
, %
76
.. 66
91
: .
1 , . - 2. , (, 1,2, , .), , ,
, , 623 3.
383-393 .
3 4, . 5,
8, -
7 . ,
, , , ,
, 9, 278 ,
10 11,
10-20 1 .
12.
,
89%, .

, .
.
.
"" .. , :
- ;
- ;
- ;
188
- - .
, ,
.
- - , - .

.
723-823 . (573-623 )
, .
. :
C2H6 + HCl + O2
CO + CO2
C2H5Cl
-HCl
2H4
C2H4Cl2
-HCl
C2H3Cl
C2H3Cl3
..
-HCl
C2H2Cl2
..
CO + CO2
1,2. . - ()
( 5.1)

820 0,2 . , .
189
5.1
Cl2
HCl
35% -
HCl
-.
Cl2
- HCl

, :
CHCH + HCl
CH2=CHCl
= 112,9 /
, , ,
.
,

40%.

, 10-15% , 425-535 0,2-1,5 . 98,5% 98%.
,

HgCl2 (), .
.
190
.
5.5.
. 5.5.
1 ; 2, 3 ; 4 ; 5 ;
6 ; 7 ; 8 ; 9, 10 ;
11 - .
: I ; II ; III NaOH; IV ; V ; VI ; VII
,
1 70 2 3. 308 4. - . , 5. 6
7 8 9 10.
11.
""
" " .
:
- ;
- ;
- ;
- ;
-
191
5.1.7.
(1,1-) 2=CCl2 -
, .
:
. .,
304,7
.., 150,47
d420 1,2122
nD20
1,4271
, .
,
. [212]n. . , . - ,
.
.
1,1,2- (
) ()2 ~373 :
CH2=CHCl + Cl2
l22l
l22l
2=l2 + l
,
. , .
.

. 5.6.
1 2, 1,1,2-.
. 298 0,3 , :
, 1:1,05 (), . 3 4 . 1,1,2- 5
l
2%- N.
192
. 5.6.

1 - ; 2, 10 - ; 3, 6, 9, 11, 13, 16 - ; 4, 17 ; 5 - ; 7, 8, 12, 14 - ;
15 - ; 18 - .
: I - ; II - ; III - ; IV - ; V Ca(OH)2; VI - ; VII - ; VIII - ; IX - ; X -
1,1,2- 7, 6 7 . 1,1,2- 5. 1,1,2- 8. 8

, .
1,1,2- 10 () 160-200 / 353 .
50%- ( ). . 1,1,2-
11 17 ,
.
15, 12 14. .
263 0,06 .
12.
.
773 ,
,
. 1,2-,
193

.
5.1.8.
(2--1,3) CH2=C(Cl)CH=CH2 -
,
. (315%) : , , . - .
: , - , -
, .
, ,
, , , , , , ..
.
1940 .
, , ,
. 2000 . 500 . .
- ,
. ,
.
:
. ., 143
. ., 332.4
n420 1,42194
d420 0,958
,
. ,

.

1,2,3- 2,2,3- ~600 . :
2(l)(l)(Cl)3 2==(l)3 + 2l
2==(l)3
2=(l)=2.
1,3--2 530 SiO2 :
194
3(l)=2l
2=(l)=2
:
2=(l)=2.
2=l +
.
700 , , :
22=l
2=(l)=2 + l
.

.
. : , - .
333-353 - :
2
2=
: Cu2Cl2, NH4 C1, N1.
:
0,5Cu2Cl2
C2H2
CuCCH
CuCH=CHCCH
HCl
C2H2
HC
CuCCH
HC
0,5Cu2Cl2 + CH2=CHCCH .

313-323 .
Cu C1
2
2
2=(l)=2
H2=CCH + l
1,3--2:
2=(l)=2 + l
3(l)=2l
. 5.7.
1.
333-353 , 15-17 .
2, .
195
. 5.7.
1 - ; 2, 7 - ; 3 - -; 4 ; 5, 6, 9, 11, 12 - ; 8 - ; 10 - .
: I ; II ; III ; IV ; V
; VI ; VII ; VIII
- 3 , 4 .
5 6, 7 8 . 303-323
~5 . .
,
,

. , .
4. 1966 .

.
-1,3 ~573 .
. -1,3
. - - 1,4--2 3,4-1:
196
CH2ClCH(Cl)CH=CH2
3,4-
CH2CHCH=CH2 + Cl2
CH2ClCH=CHCH2Cl
1,4-
.

3,4- .
3,4- .
1,4-. , :
CH2=CHCH=CH2 + Cl2
+
CH2ClCHCH=CH2
CH2CCHCH=CH2
Cl 3,4-
CH2CHCH=CH2
Cl
+
CH2ClCH=CHCH2
CH2ClCH=CHCH2Cl
1,4-
(573
) (0,01 ).
3,4- 60-70%. 3,4-
1,4-. .
- 1,3 . 5.8.
- -
1. 2, . 3 , 4 .
: 3,4--1, - -1,4-2 2 5. 5 6, 3,4--1 , 1,4-2 . 3,4--1
7,
197
NaOH. 9, .
. 5.8. -1,3
1 - ; 2 - ; 3 - ; 4 - ; 5 - ; 6 - 3,4--1; 7 ; 8 - ; 9 - .
: I ; II ; III ; IV ; V
NaOH; VI ; VII ; VIII 1-; IX
NaCl
-
, , , 4 , , .
-
. : , , .
5.1.9.
(1--2,3-, ) - ; .. 216 , .. 389,1 . .
22l
198
- - .
[2(21)O]n ,

[2H(H2Cl)22]n ,
,
[2(2l)22O]n2(2O2=2)O

(, , , , , ),
, - . .
,
.
:
2=2l + R
22l + R
350-410
. ,
(3)3 1-4 300400 .
773-793 :
2=3 + l2
2=2l + l.
.
,
: 5:1.
, - 20% .
1,2-, :
2=3 + l2
2(I)(l)3 .
199
1- 2-,
.

:
2=2l + l2
2(l)(l)CH2Cl ,
2(l)(l)2l
l +(l)=2l .

. 9.6.
5.2.
- -
: , -, - , ,
, , -
.
- ,
. -
, , ,
, .
, , ,
, , , .
5.2.1.

, - :
+ F2
F + F
= 435,8 / ,
CFCF
= 452,5 / .
+ F2
200

- (335-356 /),
- , . , .
, 10% . - .

, :
3
=2
1
1,3
2,5
C1
1
4,6
10,3
, , . , . , , , . , ..
. :
1273 . , F , , , .. .
5.2.2.

.
:
+ F2
C + F2
C + F + F
:
+ F
C + F2
C + HF,
CF + F .
201

363 , :
CCl3CCl2H + F2
CCl3CCl2H + F
2CCl3CCl2
CCl3Cl2 + HF + F,
CCl3Cl2 + HF,
CCl3CCl2CCl2CCl3,
2CCl3CCl2
CCl3Cl2 + F2
CCl3Cl2 + F
CCl2=CCl2 + CCl3CCl3,
CCl3CCl2F + F,
CCl3CCl2F.

.
5.2.3.
. , ,
.

. F3, AgF2, MnF3
, , :
+ 2CoF3
CF + HF + 2CoF2
= 217,9 /.
o
o :
2CoF3
= 243 /.
2F2 + F2

(240-354 ) 100 .
202

()
293 383 .
, , , . , .

. , ,
, F3, . ,
- . 423-473 , - 573-653 . 2-3 . 8085%. 50%- , , , .
.

. .
5.9.
. 5.9.
1 - ; 2 - ; 3 - ; 4 ; 5 -
2 ,
.
-
203
. 1, .
,
1-4. 2 , 4. 4, 5. 3
1, .
, 1,
1 2, 3, 4. .
.

.
.

. , , . , C2H5F
75%.
(RH)2NiF6, (RH)3NiF6 (RH- ).
,
, - . ,
:
CH3COO-(.)
CH3COO(.)
CH3(.) + CO2 ,
C2H6 ,
2CH3(.)
H3(.)
+ NiFx
F- -
CH3NiFx+1
F(.)
CHF2NiFX+1
CHF3
2F(.)
-HF
F(.)
2F(.)
CF3NiFx+1
- HF
2CF3NiFx+1
C2F6 .
CH2FNiFx+1
CF4
2F(.)
- HF
204
5.2.4.
,
.

, .
-, - F2 - 2% (.) F2. 353 288 HF, F3. .
1:5.
. , ,
.

.
Na, K, Pb, Mg, Ca .:
O
RFC
+ F2
RFCF2OF.
F
:
.
F2
F + COF2
CF3O + F
2CF3O
2F,
CF3O,
CF3OF,
CF3OOCF3.
CF3OF CF2(OF)2
C. 80% COF2
205
F2 -. ~473 523 :
CF3OF
COF2 + F2
ROF
(R - C1-C5) SF5OF - (- -) 193 283
(, F13). .
-.
, .

SbF3 .
XIX .
-
.
, , . , .

. :
SbCl3 + 3HF
SbF3 + 3HCl
,
. 323-373
3,0 .
473-723 .
. - (
F). F
81%. F . 325 , ~36 . :
CH3CH=CH2 + HF
CH3CHFCH3
206
- HF
, ., -
60%- 335
- ( 60%):
(3)3 + HF (3)3F + 2.
5.2.5.
() 2=F . . 200,7 , . . 112,5 200,7 , 0,853. , .

.
CH2=CHF.
+ F
0,01% 373 19,6-29,4 .

, 673
.

:
2CH3CH3 + F2 + 1,5O2
2CH2=CHF + 3H2O,
:
CH2=CH2 + F2
CH2=CHF + HF
:
CH2=CHCl
HF F
Cl
CHCH3
CH2=CHF + HCl .
1,1-- 1,1-, 673-1073 85%.
207
5.2.6.
( 1,1- ) CH2=CF2 . . 187,3 , . . 129 , 0,580 298 .

1,1--1- 873-973 , 1,1- 293-343
1,1- : , 1,1:1,2, 20-90 .
(, ) 108 :
h
- HCl
CHF2CH3 + Cl2
ClCF2CH4
923-993
- HCl
CF2=CH2.
1,1--1-
20-60% (.)
1-15 . 1,1--1- - ~ 48%,
- 98%.
1,1- :
CHCH + 2HF
HCF2CH3 .
3% C2H2 8% CH2=CHF.
-Al2O3 Bi Mn.
0,1-20% Bi, 35-66% F, 24-42% Al, 0,1-10% Mn.
5.2.7.

() F2=CF2 - .
. 196,7 , . . 130,4 , 1,519 196,7 .
. ,
.

923-973 :
2CHF2Cl
2CF2
F2C=CF2 .
:
CHF2Cl
CF2 + HCl
208
2CF2
CHF2Cl + :CF2
CF2=CF2
:CF2
HCF2CF2Cl
HCF2CF2CF2Cl ..
CF2=CF2 + :CF2
CF2CF2
CF3CF=CF2
CF2
2CF2=CF2
CF2CF2
CF2CF2
, . , 49 50%, - 90%.
. (3:1)(1:2), 1023-1173 , 0,10,4 65-70%, - 90-94%.

:
F4
CF2=CF2 + CF2=CFCF3.
. , , 1173-1473 . 1373 ,
980 0,03 52,1%,
72,1%.
- .
. . 323-403 .

() CF2=CFCF=CF2
:
CHF2CF2CF=CF2
Cl2
CHF2CF2CFClCF2Cl
Br2
Zn
BrF2CF2CFClCF2Cl CF2=CFCF=CF2.
72%.

.
209
(513 ):
CF3
I
CF3
CF3
C=C
+
C=C
CF3CCCF3 + RFI
RF
CF3 RF
I
:
Cu
R (CF3)C=C=CF2.
473 F
RF(CF3)C=C(l)CF3
5.2.8.

() CCIF=CF2 - . . 246,2
, . . 115,8 , nD20 1,3960, d420 0,934. CCl2FCClF2 323-423 , 2 ,
3-4 :
Zn
CCl2FCClF2 - ZnCl
CClF=CF2.
2
763-823
0,1 .
C -
- 90-95% :
CFCl2CFCl2
Zn
CFCl=CFCl.
C2H5OH
3,3,3-
3,3,3- CF3CH=CH2 - . . 498 d420 0,996
298 .
3,3,3- :
2=CHCOOH HX (X=Cl, Br) XCH2CH2COOH
XCH2CH2CF3
. - KOH
-HX
SF4
CH2=CH-CF3.

:
CF3COOH
C2H5COOH
CF3,
CH2=CH2,
-CO2,-2
210
CH2=CH2 + CF3
CF3CH2CH2
CF3CH2CH2,
-RH
CF3CH=CH2.
5.2.9. ()
() - .
,
. , ,
. .
.

.
; () -
; - . - - , . . 5.2
.
5.2.

-11
-12
-13
-14
-21
-22
-23
-112
-113
-114
-124
-142
-143
. .,
..,
CCl3F
CCl2F2
CClF3
CF4
CHCl2F
CHClF2
CHF3
CCl2F-CCl2F
CClF2-CCl2F
CClF2-CClF2
CClF2-CHF2
C2H3ClF2
C2H3F3
162
115
92
89
138
113
110
299
238
179
156
142,2
261,7
296,8
243,2
191,5
145,1
281,9
232,2
198,8
365,8
320,6
276,6
262,8
263,2
225,4
..,
471
385
301,8
451,5
369
551
487
418,7
399,7
-
4,32
4,01
3,81
5,10
4,87
3,40
3,37
3,21
3,67
-
. :
nCCl4
HF
CCl3F + CCl2F2 + CClF3

3%
90%
0,5%
211
SbF3 SbF5 383 3
523-723 ,
FeCl3 . .
(-12) (-11) AlF3:
Cl2, HF
nCH4
CCl2F2 + CCl3F + HCl.
(-113) Cl2 HF 573-773 AlF3, CrF3

SbF3.
, :
CClF2Cl2F + H2
CClF=CF2 + 2HCl.

: , 5:1, 763-823 0,1 .
, , . ,
.
-113 323-423
0,2 .

. , - -, , .
212
6
, -, , , , .
6.1.
(, )
CH=CH2
.
1831 .
.

1930 . 1933 ., .

.
, ,
.

.

,
. 1960- , , -
.
. - -- (-),
.
,
. -
213

,
, . , , .
--, - , ---,
-- -
.
6.1.1.

.

t
65=
65=2 + 2
393-403 .
~ 40%.
:
CH3COOK
C6H5CHO + (CH3CO)2O
C6H5CH=CHCOOH + CH3COOH
- - . -
, ,
, , :
C6H5CH(OH)CH3
-H2O
C6H5CH=CH2
, .
- .
: , . 90%
.
- :
.-
C6H5CH2CH2OH
-H2O
C 65CH=CH2
. :
C6H5COCH3 + CH3CH2OH
30%.
SiO2, 623
C6H5CH=CH2.
214
. :
C6H5CHXCH3
C6H5CH2CH2X
,
-:
C6H5CH2CH2Cl
-HX
C6H5CH=CH2
C6H5CH=CH2 + HCl.
273-283
:
C6H5CHO + CH2=C=O
C6H5CHCH2C=O
O
t
C6H5CHCH2C=O
C6H5CH=CH2 + CO2.
O
-, , :
Mg
2C6H5CHBrCH2Br 2C
6H5CH=CH2 + MgBr2.

30-
. .
. 8 - , .

:
C6H6 + CH2=CH2
AlCl3
C6H5CH2CH3.
. ~ 358 0,1 . -
215
90%.
, .
; (~873 )
, .. , :
C6H5CH2CH3
C6H5CH=CH2 + H2.

, , .
, , .
, , ,
. , , , .
"" : F203 75-80%, 23 15-20%, r23 23%, Si2 - 0,1-0,5%.

. 6.1.
. 6.1.
1 - ; 2 - ; 3, 4 - ; 5 - ; 6 ; 7-9 - .
: I - ; II - ; III - AlCl3; IV - - ; V -; VI ; VII ; VIII
; IX ; X ; XI
.
. -
216
, - . , ,
. , ,
( , ), ( ).
.
( % (.)) .
..
37,0
..
0,6
..
61,1
..
0,2
1,1
.
.

:
O2, 403
C6H5CH2CH3
C6H5CH(OOH)CH3.

. ~
10% .

:
C6H5CH(OOH)CH3 + CH3CH=CH2
C6H5CH(OH)CH3 + CH3CHCH2
353-403 1,6-6,5 ,
.
90%.

:
TiO2, 373
C6H5CH(OH)CH3
C6H5CH=CH2 + H2O
. .

PbO2 Bi2O3 ~ 873 :
2C6H5CH3 + O2
C6H5CH=CHC6H5 + 2H2O
WO3 723 :
C6H5CH=CHC6H5 + C2H4
2C6H5CH=CH2.
217
.
4-:
2CH2=CHCH=CH2
O2
CH=CH2
C6H5CH=CH2 + H2O

. 553 1
98% . .
, .
6.1.2. -
- , ,
. -.
- .
- .
.
, , -
80-100 , .
60-70% 90%.
- ()
.
:
C6H5CH(CH3)2 + O2
C6H5C(CH3)2
OOH
.
:
C6H5C(CH3)2
OOH
NaOH
-H2O
C6H5C(CH3)2 H2O
C6H5C(CH3)2 + 0,5O2
-NaOH
OONa
OH
218

593 :
C6H5C(CH3)2 - H2O
OH
C6H5C=CH2
CH3

.
6.2.
4
5
N
1
CH=CH2
- ,
. . 6.1.
2- 1887 .
.
. 2- 2- (2-) 2- 2-:
CH3
+ CH2O
CH2CH2OH
-H2O
CH2CH2OH
CH=CH2
" ".
30- . ".. " 2.

.

-- -. -
219
2-- 5--2-,
5-25%. . , ,
- , 15-25% 5--2-, -
, , .
6.1

2-
3-
4-
5--2-
2--5-
., /
.,
d420
333/167
341/176
331/147
348/147
370/176
431,0
421,0
448,0
433,0
402,5
0,9757
0,9879
0,9836
0,9779
0,9449

, , ..
. , .
, .
2- 5--2-.
10% 5--2-, , , , ,
2- 70:15:15.
2--5.
5--2- .
, , ,
.
6.2.1.

:
- ;
220
-
.
. ,
, .
- ,
2-, 4- 6 .
:
R
N
CH3 + CH2
R
N
CH2CH2OH ,
R = H, CH3 C2H5 3- 5- .

:
CH2CH2OH
.
- H2O
CH=CH2
N
N
2- 4-
2- 4- .
6.2.2.
5--2-
5--2- . ,
.
NH3
473-523 5,0-10,0 2--5-. :
4CH3CHO + NH3 -2
CH2=CH
C2H5
N
CH3
-H2
CH3
221
2- 4- . .
2--5-. .

.
848-923 , .
, Fe2O3, ZnO,
Mg2O3, Al23. Cr2O3, K2CO3, KF, CaO.
35-70%,
- 40-85%.

,
50%; 70-80%. .
863

2--5-,
%
29
5 -2 ,
%
80
883
38
76
903
49
73

,
, .
. , 2- 3-, 2,5-, 3-,
3-, 2,5- .
,
.
2- 4- 2--5-
2- 4- . -
222
, , . , , 648-723 .
2- 4-
50-60%:
CH3
6CH3CHO + 2NH3
+
N
CH3
+ 6H2O + 2H2.
N
4- 3 , 4--3- . .
: .
.
:
( ) - -
:
N
n
N
CH3
+ n CH2O
N
N
CH2CH2OH
CH(CH2OH)2
C(CH2OH)3

, . (
) , .. .
, ,
413-593
2,0-17,0 . .
. , . ,
- .
:
223
- 97-99%.
- ~ 673 .
2-. 2
2- :
N
CH3
H+
CH2CH2OH - H2O
+ CH2O
N
CH=CH2
2--5-. 2--5
.
473-523 5,0 2--5-:
4CH3CHO + NH3
C2H5
-H2O
CH3

2-- 5- :
C2H5
N
CH3
CH2O
C2H5
C2H5
N
CH2CH2OH
-H2O
CH=CH2
6.3 N-
, , ,
.
.
:
- ( - ~ 10 000-15 000);
- (
25 00040 000) ;
- ( ~ 60 000);
- ( ).
224

, , , , .
N- . , (,
..) (). ,
, .
.
6.3.1. -
-
373-573 1,5-4 . :
2+ 2
= 226 /.
C22
. ,
, ,
. . , .
, , - .
, ..
.. , .
:
H
2CH2O + HCCH
CH2CCCH2 2 CH2CH2CH2CH2 -H2
OH
OH
-1,4
CH2CH2
CH2CH2
CH2 CO NH3
CH2 CO
OH
NH
OH
-1,4
CH2CH2
CHCH
CH2 CO
NCH=CH2
N-
-1,4 , 30%-
, , 373 0,5-
225
0,7 . 35%- -1,4
20 . -1,4
- 523
. - 443-453 . , ,
373-378 1,5 .

, , , , .
. - , N, , , , .
:
CH2CH2
CH2 C=O
CH2CH2
Me+ + CH2
N-
NMe
CH2CH2
CH2CH2
CH2 C=O + HCCH
CH2 C=O
N-
()
NCH=CH-
H2CH2
CH2CH2
H2 C=O
+ CH2 C=O
NCH=CH-
C=O
NH
CH2CH2
CH2
CH2CH2
C=O + CH2 C=O
NCH=CH2
()
N-
. .
226
6.3.2 -
,
, -. -, .. .
N-
N-(-), N-(),
N-().
N-(-). N :
CH2CH2
CH2CH2
CH2
CH2
C=O + H2NCH2CH2OH
C=O + H2O
NCH2CH2OH
CH2CH2
CH2 C=O
CH2CH2
CH2 C=O + HCl + SO2
+ SOCl2
NCH2CH2OH
CH2CH2
CH2 C=O
NCH2CH2Cl
CH2CH2
KOH
-HCl
NCH2CH2Cl
CH2
C=O
NCH=CH2
- 453-463
N-(-) 90%. , 308 ,
N-(-). 76%.
N-(-)
293-308 .
N-(-) N-
N-():
227
CH2CH2
NaI + (CH3)3N
CH2 C=O
CH2CH2
CH2 C=O
NCH2CH2Cl
Ag2O
CH2CH2
CH2 C=O
NCH2CH2N(CH3)3I
NCH2=CH2
. 55%. N 81%.
. N-
N-(--).
:
CH2CH2
H2NCH2CH2OH
COOH COOH

[H]
CH2CH2
C=O C=O
NCH2CH2OH
N-(-)
CH2CH2
CH2 C=O
CH2CH2
(CH3CO)2O
CH2 C=O
NCH2CH2OH
N-(-)
CH2CH2
733
NCH2CH2OCOCH3
CH2
C=O + CH3COOH
NCH=CH2
N-

423 , N-(-) 90-92%.
50%-
274-278 . N-(-) 55%.
. ~ 90%. 733 N-
50%.
N-(-). N N-(-)
573-673 (93% l2O3, 2% Fe2O3, 5% ).
80%.
N- N-(-). -
228
- :
CH2CH2
CH2
C=O
CH2CH2
+
NH
CH2CH2
CH2
C=O
NCH2CH2OH
6.4. N-
N-
N
CH=CH2
. -N-
[-(N-)] - , ,
, , , , ; , , .
-N- . . 1924 . -N-
. 1937 . .
. , -N-
"" "" , .
. - - .
50- . -N-.

. N-
: , ,
.
N- :
229
N
(CH2)nCH=CH2
N-

N
RC=CR'R"
N-
N-
. N-.
,
. .
6.4.1. N-

N . :
+ CHCH
N
H
N
CH=CH2
1,0-2,5
393-553 ( ).
, -, N--2 .
N- .

: ,
, .. ,
,
.
230
N-
363-433 N- 99%.
,
, , . , 40%.
.
6.4.2. N-

, -
,
N-:
RRNH + CH2=CH-OR
CH2=CH-NRR + ROH.
, F3.
- N-
, , - N-.

. ,
,
, , -N-. , N-, N-
. N- - .
, N -
N. : N-
- -
231
-.
, ( ) , , , .
. 1-10% (.)
N- . : 6.

N- N-(1):
Y
+ CH2=CHOR
Hg(OCOCF3)2
N
H
+
N
CH=CH2
N
RO
Me
X = H, COMe, Cl, Br, I, Me, -[c]-; Y = H, Cl, Br, I; R = Et.

- , , -
,
.
6.4.3. 9-

N- 1- 2- N-.
N-(2-)
N-(2-)

, :
232
H2CCH2
O
HOCH2CH2Cl
H2CCH2
O O
CO
N
H
N
CH2CH2-OH
N- () ( -) 3-- 3,6--9- :
Br
CCl4
TsCl
C5H5N
CH2CH2-OH
CH2CH2-OH
Br
N
CH2CH2-OTs
Br
KOH
N
CH=CH2
Br
Br
Br2
CCl4
TsCl
N
CH2CH2-OH
CH2CH2-OH
Br
Br
N
CH2CH2-OTs
KOH
Br
Br
N
CH=CH2

423-453 .
N-(2-) . -
233
443-543 . N- 80%.
N(2-) .
- N-
.
, , N-(2-).
3-- 3--N-:
COR
COR
ArSO2Cl
N
CH2-CH2OH
KOH
COR
N
CH2-CH2OSO2Ar
N
CH=CH2
1- N-
N-
1- , N(1-):
Y
ROH
N
RO
Me
N
CH=CH2
R = lk; =Y = Aik.
1- , N- ~ 473 N- , . 7080%.
N-(1-) 9-.

( ) ,
234
19,6-49 .
N-(1-) .
N-(1-) :
CH2=CHOCOR
RCOO
Me
N
H
N
COR

: 263 , N-(1-). () . , , , .
,
40-50%- .
6.5.
6.5.1.

- -- .
, 95% - .
,
-1,4 . .
- :
235
CHCH3
CH=CH2
-1,3:
+ CH2=CHCH=CH2
t0
CH=CH2
6.5.2.
, , .

: , , .
.
.

C6H5CH3 + CH2=CH2
CH3C6H4C2H5
, 348-368
: , 1,7- (3:1). ll3.
:
CH3C6H4C2H5
-H2
CH3C6H4C=H2.
- -
, ZnO,
F2O3 MgO. ~ 873 : , 2,5:1. 28-32% ( 10 ).
90-92%.
" "
().
236
. :
- 573
2C6H5CH3 + CH=CH
CH3C6H4CH(CH3)C6H4CH3
-
CH3C6H4CH(CH3)C6H4CH3
CH3C6H4C=H2 +
.
-
:
2C6H5CH3 + CH3CHO
CH3C6H4CH(CH3)C6H4CH3 + H2O

.
6.5.3.
. , , , . , , , , . .

(-1--3) 2=--3 1908 . -. , .
, .
: , ,
().
. . , .
:
CH2=CHCCH + H2O
333-335
HgSO4 + Fe(SO4)3
CH2=CHC=CH2
OH

237
CH2=CHCOCH3.

, ,
,
.
.

OH
573
CH3COCHCH3
H2O + CH3COCH=CH2
[Al2O3 + SiO2 + WO3]
:
OH
CH2=CHCCH + 2H2O
CH3COCHCH3 + ,
-2,3. .

Bacillus subtilis.
-1,3. -1,3 :

(47%- ) ,
3--1- .

.
CH2OH
CH2O
H2O
273-283
H2 C
+ SO3
H2C
SO2
CHOH
CHO
CH3
CH3
CH2OSO3H
CH2
Cr2O3; [O]
H2 C
HC
+ H2SO4 + 2 .
CHOH
CO
CH3
CH3
238

2=(3)--3
1891 . . .
1910 . 1935 .

.
1--2-3.
1--2--3, ,
, :
CH3
367-369
CH2CHCOCH3
OH
CH3
H2O + CH2=CCOCH3 .
. :
, , ,
403 , , , , .
1--2--3 = 8,2-8,6.
. , , ,
, . 588-693 .
-
(, , ).
.
1945 . 288 . , :
CH3
CH3CO + CHCH
KOH
CH3
CH3CCCH
OK
H2O
CH3
2O
CH3-CCCH H
Hg2+ , H+
OH
239
CH3
CH3
P2O5 CHCl3
CH3-CCOCH3
CH2=CCOCH3.
-H2O
OH
278 ,
, .
- .
.
. .

65-=2 1906 . . ., .
1936 .
.

-
:
CO-CH2-CH2-Br
CH3COK
C2H5OH
CO-CH=CH2
+ HBr .

.
N---
. ~ 75%. , ,
.

,
:
nHC=CH
HCCH nH2O
CHCH
-CO2
OO
O O
OH OH
CO
CO
n
n
240

poxoppoae .
H2CCH2
O O
CO
Cl2
HCl
RN
3
H2CCHCl
-R3NHCl
O O
CO
HC=CH
O O
CO
241
7

(, ) 2= 1843 ., , .. 1860 .
. 1862 . .. - . 10 .
- - , , - 1865 . .
- . 1932 .
, , , , , : -, --, -, - , .

(2- , .) () .
-, - , -, .

.
, ,
, -, , ,
.
. . 10-15 ,
, , .
. ,

,
242
, , N-, , , , , , .

.
7. 1.
2=-N 1893 .
, 1930 . - ,
, . .
, .
( ) ,
, , , , .
, , . . ,
. - . (72% 28% ) (60% 40% )
30-100 , 10-20 ,
.
- .
. 350,3 , . . 191 , d420 =0,8064, nD20 =1,3914.
( 293 7,3% (.)), ,
87,5% (.) 12,5% (.) , . . 344 .
.

:
-
CH2=CH2
O2
H2CCH2
O
HCN
CH2CH2
OH CN
-H2O
CH2=CHCN;
243
-
CHCH + HCN
CH2=CHCN;
- :
CH2=CH2 O2
CH3CHO
HCN
CH3CHCN -H O CH2=CHCN;
2
OH
- :
CH2=CHCH3 + NH3 + 1,5O2
CH2=CHCN + 3H2O;
-
4CH2=CHCH3 + 6NO
4CH2=CHCN + 6H2O + N2;
- ,
2=2 + N + 0,5 2 2=-N + 2;
-
323 + N3 + 2 2 2=-N + 4 2 .
7.1.1.

. 1947 .

443-483 :
CH2OHCH2CN
CH2=CHCN + H2O
:
H2CCH2 + HCN
CH2CH2CN
OH
CH2=CHCN + H2O
323343 .
, . 328-338 0,2-0,25
244
. - 91 % , 0,5 % 2% .
, , :
(
)

, % (.)
91
0,01
1,0
2,0
< 1,0
90%-
25%- .
:
HCONH2
HCN
-H2O
493-553

.
:
- -
CH2=CHCN + 2H2O
CH2=CHCOOH + NH3,

CH2OHCH2CN + 2H2O
CH2OHCH2COOH + NH3;
-
CH2CH2CN
CH2OHCH2CN + CH2=CHCN
O
CH2CH2CN
, -
, .
- 13-17%-
:
CH2=CHCN + 2H2O + H2SO4
CH2=CHCOOH + NH4HSO4.

245
2-3%- :
H2SO4 + Na2CO3
Na2SO4 + H2O + CO2 .
:
2CH2=CHCOOH + Na2CO3
2CH2=CHCOONa + H2O + CO2,
NH4OH + H2SO4
NH4HSO4 + H2O .
, , .
.
7.1.
. 7.1.
1 - ; 2 - ; 3 - ; 4
; 5 - ; 6 - ; 7 - ; 8 - ; 9 - .
: I ; II ; III ; IV -; V ;
VI ; VII ; VIII ; IX .
246
1 2
, 3 4. .
443-483 , . . - , ,
- 4 ,
8, , 15% (.) ( ,
.), .
9. : 9 - 8 - 9. . . 3,
5,
4 .
, 6
7, . -
, , 6% , .
443-483 .
.
7.1.2.
1949 . " " () , :
CH2=CHCH3 + NH3 + 1,5O2 Mo CH2=CHCN + 3H2O
"" () , .
.
""
() 1960 . . , , , , ""
247
673-773 0,4
.
: , , , , . .
,
.
- .
: ,
, . ,
"
, 30%-
(). , :
Bi2O33 MoO3
Bi2O32 MoO3
Bi2O3MoO3
-.
0,2 % - .

.
80% N3:36 (0,9:1)-(1,05:1).
.
1,5% (.)
- - .
:
-
CH2=CHCH3 + O2
CH2=CHCHO + H2O;
-
CH2=CHCH3 + O2
CH3CHO + HCHO ;

248
-
CH2=CHCH3 + 0,5O2
CH3COCH3 ;
-
CH2=CHCH3 + 3O2
3CO + 3H2O ;

CH2=CHCH3 + 4,5O2
3CO2 + 3H2O;
-
CH2=CHCH3 + NH3 + 2O2

HCN + CH4 + CO2 + 2H2O ;
-
CH2=CHCN + NH3
H2NCH2CH2CN
H2NCH2CH2CN
CH2=NH + CH3CN
, (, , ), . , 80%-
0,9:1
1,05:1.
.
7.2.
: ; ; ; ; .
2 3,
4 ,
. 7
8 4. 10 11 4.
4 5 12 (
723-743 0,4 ).
, . - - , 40% (.)
NaNO2, 53% (.) KNO3 7% (.)
NaNO3.
- . 12
14 . 14 ,
249
1,7 .
(793 ), 9 .
.7.2.
1 ; 2, 7 ; 3 ;
4 ; 5 ; 6
; 8 ; 9 ; 10
; 11 ; 12 ; 13 ; 14 - .
: I ; II ; III ; IV ; V
; VI .
- 13
523
.
7.1.3.

. , ,
:
CHCH + HCN
CH2=CHCN
= 195,7 /
250
Cul, NH4Cl (l, Nl).
:
- -
nCHCH
CH2=CHCCH CH2=CHCCH=2;
-
CHCH + HCl
CH2=CHCl ;
-
CH2=CHCCH + HCl
CH2=CHCCl=CH2;
-
CH3CHO;
CHCH + H2O
-
CH3CHO + HCN
CH3CHCN;
OH
-
CH2=CHCOCH3 ;
CH2=CHCCH + H2O
-
CH2=CHCH=CHCN ;
CH2=CHCCH + HCN
-
HCN + HCl + 2H2O
NH4Cl + HCOOH.
: 0,1-0,15
; - ;
; ; .
. 7.3.
251
. 7.3.

1 ; 2, 4, 7 ; 3, 5 ; 6
; 8 ; 9 -.
: I ; II ; III - ; IV - ; V ; VI ; VII ; VIII ; IX ; X
6 ,
, . 358 . , ,
8 ,
. - 9,
. , , . , 318-323 ,
. 7 .
7.1.4.

.
:
CH3CHO + HCN
CH3CH(OH)CN.
283-293
~ 7-7,5 97-98%.
:
CH3CH(OH)CN
CH2=CHCN + H2O.
873-973 3 .
252
90% 92%
.
7.1.5.

4CH2=CHCH3 + 6NO
4CH2=CHCN + 6H2O + N2
723-823
, , . 79% . "".
7.1.6. ,

"" ( ) ""
, 603-633
, :
CH2=CH2 +HCN + 0,5O2
CH2=CHCN + H2O.
~ 90%.
7.1.7.
"" " -" , :
CH3CH2CH3 + NH3 + 2O2
CH2CHCN + 4H2O
753-793 , , .
7.2.
. , -, - , . , , , .
253
,
, .

(-3), , ,
:
nCH2=CHCNH2
O
[CH2CH2CNH]n
O
7.2.1.
2=-()NH2
. . 357,5 , d420 1,127, nD20 1, 46; , , .
1893 .

283 :
CH2=CHCOCl + 2NH3
CH2=CHCONH2 + NH4Cl

. .
.
,

(CH2=CHCO)2 + 2NH3
2CH2=CHCONH2 + H2O,
-
CH2=CHCONH2 + H2O.
CH2OHCH2CONH2
~ 428 .
- 523-773 498-673 . :
CH3OCH2CH2CONH2
CH2=CHCONH2 + CH3OH
- 373-573 :
R2NCH2CH2CONH2
R2NH + CH2=CHCONH2.
, - - :
CHCH + CO + NH3
Ni(CO)4
CH2=CHCONH2.
254
7.2.2.

353-373 . .
1954 . " " ().

1961 . 80-85%- 358-373 :
CH2=CHCN + H2O + H2SO4
CH2=CHCONH2H2SO4
( 4%):
CH2=CHCN + 2H2O + H2SO4
CH2=CHCOOH + NH4HSO4

:
2CH2=CHCONH2H2SO4 + Ca(OH)2
CH2=CHCONH2 + Ca(SO4)2 + 2H2O.
()2, , ,
. ,
, . 1970 .
, , , --, , , .
- .

, .
10%-
. , 30-50% (.) . ,
: .
255
7.3
(, ) 2=- ; . . 285-286,5 , . . 413,9-414,6 ,
d420 = 1,0511, nD20 = 1,4224. , , 13, .
.
, ,
, . -
. ,
. .

.
, .
-, - 2-
, .
.
:
- ( );
- ;
- ;
-
;
- -;
- .
7.3.1.
. :
RCN + H2O
k1
k2
RCONH2
RCOOH + NH3
RCONH2 + H2O
323-353 . ,
. k1>>k2, , , .
k1:k2 -
256
. ,
(k1:k2>100). . 50%- , ,
. .
, ,
(k2>>k1) .

: , .
, , .

.
, .
,
.
, . -, , -, .
. , , ,
, .
, - , , , .

, , . ,
, .
. , , ,
, , , - , .
, ,
257
, .
, ,
,
N
X
= , I, AIk, Ph; R= H, AIk, O.

, 1%-
.
, .
7.3.2.
( )
(, , ,
):
4 + 42 + Ni()4 + 21
42=- + Ni12 + 2
, :
422 + Ni()4 + 4R + 21
42=-R + Ni12 + 2.
313 ,
:, 1:1, .
.
7.3.3.
. :
CH2=CHCHO + H2O
H298 = -340 /,
CH2=CHCH3 + O2
258
CH2=CHCHO + 0,5O2
CH2=CHCOOH
H298 = -250 /
, .
. :
O2
2O
CH2=CHCH3 + O
CH2=CHCH2 + H2O, ( )
CH2=CHCH + OH , ( )
CH2=CHCH2 + O
CH2=CHCHO, ( )
H2=CHCH + O
CH2=CHCO + H2O,
CH2=CHCHO + OH
CH2=CHCOOH.
H2=CHCO + OH
, (, , , 2) .
, , : 673-773 .
.
573-623, 0,1-0,3
, , , , , . : 4-5, : - ~ 2.
,
. , , 24 .
90-95% 8090%.
. ,
, , ,
, , .

:
MoO3 > V2O5 > WO3 > SeO2 > TeO2 > Nb2O5 > Ta2O5 >CrO3.
2,93. 23 b2 34. : 34, 2SO4, 3, 33,
2.
3.
259
523-553 0,1-0,2
:, 2: 1.
95-97%, -
90% .
"", , "", " ", " ", " ".
.
, " " ().
. 7.4.

1 2 . ,
, 4-7% (.), 20-50% (.), ,
1.
573-673 . 2, 473-573 .
. 7.4.
( " ")
1, 2 ; 3 ; 4 ; 5
; 6- 8 .
: I ; II ; III ; IV ;
V
; VI ; VII ; VIII
; IX .
2 3 , , .
20-30%-
260
4. ,
6-8. 98,5% ().
" ", " " "" . . , " " .
7.3.4.
:
CH2CH2 + HCN
HOCH2CH2CN.
O
:
H2SO4
HOCH2CH2CN + 2H2O
HOCH2CH2COOH + NH4HSO4
CH2=CHCOOH + H2O.
60-70%.
" ".
: 1971 .
7.3.5. -
:
CH3COOH
CH2=C=O + H2O.

:
CH2=C=O + HCHO
CH2CH2
O
CO
261
- 373-423 ,
533 :
H2O
CH2CH2
CH2=CH-COOH.
O
CO
""
323
.
7.3.6.
, " ",
408-423 7,5
. :
CH2=CH2 + PdCl2 + H2O + CO
Pd + 2CuCl2
2CuCl + 2HCl + 0,5O2
CH2=CHCOOH + Pd + 2HCl,
2CuCl + PdCl2,
H2O + 2CuCl2
, , . 2 , :
CH2=CH2 + CO + 0,5O2 + CH3COOH
CH3COOCH2CH2COOH.
, , , , .
7.4.
(2- ) 2=(3)-
; . . 289 , . . 435-436 . , , , . , .
70 ,
.
, ,
.

.
"" 1937 . .
262

, .
: , .
7.4.1.

573-723 :
O
CH2=CCH3 2 CH2=CCHO
-H2O
CH3
CH3
O2
CH2=CCOOH
CH3
, , . ,
""
Mo12Co4Bi1Ni4,5Fe1Te0,6P0,1O48,6 435 ::, 1:3:27, 88% 79% 99%.

, , .
,
, , , , , , , , .
90-98% -75-90%.
7.4.2.

:
CH2=CCH3
CH3
O2
CH2=CCOOH
CH3
, . : .

-
263
. ,
.
7.4.3.

, , , .
80-90%
75-90%. " " (). , 593 . 623-673 .

, , .
95% 95-97%.
7.5.
:
- ;
- ;
- ;
- , ;
- ;
- .
7.5.1.

, :
CH2=CHCOOH + CH3CH2OH
CH2=CH-COO-CH2H3 + H2O
H298 = 35 /
, .
, , , -
264
. .
. .
-, - . .
, , .. .
,
( 20-100 ) 343-373 .

, . , , , , .
.

, , 2,4--6--, 2,5-- ,
.

.
- , . , , . , , -1, -2,
-2/8 . 373-408 .
(423-453 ) 0,78-1,18 , 90%.
, , .. -
265
. , .

:
CH2=CHCOOH + CH2=CHR
CH2=CHCOO-CH2CH2R

:
; ; ;
.
7.5.2.

,
, , , .

CH2=CH-COOR + ROH
CH2=CH-COOR + ROH.

, ,
. , -, -
.
, , , , .
.
,
.
, , , -, , N,N-2-(1,4-)--. , , .
266

.
, . .
, 93%
( ), .
-2/8
.

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

. .
7.5.3.

.
:
CH2CH2 + HCN
O
HOCH2CH2CN.
267

:
HOCH2CH2CN H2SO4 CH2=CHCONH2H2SO4 ROH
CH2=CHCOOR + NH4HSO4.
, ~ 423 :: , 1:2:2. 80% .
7.5.4.
, ,
, ,
"" :
Ni(CO)4 + 4C2H2 + 4ROH + 2HCl
4CH2=CHCOOR + NiCl2 + H2 .
( " ") (
). , - . , 298-343 .
:
295 = -250 /.

,
( 423-573 , 3-20 ):
HCCH + CO + ROH
CH2=CHCOOR
H238=240 /
: , - .
" "

. , , "" . :
268
4C2H2 + 3,2CO + 0,2Ni(CO)4 + 4ROH + 0,4HCl
4CH2=CHCOOR + 0,2NiCl2 + 0,2H2.
303-323 ,
, 1:1,
. .
,
.
, , .
7.5.5.
"" "" ().
:
CH2=C=O + HCHO
CH2CH2 + ROH
O
CO
CH2CH2
O
CO
H238 = -190 /,
CH2=CHCOOR + H2O
H238 = -45 /
.
7.5.6.
:
CH2CHCN + H2O + H2SO4
CH2=CH-CONH2H2SO4 + ROH
CH2=CH-CONH2H2SO4
CH2=CHCOOR + NH4HSO4.
423
.
95-97%. 433-453 .
85-90%.
269
7.6 .
2=(3)-3
,
.
( ) (, , ,
.), (, , ), ,
(, , .), (, ..). ( , , , ). , ,
, , .
.
1,7 . /.

60 .
.

.
, , , .
:
- , ;
- , - .
7.6.1.
"" 1937 . :
; ; ;
.
( )
, .
.
270
.
:
CH4 + NH3 +1,5O2
HCN + 3H2O
H238 = -480 /
1373-1473 : :,
5:1:1, . , ~ 6-8% (.) N.
673 , .
80%.
" ".
:
HCN + 3H2
H238 = 250 /.
CH4 + NH3
, , 1473-1573 . 20%, . 85%.
" ". :
C3H8 + 3NH3
3HCN + 7H2
H238 = -45 /
1773 "
" . 85-90%.

CH3COCH3 + HCN
(CH3)2C(OH)CN
H238 = -45 /
.
( , , .) . 298-313 ,
N:, 0,7-1,1.
. 90%.

:
(CH3)2C(OH)CN + H2SO4
(CH3)2CCN + H2O
OSO3H
271
(CH3)2C-CN + H2SO4
OSO3H
(CH3)2CC=NHHSO4
OSO3H
+
(CH3)2CC=NHHSO4 + H2O
OSO3H
(CH3)2CCONH2H2SO4
OSO3H
CH2=CCONH2H2SO4 + H2SO4.
(CH3)2CCONH2H2SO4
OSO3H
CH3
-, , .
353-383
398-418 98%- .
1 .
: , 1,5:2.
95-98%.
.
,
: , .

:
CH2=CCOOH + NH4HSO4,
CH2=CCONH2H2SO4 + H2O
CH3
CH3
CH2=CCOOCH3 + NH4HSO4.
CH2=CCONH2H2SO4 + CH3OH
CH3
CH3
353-383 . 373-423 ,
0,8 , ~ 1
0,02%. 90% 80-90% - . , ,
, - , -- -. .
272

"", "", " "
. "", "", "", "" .
.
- (. ). 403-423 0,7-0,8 .
333 , , .
, , ( ).
-
, .

. 7.5.
1 - 4
, . 2 .
398 . 353-363 .
H2SO4
CH3OH
2
4
6
5
. 7.5.
1 - ; 2 - ; 3 - ; 4 - -; 5 - -; 6 ; 7 - .
5 , 4,
3
. -
273
6 . 7.
.
, .
~ 1273 1 . ,
, ,
.
7.6.2. -
- :
, , 4
. " " " " .
- .
-

(CH3)3COH + O2
CH3=C(CH3)CHO + 2H2O
H298 = -275 /
603-633 , 0,3-0,4 - : : ,
1: (10-15): (6-12). , , , , , ,
, , .
2-3 - 85%.
2, , , , .

573-623 0,1-0,5
a , .
274
O
CH2=C(CH3)C
O2
2=C(CH3)COOH.
H
: 3-6%, 10-60%, 20-75%.
, , , , , , ., , - , .
2-5 90-95%
85-90%.
, 2, .
"", " ", "", "" .

CH2=C(CH3)COOH + CH3OH
CH2=C(CH3)COOCH3 + H2O
H298 = 1,2 /
383-388 , 30-50 . 1 , ~ 99 %.
7.6.3.
7.1.
1950- "" ()
,
. - - .
.

,
, - :
2=(3)2
N3; 2
2=(3)N
H2=(3)N22S4
2; 2S4
2=(3)3 + N4S4
275
7.1
O2
CH2=CCHO
CH3
O2
CH2=CCH3
CH3
O2
O2, CH3OH
N2O4, HNO3
(CH3)2C(ONO2)COOH
NH3, O2
CH2=CCN (CH3)2C(OH)COOH
CH3
CH3OH
CH2=CCOOH
CH3
CH3OH
H2SO4, CH3OH, H2O
(CH3)2C(OH)COOCH3
CH2=CCOOCH3
|
3
H2SO4
, ,
4, -
, . . - , .
, ,
, .
.

95% 70-75%.
,
, .
. : 733 , 5
, -48:NH3:2, 1:1,7:2,6, 0,25
. 95%,
276
- 65-70%. 10-15%,
8-10%, 8-10%, 2%.

( ) . 7.6.

. , .

: ,
,
( ).
. 7.6.
1 - ; 2 - ; 3, 13, 19 - ; 4 - ; 5 - ; 6-10 - ; 11 - ;
12 - ; 14 - ;
15 ; 16
- ; 17, 20 - ; 18 - .
: I - ; II - ; III - ; IV - ; V ; VI - ; VII - ; VIII - ; IX - ; X - ; XI - ; XII - ; XIII - ; XIV - ; XV - ; XVI - ; XVII - -
277

( 2 ) ,

( 3 ).
- , ,
, .
" " ()
, . ,
.
7.6.4.
70-
, . . ,
, .

:
O
O
2CH2=CHCH3 + 2CO + 2H2
CH3CH(CH3)C
+ CH3CH2CH2C
H
H
293-393 :
O
O
O2
CH3CH(CH3)C
CH3CH(CH3)C
H
OH
323-373
. 323-423 -
278
, 333-413

.
CH3 O
CH3-CC
+ CH3OH
OH
CH3
O
O2
CH3CHC
OCH3
CH3
O
CH3
CH3CHC
- 2
CH2=CC
OH
OCH3
OCH3

.
, .
-. , .
.
:
CH2=CHCH3 + CO + CH3OH
CH3CH(CH3)COOCH3.
.
, , , , , . : .
, , ,
, .
423 ,
. , , dl2,
, -
279
(h)3. - d (II) :
Pd(O) + CO2 + 2HCl
PdCl2 + CO + H2O
:
CH3CH(CH3)COOCH3
CH2=C(CH3)COOCH3 + H2
623-723 , , , .

1990- "":
3 + + 3
2=(3)3.
d(A)2, 2 , , N.

2- (2-h2)
. , .
2-h2 4-
. (, ) , 20- . , ,
:
Ph-P
Ph
COOCH 3
Pd
H
C
R)
C
H
H
CH
CH3CH=CHCOOCH3
280
Ph
COOCH3
Ph-P
Pd
R) HC
C
H
H
H
CH2=C(CH3)COOCH3.
723 40 000 -1
99,9%.
.

-
"" ), , :
. - , ().
"" 1%. 99%
, .
( .
.. ; .. , .. ).
CH2=C=CH2
+ CO + CH3OH
CH2=C(CH3)COOCH3.
CH3CCH
, , , : 413 , 5,0 , 1,110-3 /
, 100% 700
-1.
-
, ,
- 383 , 5,0 , 8,510-3 / - 75% 96-97%
300 -1.
281
7.6.5.

2=(3)N2 . N- .
. . 383-384
, , , , .
:
(CH3)2C(OH)CN
H2SO4
398-413
CH2=C(CH3)CONH2H2SO4
CH2=C(CH3)CN
NH3
CH2=C(CH3)CONH2.
, . , . ~ 96%.

;
, , .

60- XX .
( ).

().
CH2=CC-OCH2CH2OH
CH3 O
:
282
CH2=CC
+ OHCH2CH2OH
CH2=CC
-H2O
CH3 OCH2CH2OH
CH3 OH
7.7.
() (, .) . 300-5000.
,
, -
( ) - . , ,
- , .
.
:
- , , -, -
, 1,3- , 1,4- , 1,6, , , , , , ;
- 2-8, - , , , , ;
- ,- ,
, .
.

.
283
8

: ; , , -, ; , ; , , , , .
,
,
().
( 2-2,5 )
. , .
.
" ." N-2 .
, ,
2=2N-(2)2--(2)2-NC-2=2.
, , .
" " , ,
R1
2=2-N-R-(2)2-=2 ,
R-Alk, 1-4 ; R1 = 3.
284
(, ..),
( ..).
8.1.
[-CH2CH(OH)-]n , ,
, . 443-493 , . , , . .
2=,
. ,
. , ,
.

:
, , ,
. 3000.

. (, -- .) . .

1946 . .
(-2--1) ; . . 275,15 , . . 369,9 D420 0,850.
, , .
285
, , , :
OH
Cl2; H2O
H2C=CHCH2OH HCl
ClCH2CHCH2OH
OHCl; H2O
H2CCHCH2OH
O
:
H2C=CHCH2OH + H2O2
H2CCHCH2OH
OH OH OH
, , ,
:
H2C=CHCH2OH

H2C=CHCH2Cl
ClCH2CH(OH)CH2Cl
H2CCHCH2Cl

O
CH2(OH)CH(OH)CH2OH
, , :
CH2=CHCH3
Cl2
HCl
CH2=CHCH2Cl.

, .
0,2%-
2,5-3,0%- 350 . ( ):
2=2
32.
286

. :
3()3
2=
2=-
2=2 + 33.
.

.
, . , , .
8.2.

. , , , , , , .
:
CHCH + RXH
= O, S N.
CH2=CHRX,
..
1870 .
:
CHCH + ROH
CH2=CH-OR.
287
:
ROH + CHCH
Hg2+
CH2=CH-OR.

ROCH=CH2 + ROH
H+
(RO)2CHCH3
.
. ,
.. , .. .
,
.
, .. .
~
95%.

. -
. , :
CHCH + CH3COOH
CH2=CH-OCOCH3
C3COOH
(CH3COO)2CHCH3.
.
.
-
,
, :
HCH + Zn
2+
+ +
CHCH CH3COOH
Zn2+
OH
CH O=CCH3
Zn2+
288
O
H2=CHOCCH3 + Zn2+.
. (I)
, . ,

Cu2Cl22NH4Cl.
, - .

, ,
, , - :
CH2CH2
CHCH + CH2 C=O
NH
CH2CH2
CH2 C=O
N=2

.
.
.
-, - ,
:
(HOCH2CH2)3N + CHCH
CH2=H-OH2H2N(H2H2OH)2
(CH2=CH-OCH2CH2)2NCH2CH2OH
(CH2=CH-OCH2CH2)3N
,
, . 433-473 0,2 1,2 . . .
8.1. , -
289
(), () () .
. 8.1.
.
,
.
:
CH=CH2
CH2-CH2
8.3.
ROCH=CH2
, , ( R), , , ( 473-523 ) ,
.

(.. , .. ).

30- - ,
, . . 1966 . " ." . :
290

--
--
-2-
--
-1,4

" "(), (), "" ().

1978 . - . "" 1975-1978 .
.
,
, , --
.

:
- ;
- ;
- ;
- -;
- .
.
8.3.1.

, ,
.

,
. -
291
.
. . 393 . : N, , Li
. 453-473 .
75%.
10%: 1,2- 1,3- .

.
8.2.
. 8.2. .
453 ;
KOH - 5%.
1 -1 3(2)82;
2 -1 3(2)102;
3 -1 3(2)122;
4 -1 3(2)142;
5 -1 3(2)162.
, , , . ,
90%-
5 , ~ 3 .
,
. 2%.

9,8-19,6 .

,
. .

1-5.
, 5-15% .
292
4 , .
1-3 ,
.

.

, .
, , . .

.
, , ,
.
: , .
,
. , 25 12,5 .
. ,
12- .
, .
. . , , . , -
293
, .

400-530

.
, ,
,
.
8.3.2.
. 473-673
:
OR
CH3CH
CH2=CHOR + ROH
OR
,
543 , -
- 573 .
.
, .
, , , , , .
.
. , ,
:
2+
Hg
CH2=CH + ROH.
CH2=CH + ROH
OR
OR
.
, .
523-573 .
294

.
:
CH2=CHOCOCH3 + ROH
CH2=CHOR + CH3COOH.
,
. : ; ; , .
-. -2- . 2,2 -2 , :
ClCH2CH2OCH2CH2Cl
NaOH
CH2=CHOCH2CH2Cl + NaCl + H2O.
.
.

.
,
. : , , .
, .
8.4. .
RCOOCH=CH2
~ 1,5 ~ 423-523 .
- , (R = C5-C12) (R>C12) . .

295
, - , , .
( ) , . 1909 .,
1912 . . .
- . . - 373,2 , . .- 345,7 , nd20
1,3953, d420 0,9342. ,
293 2,0-2,4% (.). , , .
, , : , , , , , .
. .
, ,
2-. , .
8.1 .
, , .

. 1967 . .
1981 . 66%
, 33% - 1% - . . , , -
.
296
8.1

--

: .
. 1920 .
, , .

:
CHCH + CH3COOH
CH2=CHOCOCH3.
, -
, .
,
:
CH3CH(OCOCH3)2
CH2=CHOCOCH3 + CH3COOH.
297

- .
.

1928 .

,
. .
, , . .
60% , ;
- 0,5-1,8%. :
-
CHCH + H2O
CH3CHO;
-
CH2=CHOCOCH3
CH3CHO + CH2=C=O;

:
CH2=C=O + CH3COOH
(CH3CO)2O
-
H2=CHOCOCH3 + H2O
CH3CHO + CH3COOH.
, , :
2CH3COOH
CH3COCH3 + CO2 + H2O .
298
,
:
2CH3CHO
CH3CHOHCH2CHO
CH3CH=CHCHO + H2O.

:
CH2=CHOCOCH3 + CH3COOH
CH3CH(OCOCH3)2.

:
HCCH + 2CH3COOH
CH3CH(OCOCH3)2,
2
HCCH + (CH3CO)2
CH3CH(OCOCH3)2.
, ,
:
Zn(OCOCH3)2
ZnO + CH3COCH3 + CO2
:
(CH3CO)2O
CH3COCH3 + CO2

1934 . ().
:
CH3CHO + (CH3CO)2O
CH3CH(OCOCH3)2
CH3CH(OCOCH3)2
CH3COOH + CH2=CHOCOCH3
75%
CH3CHO + (CH3CO)2O
25%
299

0,4% . - . 383-390 5060%- . , 60 ,
413 - 363-383 . . 8.3.
1. ,
2, , .
. , 1 4,
,
, 5.
. 8.3.
()
1 ; 2 ; 3, 8-11 ; 4
; 5 ; 6
; 7 - .
: I ; II- ; III ; IV
; V
300
5, , 4
1. 5
6, .
. 6 7, .
5 ,
- 6 .

.

: .
.. .. . , - , . 1966 . "".
353-403 1,07,0 . :
CH2=CH2 + CH3COOH + PdCl2
CH2=CHOCOCH3 + 2HCl + Pd.

+2
-,
, , . +2
:
Pd + 2CuCl2
PdCl2 + 2CuCl
2CuCl + 2HCl + 0,5O2
2CuCl2 + H2O.
, , , ,
301
. ,
:
PdCl42- + C2H4
(C2H4)PdCl3- + Cl-
(C2H4)PdCl3- + NaOAc
(C2H4)PdIICl2OAc- + NaCl,
(C2H4)PdIICl2OAcCl2PdIIICH2CHOAc
Cl2PdIIICH2CHOAc,
C2=-c + Pd + Cl- + HCl

Cl2PdCH2CHOAc
H+
CH3CH(OAc)2 + Pd + 2Cl-,
OAc
Ac .
, , ; ,
- , , - . , 20-50%,
- ,
.

- . . 8.4.
. 8.4. ()
302
1 ; 2 ; 3 ; 4 ; 5 ; 6 2; 7 ; 8
; 9 -
; 10 ; 11 ; 12 ; 13 ; 14 .
: I ; II ; III ;
IV ; V ; VI 2; VII ;
VIII ; IX ; X ; XI
,
1. ,
. 50-200 / .
, , ,
, ,
.
, . 100%.
. ,
. , .
0,1-10% (.).

1,0 20%. ,
, . 373-523 0,5-1,0
. 2-10%, 10-30% - 50-80%. 50 500 /
(.).
, . , , , , .
303
" "
" ". ,
" ", . 8.5.
. 8.5. ()
1 ; 2 ; 3 ; 4 ; 5, 6 ; 7 ;
8 CO2; 9
; 10 ; 11 (
) ; 12 ; 13 ; 14
: I ; II ; III ; IV ; V
; VI ; VII ; VIII ; IX
; X ; XI ; XII
3,
. .
423-473 0,5-1,0 .
6, . , , ,
5, , ,
. , , , . ,
,
.
304

.

1-.

:
33
2+
3
- 2
(3)2
(3)2
3 (3)2
2=3
2()

.
, .
3I
23 + 33,
3I
(C3)2+ C 33.
,
, , , .
.

.

:
3I
3
+
(3)2.
3
305
//
3I
23
+ 2 + 2 3(3)2 + 3.
3

:
||
//
3
3
/
2
+ 2 3
+ 3.
/
\
3
3
\\
||
.
:
(3)2 + 2 3 + 3.

:
3 + (3)2 3(3)2.
, .
. .
VIII ,
.
373-473 2,0-8,0 . PdCI2 83,5%.

CH3I.
" " (). (1,1-, ) 3(3)2
3()2.
306

. :
,
.
..
442
291,9
340
347
673
d420, /c3..
1,074
nD20
1,3985
1858 . ~ 453 :
3
3
+ H3CHO
CH3
3
3
, ZnCl2. , :

OC3
H3C O
O CH3 + 3(CH3CO)2O
3CH3CH
OC3
3
" " , 0,1% ZnCl2. 373 .
88,3%, 7,4%. , (3,6%),
(0,3%), (0,18%). .
. 1912
. .
(2-5%). .
" "() -
307
, HgO CH(SO3)3.
Zn(CH3CO2)2, , 2r27, , , .
2r27, , ~2%
.
" ".
Zn-Co-Hg- . , 3:1. :
OCOCH3
CH2=CH-OCOCH3 + CH3COOH
CH3CH
OCOCH3
" .
, " ().

,
3:
CH2-CH3
O2, MoO3, (CH3CO)2O
OCOCH3
OH
OCOCH3
OCOCH3
+ CH3
OC3
CH2=C=O +
50:1 1:10 ( 10:1 2:1), 510-4 110-2 ( 110-3).

423-523 . 2:N2
10:1 1:20. 2S28,
308
Na2S2O8 2S5; 10-3
0,1 1 .
- 8.2.
8.2
H2SO4
,
. 773-1273 ( 898 )

.
. 443 10,7 .
.
:
CH3CH(OCOCH3)2
CH2=CH-OCOCH3 + CH3COOH
3 + (3)2
, . .
309
, , .
,
. 1540% . , -
15-25% ,
, , .
. , .
"". "" . ,
,
. .
( 8.3).
, , .
313-393 .
.
H2SO4, BF3, .
, - .
8.3
CH3CHO
CH3CO
CH3OCOCH3
CH3CO
CH3CH
OCOCH3
OCOCH3
CH3OH
CH2=CH
OCOCH3
CH3COOH
373473 1,34 . , , , ,
310
, . , , .
.
1980 . "" , ,

, .
- ( 8.4.)
8.4
+ 2
+ 2
, ,
,
. . -
.
,
.
" ". " "()

PdCl2 I II . 313-373 .

.
dCl2 . -
311
, ,
.
I ~ 66%
- , 33% - 1% - . .
8.5.
CHCH2CHCH2
O CHRO
x
CH2CH
OH
y
CH2CH
OCOCH3 z
R = H, Alk, , , .

( ) .
. .
1927 ., 1932 .
, , , .

CHCH2CHCH2
x
O CH2 O

363-368
- . 68-72%.
, , , - . , ,
.
312
, 6578%
CHCH2CHCH2
O-CH-O
CH2CH2CH3
n
32-19% 3% . ,
, .
, ( ), , , . .
, . , ,
.
, , . .
,
, , .
,
.
313

,
().
:
(RO)n, R=, Alk;
[(2))]n;

[(CH2)xO]m[(CH2)yO]n;

[(CH2)xO]m[CHRO]n

[(CH2)xO]m[CH2CHX]n,
= - .

:
(CH2)x
OCH2CH
(CH2)x
CH
(CH2)y
CH2CH
CHO
-
(r)n
(Arr')n, r r' :
Rx
Rx
X
Rx
(R = , Alk, Alkenyl, Hal, 65; - ).
314
203 273 313 453 . ,
. ,
(. . 451-453 ).

339 .

308 ( ) 403 ( ). (. 9.1).
9.1

.
.
. .,
393-403
356
565
478
540
463-468
543-546
458-461
O
n
CH3
O
CH3
Cl
O
Cl
Cl
O
n
Cl
Cl
Cl
O
Cl
315
433
623
478
428
521
423
453
523
CO
n
O
SO2
CO
C(CH3)2
CO
n
C(CH3)2
O
NO2
C(CH3)2
O
N=N
. , , , .

, -, - , , , , , , , 1,4-,
-1,2,5,6-,
-1,2.
316
9.1.
2= ,
. (, )
[2]n - 1000, .
. 448-453 , . . 213 . .
, , -, - ,
,
, , .
,
. ,
, , , .
.
9.1.1

- :
CH2O + H2O = 147,4 /.
CH3OH + 0,5O2
, , .
90-
XIX . . 20- - , , .

:
CH3OH
CH2O + H2
= -93,4 /,
CH3OH + 1,5O2
CO2 + 2H2O
= 575,1 /,
CH2O + 0,5O2
HCOOH +0,5O2
HCOOH
CO2 + H2O
= 270,4 /,
= 14,5 / ,
317
HCOOH
CO + H2O
= -53,7 /,
CH3OH + HCOOH
= 122,0 /,
2CH2O + H2O
H2 + 0,5O2
2CH3OH + CH2O
H2O
CH2(OCH3)2 + H2O
= 241,8 /,
= 131,0 /,
HCOOCH3
= 132,6 /,
2CH2O
HCOOH + (n-1)CH2O
HCOO(CH2O)nCH2OH ,
CO2
= 283,0 /,
CO + 0,5O2
= 172,5/,
2CO
CO2 + C
, . ,
-
, , .

~60%, - 10%.
.
, .. .
,
, , . ,
, (). ,
0,01 1 .
, .
, . 0,10-0,12 3 2/2 Ag, ..
,
(Ag2O). 0,22-0,26 3 2/2 Ag , (Ags Ags2O2).

.
:
O
O
O O
OOO
s
s
s
s
s
Ag Ag ; Ag ; Ag Ag ;
Ags
Ags
318

. ,
- ( 2-), , 2- ( 22-).
-. 2- .
,
, - . , .. , 2- -,
, . , - .

, , , , . -, - , 653-903 : 3, -, 2.
:
s
O2()
2O
CH3OH
[]
(CH3O) + (HO)
(CH3OH).
(CH2O) + O2
(HCO) + (HO2)
[]
(CH2)O
(H) + O2
(HCO) + O2
(CH3) + (HO2)
(HCO) + (H)
CO + H2
(HO2)
(HO2) + CO ..
319
, , .
, () .
,
.
, , , .. .
573 . 3,6 4,6% (.), . 9.1.
. 9.1.

- , 0,51,0 )
643-673
. .
, .
(1)
(2) 573-1073 , .
(2) 5-20
(1), . 9.2.
. 9.2.
(1) (2) .
320
, (1)
, . , , . , , 60%, - 40%.
- 413-433
, 923-1023 .
, , :. , . . 9.3. , (1) .
. 9.3.
- 20% , - 2500 /2 ; - 90%-
.
1 ; 2 -
; 3 - ; 4-7 H2, CO, CO2 O2
.
(2) 673 973 , . () (4-6) .

, ,
. , .. -
321
. ,
. .

1 0,5 .
- 2:3, 0,5,
. 2:3 0,3-0,33.
,
, : . , 85-90%.
: , , 97-98%. , : , (5-3) : 1. : 0,35-0,42. , , .
0,7-1,5 /, 2433 -1. (0,2 -1) ,
, .

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

- . , .

, :
322
- 6231173 ;
- , (
, , );
- - , ( ).
,
,
. ( %): SiO2 6770, Al2O3 14,0-17,0, F23 0,9-1,6, TiO2 0,13-0,24, n 0,06-0,09, MgO
0,08, 1,6-2,5, Na2O 3,0-4,1, K2O 3,0-3,9.
, , ~ 40%.

.
.
, , , .

: , , , ,
.. 2-3 18-24 . - , , , .
, (
): , .
, ,
.
. -.
, "" , .. , - .
, , .
323
. 9.4 .
. 9.4.
1 - ; 2 - ; 3
- ; 4 - ; 5 - ; 6 - ; 7
- .
: I - ; II - ; III ; IV -
, 2025% , nocya 1,
.
383 2 3.
523-573 , "" (873-973 ) . 5, . 6, . , , . , - , 15-20% , - . . 77
97%.
,
.
.
9.1.2.

(III) (VI) 1,7 2,5. , ,
.
324
(VI) . - :
CH2O + H2O + Mo2O5,
CH3OH + 2MoO3
Mo2O5 + 0,5O2
2MoO3
CH3OH + 0,5O2
CH2O + H2O
= 147/.
523-673
98-99%.
. 9.2
. ,
. .
"".
9.2

8-11%
0,6-1%
0,02% -

,
. , -
325
.

873 . 673 . ,
.
,
.
.
. . , - , ,
, , . . :
NO + O2
NO2 +
O + CH4
CH3 + O2
O
()
CH3 + OH
CH3OO
k1
CH3OO
k2
CH3OO + NO
CH3OO + CH4
OH + CH2O
CH2O + OH
CH2O + OH
CH3O + NO2
CH3OH + CH3O
H2O + HCO
CO + HO2
HCO + O2
CH3 + HO2
CO2 + OH
CH3O +
HO2 + CH2O
CH3O + CH4
CO + H2O + OH
CH3OH + CH3
()
326
()
CO + 2OH
CH2O + O2
CH3OO
HO2
OH
HCO + HO2
k3
k4
()
CH3O + NO
[CH3NO2]
() 117, ()
30113 .
.
, , ,
773-973 . , , .
, 20% 30-40%.

.
. 1:3,7. 673
, 0,08%
. ,
. 873
.
473
, , .
.
, 34% 3% .
( ) ~ 3-5% 10%. 97% .
2-4
, .
" " ().
327
9.2.
[22]n, - , , , , .
,
, , ,
.
, ,
, .
, , , .

. .

.
.
, ,
, , , .
9.2.1.

. .
-:
RCH(OH)CH2Cl + l.
RCH=CH2 + l2 + 2O
1,3- , ,
.
,
.
:
Cl-
Cl2
RH=CH2
RCH=CH2
Cl-Cl
RCH(Cl)CH2Cl
[RCHCH2Cl]
H2O
RCH(Cl)CH2CI
328
+
[RCHCH2Cl] + [RCH(OH)CH2CI]
RCH(CH2Cl)OCH(CH2Cl)R.

1,2- -
-1,2:
RCH(OH)CH2Cl + OH-
RCHCH2 + Cl- + H2O

O
RCH(OH)CH2OH + Cl-

.
():
CH2=CH2 + Cl2 + H2O
ClCH2CH2OH + HCl .
- ,
c ()2, :
2ClCH2CH2OH + Ca(OH)2
2H2C
CH2 + CaCl2 + H2O
318 . 10%- . 5%,

. , 10-20% , .
, , ,
.
, , 1012%- ,
369-375 . , , 313323 .
,
.
()2,
,

329
.

.

.
9.2.2.
1931 .
.
: ,
, , 99,5%- .
1937 . "
".
CH2=CH2 + 0,5O2
H2C
O
:
CH2=CH2 + 3O2
H2C
CH2
CH2=CH2 + 0,5O2
CH2=CH2 + O2
CH2
2CO2 + 2H2O,
CH3CHO,
CH3CHO,
2CH2O.
473-573 .
, ,
. , .
.
1,0-2,3 .
. -123 3-8 . ,
, , , , . -
330
, 523-673 ,
, . : , s,
Rb.
,
.
, , 4%
7% . [10-20 .(%)] ,
7:1.
,
0,001% ,
.

, , .
.
+
+
2
, % (.)
5-40
4-11
15-85
3-8
3-15
, % (.)
20-35
5-9
40-70
7-15
5-10

. 9.5.
. 9.5.
""
1 - ; 2 - ; 3 - 2; 4 - 2;
5 - ; 6 - ; 7 ; 8 - .
: I- ; II 2; III ; IV 2; V- ;
VI-
331
9.3.
(; 1,2-)
H2CCH-CH3
O
- . . 161 , . . 307,3 , : 283 40,8% (.) .
1--2 :
ClCH2CH(OH)CH3
H2CCH-CH3
O
- , ,
, , , , -
.
c , , -
(, ):
[OCH2CH]n[OCH2CH]n
CH2OCH2CH=CH2
CH3
(, .), , , .
: , -1,2
, , ,
. , (,
).
9.1.
, 2 , , .
332
9.1

(, n,
,
)
(, )
333
9.3.1.

, , , 25% (
40%).

673 2,0 , , .
, , .
2, , .
. 1 ~12
, .
:
2/

,
/
3,11
4,17
10,20
0,3
-
,
/
0,77
0,66
2,43
0,10
12,00
, , .

~ 433 5,0-6,0 . , "", , " " ()
.
"" 40%.
~11%, 30-40% .
334

, - , , , , - , .

, , , , , , , , . 50-70%. , 87%, 433 . .

,
(, , ) in situ
, .
. ( ), (, , ) 288-353 .
22 .
. 22.
" ".
"" "" ()
, 22 .
. .
,
, .
(ROOH)
(RCOOOH).
, -
335
, ,
:
3-2 + ROH,
3=2 + ROOH
3=2 + RCOOOH
3-2 + ROH
,
, , -
- , .
. , , ,

.
: , , , , , , . ,
. "" () ~ 120000 /.
. 9.6 .
. 9.6.
( "")
1 - ; 2 - ; 3 - ; 4 ; 5 ; 6 -
336
; 7 ; 8
; 9 ; 10
.
: I ; II ; III - ;
IV (2, 4, 24, 2, 36); V - ; VI +; VII ; VIII ; IX
+ ; X ; XI ; XII ; XIII ; XIV ; XV
.

.
, -:
CH3
CH3
CH3
2CH3CH + 1,5O2
CH3COOH + CH3COH
CH3
CH3
CH3
-

383-403 , 3-3,5 , ~ 7
~ 35%. ~ 95%.

:
CH3
CH3
CH3COOH + CH3CH=CH2
CH3HCCH2 + CH3COH
O
CH3
CH3
353-383 , 3-4
::, 1:1:3. 2,5 .
90-95%, - 15%. 85% 95%.

-, .. 2,51 - 1 . ~ 3 - 1 ,
- .
337
23 .
. 9.3 ( ), .
9.3
,
(
-
" " ()
.
9.3.2.

, , .. . ,

()2 HCl 12.
:
Cl2 + H2O
HOCl + HCl
ClCH2CH(OH)CH3
2CH2=CHCH3 + 2HOCl
CH3(OH)CHClCH3
ClCH2CH(OH)CH3 + 0,5Ca(OH)2
H2CCH-CH3 + 0,5CaCl2 + H2O.
O
338

:
ClCH2CH(OCl)CH3,
ClCH2CH(OH)CH3 + 0,5Cl2
ClCH2CH(OCl)CH3 + CH2=CHCH3
CH2=CHCH3 + Cl2
ClCH2CH(CH3)OCH(CH3)CH2Cl,
ClCH2CH(Cl)CH3
, 323-333 .
. ( 10 ), .
9.4.
-
(OC6H4-xRx)n,
R = Alk, Hal, C6H5, All (=02).
-2,6--- (), . , ,
- , , , , .

( 2 6) :
Rx
OH + n/2 2
Rx
O
H + 2,
n
nX
Rx
OH
- , Hal.
Rx
O
H
n
339
9.5.

CH2=CHCH2OCH2CH2
\/

:
[OCH2CH]n[OCH2CH]m
CH2OCH2CH=CH2
CH3
~ 2% (.). 213 423 , - , .
(, .).
, , .
- , . . 426,9 , , , .

.

, (, .),
.
:
CH2=CHCH2OH + H2CCHCH2Cl
CH2=CH-CH2OCH2CH(OH)CH2Cl.
O
1,2%
. 373 . (5:1). 1,52,5 .
:
CH2=CH-CH2OCH2CH(OH)CH2Cl + NaOH
CH2=CH-CH2OCH2HCCH2 + NaCl.
O
340

.
9.6.
:
[2(21)]n, [2(21)22O]n ,
[2(21)22O]n-2(CH2OCH2CH=CH2)O.

(, , .), , - . .
(1--2,3-; )
; . . 216 , . . 389,11 .
H2CCH-CH2Cl
\ /

, (I), (II)
CH2CHCH2
O
(I)
(II)
, ,
- , , , ,
, ..
.
RH2 + CH2CH-CH2Cl
O
HRCH2CHCH2Cl
OH
R2
HRCH2-CHCH2
O
.
HRCH2CHCH2RH
OH
..
341
CH2CH-CH2R[CH2CHCH2R]nCH2CHCH2
O
OH
O

2,2-(4-) ( ), , :
CH3
R
CH3
OCH2CHCH2O
CH3
OH
CH3
R
n
.
9.6.1.
1854 . :
373-393
CH2CHCH2 + 2HCl
OH OH OH
CH2CHCH2 + 2H2O.
Cl
OH Cl
4-5%-
()2 NaOH 373 :
353-373
CH2CHCH2 + NaOH
Cl
OH Cl
CH2CHCH2 + NaCl + H2O.

Cl
O
. . 99,5%
.
342
9.6.2.

:
CH2CHCH2 30%
Cl
OH Cl
Ca(OH)2
2CH2=CH-CH2Cl
2HOCl
292-313K, pH 3-5
CH2CHCH2 70%
Cl
Cl
OH
CaCl2, H2O
2H2CCHCH2Cl
O

. 9.7.
. 9.7.
1 ; 2 ; 3 ; 4 ; 5, 7
; 6 .
: I ; II ; III NaOH; IV ; V -
VIII ; IX ; VI ; VII Ca(OH)2;
; X ;
XI
2 . [
0,36% (.) ], , .
.
1
343
1-2%-
. ,

:
Cl2 + H2O
HOCl + HCl.
, , . 3, . 4 15%- Ca(OH)2 5, , . 6
, 7. 90%.
9.7.
. 1965 .
- ,
SO2. , .
(, S)
CH 3
SO 2
CH 3
4,4:
CH 3
nNaO
ONa
SO2
+ n Cl
Cl
CH 3
CH3
SO2
C
CH3
O
n
344
(, )
SO2
O
n

4,4-.
()
SO2
O
n
4,4 4,4- .
. ,
, ,
, .
673 , .. 40-60
.
, - 373 473 ,
.
RRSO2, R R= Alk,
Alkenyl, Alkinyl, Ar. , , .
. H2O2, KMnO4, Na2Cr2O7 .:
[O]
[O]
RSR
RSO2R
RSOR
:
RS(O)OH + ROH
RSO2R
RS(O)ONa + RX, X Hal,
:
RSO2CH2-CH=CHR
RS(O)OCH2-CH=CHR
RSO2CHR-CH=CH2
345

:
RSO2Cl + RCH=CH2
CaCl2
RCH(Cl)CH2SO2R
SO2 :
R
RCH=CH-CH=CHR + SO2
SO2
,
.

,
S
O
, , .
346

10

, ():
[(O)-CR-C(O)O-R'-O]n [R-C(O) O]n
R R' .

. , . , , , .
.
, -1,4 , , 1,4 (2-6102). -1,4
.
, , ,
. , : , , , .
293
65%- 0,3-0,4%, -
347
100%, 80-90%, 80-150 ,
5-10%. . . 533 , - 213 443 .
, , -2,6-
(2,6-). , , , . , ..
-2,6-
, . -2,6- . 2,6-
,
, ,
, .
10.1.
()
-:
Co, Mn, O2
CH3
COOCH3
COOH
CH3
CH3OH
CH3
COOCH3
COOH
CH3OH
Co, Mn, O2
CH3
COOCH3
COOCH3

( )
348
, . , - - (. 10.1).
,
, .
() ,
, . .
""- -
:
64 + 2 22
226422 + 22.

.
10.1
II
II
II
II
III
III
III
II
-
-
II
III
III
. I - ; II - ; III - -
349
1963 .
, .
( "")
:
- - -
- ;
-
- ( ).
"" ,
( "-I").
" " ,
( "-II").
, . ,
.
-- (),
. .

.
"" (), , .
, .
70- "", " " "" . ,
. , , .
10.1.1. ""
.
- 438 1,0 :
CH3
COOH
+ 42 + 4N
+ 4N3
CH3
COOH
= 750 /.
350

.
423 . 90%.
,
.
-
.
10.1.2. ""
.
- - :
64(3)2 + 1,52
364 + 2 = -690 /.
413-443 0,4-0,7 .
- :
364 + 3
3643 + 2
= -30 /.
473-523 .
n- :
3643 + 1,52
643 + 2 = -675 /
:
(3)264 + 2 = -30 /.
643 + 3
- ,
- , . : .
.
, - --.
. 413-443
0,4-0,7 .
351
.
. 473-523 .
, -, , .
- . , ,
,
40-50 . .
- ~ 87%.
10.1.3. "Aoo"
-
" " 1958 . .
.
"Aoo" -
448-503 1,5-3,0 ( ) (,
, ):
COOH
CH3
+ 22
+ 32
CH3
= -1360 /
COOH
, . - .

, -. :
.
-
:
-
-
-
-
.
352
- , , - , .
:
Co(CH3COO)2 + NaBr
Co
OOCCH3
Br
+ CH3COONa.
- -
H3C
CH3
+ O=O
2 H3C
CH3
+ O=O
t0
H3 C
t0
2 H3 C
CH2 +
HO2,
CH2 +
H2O2
:
H3C
CH3
+ Co3+
H3 C
CH2
+ Co2+ + H.
-, ,
:
H3 C
CH2
+ O=O
H3C
CH2OO
- .
2
HOO + H2O
H2O2 + HO,
:
H2O2 + Co2+
HO + HO- + Co3+
353

:
H3C
CH3 +
HO
H3C
CH3 +
H2O2 +
H3 C
-2
CH2
H3C
CH3
-22 2 H3C
CH2
-
H3C
CH2OO
H3C
CHO
+ OH

:
H3C
H3C
CH2OO
CH2OOH
H3C
CH3
H3 C
CH2
.
, :
Co3+ + Br -
Co2+ + Br ,
Br + ArH
HBr + Ar ,
HBr + Co(3)2
Co3Br + H3.

H3C
2+
CH2OO + Co LBr
H+
H3C
CH2OOH
+ Co3+
354
H3C
+ Co2+
CH2OOH
H3C
CH2O
H3C
CH2O
+ Co2+ + OH-,
+ HCHO
H3C

3642, , - :
CH2 + ArH
H3C
H3C
+ Ar ,
CH2OH
-
H3C
CHOH +
H3C
CH2OH + O2
HOO
:
H3C
CH2OH + CH3COOH
CH2OCOCH3 + H2O .
H3C
- ,
:
H3C
CHO
+ Co3+
H3C
C=O +
Co2+ + H+,
, , ,
:
H3C
C=O
+ O2
H3C
COO
O
355
, , :
H3C
COO
+ ArH
H3C
COOH
+ Ar .
:
H3C
COOH
+ Co2+
H3C
COO
+ Co3+ + HO-,
H3C
+ CO2.
H3C
COO
,
. , , , - :
H3C
COOH
H3C
CHO
H3C
COOH
-
- :
HOOC
HOOC
2+
CH3 + Co +Br
CH2
+ O2
HOOC
HOOC
CH2
CH2OO
+ Co2+ + HBr,
356
CH2OO
HOOC
CH2OO +
HOOC
CHO + HO ,
HOOC
H3C
CH3
CHO + H3C
HOOC
CH2
+ H2O .

.
- :
HOOC
CH2OO
CH2OOH
HOOC
+ Co2+
+ Co2+
CH2O
HOOC
HOOC
HOOC
HOOC
+ H
CHO +
HOOC
CH2OOH
HOOC
CH2OH
+ O2
HOOC
HOOC
+ Co3+-
+ Co3+ + OH,
+ HCHO,
HOOC
+ ArH
+ Co3+
CH2O
HOOC
CH2O
CHO
HO + Co3+
HOOC
CH2OH
CHOH
CO
+ Ar ,
+ HO2,
+ Co2+ + H+ ,
357
CO
HOOC
+ ArH
COOO
HOOC
COOO
HOOC
+ O2
COOOH
HOOC
+ Ar .

COOOH
HOOC
2+
+ Co +Br
HO
+ Co3++Br + OH
- :
HOOC
COOOH
CHO
HOOC
HOOC
COOH
, , , :
HOOC
COO
H+
HOOC
COOH
:
HOOC
COO
HOOC
+ CO2 .
- - .
3+
ArH + Co3+
.
Ar + Co2+ + H+
358
k, /
, /
45,48
62,10
-
-
15,67
6,58
68,00
69,14
2,321
73,74

(ArH)
-
, - , 3+ 2+,
:
H2 O
OH
(RCO)2Co2+
H2 O
Co3+(OCR)3Co2+
OH
, .
, (3+) .
- , .
,
3.
3+ .

-
-
453 2,0 , :
CH3
CH3
n-
CH3
CHO
CH3
COOH
CHO
COOH
COOH
COOH
359
n--
()
:
..
.CO2
...CO
- .
..CH3C6H5CH2OOH
- ..
CH3C6H5OH

..HCHO
...
.

C1-C3 ..
-

:
CH3
CH3
CH=CH
4--4-
CH3
4--4-
CH3
CH3
CH2CH2
CH3
CH2CH2
CH=CH
C24H24 C24H26
CHO
CHO
360

, .
.
" " ""
, .
-
. 10.1.
1, -
, - , -
. 473 1,5-3,0 .
40-60 .
- ~ 1260
/.
. 5
-8%
. 10.1. - ""
1 - ; 2 - - ; 3 - ; 4 - ; 5 ; 6 - ; 7 - .
: I - ; II - ; III - ; IV - ; V - ; VI - .
.
90% (.), 99,5%.
500-550 , . - - , .
361
-: "", "", " ", "", " ", " ".
, "-".
10.1.4.
70- - (, . ) , - . - 0,03% (.), - 0,005% (.) 10 .
-
, .
10.1.5.

- 100 .
50- , ,

- .
,
- (1) (2):
2652
-, -64(2)2
66 + -64(2)2 ,
-64(2)2 .
(1)
(2)
,
.
362

:
A(CO2M)2
A(CO2M)2xx
-CO2, -CO, -AH
-CO2, -CO, -H2
- ,2 ,
, , .
. . 10.2

, -2- -2- .
. 10.2. (), 2- () -2- ()

1 - ; 2 - -2- ; 3 - -2 ; 4 - ; 5 - ; 6 - ; 7 - - ; 8 - ; 9 - -2,5-; 10 - -2,6; 11 2; 12 -; 13 - ( % (.))
6-8 /, - .
, : - , -
.
.
363
, .
, (. 10.1).
10.1
()
() ()
-1,8- (1,8-)
()
,
/
736
374,2
5,39
676
651
568
343,4
236,7
207,0
5,14
4,34
3,89
1,8-
723
711
691
593
R
, .
. .
-1,4-, -2,6- -2,5-. ;
, , , , , , ,
, .
: > > > .
, ,
: , , , ,
( ).
-
-. , ,
364
.
, - -
( ).

: ,
-, - , .
.

"" "".
:
C6H5CH3 + 1,5O2
C6H5COOH + H2O ,
()
C6H5COOH + KOH
C6H5COOK + H2O ,
()
2C6H5COOK
C6H4(COOK)2 + H2SO4
C6H4(COOK)2 + C6H6 , ()
C6H4(COOH)2 + K2SO4 .
()

"" . 10.3.

. , , , . 673-703
2 1,5-3
. . .
. 10.3. "
" ( "-II")
1 - ; 2 - ; 3 - ; 4 ; 5 - ; 6-9
.
365
: I - ; II - ; III - ; IV ; V - KOH; VI - ; VII - 2; VIII - ; IX ; X - ; XI - H2SO4; XII - ;
XIII - ; XIV -
, - , ,
, .
, .
10.4.
, , . .
.
698-743 , 2 1,0 , 8-25 ,
3 5%
81-92%,
85-90% (.) .
. 10.4.

1 - ; 1 - ; 2 - ; 3 -
; 4 - ; 5 - ;
6 - ; 7 - ;
8 - ; 9 - ; 10 - ;
11 - ; 12 - ;
13 - .
: I - ; II - ; III - ; IV
- ; V - ; VI - ; VII - ; VIII - ; IX -
; X - , ; XI - 2
366

-
.
- . "" "", -,
.
- ,
. 673
2 2,0 . :
COOK
KOOC
COOK
COOH
COOH
COOK
COOK +
KOOC
COOK
COOK
COOK
COOK
COOH
COOH
COOH
COOH
+
COOH
COOK
COOK
COOH

90%. .
10.1.6 ""
- ( )
. :
653 +
364
= 15 /,
367
273 1,5 1 F3 5
F 1 . (248 ) -F4.
BF3. 273 - -F4.
F3 . - .
~ 90% - 98% 2%. - .
- F4
403-453 . F3, 2 ; - - .
- ,
, .
364 + 22
64 + 2.
473 2 .
10.1.7.
:2, 0,8, , . , , - .
, " " (),
(1:3)-(3:10) 533 10 30 . 2 . 6%
(.) . 673 2
4,0 , 2,5 . - -
. 34% (.)
.

.
368
10.2.
( --1,2- )
O

O
CHC
O
, .
. 325,85 , . . 475 . , , , , .

.
. .
. , , -, , .
1970 . 90% , -
. 1980 . 81,3%. -
. .
, ,
.
, - -. . , , , .
10.2.1 .

, "" "
"(), 1957 .
.
369
:
O
CHC
O + CO2 + CO + 2H2O H298 = -1470 /
C6H6 + 4O2
CHC
O
C6H6 + 6O2
3CO2 + 3CO + 3H2O
H298 = -2320 /.
,
, .. 1,4-7,1% (.) 298 .
1,2-1,3 %, .. .

,
. .
623-723 0,1-0,2
: ,
1:30, 1,2%. " " . 10.5.
. 10.5.
" "
1 - ; 2 - ; 3 - ; 4 - ; 5 - -; 6 - ; 7 - ; 8 - ;
9 - ; 10-12 -
.
370
1 393-423
4, . - 3, 1, , 2.
- 5,
.
6.
40% (.), -.

.
95%, - 67%,
64%.
,
("", "", " ", " "
.), .
10.2.2 .
- "" 1974 . "",
"", " ", " ", "", " ",
"", " " , -.
- ( )
, , , .
, V:,
1: (1-1,2). , , ,
, .
, , , . , ,
.
, +4,1 +4,6.

, ,
, , .
371
- :
O
C4H10 + 3,5O2
CHC
CHC
O + 4H2O
H298 = -1240 /
O
:
C4H10 + 5,5O2
2CO2 + 2CO + 5H2O
H298 = -2090 /

, ,
2, 4
.
, ,

2.
.

.
10.2.3. -
50- "" () -. . 4 , ~90% -1 - -2 ~10% .
, .

O
CH3CH2-CH=CH2 + 3O2
CHC
CHC
O + 3H2O
O
H298 = -1130 /
372
:
2CO2 + 2CO + 4H2O H298 = -1980 /.
CH3CH2-CH=CH2 + 5O2

: , , , .
. 633-713 ~
50% .
"" " " , . " "
.
10.2.4 .

-
5-6% ,
. 15-20%. 10% .
10.3.
( -1,2- ) , . . 403,85 , . .
567,5 , , , ,
.
O
O
O

, , , , .
- -
373
" " .
. -, .
1960- ""
, ~
80% . . -
70-95% - .
-
.
:
O
+ 4,5O2
+ 2CO2 + 2H2O H298 = -1790 /
:
C10H8 + 12O2
10CO2 + 4H2O,
O
C10H8 + 9O2
CHC
CHC
O + 6CO2+ 3H2O.
O
-:
O
CH3
CH3
+ 3O2
+ 3H2O H298 = -1780 /.
- .
.
374
10.3.1. -

, , .
- () .

(), 77-83% (.).
( " " " ") , 10% ( ). .
623-673
: 60 120, ..
.

. , , . 99,5% , .
: , , . .
- 75-80%,
85-88%.
( "-" ,
.
613-658 . ,
.
,
. (723 )
, .. -
.
375
10.3.2. -
1960-
-
, .
85%. - , ,
.
10.3.3.
- . 90%.
- (-) . -
- 463
. - , .
:
-
CH3
CH3
COOCH3
3O2
CH3
COOH
CH3
COOH
CH3
+ CH3OH + 2H2O
COOCH3
+ CH3OH
CH3
-
+ H2O
:
- - -;
- ;
- - .
376
- - ,
:
= k1,2
- , / ); k , / ); - , /; 1,2- .
- - . 1,0 453473 .

. ,
,
. 10.6.
. 10. 6. -
: = 1:3, 473 , 1
1 - -; 2 - -; 3 - ; 4 - ; 5 - ; 6 ; 7 -
20 - .
- - 56%,
- - 25%.
98%.
- - , , , , .
373378 0,12 .
. 313 , 503 99,9%.
- -
377
. :, 1:10, 98%
100%.

- .10.7.
. 10.7. . -
1, 11 - ; 2 - ; 3 - ; 4 - 7, 9, 10 - -; 5 - ; 6 - ;
; 8 - .
: I, II - ; III - -; IV - ;
V - ; VI - ; VII - ;
VIII -
; IX - ; X - ; XI - ; XII - XIV - ; XV -; XIII,
;
XVI - - ; XVII - .
- . 10.2.
378
10.2.
-

0,95
0,92
0,80

-, /
75
75-79
90
, %
, /
750
320,5
0,85
85
10.4.
(--1,2-) (-1,2-)
H-C-COOH
H-C-COOH

HOOC-C-H
H-C-COOH

1819 . . 1919 . ( "") .

, , .
,
, .
- . .
.
378 .
.
, , , -,
.
379
10.5.

,
. . 1883 ., : , . , 10% (1-4)

.
(80-95%)
N (5-20%) ,
.
, , , , , , , ,
, , .

, . . 393 , . . 403 .
10.5.1.
- 403 F13 453
~80%:
C
C
Cl2
H C
Cl
C
Cl
Cl2
H C
H C
Cl
Cl
Cl
H
O
Cl
O
-HCl
O
O
Cl
-HCl
O
Cl
O
380
:
O
Cl
O
H2O
Cl
O
CC(Cl)=C(Cl)C
HO
OH

10.5.2.
50% l5.
, ~20% .
.
10. 6. -2,6-
-2,6-
COOH
HOOC
,
. -1,4 .
-2,6- - 2,6- .
-2,6-
2,6-:
CH3
H3C
COOH
HNO3
HOOC
2,6- .
2,6- -
381
, 523-553 ,
,
531-541 . 533-536 ,
2,6- 363-368 .
-2,6- . 1-, 2- , - , ..
, , -2,6 ,
, .

,
. , , , 1:1:0,1:2 723-733
2 1,0 .

. ,
353-363 . -2,6-
.
10.7. -2,5-
-2,5-
HOOC
COOH
.
-2,5-
,
"", 2--5 . .
-2- -
382
, 2, , , .
10.8.
(2)7
- , , . -, -, (2-)-,
- -(2-) , , .
, . , 348-393
:
3
3(2)7=(2)7

(2)7
3(2)7
3(2)7 + (2)7 .

330-370
.
1837 .
. . ,
, .
383
10.9.
10.9.1.
22
. . 470,6 . , , , , , , .
( )
.
, , . 40% .

.

:
CH2CH2 + H2O
O
HOCH2CH2OH
H238 = -75 /.
:
- ;
- ;
- .
423-473 , 1,5-2,0
:, 20:1.
,
. . 10.3 .
, . . 1 ~90%,
~ 10% 0,5%.
,
384
10.3
:

, % ( )
: ,
- -
10,5
7,9
6,66
4,2
2,64
2,10
1,40
0,61
82,3
77,5
76,5
65,7
51,6
47,2
35,0
15,7
12,7
17,5
18,5
27,0
33,0
34,5
33,0
26,0
0
0
0
2,3
10,3
13,0
19,2
19,8
0
0
0
0
0
0,3
5,7
19,0
0
0
0
0
0
0
2,1
14,5
: .
(0,6 0,01 ).
, .
.

:
HOCH2CH2Cl + NaHCO3 + H2O
HOCH2CH2OH + CO2 + H2O + NaCl.
, , :
CH2=CH2 + HClO
HOCH2CH2Cl
.

473 10 :
ClCH2-CH2Cl + Na2CO3 + H2O
HOCH2-CH2OH + 2NaCl + CO2
.
385
""
:
HCHO + CO + H2O
HOCH2COOH,

HOCH2COOH + CH3OH
HOCH2COOCH3 + H2O,
HOCH2COOCH3 + 2H2
CH2CH2OH + CH3OH.
, , .

353-373 2-5 :
H2CCH2
O
+ CO2
H2CO
H2CO
C=O
CH2OH
CH2OH
95%.
, , :
CH2=CH2 + 2HOOCCH3 + 0,5O2
CH3COOCH2CH2OOCH3
H238 = -125 /,
98%:
CH3COOCH2CH2OOCH3 + 2H2O
HOCH2CH2OH + 2CH3COOH
H238 = -17 /,
"
", "", "", "", "".
, ,
.
386
:
CH2=CH2 + H2O + 0,5O2
HOCH2CH2OH.
,
, .
" "
-
403 100 .

.
10.9.2. -1,2
-1,2
(-1,2;
1,2-)
3()2
. . 213 , . . 462 . , , , , ,
.
-1,2 , , , , , .
,
. , , .

:, ~ 15, 443-473 2 80-85% :
CH3
CH2CH + H2O
O
CH3
CH2CH
OH
OH
- . : : -
387
5 25
63 91%.

, ~473 1,5 30 .
.

423-453 1,5-1,8 .
1,5-2,0%.
, .

. , "" . 373-398 , 1,5-2,5 :, 2-2,5.

:.
.
2 353-393 , . , , , 2 .
CH3HCCH2 + H2O + CO2

O
353-393 K
CH3CH(OH)CH2OH + CO2
CH3HCCH2
O O
C=O
388
,
2 ( 0,1-0,5 1 ) ~ 423 , 3-4 , 100%, 9597%.
-1,2
"" 1,2 .

443 :
3=2
3H23
3
92%
98,5%.
363
0,5 :
3H23
3
3H2 + 23.
~ 88%.
, ( ) ;
, . . , , "", ,
,
2. 383-453 0,1-5,0 .
, .
-. -
:
n + (n+1)2 -(--)n-,
n > 1.
389
373-650 3,5-350 . . , , ,
, .
(, .) .
- (, ,
) - : , , . ,
, , , :
22
C6H12O6
2CH2(OH)CH(OH)CH2OH
3H2
3CH2(OH)CH2OH
C5H10O5 + H2
C5H10O5 + 2H2
CH2(OH)CH(OH)CH2OH + CH2(OH)CH2OH,
CH2(OH)CH(OH)CH(OH)CH2OH + CH3OH,
CH2OHCH(OH)CH2OH + H2
CH3CH(OH)CH2OH + H2O.
.
10.9.3. -1,4
-1,4 (-1,4) (2)4
. . 293,2 ,
. . 501 . , , .
(
), , , -
.
-1,4
, . -1,4.
390
-1,4
, ,
-2--1,4
.
- -1,4
( 10.2).
10.2
-2--1,4
-2--1,4
-1,4
.

, .
-2--1,4, (2--1) :
HCCH + HCHO
HCC-CH2OH,
HCCCH2OH + HCHO
HOCH2-CC-CH2OH.
-2--1,4

- .
~368 . . . -
391

. , , , .
35%- .
-2--1,4. -2-1,4
HOCH2CC-CH2OH + 2H2
HOCH2CH2CH2CH2OH
, , .
. 323-333 1,4-2,0
. , , ,
, .
393-413 14-20 . , ,
( ) 15:78:0,5.
.
-1,4
-1,4
. .
" ".
:
O
CH2=CHCH3 + CH3COOH + 0,5O2
CH2=CHCH2OC
+ H2O.
CH3
,
, ,
,
, .
1960-1970- .

392
, , , -1,4,
(). 453-473 0,7-0,8 .

, .
, ,
4000 .
4-:
O
CH2=CHCH2OC
+ CO + H2
CH3
Co2(CO)8
O
HO(CH2)4OC
CH3
398 2,0 . .
4- -1,4
:
O
HO(CH2)4OC
+ H2O
HO(CH2)4OH + CH3C.
CH3
" - ".
-- :
CH2=CH-CH2OH + CH2=C(CH3)2
CH2=CHCH2OC(CH3)3,
, -
(CH3)3C-O-CH2-CH=CH2 + CO + H2
(CH3)3CO-CH2CH2CH2CH2OH ,
393
(CH3)3CO-CH2CH2CH2CH2OH (CH3)2C=CH2 + HOCH2CH2CH2CH2OH.
- . :
2= + 2ROH
2=(R)2 + 2,
2=(R)2 + + 2 22(R)2.
-1,4.
-1,4
( " ")
-1,4 , , , , , .:
CHO
H2
-CO
HOCH2CH2CH2CH2OH
-1,4
-1,4
( "")
-1,4 :
- 1,4--2;
- 1,4--2 1,4- ;
- 1,4- -1,4.
353 3
, . . ,
394
, . ~ 2 , 1,4--2
.

: 333 383 . 1,4 94%.
1,4- 333
. -1,4 .
-1,4

( " ")
-1,4 :
- 1,4--2;
- 1,4--2;
- -1,4.
523-573 - 1,4-- 2 3,4--1:
CH2=CH-CH=CH2 + Cl2
ClCH2-CH=CH-CH2Cl +
+ CH(I)=CH-CH2-CH2Cl
H298 = -165 /.
- . : 6:1.
95% 1,4--2 ~60%.
.
, , , :
ClCH2-CH=CH-CH2Cl + 2HCOONa + 2H2O
HOCH2-CH=CH-CH2OH + 2HCOOH +2NaCl.
1,4--2,
. -
395
(383 ), . .
-1,4 373 3 , .
-1,4

( "")
-1,4 - 4- ( 1,4 ):
O
CH2=CHCH2OH + CO + H2
O
CCH2CH2CH2OH + CCHCH2OH
H 4-
H
CH3
Rh
H2, Ni
3--2
OH
CH3
HOCH2-CH2CH2-H2OH + HOCH2CHCH2OH
,
2-, - 3--2 , 2--1,3.
,
.
396
, ,
. - . .
:
[LmRh(CO)nXq]r,
L , , YRRR,
( Y , , R, R R , 6 20, , 1 12 , ,
7 24); , ; m = 0,
1, 2, 3 4; n = 0, 1, 2, 3 4; q = 0, 1 3; r = 1 2, , m, n
q .
, , , h3:Rh.
323-343 2,0-3,0 4 ~ 90%.
, . , , , , ,
.
( )

373-523 :
CH2=CHCH3 + CH3COOH + 0,5O2
Pd
O
CH2=CHCH2OCCH3 + 2,
O
H+
CH2=CHCH2OCCH3 + H2O
CH2=CHCH2OH + CH3COOH.
-1,4
, . -1,4 (
397
), .
"" () ( .. , ..
) . .. (.., .. )
-1,4 , . . 353-373 0,5-1,0 .
-1,4 - :
O
I
CH2=CHCH2OC
+ HOH
CH3
- CH3COOH
(CO, H2)
- ROAc
(H2)
II
CH2=CHCH2OH
(CO, H2)
OH
O
III(CO, H2)
IV
(CO, 2)
CH2CH2CH2CH2
OH
OH
(H2)
:
I Rh()2()2
NR ( - - 2-);
II , ;
III Rh()2()2 + 1()3;
IV - Rh13, .
398
10.9.4. 1,4-

, ,
. , .
" " 1,4 . :
COOCH3
COOCH3
+ 3H2
COOCH3
COOCH3
COOCH3
CH2OH
+ 4H2
COOCH3
+ 2CH3OH.
CH2OH
433-453 30-40 .
95%. ,

. ~ 33% - ~76% .
399
11

,
-N.
.
. , , .
.
,
, . , . , . , , . , "-6"
-2,5- .
, , , , .
,
, , , ,
, ..
.
-6,6 ( , -6,6) - .
1934 . ( ""). 1939 . - , .
, .
400
O
-4
-5
-6
-7
H2CC
|
NH
H2CCH2
HN(CH2)4CO
HN(2)5CO
H2N(CH2)6-COOH
-8
HN(CH2)7-CO
-9
-11

11-
H2N(CH2)8-COOH
H2N(CH2)10-COOH
-12
-6,6
-6,9
-6,10
HN(2)11-CO
HOOC(CH2)4-COOH
H2N(CH2)6-NH2
C(CH2)7-COOH
H2N(CH2)6-NH2
HOOC(CH2)8-COOH
H2N(CH2)6-NH2
HOOC(CH2)4-COOH
H2NH2C
-8,6
CH2NH2
11.1. ,

-- (, -6), . ,
, , , .
401
11.1.1.

( - )
___________
|
|
OC (CH2)5NH
, . . 342,2 , . . 535,5 , 343
d4 1,020. , .
. 1899 . (2)5. , . .

, . 1935 . -
- .
"", " 6", "", "", "" .
, 1943 . 3,5 . / . .
,
.
. . :
C6H6
C6H5OH
[O]
H2
C6H11OH
NH2OH
C6H10O
H2SO4
C6H10NOH
CO-(CH2)5-NH
"
". ,
402
:
[O]
C6H6
C6H5OH
[H]
NH2OH
H2SO4
C6H10O
C6H10NOH
CO-(CH2)5-NH
(~293 ) -
. .
.
.
C6H6
[H]
C6H12
[O]
H2SO4
C6H10O NH2OH C6H10NOH
CO-(CH2)5-NH
, ~ 473 2-5
, .
" "
()
293-323
0,5 :
O
+ CH3COOOH
+ CH3COOH.
403
:
O
+ CH3CHO + 1,5O2
+ CH3COH.
:
O
O
+ NH3
NH +
H2O.
573-698 20 30%.
: -
, -
:
O
NH3
NH4OH
CH2OH(CH2)4CONH2
NH +
CH2OH(CH2)4COONH4
H2O.
.
""

C6H6
[H]
C6H12 NO2 HNO3 C6H11NO
C6H10NOH
H2SO4
CO-(CH2)5-NH
404
~573 .
423-443 , , , . .
" "

C6H6
NOCl
C6H12
C6H10NOH
H2SO4
CO(CH2)5-NH

, ().

:
[H2O]
HNO3
C6H6
C6H5NO2
H2
C6H11OH
[O]
C6H5NH2
H2
C6H10NOH
NH2OH
C6H11NH2
C6H10NOH
H2SO4
CO-(CH2)5-NH
433-523 10,0-16,0 .

433 . .
405
" ".

H2
[O]
C6H5CH3
C6H5COOH
C6H11COOH
NOHSO4
CO-(CH2)5-NH
423-443
. ~
423 1,0 , .
,
.

.
.

,
.
. , :
C6H6
H2
C6H12
H238 = -207 /
.
.
,
.11.1.
. 11.1. , 2:66
1 - 2:66 = 3, = 0,1 ;
2 - 2:66 >3, = 0,1 ;
3 - 2:66 = 3, = 5 ;
4 - 2:66 > 3, = 5
406
, 473 ( ), 623 . (,
), 623-643
, ~30
.
. 11.2 .
373 80%, . 80%
,
. ,
458 0,5.
. 11.2.
, : ) 1 - 358, 2 - 370, 3 378; ) 4 438, 5 - 458
373 0,5.
1,2, . - . ~50 /.
407
. .
. , . , , . , , .
,
, , .
.

( 3 ) 423-473 .
,
.
,
. : , , , , .

( 48%), . .
393-423 , 2,0 - 6,0
0,5-2 -1.
99,9%.
, , .
,
. 27-30
653 .

, : 423-523 , 3 ,
:, 8:1, , 100%. , 0,3% ,

. , .
,
, .
408
,
, : ~30 523-653
: 0,2-0,4 -1.
, :
CH3
.11.3.
. 11.3.
1 - ; 2 - ; 3 - ; 4 - ; 5 ; 6 - ; 7 - ; 8 - ; 9 - -; 10, 12 - ; 11, 13 - ; 14 - .
: I ; II ; III ; IV ;
V ; VI ; VII -
2, , 3 5, . 6 8. 40%
- 60%. 99,9%.
8 2 - 9,
308 10,
409
. 10 12 14.
. - .
.
:
K1
OH

:
O
3(2)4OOH
OH
OOH
OH
OH
HO
O
OOH
OOH
OH
COOH
CHO
3(2)4OOH
HO(CH2)5COOH
COOH
COOH
410

. :
Co > Cr > Mn > Fe > Al > Pb.

: , , .
: 403
473 . 0,9-5 .

, ,
, . ,
"". ~423 , 1,7 1 .
15-20%
60-70%, ,
, 80-85%.

.
418-423 1-2 ; ,
. ~30 ,
- 40-60 3 1 3 .

, .
.
,
.
, :
1'
2--1
2-(1-)-1
411
, , .
, , ~338 . ,
,
. ,
.
, . . ~0,15%.
,
.
.
. : .
:
OH
OH
H2
H298 = -210 /
473
.
:
O
OH
-2

(1-10%
, ). 413 30
79% , 1%
~ 20% .
, 5% , . 458
99,5%- 97,5%.
412
.
. :
,
.
, :
OH
OH
+ 2H2
, .
, ,
.

.
: , .
.

: , , . .
-123 .
4-6 , 433-443 .

403-423 , 1,5-2,5
0,15-0,2 -1.
98-99% 100%- .

393-413 - 0,3 . ~ 0,8-1,2 / (.).
.
1940 .
: , -
.
413
.
433-523 9,5-16 :
NH2
NH2
+ 3H2
= 225 /.
, :
2C6H5NH2
2C6H11NH2
C6H11NH2
C6H5NHC6H5,
-NH3
-NH3; -H2
H2
-N3
C6H5NHC6H11
H2
C6H5NHC6H11,
C6H12,
C6H11NHC6H11.
( % (.)):
.
.
..
60-90
3-5
1-10

..
8-37
<1
.
11.4.
. 11.4.
414
1 - ; 2, 3 - ; 4 - ; 5
- ; 6, 18 - ; 7 - ; 8 - -; 9 - ; 10 - ; 11 - -; 12, 13 - ; 14 - ; 15 - ; 16 ; 17 - .
V
: I 2; II ; III ; IV ;
; VI
1, 2 3 443-473 ,
4 .
5 6 7, ,
10 438-443 . 9 -
, 473 15 .
, . 16.
,
10, , . -11 12, .
- . -
NH2
OH
H2O
+ 2NH3 + H2
NH
H = -100,8 /,
OH
+ 2H2O
+ NH3.
,
:
NH2
+ H2O -NH
3
OH
-H2

433-498 , . 75-90%.
415
( %
(.)):
15,0-15,5

3-5
1
1
.
1-4
1
0,3
4,3
65-70
. :
(C6H11NH2)2H2SO4
= 62,5 /.
2C6H11NH2 + H2SO4
. ~75% ~25% . , ,
. .
.
. :
OH
O
+ H2.
, 573
-67 /.
. 433-653
. 11.1.
513
60%, 623 .
, , , , , , .
.
, . 673-693
1,2 -1.
,
, , 673
2%
.
416
11.1
()
()
, %
, %
433
453
473
493
513
533
0,0331
0,0739
0,1544
0,3037
0,5667
1,0090
17,89
27,16
36,58
48,19
60,14
71,09
553
573
593
613
633
653
1,7240
2,8370
4,5140
6,9690
10,4700
15,3300
79,56
85,99
90,47
93,52
95,50
96,89
613-633 1,0-1,5
80-85%-
98%.
573 .
, , ,
. 523-553 0,8-1,0 -1 .

. ,

-1
+ H2 ,
.
2, 423 2-:
O
-H2
:
O
H2
OH
OH
417

.

NH2OH0,5H2SO4
1865 . . 1 .,
.
" ".
:
NaNO2 + 2NaHSO3
HON(SO3Na)2 + NaOH.
~273
.

:
2HON(SO3Na)2 + H2O
NH2OH0,5H2SO4 + 2Na2SO4 + H2SO4.
NOH
. . 361,6 .

.
, .
, .
. 1882 .
.

O
+ NH2OH0,5H2SO4
NOH 0,5H2SO4
+ H2O
=118 /
418
. :
NOH 0,5H2SO4
NOH
+ NH4OH
+ 0,5(NH4)2SO4 + 2.

.
. .
.

:
O
+
+ OH
H+
+
NOH 0,5H2SO4
OH
NH2OH0,5H2SO4
NOH 0,5H2SO4
+ H2O.
6,4
, %
65,0
88,0
84,5
87,8
88,5
348-353 .
, , . , 2-, , .
-
, ,
419
, , :
O
+ NH
SO3H
NSO3H
NOH
OSO3
N
NOH
N
N
:

.
1886 . . , .
.
, :
NOH
O
NH
= 235 /.
, . .

:
NOH
+ H2SO4
+
NOH
H
+ HSO4

, .. .
, , .
, .
420
:
NOH HSO4
H
,
. ,
: ,
.

, :
NOH HSO4
H
N HSO4
-H2O
SO3H
N
H2O
NH
+ H2SO4
. , , , -
, :
O
NH +
2NH2OHH2SO4
[H3N(CH2)5CONHOH]2SO4 .
, , :
N
-H2O
N
H
-H2
[H2SO4]
NOH
421
- : . : SO3 : ~ 1, 5%.
. 11.5.
. 11.5.
1 ; 2 ; 3, 7 ; 4, 8 ;
5
; 6 ; 9 .
: I ; II ; III ; IV ; V
; VI ; VII -
1, ( 10 ). ,
. 3.
1 4. ~ 398 .

.
- - .
"" , -
422
N-,
.
403-503 ,
.
. , N:
NOH
NCOCH3
NH
NOCOCH3
: , N 2 10% .

, 573 :
O
NOH
+ CH2=C=O
NCOCH3
.
.
(, , ),
- .

" " . , ,
423
:
CH3
O2
COOH
COOH
H2
NOHSO4
H2SO4; CO2
O
NH
,
.
CH3
CH2
+ Co2+ + H.
+ Co3+
:
CH2
O2
CO
O2
CH2OO
COOO
[Co2+]
C6H5CH3; [Co2+]
-C6H5CHO
CHO
[Co3+]
COOH
423-443 1,2 .
93-95% ~30%.
~ 2,5% : , , , , , ,
, .
:
COOH
COOH
+ 3H2
443 ~ 1
.
424
. , 99,5%
, .
:
COOH
COOSO3H
SO3
NOHSO4
-H2SO4; -CO2
OSO3
N

:
OSO3
N
H2O
-H2SO4
O
NH

873 323 . :
2NH3 + 2,5O2
2NO + 3H2O,
2NO + 0,5O2
N2O3,
N2O3 + H2SO4SO3
2NOHSO4.
:
-

COOH
H
H2SO4
-HSO4
+ OH
C
H OH
+
CO
H
+ H2SO4,
425
-
NOHSO4
+
CO
H
+
CO
NO
-H
-CO2
N+
-
HSO4
N+
OSO3H
N
H2O
-H2SO4
NH
.
30-33%.

353 . . ,
50%- ,
:
C6H11COOH : NOHSO4 = 2 : 1; SO3 : NOHSO4 = 0,8 : 1;
(NOHSO4 + SO3 + H2SO4) : NOHSO4 = 3 : 1.
, ,
.
1 - 4
1,17 ,
1,67 (75% NOHSO4), 1,5 (36% SO3) 1,05 ( ).
. , ~
60% , ,
.

. , :
RCONH2 + NaOCl
RNH2 + NaCl + CO2.
,
~ 40%- .
.
426

1950-
"" (), 1962 . . . - ,

. ,
:
h
NOCl
Cl
-HCl
NO + Cl,
NO
NO
NOH
HCl
NOH HCl
- 1--1- :
Cl
Cl
,
Cl
NOCl
NO
Cl
NOH
NOCl
+ HCl,
NO
Cl
+ HCl + 2NO.
1, .. . -,
- (400-600 ).
, .. , , , .
427
"" "" 40 , . 7000
80-83%
300-320 1 .
283-288 . ~ 85%.
: , , , .
11.1.2.
5.
- .
, :
NOH
HN(CH2)nCO
11.1.3. 7-
7- (7-)
-7.
523
nH2N(CH2)6COOH
[NH(CH2)6-CO]n + nH2O.
1,5
-7 -6 15-20%
.
.
-7 "". 1953 . .. .
.. 1945 ., , .. , ..
. .
. :
nC2H4 + CCl4
Cl(C2H4)nCCl3.
428
1020 ~373
. . :
CCl3 + RCl,
R + CCl4
CCl3 + C2H4
CH2CH2-CCl3 ,
Cl3CCH2CH2 + 2C2H4
Cl3C(CH2)4CH2CH2
Cl3C(CH2)6Cl + CCl3
Cl3C(CH2)4CH2CH2 +CCl4
1,1,1,7- , . .

363 :
Cl
O
H2SO4
Cl(CH2)nCCl + 2H2O 363-373 Cl(CH2)n C
+
Cl
OH
+ 3HCl.
, , , :
O
Cl(CH2CH2)3C
+ 2NH3
OH
H2N(CH2CH2)3C
OH
+ NH4Cl.
7-
O
CH3COOH
O
C=O
RX
RX
Cl-(CH2)5COOH
Cl-(CH2)5COOR
H2N(CH2)6COOR.
NaCN
HCl
ZnCl2
N(CH2)5COOR
H2
429
11.1.4.
-8.
, .
-
2
HOOC(CH2)6COOH

- H2 O
NH2OH
O
NOH
SO3
CH2CH2CH2C
NH
CH2CH2CH2CH2
11.1.5. 9-
9- ( )
9:
nH2N(CH2)8COOH
[HN(CH2)8CO]n + n2.
-6 -7, .
9- . 9- ""
(.) 1950- (.. .).
11.1.6. 11-
11- -11.
nH2N(CH2)10COOH
[HN(CH2)10CO]n + n2.
-11 ,
, ,
.
430
11-
, : 3-6% 16-18, 3-9% , 3-5% , 3% ,
80% . ,
.
: (12--9-) , . r 11 .
( 11.1).
11.1
NH3
11-
NH4Br
11-
, 353
: , 3:1.
431
.
. ~1
.
523 ,
873 . 673-848 10 .
CH3(CH2)5CH(OH)CH2CH=CH(CH2)7COOCH3
CH3(CH2)5CHO + CH2=CH(CH2)8COOCH3.

: , , , , , 14-18.
:
CH2=CH(CH2)8COOCH3 + H2O
CH2=CH(CH2)8COOH +

+ CH3OH.
298 .

Br, , ()
, .. .
()
. . ,
~273 . 11-
95%.
CH2=CH(CH2)8COOH + HBr
BrCH2(CH2)9COOH.

BrCH2(CH2)9COOH + 2NH3
NH2(CH2)10COOH + NH4Br
303 . , .
432
11.1.7.
- 12:
nHN(CH2)11CO
[HN(CH2)11CO]n + nH2O.
-11 -12 ,
-12 . .
:
1,5,9- , ( , ).

4 .
:
3H2=CH-CH=CH2
1,5,9-
, . 90%-
77%.

+ 3H2
(CH2)12
;
473 1,4
. 100%.
433
,
: "
" () "ATO " ().
" "
, , .
423 .
92% 7%.
. , . , , . .
~473
, . 75% 98%.
.
, , , 373 . . . ,
>7.
.
.
383
. 92%. . . , .
"ATO " .
""
, .
1,1- -
434
-
:
O
+ H2O2 + NH3
O O
N
H
773 :
O O
N
NC(CH2)10COOH.
11- ~ 60%.
: , , .
11-
, , 373
4,5 . 12- :
NC (CH2)10COOH + 2H2
H2N(CH2)11COOH.
11.1.8. -
- -4. -4
:
C=O
n(CH2)3
(CH2)3CNH
NH
O
n
-4 1951 . - .
, - . ,
.
-4 -6,
(9,5%), , 523-533
. -4 , (~4,5 /), , , .
435
-4 , , , ,
, , ..
- , ( ) .
- 1936 .
- 473-503 .
-.
503 -:
H2CCH2
O
H2CC=O
NH3
O
HO(CH2)3C
NH2
473-503
-H2O
H2CCH2
NH
H2CC=O
-
- -
. ,
: , , ,
.
- (l23) 523 . - 50%.
. 533 - 3
- 90%.
- -.
-
- ( )
. -.
- -
. - 258
436
. 313 ,
0,8-1,0 . -
,
553 8,0-9,0 -
90-95%.
-
"", " ." .

- :
O
HCC
H2CCH2
O
NH
HCC
H2CC
O
O
, :
H2, NH3
O
HCC
O
HCC
O
O
H2
H2CC
H2CC
NH3
O
O
O
H2CC
H2CC
NH
O
O
H2
H2CC
O
H2CCH2
-
NH3
H2CCH2
NH
H2CC
O
- , ,
, ,
. , , e,
, .. -
437

- .
473-548 , 7,015,0 VIII .
20,0-25,0 . - . , , 80%.
-
-
: , , -.
. - :
O
H2CC
H2CCH2
H2
NH
NH
-H2O
H2CC
H2CC=O
O

VIII (, ) 473-553
20-60 ; - 80%. 1,4- ,
. :
O
H3 C
H2CC
CHOH +
NH
H3 C
H2CC
O
H3 C
H2CCHOH
C=O +
NH
H3 C
H2CC=O
H2
-H2O
H2CCH2
NH
H2CC=O
438
- .
- . - :
H2CCH2
NC CN
H2
H2O
H2CCH2
O=C CN
NH2
H2CCH2
NC CH2NH2
H2O
H2
H2CCH2
O=C CH2NH2
NH2
H2CCH2
O=C CH2NH2
OH
H2CCH2
O=C CH2
NH
520 353-473 (, ) (Ni/, Pd/,
). N4 . 473-573
3,0-9,0 . - ~ 70%.

. - 85%.
- . - -
:
H2CCH2
H2CH2
H2CCH2 H2
-H2O
O=C CH2
O=C CN
O=C CH2NH2
OH
OH
NH
573
10 .
-.
- -
439
- 473-573 .
- ~ 80%.
11.2. ,

, .

.

,
, ,
.
.
, 2- , , .
. , -, :
H2N(CH2)nNH2 + 2HOOC(CH2)mCOOH
CO
(CH2)m
CO
CO
N(CH2)nN
CO
CH2)m;
2H2N(CH2)nNH2 + HOOC(CH2)mCOOH
NH
(CH2)n
N
C(CH2)mC
(CH2)n
N
NH
,
, -
. , . . 11.2 ,
,
, .
440
11.2

..,
- ()
439-453
(2)2 ()
563-583
(2)3 ()
553-563
(2)4 ()
573-593
(2)5 ()
563-583
(2)6 ()
613-633
(2)7 ()
593-613
(2)8 ()
623-643
, , .
.
, 1%, .
, .

,
. (-6,6), (-6,10), -6,8, -6,9.
, , , .
- .
11.2.1.
-6,6
( ):
HOOC(CH2)4COOH + H2N(CH2)6NH2
OOC(CH2)4COO-H3N+-(CH2)6-NH3+
C
O
(CH2)4
NH
(CH2)6
NH

, .
441
, , ,
.
, .

.

. ,
.
.
418-448 0,8-1 . 4-6%.
, , - 80%.
( " ") 10%,
- 95%
: , ( 9-10) : 1 1:1.

,
.
50% , . : .
.

.. 1903 . ,
, 60%- 0,2-1
. 333-353
57 . 82-86%
(.).
343-353 0,7
. , , .
.
.
293-333 0,10-0,3 , -
442
. , , .

, , -
.
- ,
:
H2C CH2
H2C CH2 + 2HCl
Cl(CH2)4Cl + H2O.
O
():
Cl(CH2)4Cl + 2NaCN
NC(CH2)4CN + 2NaCl,
.

~423 0,3 . 99,5%.
, .
85-90% .

(
""(). 363-373 , 5075%..
( "").
.

393 6,0 . , :
CH2=CHCH=CH2 + CO + CH3OH
CH3CH=CHCH2COOCH3
443
3. 458
- 3 . 75%.
H3CH=CH-CH2-OOCH3+CO+CH3OH
CH3OC(O)(CH2)4 COOCH3.
.
:
CH2=CHCH3 + O2
CH2=CHCOOH
CH2=CHCOOCH3.
PdCl2 353 . 35 45% 92% (.):
2CH2=CHCOOCH3
CH3COOCH2CH=CHCH2COOCH3.
.
11.2.2.
(-1,6)
. . 276,5 . . 568 .
. 1 . / .
: , .

:
HOC(CH2)4COH + 2NH3
NC(CH2)4CN + 4H2O.
20:1 573-623
80%. , " " "" 473-573 .
90%.
444

:
.
"" 1950 .
: , .
. 398-503 96 %:
CH2=CHCH=CH2 + Cl2
ClCH2CH=CHCH2Cl ~ 66%
- + CH2=CHCH(Cl)CH2Cl ~ 33%
~353
.
ClCH2CH=CHCH2Cl
HCN
| NCCH2CH=CHCH2N.
CH2=CHCH(Cl)CH2Cl
95%.
573 . 95-97%.
"" 1971 . .
: HCN:N2:HCl =
1:1:1:0,1
483-493 . 1
:
l CH3CH=CHCH2CN
CH2=CHCH=CH2 + HCN
1--2
HCl
CH2=CHCH2C2N
4--1

445
SnCl2 .
CH3CH=CHCH2CN
+
H2CHCH2CH2CN
CN
HCN
(C2H2)4
CN

, , , 60- "" . , -6,6 - ", "", "", - , :

2 CH2=CHCN + 2H2O + 2e

H2O
NC(CH2)4CN + 2OH-
2H+ + 0,5O2 + 2e;

2 CH2=CHCN + 2H2O
NC(CH2)4CN +0,5O2.
:
CH2CHCN
CH2=CHCN + 2e
- :
CH2CHCN + CH2=CHCN
CNCHCH2CH2CHCN.
, :
NCCH(CH2)2CHCN + 2H+
NC(CH2)4CN

. .
446

". ( ):
2CH2=CHCN + 2K(Hg)n + H2SO4
NC(CH2)4CN + nHg + K2SO4.
"". "" .
:
CH2
2CH2=CHCN
NCCCH2CH2CN

-- .

0,5% (.) :
CH2
HCN
NCCCH2CH2NC
CH2CN
NCCHCH2CH2CN
CH2CN
NCCHCH2CH2CN -HCN NCCH=CHCH2CH2CN +
+ NCCH2CH=CHCH2CN.
1,4--1 -2
83% 70%.

.
" ".
.
, , ,
( ) 303-373 . 1,4--1 -2 - 95%. .
447
11.2.3.
(-1,6;
1,6-)
H2N(CH2)6NH2 ; . . 312-315 , . . 477-478 .
.. 1896
. NaOH ( ).
-6,6 (95%)
O=C=N(CH2)6N=C=.
, .
-1,6.
11.2.

(. 11.2) , .
.
- :
NC(CH2)4CN + 4H2
H2N(CH2)6NH2 .

60-65 373-408 . 90-95%.
" "
. 348 3
. 99%.
, - :
N(CH2)4CN + 2H2
HN(CH2)4NH.
.

.
448
OH
O
O2
HNO3
HOOC(CH2)4COOH
NH3
NC(CH2)4CN
H2
ClCH2-CH=CH-CH2Cl
H2C=CHCH=CH2
Cl2
HCN
NCCH2-CH=CH-CH2CN
NCCH=CH-(CH2)2CN
CH2=CH-CHCl-CH2Cl
H2N(CH2)6NH2
CH2=CHCH3
HN3
CH2=CHCN
O
H2
(CH2)4-C=O
CH2 O
- H2
HO(CH2)6OH
N3
NOH
NOCl; h
(CH2)4-C=O
NH3
CH2 NH
11.2
H2N(CH2)5CN
H2
449
-1,6
"" -1,6. 423 3,3 . , .
-1,6, .
Ni
473 23,0 . 90% (.). 6-.

. .

"". 11.2. ,
. , , , .
""
.
15%. :
CH2=CH-CH=CH2 + HCN Ni-.

HCN
.
" ". .
, HCN
450
. , ,
.

"" 1965 .(. 11.2). , , -- . . , .
11.2.4.

, . ,
,
.
, , -,
- -- .
. - . N- ,
, .
,
, , -6 -6,6
-.
, ,
, , ,
.
:
nH2NRNH2 + nHOOCCOOH
[NHRNHCOCO]n
451
11.3

(n-)
CH2COOH
H2NCH2
. .
,
623-628
568-573
538-540
500-506
552-556
648-655
495-497
546-548
-
(CH2)2COOH
H2NCH2
-(-)
(CH2)3COOH
H2NCH2
-(-)
(CH2)4COOH
H2NCH2
-(-)
H2N(CH2)2
CH2COOH
-
H2N(CH2)2
(CH2)2COOH
-(-)
H2N(CH2)2
(CH2)3COOH
-(-)
H2N(CH2)2
(CH2)4COOH
-(-)
, , , , (. . -6,6 503533 ). ,
452
. , , .
, ,
, -6 -6,6,
, .

,
-()
(. 11.3).
11.4
(n-)
. .
,
H2N
CH2COOH
633
-
H2N
(CH2)2COOH
-(-)
H 2N
(CH2)3COOH
633
603
-(-)
H2 N
(CH2)4COOH
608
-(-)
H2N
H-(CH2)3COOH
CH3
463
---(-)
H2N
CH3
- CH2COOH
CH3
433
H-CH2COOH
CH3
563
,---(-)
H2N
---(-)
H2-CH-COOH
CH3
H2 N
588
---(-)
H2N
(H2)2-CH-COOH
CH3
---(-)
533
453
,

. -
.

,
(. 11.4). :
. -
, .
- - ,
673 . - 973
773 .
(.
11.5). , -- , -,
- .
11.5

1
H2N
COOH
. . ,

2
3
4
5
> 673
(.)
6
-
n-
COOH
H2N
> 673
(.)
454
CH2COOH
H2N
658485
783789
> 673
(.)
> 673
(.)
473477
763
(.)
573578
443448
468473
617625
573578
428433
623-633
696701
388-403
570
n-
H2N
(CH2)2COOH
-(n-)
(CH2)2COOH
H2N
-(-)-
- ,
-

- ,
-

-

H2N
(CH2)3COOH
-(n-)-
(CH2)3COOH
H2N
-(-)-
H2NCH2
COOH
n-
COOH
H2NCH2
-
H2NCH2
CH2COOH
n-
CH2COOH
H2NCH2
455
H2N(CH2)2
(CH2)2COOH
535-544
-(n-)-
- : 670 676 .
, - , .
-6, :
nH2N(CH2)6NH2 +
nHOOC
COOH
H2N(CH2)6NHCO
CO
-6
, ,
-6 -6,6. -6,6 . .
. 11.6 -6 -6,6.
11.6
-6 -6,6
. .,
. .,
20
d4 , /
-6
-6,6
643
538
453
333
1210
1140
456
, /
4,5
4,9
, %
35
57
, /

, %:
423
458
493

493 1
45
15
100
100
60

85
40
0
5-
, -6.6,
,
-6 , .
.
6,6 .
.
, 553-623 , ..
-6,6. , ,
-
. - -

(623 ).
2,4,6--- .
. 1,4 4,4- . . 573-603 .
457
11.2.5. -
8,6 (. . 11.1) .
, -6,6, -8,6 . -8,6
- .
11.2.1.
- -
-.
-
- . -
CH3
CH2Br
Br2
CH2Br
CH3
- -.
473 . :
BrCH2
CO
CH2Br
+2
NH
CO
CO
CO
N-CH2
CH2 N
CO
H 2NCH 2
CH 2NH 2
CO
458

,
" " ().
CN
CH2
CH2
+ 2NH3 + 3O2
CN
+ 6H2O ,
CH2NH2
CN
CN
+ 4H2
CH2NH2
- - . . ,
.
: -F, -Ni -Co.
-F 1:3.
11.3.
11.3.1.
1,4-
1,4-
H2NCH2
CH2NH2 +
HNCH2
nHOOC(CH2)6COOH
CH2NHCO(CH2)6CO
459
, .

:
4C2H2
2CH2=CHCH=CH2

:
[O]
HOOC(CH2)6COOH .

.
1,4-
1,4- -. , ,
-.
11.3.2.
4,4-
nH2N
NH2
CH2
HN
4,4-
+ nHOOC(CH2)10COOH
CH2
NHCO(CH2)10CO
, "" "", ,
460
. 3,6 /,
37,8% 34,5 /,
, ,
, .

,
-1,5,9:
3CH2=CHCH=CH2

,
:
O
CH3C-OOH
O
2,MgI2
. 50-70%-
N4VO3 333 - . :
O
[O]
HOOC(CH2)10COOH.
OH
4,4-
4,4-
. 4,4- 30,0 513
:
461
2 H2N
+ CH2O
H2N
CH2
H2N
CH2
NH2
NH2
11.4.

, - , (, -6 -6,6)
: , 573 . , N,N---
. . 663 . , , . . 623-673 .
.
, 2,5- (-) . . 673 .
, , . . 588 . , 4,4, 648 . . . 473 .
: , , , .
, .
11.4.1.

,
.

. -.
462
. l:
ArCCl3 + RCOOH
ArCOCl + RCOCl + HCl.

423-428 - 543-603 .

, 1901 . ,

:
ArCOOH + SO2Cl2
ArCOCl + SO3 + HCl.
, ,
- . .
- ,
. :
673 .
: --, -n,
--
-n- (. 11.7).
,
,
.
n- "" ""
-
.
, -, , . "", (- 6,6) (6,4 /) (25%),
(150 /), ,
.
558 50% , -6,6
478 .
463
11.7

.
HOOC
COOH
H2N
. . ,
NH2
603-663
()
NH2
663-743
H2N
H2N
COOH
NH2
683-753
HOOC
NH2
( )
663-773
H2N
11.4.2.
4,4-
4,4- - ,
"-" "-".
4,4-
4,4-
:
2
O2N
Cl+ Na2S
[O]
O2 N
NO2
464
[]
O2N
NO2
SO2
H 2N
NH2
SO2
"-" "-" .
573 40-50 ,
. "-" [

"-" , 4,4- .
"-" ,
.
. , , . . .
11.4.3.
2,5-(n-)-1,3,4-
- :
H2N-NH2SO3H
COCl
2O2N
O2N
CONHNHCO
NO2
1
O2 N
O
NO2
N N
3 4
H2
Ni-
1
O
H2N
N
3
POCl3
NH2
N
4
. 2,5-(n-)-1,3,4.
465
11.4.4. 5,5'-(-)-2,2'-(1,3,4-)
- ,
5,5'-(-)-2,2-(1,3,4-),
:
2
O2N
COCl
+ H2NNHCOCONHNH2
O2N
CONHNHCOCONHNHCO
3
5'
O2N
N N
2'
C C
N N
H2N
P2O5
NO2
[H]
NO2
O
1
N N
C C
NH2
N N
11.4.5. 4,4'-(-)-2,2-
- , .
:
S S
2 O2N
COCH2Br
O2N
+ H2NCCNH2
C
C C
CH S
H2N
S CH
C
NO2
N
N
CH S
C C
S CH
C
N
NH2
[H]
466
11.4.6. (-)(5,4-d)
- (-)(5,4-d)-, :
S S
2
O2N
CHO
+ H2N-C C-NH2
O2N
SS
CH=N-C-C-N=CH
NO2
O2N
H2N
S
C
C
C
S
N
4
N
NO2
S
C
C
S C N
NH2
, , ,
, , -
.
-. . 17.
11.4.7.

.
, , VIII .
473-493 15,0-20,0 :
2HOCH2CH2NH2
HN
NH
467
-(2):
HCl
HCl
HOCH2CH2-NHCH2CH2NH2
HCl HN
NH HCl
- ,
, : 4,4-, 2,6--.
4,4 .
4,4-
4,4- , 13 VIII (2,2) :
O3
COOH
COOH
,
653 2 (13,0 ) , 4,4- :
COOK
COOK
COOH
HOOC
:
HOOC
= S, SO2, , 2, .
COOH
468
n-
- ,
:
H3C
SO2Cl
AlCl3
CH3
SO2
HOOC
CH3
SO2
H3C
[O]
COOH
4,4- ,

CH2O, HCl
ClH2C
CH2Cl
H3COC
COCH3
HOH2C
CH3COCl
[O]
HOOC
CH2OH
COOH
4,4'-
4,4- ,
:
[]
2 H3C
+ CH2O
HOOC
H3C
CO
CH2
COOH
CH3
469
2,2-(-), .. .:
CF3
CF3
2 H3C
+ C=O
H3C
CF3
CH3
HNO3
CF3
1 CF
3
HOOC
COOH
CF3

2,2-(-), 20%- .
470
12

, ,
,
O
C
Z
C
O
Z .
5-, 6- 7- . 5 ,
,
3,3,4,4-,
3,3,4,4 4,4-, -
.
- , . , ,
: 43 673-773 .
, , , , ,
, , , , . , ,
.
,
, .
, .

, ,
, , , ,
.
-
471
. , :
OC
CO
nO
Ar
O + n H2NRNH2
OC
CO
OC
CONHRNH
Ar
HOOC
COOH
OC
CO
N
Ar
NR
OC
CO
n
Ar =
X
,
-H2O
,
,
( = , );
R=
(Y = O, CH2, C(CF3)2) ,
, N .

OC
CO
nO
Ar
O + n OCNRNCO
OC
CO
RNOC
COO
OC
Ar
CO
-CO2
OOC
CONR n
N,N- .
- ,
.
, .
(, , , -
472
.) , ,
. , .
433-473 , ,
(), , 4,4, , 4.4'-,
. - ( ) :
OC
CO
m
NRN
+ n H2NRNH2
OC
CO
(m>n)
~HNRNHHCOC
COCH~
NRN
COCH2
H2COC
~HCOC
COCH~
NRN
~HCOC
COCH~
, ( 673 ) . . 523-548 , 50 , .
,
, , , , , , .
12.1.
( -1,2,4,5--
)
CO
OC
O
OC
O
CO
.
. . 560 , . . 670 ; ;
, . ,
, 583-603 .
473
-
(
)

"
"
"
"
"
"
"
"
"

"
"
.
..
,....................561-562
..,
7,4 670-673
0,3 578-583
. .> 473
d420, /3 1,680
. (), 3/ 0,103
, /.1,.09
, /:
77,31
.3017
.. -913
. , / ..1028,8
.... 54,53
109,06

1,2,4,5-. 1960 .
"".
"" ().
, , ,
.
12.1.1.
1,2,4,5- -
. 9-10 .
9 ~41%, 10
- ~ 8%. 1961 .
.
474

. ()
.
.
.12.1 - .
12.1.
-
.
- - 1
100%- -
100%-

100
100
100
100
9

100
245
200
215
100
400
570
170
100
190
240
290
100
460
950
420
100
235
200
105
- 1 , 9 .
-
475
,
.
12.1.2.
. ,
:
H3C
H3C
CH3
+ 6O2
CH3
OC
CO
O
OC
+ 6H2O.
CO
683-723 ,
0,1-0,2% (.), -
6000-15000 -1.

, ,
.
.
.
, , , , , , , , .
- ,
, , .
, ,
. 12.2.

,
.

, , , , , .
, , ,
, , , .
12.2
,

" -
/
- /
703 (728 )
v = 10000 -1
,
% (.)
62,5
476
"
" "
"ep
"
= 0,1% (.)
- - / ;
- -
/
-
( , ,
)/
"
"
- /
" - "
/ ()
693
v = 16000 -1
= 0,2% (.)

653-673
-nv = 2200-3000 -1
,
= 0,165% (.)
-
673-713
(703-803 )
v = 1000-1500 -1
68,6
69
67
65-67
50-70
593 (703 )
v = 15000 -1
67,5
" - "
- / ()
703 (653 )
v = 5000 -1
32,5
" - "
/
()
713 (653 )
v = 15000 -1
67
633
= 0,50% (.)
60,5
748
51
773
v = 11 000 -1
=0,15% (.)
62
693 (713 )
v = 11000 -1
= 0,11% (.)
58,5
""
" "
" "
-
-
/
-
- ( ,
, ,
)/
- /
" -
- /
477
""
-
/
""
- - /
""
- -
""
- ( )
673 (773 )
v = 18000 -1
=0,33% (.)
723
v = 6000 -1
= 0,33% (.)
773
v = 6000 -1
=0,48% (.)
723 (788 )
69
73
62
54,5
( %(.)),
82,5%- .
, % (.)
..
2,4,5- ...
..
.
4,5- ..
2,5- + 2,4-- ...
4--2, 5- .
2,5- ...
4- .
...

.
..
.
.96,23
...0,09
...0,66
...1,25
...1,26
...0,03
...0,06
...0,02
...0,16
...0,03
...0,03
...0,03
...0,03
...0,03
, .

, ,
. .

62(3)32, 62(3)32.
478

:
[O]
-H2O
-H2O

5- , . 5 ,
:
479
,
, .
. , :
4,5-
4,5-
4,5-

+ 2
. , , , . ~ 90% (.). .
.
, , , , , .
,
,

.
"". , .
,
:
- ,
;
- ( 10%) , ;
- ;
- ;
- ,
.
480
,

.

: , . . 410 - 505 .
, , .
.
1,5 438-443 250-300.
17-20%- 468478 2-3 .
2-3 , - 1,5-2 . 80-85%.
,
.
: - 1,5 433-443 , - 17-20%-
1,96-2,94 468-478 . 8085% (.) .. , .
,
.
.
623-773 , - 0,1-0,5%,
- 6 000 18 000 -1 65-75 %.
(
) :
, %
99,7
96,0

, %
66,6
71,8
, /3(.)
82,0
84,8
90,0
81,0
72,0
74,2
78,5
83,2
81,6
78,1
73,4
481
. .
90% .
H3C
CH3
CH3COCl
AlCl3
H 3C
H3C
CH3
H3C
COCH3
:
H3C
CH3
H3C
COCH3
NaOBr
H3C
CH3
H3C
COOH

623-633 :
H3C
CH3
H3C
COOH
KMnO4
HOOC
COOH
HOOC
COOH
, ( 10 ) 498-513 :
HOOC
COOH
HOOC
COOH
OC
O
OC
CO
O
CO
12.2.
12.2.1. -2,2',3,3'-
3--1,2-
-2,2,3,3 (1).
-2,2,3,3- (2):
I
H3CO2C
H3CO2C
CO2CH3
CO2CH3
Cu
CO2CH3
CO2CH3
OHH+
482
CO2H
CO2H
HO2C
HO2C
2'
CH3COCl
2
1 1'
3'
O
3
540 .
12.2.2. -2,3,5,6-

(3) -2,3,5,6- (3). , (4):
O
C C-CO2H (CH3CO)2
HO2C
HO2C
KMnO4
CO2H
CO2H
to
O
4
5
6
3
2
3a
-2,3,5,6- 483 .
483
12.2.3.
- 2,2,6,6-
V2O5/Ag2O
-2,2,6,6- (5):
O
2'
[]
1
6
6'
4
5
.

(6).
HOC
CO2H
O3
HO2C
CO2H
HO2C
CO2H
KMnO4
(6)
(7), (5) - :
HO2C
O O O
CO2H
Cl
(CH3CO)2O
Cl
CO2H
HO2C
O=C
O
O=C
H3C
C=O
O
C=O
CH3
NO2
484
12.2.4.
-3,3,4,4-
-3,3,4,4- (10)
.
- .
3,3--4,4- (8) . (9), (10):
CH3
NH2
H3C
1)HNO2
2)Cu2(CN)2
H3
NC
CN
O
HO2C
CO2H
HO2C
CO2H
1) . H2SO4
2) KMnO4
2
1
10
3,3,4,4- -4--1,2 (11). 11 513 ,

, 533 .
1 (12) - (10).
CO2CH3
2
I
11
Cu
CO2CH3
CO2CH3
H3CO2C
H3CO2C
12
CO2CH3
O
HO2C
CO2H
HO2C
CO2H
CH3COCl
NaOH
HCl
O
O
10
485
12.3.
12.3.1.
-1,4,5,8-
(15) -1,4,5,8- ,
, 5,6-
. (13) , (14). -1,4,5,8- (15)

:
[O]
+ CH2(CN)2
6
Alk
Alk
HN
NH
13
HO2C
CO2H
7
6
HO2C
CO2H
2
5
14
15
O
[O]
15
(15)
633 .
486
12.3.2. -2,3,6,7-
1,2,3,4,5,6,7,8--2,3,6,7- (16):
O
CH2=C=CH2 + 2
O
7
16
, -2,3,6,7- (17):
O
O
O
Br2
-HBr
O
O
O
O
16
17
673
.
12.4. -

12.4.1.
-3,3,4,4-
-3,3,4,4- - 1,1-(3,4-) (18)
:
CH3
CH3
CH3CHO
CH3
H3C
CH3
H3C
18
CH3
HNO3
487
O
3
4'
HO2C
C
O
CO2H
O
HO2C 3'
CO2H
-
, 2,2-(3,4) (19)
1,1-(3,4-) (20) 20
:
CH3
CO2H
CH3CCO2H
H3C
CH3
CH3
H2SO4
CH3
CH3
H3C
19
CH2
H3C
H3C
2CH3 1) Cr2O7 2) MnO4
HO2C
CH3
HO2C
CO2H
CO2H
20
O
C
O
O
O
12.4.2. -3,4,9,10-
-3,4,9,10-
,
. (21) -3,4,9,10- . (22) .
488
O
NH4OH
HO2C
2
3
10
KOH
HO2C
H2SO4
21
22
- 633 .
12.5.
12.5.1. - -
- .
CH3
HNO3
-H2O
CH3
O2N
NO2
H2
-H2O
CH3
H2N
NH2
COCl2
-HCl
CH3
OCN
NCO
.

:
489
H2N
nH2N
NH2
+ nHOOC
COOH
NH2
N
C
NH
-H2O
NH
N
- Fe l ( 74%) Zn HCl:
NH2
NO2
NH2
NO2
- - NaHS:
NH2
NH2
NaHS
NH2
NO2
- N. Pd/ 343-363 3
85-90%.
12.5.2. n-
- . .
n- Na2S, Fe 1 Zn :
NH2
NH2
.
NO2
NH2
490
n- :
- - ;
- n-.
, . , n-. .
n- ( , Na2S).
"" n .
:
NH2
NHCHO
CO
NHCHO
H2
HNO3+H2SO4
Pd/C
NO2
-
NH2
NHCHO
H2O
NH2
NH2
-
N---
523-673 50,070,0 . ( 81%) (HNO3 + H2SO4) 278 . 93% n- n- 373-423 3,5 . .

53% n-, 9% -,
.
, .
n, :
NO2
NH2
NHCOCH3
NHCOCH3
NHCOCH3
NH2
NO2
-
NH2
NH2
491
"" n-
n-:
Cl
Cl2
Cl
Cl
NO2
HNO3 + H2SO4
-
33 %
NO2
-
65 %
NH2
NO2
H2
Pd/C
NH2
NO2
-
n- 37%.
, "", n-
323 .
. .
, ,
, n- :
NH2
NH
H2N
-
H2N
NH2
NH2
492
n-
.
n-
- , .
370-410 0,5-1,0
:
CH2CH2OOC
NH3
COO
HOCH2CH2OH
HO
CH2CH2OOC
n
CONH2
NH3
HOCH2CH2OH
CONH2
H2NOC

. 95% .
-
:
H2NOC
CONH2
Cl2
-HCl
ClHNOC
CONH2
Cl2
-HCl
CONHCl
ClHNOC
_
:
ClHNOC
CONHCl
6NaOH
H2N
NH2
2NaCl
2Na2CO3 2H2O.
310-410 .
493
12.5.3.
(4,4; ,-) , .

, :
2
NO2
[H]
N=N
[H]
N-N
NH2
NH2
HH
,
- , .
. . . N-N, -, ,
.
12.5.4. 4,4-
4,4-
NH2
CH2O
NH2
CH2
NH2
+2.
12.5.5. 4,4-
4,4- , .
494
. - - :
NO2
OK
+ Br
NO2
NO2
NO2
4,4'-
4,4-:
NO2
NO2
H2
NH2
NH2
"" "".
12.6.
12.6.1
-
:
COCl
COCl
AlCl3
NH-CO-NH
NH-CO-NH
C
O= C O
NH-CO-NH
NH2
H2N
C
O
C =O
H2O
HCl, H2SO4
(C2H5)3N
495
12.6.2.
448
:
NH2
HN
O
+2
NH2 HCl
71% .
, ,
, , ; - ; , , .
12.6.3.
:
O
NH2
H2N
+2
NH2 HCl
C
O
C
O
18% .
, , ; , ,
.
496
13

- ,

OCN,
O R
R=H, Alk, Ar Ac. - . :
RN=C=O + ROH
RNCOR
H O

30- :
nHOROH + nO=C=NRN=C=O
(OROCNRNC)n
OH
HO

:
nClC(O)R(O)OCl + nNH2RNH2
Cl- COOROCONHRNH nH
,
.
1934 .
, 1941 . , , . , -
. -
497
.
" U" " U".
1940 .
.
, , ,
. , , , . -1,4, "" .
.
: , , , , , , . (~ 90%)
( ).
, ,
. . -
, . (50-70%)
. , , ,
, , ,
. , , , , , .
.
, , , , .

. ,
, ,
223 , ,
30% . - "".
,
498
,
.
, , , , - :
nOCNRNCO + nHOROH
[RNHC(O)OR]n,
R AlkCO, Arylen; R - Alkylen, , .

.
.

. ,
, . , (, , .).
,
.
. . , , ,
:
2OCNNCO + HOH
OCNNHC(O)RNHNCO + CO2.

:
2OCNRNCO + H2NRRNH2
OCNNHC(O)RNHRNHRC(O)NHNCO.
, .
499
,
:
RN=C=O +
RNH2
RCOOH
HOH
RNHCONHR
RNHCOR + CO2
RNHCOOH
RNH2 + CO2
R-N=C=O
RNHCONHR
, ,
,
:
RNHC(O)OR
RNC(O)OR
C(O)NHR
RNHC(O)NHR
+ RN=C=O
RNC(O)NHR
CONHR
RNHCOR
RNC(O)R
C(O)NHR
:
O
NCO
CH3
NCO
CH3
NCO
C
N
C
O
CH3
NCO
,
, .

. ,
, .
500

, , , .
, , , . .
.
13.1.
.
.
.
,
, ,-,
, .
, .12.
13.1.1.
.
:
HCN
H2
CH3NH2,
H2
RCN
RCH2NH2.
:
[H]
RCN
[H]
RCH=NH
[H]
RCH2NH2
-NH3
RCH3.
.
, -
H2NCH2(CH2)nCH2NH2
N(CH2)nCN + 2H2
, , -
501
. , , ,
,
, , .
. -
.
:
RCN + 4Na + 3ROH
RCH2NHNa + 3RONa
RCH2NH2 + 3ROH + 4NaOH.
H2O
, ,
.
.
, , .
.
353-403 5,0-10,0 .
:
H2N(CH2)n+2NH2
NC(CH2)nCN
-NH3
0,5H2N(CH2)n+2NH(CH2)n+2NH2
13.1.2.

, . .
502

.
.
- :
Fe + 2H2O
6Fe(OH)2 + 4H2O + C6H5NO2
C6H5NO2 + 3H2
Fe + 8Fe(OH)3
Fe(OH)2 + H2.
6Fe(OH)3 + C6H5NH2.
C6H5NH2 + 2H2O.
3Fe3O4 + 12H2O.
, ,
NH4Cl, FeCl2, CaCl2, NaCl . :
NH4Cl > FeCl2 > (NH4)2SO4 > BaCl2 > CaCl2 > MgCl2 > NaCl >
>CH3COONa > NaOH.
. p > 12 .
Fe3O4 .
-, , -, 2,6---. 4,6--1,3 4,6--1,3-,
3,3--4,4--
3,3,4,4- . 3,5-n-, 3,5-.

3,3,4,4- - 3,4,4 ,
.
, , .
503

1845 . .. 4,4-, .
.
.
R
NH NH
R
R H, Hal, Alk, AlkO, AcO.

, . , .
:
NaOH
C6H5NO + ZnO,
C6H5NO2 + Zn
C6H5NO + Zn + H2O
NaOH
C6H5NHOH + ZnO,
C6H5NO + C6H5NHOH NaOH
C6H5N=NC6H5 + Zn
O-
NaOH
C6H5N=NC6H5 + Zn + H2O
C6H5N=NC6H5 + H2O,
O-
C6H5N=NC6H5 + ZnO,
NaOH
C6H5NHNHC6H5 + ZnO.
:
, - .
504

()
. , VIII
.

.. :
4
NO2
+ 6Na2S + 7H2O
NH2 + 3Na S O + 6NaOH.

2 2 3

. , . (Na2S9H2O) 380 .
, 4,4- 4,4-:
O2N
NH
NO2
Na2S9H2O
H2N
NH
NH2

.
. , ,
25%, 80%,
3 .

. , ,
- .
. : ,
505
VIII .

-
[]
RNO2
RNO
RNHOH
RNH2
RN=NR
O
RN=NR
RNHNHR
. , , .
, , ,
.
,
. 300-400 0,1-1,0
.
13.2.

RN=C=O.
==NRN=C=O .

. , (. ). , .
506
13.2.1.
1884 .

293 . (1)
(2), 323-343
(3). 373 :
2H2NRNH2 + COCl2
ClCNHRNHCCl + HClH2NRNH2HCl
1
2
ClCNHRNHCCl
-HCl
O
O
COCl2
HClH2NRNH2HCl
OCNRNCO
3
, 373 . .
, . , , N-
. :
RNH2 + SOCl2
RN=S=O + 2HCl,
RN=S=O + COCl2
RN=C=O + SOCl2.
.
13.2.2. ,
, - .
507
RCON . ,
. :
R-C-N-X
O
R-C-N
O
RN=C=O
X = N2 , N=N, .
X = Cl, Br - .
X = OH
NO2 , N(CH3)3 - .
OCR, OSO2
O
,
.
in situ , .

( ):
RCOBr + NaN3
RCON3
-N2
HNO2 + H2NNHCOR
RNCO
, , - ,
.
, , . ,
-.

. , .

: 2,4--, 2,6-, 4,4--, ,
.
508
13.2.3.
(, )
174,16
, , , , . . 13.1.
13.1.
.
2,3-
2,4-
2,5-
2,6-
3,4-
2,4- (80%) + 2,6- (20%)
2,4- (65%) + 2,6- (35%)
.,
294,8
312
281,5
286,89
278
., /
523/7448
393/91,14
393/98
393/98
523
523
d420
1,2178
1,2001
1,2271
1,2271
1,2184
1,222
2,4- (1) 2,6- (2)

N=C=O
O=C=N
CH3
CH3
N=C=O
N=C=O
80:20 65:35.
, "", "
", .

: -: -: - = 59:4:37.
CH3
CH3
HNO3
H2SO4
NO2 +
H2O.
509
:
CH3
HNO3
NO2
CH3
NO2
NO2
+ H2O .
H2SO4
, , 2,4- (~80%) 2,6(~20%).

, , . , 99%.
8,5 ~450 .

.
(273-303 ) :
CH3
CH3
NO2
NO2 +
COCl2
NHCOCl
NHCOCl
+ 2HCl.
443
2-3 . 80%.

( ) COCI2 - . . 280,56 , , . , - 3,2 / 1 .
,
.
323 :
l2
= 109,1 /.
12 +
510
.
473-523 . - 473 .
,
, , .

. .

,
, .
" Toa " () , . - ( ). .
:
CH3
CH3
NO2
NHCOOR
+ 4CO2 .
+ 6CO + 2ROH
NO2
NHCOOR

:
CH3
NHCOOR
NHCOOR
CH3
NCO
+ 2ROH.
NCO
433 7,0 . 2,5 .

523 .
511
:
CH3
CH3
NCO
NCO
NCO
NCO
2,3-
2,4-
CH3
CH3
NCO
OCN
NCO
OCN
2,5-
2,6-
CH3
OCN
NCO
3,5-
900 . /.
13.2.4. 4,4-
4,4-, 4,4-, 4,4, (4-) ()
OCN
CH2
NCO
. . 313 , . 500 . /.
98%- , 90-95% , , .
- "",
"", "", "", "", "", "" " ".
.
512

NH2+ HCHO
[H+]
H2N
CH2
NH2
NH2
NH2
CH2
. 2,4
.

H2NC6H4(CH2C6H3NH2)nC6H4NH2.
, .. 4,4-, 2,4-
2,2-:
H2N
NH2
CH2
CH2
NH2
H2N
NH2
CH2
NH2
CH2
4,4- ,
:
H2N
CH2
OCN
NH2 + 2COCl2
CH2
NCO
+ 4HCl;
513
NH2
NH2
NH2
CH2
+ (n + 2)COCl2
CH2
n
NCO
NCO
NH2
CH2
+ (2n + 4)HCl.
CH2
n
:
,
4,4- , 4,4-.

(,) 65N2 ; . . 278,96 , . . 457,4 . 1826 . . .
1 . /.
60 70% . , ,
:
NH2
NO2
H2SO4
HNO3
.
N2 - ,
.
N2+, - N2 N2..
.
N3. N3
2S4 , N2+, :
514
N2 + 2S4 N2+S3- + 2
N3 (3)2 N25. 90% N3 N2+ N3- .

:
NO
NO
+ NO2
NO2
-H2
333 95%- (.) 65%- (.) . , (, ), , (, NO2SO3F).

.

.. :
C6H5NO2 + 3Fe + 6H+
C6H5NH2 + 2Fe3+ + 2H2O.
C6H5NO2 + 2Fe + 6H+
C6H5NH2 + 2Fe3++ + 2H2O.
:, 9 : 1 (). . 0,2-2,5 553 . , , , . 99,6%,

- 99,7%.
:
NO2
NO
H2
-H2O
NH2
NHOH
H2
H2
-H2O
, - , .
515
, ""
, :
OH
NH2
+ H2O .
+ NH3
2000 . , "", . 673-693 1,6

:, 20:1, . 95%,
98,3% (.).
, "" ,
OH
NH2
NH2
+ NH3
+ 3H2
.
.
, .
N:
O
NH C OR
NO2
+ CO + ROH
R = H3 C2H5.
:
O
NH C OR
+ HCHO
O
ROC NH
CH2
NH COR
516
523-553
, , :
O
O
ROC NH
CH2
CH2
O=C=N
NH COR
N=C=O
+ 2ROH.
423 6,0 1,5 . 98%.

, .
(1015%) 373 HCl BF3. 97% (.).

493 . ~ 90%.
13.2.5.
(1.6-, )
O=C=N(CH2)6N=C=O
- , . . 206 , . . 528531 . 1922 . .
. ,
.
1,6-.
1,6- -
2 313-343 . N-(6) , .
, 343-423 :
H2N(CH2)6NH2
CO2
H3N+(CH2)6NHCOO-
2COCl2
OCN(CH2)6NCO + 4HCl.
517
353-473
60 .

O
CNH(CH2)6NCO
N(CH2)6NCO
CNH(CH2)6NCO
O
.
(1)
, (2) - 2,4- , (3) - , (4)
.
O
NCO
CH3
(CH2)2OCNH
CH3
;
HNCOCH2CH=CH2 HNCOC H
6 5
O
O
NCO
C2H5C CH2OCNH
O
(CH2)2OCNH
O
2
O
NCO
CH3
CH3
NCO
CH3
3
NCO
"" - (5) 2,4- 4,4- - .
518
,
6 .
NCO
NCO
CH2
CH2
N
C
H
CH2
n
NCO
n
NCO
. :
CH2NH2
CH2NH2
+ COCl2
CH2 N=C=O
O=C=N CH2
(- -) :
- -

O
OH
OH
O
CH2NH2
CN
NH3
-H2O
H2
CN
CH2NH2
- - - -

519
CH3
CH2NH2
CN
CH3
NH3, O2
-H2O
H2
CN
CH2NH2
.
,
:
CH2NH2
CH2NH2
CH2NH2
COCl2
CH2N=CO
CH2N=CO
CH2NH2

:
COCl2
H2N
NH2
O=C=N
N=C=O
13.2.6.

, . ""
.
N-
. , ,
~ 373 :
520
O
CH3NH2 + COCl2
-HCl
CH3NHC
CH3NCO + HCl.
Cl
, l.
N SiN,
, , N--,
:
RNHSi(CH3)3 + COCl2 -HCl
RNCOCl
Si(CH3)3
<273
RNCO + (CH3)3SiCl.
(213-273 ) , N-,
-- SiNCCI, -, .
N-
NH, SiN.
N, N-:
RN(SiR3)2 + COCl2
RNCO + 2R3SiCl.
, , ,
.
, , .
N,N-
-
521
SiN,
-:
O +
(CH3)3Si
RNC
Cl(CH3)3Si
Cl
O
RNC
(CH3)3Si
Cl
- (CH3)3SiCl
RN[Si(CH3)3]2 + COCl2
RN=C=O
- CH3SiCl
OSi(CH3)3
OSi(CH3)3 +
RN=CCl
RN=CCl
Cl
-(3)3SiCl
Si(CH3)3
N,N- :
(CH3)3SiNHRNHSi(CH3)3 +2COCl2 -HCl O=C=NRN=C=O + 2(CH3)3SiCl,
R .
N,N-

() .
, 3Si, (CH3)2Si, .
, : ,
- , , , ..
.
, , . .
522
N-
, N 423 :
(CH3)3SiNRCOOR
RNCO + ROSi(CH3)3.

"" , .
-
N- 2 SiN, - -:
R2NSi(CH3)3 + CO2
R2NC(O)OSi(CH3)3.
- : 523 . 2,
-- . , - , 373-403 :
RNHC(O)OSi(CH3)3
RNCO + (CH3)3SiOH .
(3)3Si
:
2RNHC(O)OSi(CH3)3 2RNCO + 2(CH3)3SiOH
2(CH3)3SiOH
[(CH3)3Si]2O + H2O
RNHCOOH -CO RNH2
RNCO + H2O
2
RNCO + RNH2
2RNHCOOSi(CH3)3
RNHC(O)NHR
RNHC(O)NHR+ [(CH3)3Si]2O + CO2
523
, -- , ArSi13,
. .
, --:
253 . :
RNSi(CH3)3 + CO2
RNHC(O)OSi(CH3)3
[RNHC(O)OSiCl2Ar]
ArSiCl3
RNCO + [HOSiCl2Ar].
:
CO2
CH3NH2 + [(CH3)3Si]2NH -NH

3
[CH3NHC(O)OSiCl2Ar]
ArSiCl3
CH3NHC(O)OSi(CH3)3
-(3)3SiCL
CH3NCO + [HOSiCl2Ar].
--
:
--
, --.
N-
():
[RNHC(O)OSiArCl2]
[RNHC(O)O]-[HNR3]+ + ArSiCl3
-R3NHCl
RNCO + [HOSiCl2Ar] ,
R = H, Alk.
(
) 2.
524
13.3.
,
(, , -1,4). ,
, .
. ..
1859 ., , , . ,
()
. -
.
, . , :
-
ROH + RCOOH ( )
RC(O)OR,
-
ROH + RNCO
RNHC(O)OR,
-
2ROH + RCHO
ROCH(R)OR + 2,
-
2ROH
ROR + 2.
,
. .
, , , .
, ,
: .
525
13.3.1. -
-: -1,3, 2,2,4-1,3 :
R
2RRCHCHO
RRCHCH(OH)CCHO
R
.
-1,3 :
2CH3CHO
CH3CH(OH)CH2CHO
CH3CH(OH)CH2CHO,
2
CH3CH(OH)CH2CH2OH.
1894 . (
):
CH3
CH3CHCHO + HCHO
CH3
CH3C-CHO + HCHO + H2O
CH2OH
CH3
CH3C-CHO
CH2OH
CH3
CH3CCH2OH + HCOOH.
CH2OH
2,2,4--1,3 1896 ., .
:
CH3
2CH3CH-CHO
CH3
CH3
CH3CH-CH(OH)-C-CHO
CH3
526
CH3
CH3
CH3
CH3CH-CH(OH)C-CHO +CH3CHCHO
CH3
CH3
CH3
CH3
CH3CHCHOHCCH2O(O)CCHCH3
CH3
- -.
:
.
13.3.2
( -1,2,3;
1,2,3-)
2()2 ,
. . 290,9 , . . 563 , ,
, .
.
:
2=-
2-,
:
2-
2;

:
2 + 2

22

, .
527

, . :
-
2=3 + l2
2=2l + l,
- l (Cl2 + 2)

2=2l + l2 + 2
l22l,
-
[-]
l221 -l
221,
-
222l + N23 + 32
222 + 2Nl + 2.

, :
2=3
2=
2=2 22
(3 )2
(3 )2
22

528
13.3.3.
, ----.
. : , :
COOR
[]
CH2OH
COOR
CH3
[]
CH3
CH2OH
CH2X
CH2X
[2]
CH2OH
CH2OH
Hal.
- 72% .
13.3.4.
(
) ,
, - , , , . , :
CH3CH(OH)CH2OH + nCH2CH2CH3
O
HO-CHCH2(OCH2CH)nOH
CH3
CH3
, .
529
,
, -1,4.

:
CH3
CH2O(CH2CH(CH3)O)xCHOH
CH3
HOCH2CHOHCH2OH + (x+y+z)CH2CHCH3
CH2O(CH2CH(CH3)O)yCHOH
O
CH3
CH2O(CH2CH(CH3)O)zCHOH
, , , , .
, .
, ,
.
393-413 . ,
~ 350 .
~ 92% 94% -
.
. 373 1 .
, ,
. 348 .
.

CH2CH=CHCH2 ~ CH2 + 2HCHO
HOCH2CH2CH=CHCH2 ~ CH2OH
530
CH2CH=CHCH2 ~ H2 + CH2CH2
O
HOCH2CH2CH=CH-CH2 ~ CH2CH2OH
, ,
H2O2
2OH,
OH + CH2=CHCH=CH2
HOCH2CH=CHCH2
HO[CH2CH=CHCH2]xCH2CH=CHCH2
HO
HO[CH2CH=CHCH2]xCH2CH=CHCH2OH.
* * *

, . . ~3%. : ~90% , 1%.
531
14

O
[OROC]n,
R- , .
[2,2-(4-)]
3,3,5,5-- 3,3,5,5 :
CH3
O
O
n
. 1898 . (, ) .
, . ,
.
,
, . 1958 ., , . "". "", "", "", "", "", "", "" .
CH 3
532

: ,
, , ,
, , , .

, 173 403 . ,
, ,
-
.
, , . , ,
.
,
373 .
1990- . 2000 . 80% - .
, , , , . -
, 250 . , , ,
.

HO
OH ,
R =: CH2 ; CH2CH2 ; CHCH3 ; CH(CH2)2CH3 ;
533
CH3
C ;
CH3
CH3CCH2CH3
C
;
C
CH3
CH2O
OCH2
CH2CH2CH2
S ;
O
OCH2
O
S ;
O
CHCH2CH2 ;
CH2O
O ; S;
OO
CH3C
CCH3
N
O=CCH3
,
. . ,

. , , .
- . :
534
CH 3
CH3
OH + nCOCl
nHO
CH 3
CH 3
+ nHCl .
n

, (), .

:
CH 3
n HO
O
OH + n
C
CH3

C
CH 3
CH3
O
O C
O
O
+ n
OH
.
.
535
14.1.
, , . ,
CH3
n HO
OH+
C
CH3
mCH2CHCH2Cl + NaOH
O

CH3
CH2-CH-CH2-O-
OCH2-CH-CH2O- -CH2CH-CH2
OH
CH3
+ NaCl + H2O
n .
n . n . , ,
. , ,
.
,
:
CH3
n HO
C
CH3
C
CH3
O
O C
CH3
CH3
n HO
CH3
COCl2
OH
-2HCl
O
OH +
O C O
-2C6H5OH
536
CH3
n NaO
ONa
CH3
+ n Cl
SO2
Cl
-2NaCl
CH 3
C
SO 2
CH 3
CH3
nNaO
ONa
+ n Br
Br
CH3
-2NaBr
CH3
O
C
CH3
.
:
537
O CH3
-OCCH=CHCO-CH-CH2O
CH3
C
CH3
OCH2CH-
CH3
14.1.1.

[2,2--(4-); (4); ] 1891 . :
CH 3
OH + CH3COOCH3
HO
OH + H2O .
CH3
.
. , .
. . ,
, (433 ), .
,
. .

. 70%

.
538
( 313-348 2 : 1 15 : 1 9096%.
BF3, AlCl3, AlBr3, ZnCl2,
SnCl4, SbCl5, TiCl4, SiCl4.
80-95%.
. :: 1 : 4 : 1.

.
-1 -2.
:
2S4 > -2 > -1.
, -1.
. , , ,
. : , , , , , .
SCH2COOH - (CH3)2(SCH2COOH)2, .
,
. , ,
.
. ,
, : 353 , . ,
. 303-353 .

. 2:1 (4-5):1. -
539
10-15. ( 4-7
1 ) , (, .).
.
.
(1)
(2).
- (3),
- (4).
CH3
O=C
CH3
CH3
H+
OC
CH3
+
HOC
CH3
1
CH3
CH3
HOC+ +
CH3
OH
CH3
HO
-H2O
CH3
H
OH
HC
+ H+
OH
OH
CH3
C+
CH3
OH
+
-H
CH2
CH3
3, , (5),
540
(6):
CH3
C+
OH
CH 3
OH
CH3
HO
H
CH3
CH 3
C
HO
OH
- H+
5
OH
CH3

:
H 3C
C =O + H
H 3C
H3C
H3C +
COH
H3C
1
C=OH
H3C
(1), , , (
) , .. - . . (1) ,
+
(7):
OH
H3C +
COH
3
1
OH
OH
H3C C H
H3C OH
-+
H3C
C
OH
CH3
541
, ,
- (3):
OH
OH
-H-
CH3-C-CH3
CH3-C-CH3
OH
.
.
2,2-(4'-) (,-, 8),
,- (9), 2,4-(,--4') ( 1, 10):
OH 1CH
3
2'
1'
2
3
CH3
OH CH OH
3
1'
OH
4' ;
HO
C
CH3
CH3
CH3
OH
CH3-C-CH3
1'
10
4'
OH
,
, ,
, 2,2,4--4-(4) (XI):
1
O2
C
CH3
CH3
C CH2
H3C 4
11
4'
OH
542
C(CH3)2
CH2
O
C(CH3)2
CH2
CH3
CH3
OH
2,4,4--2-
OH
2,4,4--4-
, ,-, 40% , .

. . , .
.
.
, . , , . , l, - .
, ,
. : , 2,5, 71% , , 3,0 82,7%, , 3,7 86%. , :
. 2,5:1 15,3%,
4:1 2,4%.
543

323-343 , ~ 1,0 , 20 .
90%.
. , , , , , .

443 200 , , , ,
. , .
.
, , . , , , .
, .

. 14.1.
. 14.1.
1 ; 2 ; 3 ; 4, 6, 9,
11 ; 5 ; 7, 10 ; 8
.
544
: I ; II ; III ; IV ; V ; VI ; VII ; VIII

; IX
, , l 1
2.
3, .
323 , - 335 .
( 30 )
4 ( l, , ).
5, , ,
6, .
( , ) 11
. 10
. 9.
8 . 96%, . . 426,8 .

, .
,
, .
.
-1, -2, .
-2. : (3,7 5):1 10:1.
545

, , .
" "
. 343-348 ,
1 .
-2. . 14.2 .
. 14.2. -2 ()
1 ; 2 ; 3 ; 4
; 5
; 6 ; 7 ; 8 ; 9 .
1 , . ,
3 ,
. , 3,
9
8. 7 6 .
4.
5
1. . 96% .
100%-
546
. 3500 .
, , . ,
.

:
OH
+ CH3-C CH
CH 3
HO
OH
CH3
OH
CH 3
+ CH2=C=CH2
HO
OH
CH3

, . , , ,
, .
:
HF > BF3H3PO4 > BF3O(C2H5)2 > BF3H3PO4.
. . 14.1
F3, : 6:1 12:1 .
318-323 . .
373 .
547
14.1
BF3
,
%(.)
.,
12:1
12:1
12:1
12:1
12:1
12:1
6:1
1
2
2,5
10
2
2
2
318-323
318-323
318-323
318-323
343
373
318-323
( ),
%

94
755
195
95
853
103
98
83
903
95
805
155
100
103
903
98
982
90
805
102
BF3
:
OH
65
H3C-C-CH3
OH
OH
OH
+ CH3-C CH
H3C- C=CH2
n-
OH
C-CH2
CH3
548
-, , , , . . : 318-348 ,
:, 12:1, F3
2,5% .
90-95% ( ).
,
.

-
- , :
CH2
HO
+ HO
C
CH3
CH 3
HO
OH
CH3
,
, -, , BF3, ZnCl2, AlCl3, . 291-296 , .
, ,
. 373-423 .
,
.
-.
, - (9), , - (6):
549
OH
OH
OH CH OH
3
CH3
CH2
CH3
CH 3
HO
OH
CH3
418 , . ~ 60% .
-
. 85%.

, - .
C
2--1
, , 2--1:
OH
CH 3
+ 2CH3C(Cl)=CH2
HO
OH
+ (CH3)2CCl2
CH3
(, , lCl3, BF3).
50%- :2-1, 6:1, ~ 67%. BF3 2,5% 313 96%.
550

: -
, , ,
.
- . , .
.

- , , .
- ~353 .
303
,
348 1,3 . , .
14.1.2.
- ,
.
, . , , .
, , . .
20-22% .

. - , 2,2-(4--3,5-),
2,2-(3,5--4-) .
, SO2Cl2 . ,
343 3 3,3 ~ 50%. ,
. FeCl3 ~ 0,01 1 .
551
, 4:1.
328-333 (, , .):
Cl
CH 3
C
HO
OH
Cl2
HO
CH3
Cl
CH 3
Cl
OH
CH3
Cl

. 288-293 ,
303-308 .
. . 493-497 . 75-76% .

2,2-(4--3,5-) [
], 1938 . . .
:
Cl
CH3
HO
C
CH3
[Cl]
OH
CH3
Cl
OH
HO
Cl
CH3
Cl
. , 1,2--,
, .
, .
552

,
.
2,2-(3,5--4) -
. .

.
:
CH3
OH
HO
CH3
Br
[Br]
CH3
Br
OH
HO
Br
CH3
Br
313 :, 4:1.
, ,
. 96,4%
. ,
, 454-455 .
14.2.

, (), - .
, , , 423 573 :
CH 3
n HO
C
CH 3
O
OH
+ n
O C O
553
CH3
O
O
O
CH3
+ (2n-1)C6H5OH
n
.
, .
14.2.1.

( )
:
O
OH
+ COCl2
-HCl
65
Cl
-HCl
O
O
413-423 .
.
:
O
2
OH + COCl2 + 2C5H5N
+ 2C5H5NHCl
O C O
554
.
.
,
, :
O
HO +
O C Cl
C5H5N
O C O
+ 2C5H5NHCl.

.
.
, :
R
2 NR + COCl2
R
65N
RO R
R- N-C-N-R 2Cl
R
65N
-NaCl
R
N-R
R
N-R +
-NaCl
O C O
N R Cl R
555
. 89% .
.
:
O
ONa +
COCl2
+ 2NaCl.
298 .

. :
O
ONa
O C O
Cl
+ NaCl.
14.2.2.

. ZnCl2 ZnO 393 .
,
, , :
OH + CCl4
ZnCl2
Cl
O
Cl
2HCl + ZnO
ZnCl2 + H2O,
+ 2HCl ,
556
Cl
O
+ H 2O
+ 2HCl.
Cl
14.3. S
4,4- ( S, S) 1868 . S .
S , 4,4-.
4,4--.
, 6070% :
+ H2SO4
HO
SO3H
HO
+ HO
SO3H
HO
+ H2O ,
SO2
HO
OH + H2O .
4,4'-
S ( ) 4,4-:
Cl
NaO
SO2
SO2
Cl + 4NaOH
ONa
+ 2NaCl + 2H2O.
557
, 4,4-
.
:
SO3 + (C2H5)2SO4 < 283
C2H5OSO2OSO2OC2H5,
C2H5OSO2OSO2OC2H5 + 2
SO2
Cl
Cl
Cl
+ SO3 < 288
+ 2C2H5OSO2OH.
4,4-
,
, . 1 2
. ,
1
:
OH
2
+ SCl2
-Cl2
HO
OH
1
CHCl3
OH
2
HO
OH
+ SOCl2
AlCl3
C2H2Cl4
HO
SO2
OH
558
4,4-:
H2O2
S
HO
OH
CH3COOH
SO2
HO
OH
14.4.
- , , - .
, .
.
:
+ 2SO3
HO3S
SO3H
HO3S
H2SO4
NaO
SO3H
ONa
+ 4NaOH
2Na2SO3 + 2H2O.
:
H3C
H C
H3C
CH3
C H
CH3
O2
H3C
HOO C
H3C
CH3
C OOH
CH3
HO
OH
+ 2CH3COCH3
H+
--
559
- - , () . ~ 363 , .
( 4%-) . , , ,
- , .
- 453473 :
Cl
Cl
SO3
Cl
NaOH, H2O
Cl
SO3H
ONa
OH
H2SO4,H2O
OH
ONa
SO3Na
14.5.
. ,
, . .

CH2CHCH2OROCH2CHCH2
O
O
O
O
CO
CO
, (
, , , -
560
), , . 293-413
. , , :
, .

, , , , , .
(0,1-10%)
.
, ,
, .
500-3000 ,
, , .
.
, , . .
, + , .
,
OHO
RNHC
CHR,
OCH2
- , , .
, , , .
(), .
561

. . 2,0-2,5 700-900%. , ,
, , ,
.
:
t0
HOCH2CH2OCNH(CH2)6NHCOCH2CH2OH
HO(CH2)2OH +
O
O
.
O
O
+ OCH2CH2OCNH(CH2)6NHCn

:
CH2
CH2
HOCHCH2OCN
RCHCH2 + HN
R
O
CH2
O O
CH2
C
O
CH2
HOCHCH2[OCNH(CH2)2OCHCH2]nOCN
R
O
RR
O
CH2
, 373 ,
. 373-423
562
. , , ..
.
, :
CHO
C=O + nNH3
O
O
nHCCH2OCNH2
CHO
O
O
OH
O
HCCH2[OCNHCHCH2]n-1OCNH2
.
,
, ,
. .

:
CH2=CCO(CH2)nCHCH2
R O
O
O
C=O
- , , , , , .

,

:
563
HOOC
COOH
HO(CH2)2O
O
473-523
+ 2CH2CH2 - CO
2
O
O
C=O
HO(CH2)2O
O
O(CH2)2OH
O
O(CH2)2OH 523-573
HO(CH2)2O [C
O
C O(CH2)2O-]n H
O
+ (n-1)HO(CH2)2OH.
10
.
,
CH3(CH2)7CHCH(CH2)7R,
O
O
C=O
O
O
X
,
R = CN, COX, CN
Y
.
, ; .
, 50- . (,
..), -
564
. , , , , ,
.
14.5.1. -
- , , :
R
2R + 2
=
2
30-40%. -
.
, , , , , , . , .
, , 353-473
1-20 . , , .
-
,
, ..
2. :
(CnH2n+1)4NBr
CH2CH2 + Br
O
nBrCH2CH2O
(CnH2n+1)4N+ + Br
BrCH2CH2O
(CH2CH2O)n + nBr
565
BrCH2CH2O + CO2
BrCH2CH2OCO
O
CH2O
BrCH2CH2OCO
O
C=O + Br
CH2O
( ) , , -,
.

- - , , . , 2 (Ph4SbBr, Ph3SbBr2), :
[CO2]
CO2
Sb
CH2-CH-H
O
R
CH-O
CH2-O
C=O
,
2
.
14.5.2.

,

- , , .
, :
566
Na2CO3
CH2Cl
RCHOH
NaHCO3
CH2O
C=O + NaCl + NaOH
RCHO
CH2O
C=O + NaCl + H2O
RCHO
CH2O
CH3-O-C-O-Na
C=O + NaCl + CH3OH
RCHO
14.5.3.
-, - ,
, :
RCHO
COCl2
C=O + 2HCl
COCl(OR)
RCHOH
RCHOH
O
''
R -O-C-OR'''
CH2-O
RCHO
RCHO
C=O + HCl + ROH
RCHO
RCHO
C=O + ROH + ROH
RCHO
C=O RCHO
CH2-O
C=O + HOCH2CH2OH
RCHO
RCHO
2COCl(OR)
C=O + R2CO3 + 2NaCl

RCHO
567
, -, -.
.
-
:
R1 R2
t0
RCCR3
.
X OCOR4
O
R1 R2
RCCR3 + R4X,
O O
CO
Hal.
14.5.4.
.
, -
,
:
ClCH2CHCH2
O
-HCl
CO2
ClCH2CHCH2
t, .
R(OH)n
R(OH)n
CO2
R(OCH2CHCH2)n t, .
O
O
CO
-HCl
R(OCH2CHCH2)n
O
O
CO
, , , - , , ,
568
, , , , , , , .
:
O O
O O
Cl-C-R-C-Cl
CH2CHCH2OCRCOCH2CHCH2
O O
O O
CO
CO
O
O
OCN-R-NCO
CH2CHCH2OCNHRNHCOCH2CHCH2
HOCH2CHCH2
O O
O O
O O
CO
CO
CO
Cl
COCl2
O
ClCOCH2CHCH2
O O
CO
Cl
CH2CHCH2O
OCH2CHCH2
O O
CHCH
O O
CO
O
O
CO
CH3
CH2CH2
HO-C6H5-C-C6H5-OH
O
O
CH3
CH2CHCH2OCOC6H4OCOCH2CHCH2
O O
O O
CO
CO
O
, ,
.
569
15
-
15.1. -
-
( ).
, , ,
, , . -
, ,
.
. 1900-1910 .
() () . ,
, .
" ,
, ", 12 1902 .
2 1906 .,
.
, , , . 1909 . .
1919 . , -, , , .. ,

, , , -, , .
, ,
, , , , .
15.1.1.
-
. : -,
. 9 .
570
- -, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- 3,5- , .

, . 1834 . , . 1867 . .
. .
. 30- ., , ,
. 70-
.
- .
.
,
.

0,01 0,1% , 0,5 0,7%, , , 0,8 3,7%. 0,1 0,4% ,
0,8 3,8%.
. , , ,
. , , .
. : - , ,
, , .
. 15.1 . ,
. -, . , , -.
571
15.1

.
, %

,
%
31,0
53,2
16,7
10,9
19,2
0,68
23,8
40,0
22,2
8,4
29,4
0,286
42,4
50,0
31,6
3,3
15,9
0,21
50,6
7,1
35,7
31,2
26,0
1,19
61,6
28,8
20,2
30,8
20,2
1,53
71,8
41,0
11,9
28,3
18,8
1,51
73,4
48,6
17,2
20,7
13,5
1,53
(- : -)
, ,
, .
:
- ;
- ;
- ;
-
( ).

( 15.1),
( 15.2). ,
.
572
15.1

II
15.2
10-15%- NaOH

CaCO3
Na2CO3

CaCO3
573

, , , ,
.
: 5% . .
.
.
:
- ;
- ( " );
- ( " ");
- ( );
- .

. . 1867 .:
C6H5SO3Na + 2NaOH
C6H5ONa + Na2SO3 + H2O
423 . , ,
:
2C6H5SO3H + Na2SO3
2C6H5SO3Na + SO2 + H2O
(1)
C6H5SO3Na + 2NaOH 608-613 C6H5ONa + Na2SO3 + H2O (2)
, 2 .
(IV) , (1), :
2C6H5ONa + SO2 + H2O
2C6H5OH + Na2SO4
, , , , , .
,
, ,
90%.
574

( " ")
1872 . , 573
. 613-663 . :
2NaCl + 2H2O Cl2 + 2NaOH + H2
()
6 H6 + Cl2 C6H5Cl + HCl
( )
C6H5Cl + 2NaOH C6H5ONa + NaCl + H2O
C6H5ONa + HCl
C6H5OH + NaCl
( )
_________________________________________________________
C6H5OH + H2
( )
C6H6 + H2O
:
, .
. 613-663
28,0-30,0 .

( " ")
.
, :
C6H6 + HCl + 0,5O2
C6H5Cl + H2O.

773 :
C6H5Cl + H2O
C6H5OH + HCl.
:
C6H5OH.
C6H6 + 0,5O2
1935-1945 . " " . . 15.1.
4 503 . 563
(423 ) , 383 . ::16,5%- 10:2,18:3,05 (. .).
783 4 , .
575
. 15.1. c
1 - ; 2 - ; 3 - ; 4 - ;
5 - ; 6 - ; 7-11 ; 12, 13
.
: I - ; II - ; III - ; IV - ;
V - ; VI - HCl; VII + ; VIII + ; IX + ; X - ; XI - ; XII - ;
XIII + + + HCl; XIV -
CuCl/FeCl3.
,
, .
693
. ~ 80%
10-15%.
"" , .
.

, ,

( ) .. , .. ..
.. 1942 . . 1949 .
576

" " () "" ().
.
:
+ CH2=CH-CH3
O2
AlCl3
H3C
H3C
CH3
OOH
CH
CH3
+ CH3COCH3
OH
. 15.2. .
. 15.2. ( )
1 - ; 2 - ; 3 - ;
4 - ; 5 - ; 6 - ; 7 - -; 8 - ; 9 .
: I ; II ; III ; IV ; V ; VI
; VII ; VIII - -; IX ; X
577
():
CH CH3
CH3
+ CH3CH=CH2
-, -, -
, .

:
CH CH3
CH3
[O]
CH3
COOH
CH3
,
,
. , :
CH3
C OOH
CH3
OH
+ CH3CCH3 .
, .
.

: , , . . .

: ; , ; ; ; . :
. - -
( , l ),
578
:
R
,
- .

AlCl3, -
.
-
473-573
.
.
. 15.3 . ,
. , 25-35% (.).
. 15.3. , ,
1 - ; 2 - ; 3 - .
. -
. :
< < .
579

4 , 3-.
.
:
RH
R + H,
R + O2
ROO,
ROO + RH
ROOH + R ..
- .

C(CH3)2
OH
C(CH3)2
OOH
+ 0,52.
, , -:
C(CH3)2
OH
- H2O
CH2
CH3
:
2
CH2
CH3
CH-CH=CH-CH
CH3
CH3
:
C(CH3)2
OOH
COCH3
+ CH3OH,
:
COCH3
C(CH3)2 2
+ CH2O + H.
, ,
. , .
580
:
20-30%. ,
. ,
29 25% 2,2 .
18%.

, ,
.
, , , ,
(, ) .

, - .

. - ,
,
3-4 . ,
. .
, .
.
, ,
. 15-20% 343-353 .
, .
, ( ), .
, , . ,
( ). , . ,
, ,
581
.
363 - .
10, 6-10 ~ 12%, 11-12
20-25%.
. .
, ,
.
,
.
, . - .

, ~49 . 373 , .
, , , , . . , . , .
. . :
OOH
C(CH3)2
C(CH3)2
C(CH3)2
O
-2
. , , -- ; .
582
. 98-99%-
. 90-92% 94-97%, 87-88%- 8890%- . , , , . , :
HO
CH3
HO C
CH3
HO
-2
CH3
C
CH3
-,
, , , ,
,
(CH3)2-C-CH=C-CH
, , , .
.
373-393 . , ,
.
(=309,6
/ ).
, ,
. . 0,05-0,1% , . . ~ 348 .

, .
, .
-
583
.
( -2), 323-333 .
.

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

97% .
. , . ,
,
. , 95%
86%.

. ,
. 1990-
4, .
,
.
:
O
OH
Ni
CH3CCH3 + H2
CH3CCH3
350K, 1,8
OH
Al2O3
CH3C=CH2 + H2O.
CH3CCH3
593K, 1,0
. 1992 . ""
584
200 . / . , , . :
, .

.
:
OH
+ 0,5O2
, 1865
. .
.
. :
+ H2O2
303-343
,
Ti-
OH
+ 2.
- .

, 1925 . V2O5 MoO3:
OH
+ 2HNO3
+ 2NO2 + H2O.
600700 . 52%
585
90%. (IV) HNO3

.

:
OH
+ 2CuSO4 + H2O 573 K
+ Cu2SO4 + H2SO4.
u2+ Cu+ Cu0.

, in situ.
2 2
.
:
H2 + O2
[H2O2]
H 2O
OH
2
22, .
, :
CO + O2
[CO3]
CO2
OH
:
Mn + O 2
[Mn+O2]
Mm+
OH
, ,
, ,
,
.
586
(I) . 1983 . . (I)

:
OH
+ N2O
+ N 2.
850 30% 71%

10%. ZSM-5, 100%.

(I) , :
N2 O + H+
N2 + OH+,
N=NOH
C6H6 + OH+
C6H5OH + H+.
. 15.2, (I) , .

. N2 ,
-.
15.2
(I)
Fe-
FeZSM-5
Fe2O3
,% ( ), %
27,0
99,0
N2O
623
O2
773
0,3
N2O
623
5,5
O2
623
24,5
- :
N2
() + N2.
587
. 15.4 N2 .
. 15.4.
N2 (1), N2O (2) O2 (3)
(I) FeZSM-5 523
,
N2,
. 600 -
. N2 .
(I)
c "",
( -6,6), .
(c 15.3)
: ,
, , .
(I), ( 1:1) .

.
(I) " ".
, ( /) 160
2, " ". ,
588
, N2 , .
15.3
OH
O
3H2
O2
COOH
COOH + N2O
HNO
OH
N 2O
2H2
. , .
(I) ZSM-5. , .
().
, ..
, ..
, % (.):
...

.
N2O .
,
/(.) .
673-723
1-2
97-98
0,2-0,3
1
85
0,4
, (I) . 140 . /.
15.1.2.
, ,
.
. .
-
589
. , 2,4,6-- .
. , . . , :
O-
OH
-+
Br Br2
Br
OH
Br
Br
OH
OH
3Br2
Br
Br
Br2
-HBr
Br
Br
Br
Br
Br
, 2,4,6- . . 1%- I 20%- l 2,4,6. , .

( ) 2,4,6-:
OH
Br
Br
Br
Br
+ Br-+ I2 + OH-
+ 2I + H2O
Br
Br
Br
2,4,6- :
590
OH
OH
Br
Br
+ 1,5Br2 + 1,5Cl2
+ 3HCl .
Br
. , - . HBr
, .

. .
2,4,6 :
OH
OH
Br
Br
+ 1,5Br2 + 1,5H2O2
+ 3H2O .
Br
85% ~ 90%.
15.2. -
- (- , ) - .
2NCN2 (N2)2 - , NH()NH.
- - , ,
NH2- -.
- ( 40-70%-) . , , , . , , , -
591
. , , .
- - . :, 1:(1,3-1,7). -
:
.
,
, , , .
- ,
.
- , ,

.- , , - .
,
1:1, - , , .
15.2.1.
( , ) (N2)2 , (51,8 100
293 ), (5,4) ( ).
1:1
() - . , , . .
-
,
.
-
. , .
592
. 15.5.
( "")
1 2; 2 NH3; 3
; 4 -; 5 ; 6 7 1- 2- ; 8 ; 9 ;
10 .: I 2; II NH3; III ; IV ; V ; VI - ; VII

.
,
- 442 ,
, . , ,
.
,
.
. 1818 . ; . . .
593
, 1868 . , . :
2N3 + 2
N2N4
N2N4
= 125,6 /,
(N2)2 + 2
= - 15, 49 /.
453-503 12-25 .
.
.
15.5
"" ().
1 2
,
3. 465-540 , - 4, .
8, , 9, .
15.2.2.
(2,4,6--1,3,5-, )
NH2
N
N4 3
N
H2N
1
N
NH2
, . . 637 ,
, .
,
- , , , . , - ,
: -
, -
594
,
, , ,
, , , , .

6(N2)2
36N6 + 6N3 + 32.
~600 . . 15.6. ,
, . , .
95%.
. 15.6.

,: 1 598; 2 623; 3 648; 4 673; 5 698
.
. 15.7.
595
.15.7.
1 ;
2 ; 3 ; 4 ; 5, 6 -; 7
; 8 ;
9 ; 10 ;
11 ; 12
; 13 NH3.
: I-; II- NH3; III ; IV-
.
, ,
, :
(N2)2
6N
N + N3,
36N6 + 32.
1 2 3 , ~600 " " . 4, .

95%. 5 6 8 .
596
16

,

. (1),
(2) (3)
Si
Si
n
1
; CH2CY
n
2
Si n
Y = , Alk; = N, S.
, ,
. SinH2n+2 n
10, .
(R2Si)n. n, ,
.

. .
, , - .
, , ,
(4).
CH3
SiO
n
CH3
4
,
, (5) (6):
CH3
C2H5
SiNH
; SiS
C6H4Cl
n
C2H5
n

5
6
, ,
, (7):
597
CH3
SiCH2
n
CH3
, (8):
CH3 CH3
CH2CH2Si OSi
n
CH3 CH3
8
. , ,
, :
R
RSiO;
R 1
R
SiO;
R 2
R
OSiO,
O 3
O
OSiO
O 4
, 2,
1 ,
.
, :
nCHX=CHSiR3
CHXCH
|
SiR3
, - .
. -
. . -, -
.
598

,
RnSiHmX4-n-m,
R - (CH3, C2H5, C6H5, CH2=CH .. , CH2Cl, C6H3Cl2, (CH2)nCN, (CH2)nNH2);
X - (Cl, F, Br, OCH3, OC2H5, OCOCH3 .).
, +4, (n+m)
4. n = 4 SiR4 , .. ; R 65, . (3)2SiHCl
(3)2SiCl2.
16.1.

:
- ;
- ( );
- , , ();
- ( );
- .
16.1.1.
, ,
,
(, , ) .
, , .. , R .
16.1.2.
:
2RCl + Si Cu
R2SiCl2,
599
,
(3)2SiCl2, (25)2SiCl2, 65SiCl3, 3SiCl2 .
.
16.1.3.

13:
RRSiCl2 + H2.
RSiHCl2 + RH
,
, .
, ,
.
16.1.4.

RSiHCl2 + RCl
RRSiCl2 + HCl

~873 . , .. .
823-903 30 , 823-843 28-30 .
16.1.5

-
, , .
RSiHX2 + CH2=CHR
X2RSi2CH2R
X2RsiCH(R)3
600

. -
-
2PtCl662 , -
.
. ,
,
. , ,
.
16.2.
(, ,
, , , .)
. RnSiCl4-n, -
. , ,
. 1941 .
-
. 16.1.
16.1

SiCl4
HSiCl3
CH3SiCl3
(CH3)2SiCI2
(CH3)3SiCI
CH3SiHCI2
(CH3)2SiHCI
2H5SiCI3
. ., . .,
203
145
183
187
233
180,5
162
167,4
330,6
304,8
339,1
345
330,7
314
309
373,5
d n4
n 20
D
1,4810
1,3417
1,2750
1,0637
0,8580
1,1047
0,8874
1,2373
1,4126
1,4020
1,4110
1,4055
1.3885
1,4222
1,3845
1,4256
601
176,5
(2H5)2SiCI2
2H5SiCI2
166
(2H5)2SiCI
130
2=HSiCl3
(2=)CH3SiCI2
C6H5SiCI3
(C6H5)2SiCI2
(C6H5)3SiCI
367-368
C6H5SiCI2
C6H53SiCI2
C6H5(3)2SiCI
(C6H5)23SiCI
ClCH2SiCI3
() 12(3)SiCI2
() 12(3)2SiCl
164SiCl3
402
348,4
372,7
365,5
365,5-366
1,0504
1,0926
0,8895
1,2426
1,0868
1,4309
1,4129
1,4152
1,4295
1,4270
474,5
577
651
455
478,5
466,5
568
391
394,5
388
503-518
1,3240
1,2216
1,2115
1,1866
1,0320
1,1277
1,4646
1,2858
1,0865
1,42801,4570
1,29201,3170
1,54501,5520
1,5247
1,5819
1,5257
1,5180
1,5082
1,5742
1,4535
1,4000
1,4360
1,54001,5490
1,53501,5430
1,53501,5430
503-513
()
164(3)SiCI2
CI2C6H3SiCI3
540-548
. 16.1
CI2C6H3(3)SiCI2
- F3C(CH2)2SiCI3
--
F3C(CH2)2(CH3)SiCI2
- CN(CH2)2SiCI3
(-)
CN(CH2)2(3)SiCI2
-
2N(CH2)3Si(C2H5O)3
* 300
535-543
-
386,5
394,5
1,40601,4200
1,3990
1,2610
1,55501,5570
1,3885
1,3946
307
-
382*
488
1,1900
1,4565
395*
0,9470
1,4215
602
16.2.1. -

( )
573-723 :
2RCl + Si
Cu
R2SiCl2.
.
, , ,
, . ,
.

80%.

Si- .
. - -,
:
RCl + 2Cu
RCl + Cu
RCu + CuCl
RCuCl
R + 2Cu + Cl ,
Cu + R + Cl .
,
:
Si + 4Cl
SiCl4,
Si + R + 3Cl
RSiCl3,
Si + 2R + 2Cl
R2SiCl2,
Si + 3R + Cl
R3SiCl.

,
:
603
R+ R
CH3CH3
2R + Si + Cl
RR,
CH2=CH2 + 2H,
R2SiCl
R2SiHCl,
R + Si + 2Cl
RSiCl2
RSiHCl2 ..
,
- RSiCl3, R3SiCl, RHSiCl2, R2HSiCl, RH2SiCl, HSiCl3 SiCl4, .

, , , .
, , (3)2Si12, (25)2SiCl2,
65SiCl3, 3()SiCl2 . ,
( % (.)):
.50
.
.

.
...
10,6
0,2
..0,4
0,5
.
32,0
1,0
5,0
0,3
,
; , .
-, - .

. : , , , .
.
.
604

1673-1773
. - u3Si,

. ,
, .
. ,
-. . , ,
.
, .
. ,
, .
, ,
. u3Si, . , .
.
, . ( ) 473-573 2-8
.
.
.
. ,
373 , 523
1-3 .
.
605
, , .

(3)mSiClnH4-m-n, m n
= 13 (m+n) < 4, ; .

(Si/u):
CH3Cl + Si
473-523
(CH3)2SiCl2 + (CH3)3SiCl +CH3SiHCl2 + (CH3)2SiHCl .
, . ,
. . ,
74-105 .
, .
- , . - 353-373 .
,
. , .
. , 0,3-0,6 .
,
- 473 . :
90%. . ,
. , :
3RCl + Si
RSiCl3 + RR.
. 16.1 .
606
. 16.1.
(----- - )
1 - ; 2 ; 3 -
,
, 653-663 .
" ", ,
.
" ".
,
, , , .
.
. 16.2
" " .
. 16.2.
1, 4 - ; 2 - ; 3 - ; 5 -
; 6 - ; 7, 10-13 - ; 8 - ; 9 - ; 14, 15 - ;
16-18 - ; 19 - .
: I - ; II - ; III ; IV ; V
; VI ; VII ; VIII ; IX
607
8 583
. 1 2 3 ,
0,1-0,3 / " ", .. ,
. 6 7.
573-633 0,4-0,5 .
9, 14, 13. 15
10 16-18.
. 15 19, .
, , " ".
" ",
1015% ,
.

, .

RsiH2Cl, HSiCl3. . ,
8-10 ,
. ,
.
608
" ".
- , - .
,
: (15-20%), (25-40%), (35-40%). .

.
() 423-473 . (. 16.3) , , .
. 16.3.

1 - ; 2 - ; 3 -
633-643 . 663
.
, , 20-65% , 15-60% ,10-50% - .

.
,
. 70% 5-10% . , ,, 1,5-2 .

609
,
, . , , .

.
-
. , 70-80%,
, 5% 0,005% ,
(0,01-1%). , -,
.
. .
16.4
.
. 16.4.
5%
0,001% .
(------- - )
1 - ; 2 - ; 3 -
(
70%) 0,001%
- .
610

- (65)nSiClmH4-m-n, m
n = 13, (m+n) = 4, - ( ).
, () , , . -, - . ,
, .

:
nC6H5Cl + Si
723-773
(C6H5)2SiCl2 + C6H5SiCl3 +
+ (C6H5)3SiCl + C6H6 + C6H5C6H5 + .

, . 80%. , - .
16.2.2.
, -, -, . .
, :
RH + HSiRnCl3-n
RRnSiCl3-n + H2
,
R Ar; R 3, 25, 65.
- .
473
. .
611

:
CH3SiHCl2 + C6H6
CH3(C6H6)SiCl2 + H2.
513-523 , :, 3:1, .

, SiH, . ,
- -.
(H2PtCl6) , , . 273-423 .
, .
. :
(C2H5O)3SiH + CH2=CHCH2NH2
Cl2(CH3)SiH + CH2=CHCN
(C2H5O)3SiCH2CH2CH2NH2,
Cl2(CH3)SiCH2CH2CN,
Cl2(CH3)SiH + CH2=CHCF3
Pt
RCH=CH2 + SiHCl3
RCH=CH2 + CH3SiHCl2
Cl2(CH3)SiCH2CH2CF3,
RCH2CH2SiCl3,
RCH2CH2SiCl2.
CH3
:
Pt
Cl3SiH + HCCH
Cl3Si-CH=CH2
HCCH + RSiHCl2
H2PtCl6
CH2=CHSiRCl2.
612

- 823-843 280-300 :
CH2=CHCl + SiHCl3
CH2=CHSiCl3 + HCl,
CH2=CHCl + CH3SiHCl2
CH3(CH2=CH)SiCl2 + HCl.

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

,
.
...
28
32
40
, ,
.....
.
.
...
16
10
14
60
,
. ,
. ,
, .
16.2.3.

.

:
C6H5SiCl3 + (CH3)3SiCl
C6H5(CH3)SiCl2 +
+ C6H5(CH3)2SiCl + (CH3)2SiCl2 + CH3SiCl3.
613
523-673 . .
16.2.4.

( ) 773-1023 .
, , . ,
- :
RRnSiCl3-n + HCl
RCl + HSiRnCl3-n
RH + RnSiCl4-n
, .
:
C6H5Cl + HSiCH3Cl2
C6H5Si(CH3)Cl2 + HCl.
, :
CH2=CHCl + HSiCl3
CH2=CHCl + HSi(CH3)Cl2
C6H5Cl + HSiCl3
CH2=CHSiCl3 + HCl,
CH2=CHSi(CH3)Cl2 + HCl,
C6H5SiCl3 + HCl.
614
16.2.5.

Sil.
:
(C6H5)2Si(OCH3)2 + 2H2O -CH3OH
(C6H5)2Si(OH)2,
[(CH3)3Si]2NH +2H2O
-NH3
2(CH3)3SiOH,
(Ni, Pt, Pd)

-H2
RSiH + H2O
RsiOH.

, .
:
2(CH3)3SiCl + NH3 -HCl
(CH3)3SiNHSi(CH3)3.
, :
CH3
H2O
[(CH3)2Si(OH)2] -H2O SiO + (CH3)2SiCl2
-HCl
CH3
n
- , , , .:
(CH3)2SiCl2 + 2C2H5OH -HCl
C6H5SiCl3 + 3CH3COONa
(CH3)2Si(OC2H5)2,
C6H5Si(OCOCH3)3,
-NaCl
O
O
RSiCl + CH3-COC-CH3
- CH3CCl
O
RSiO-CCH3
615
. :
H5C6 CH3
H5C6 C6H5 H3C CH3
H5C6
OSiO
CH3
HOSiOSiOH + ClSiOSi -HCl
Si
Si
H3C CH3
H 3C
OSiO
CH3
H3C CH3
H3C CH3
:
ZnCl2
CH3)2SiCl2 + 2CH3OH
2CH3Cl + [ (CH3)2SiO]n +
H2O.
16.2.6
, , - , . :
Si + 2Cl2
SiCl4.
473-513 .
, 413 . .
1173-1273 , :
2Si + SiCl4
2SiCl2
SiCl2 + HCl
HSiCl3.
SiCl2 , .
616
333 , (Cl2SiNH).

RR
RR
SiO
OSi
O
Si
O
SiO
OSi
R R
R R
,
R- .
:
(CH3)3SiOCH3 + SiCl4
(CH3)3SiCl + CH3OSiCl3.
HCl ROH (R=, 3 .).
16.2.7.
.
, .

, ,
.
,
0,01% (.) 0,02% (.) .

, .
, , .
,
617
. , (343,1 ) (339 ) ~ 4. , , 347,5 .

,
380 .
16.3.
.. 1935-1936 . , , :
R
SiO,
R
R, R , Alk,Alkenyl, Ar ( R, R ).
, Si 440-495 / 360
/ . ,
, Si , 213 173 .
:
H
CH3
CH=CH2
C6H5
C6H5
SiO > SiO > SiO
> SiO > SiO
CH3
CH3
CH3
C6H5
CH3
16.3.1.
1950- 1980-
~200 . /.
618

CH3
CH3
HO[SiO]nSiOH,
CH3
CH3
(n = 5400-8780)
-1
CH3
CH=CH2
CH3
HO[SiO]n[SiO]mSiOH
CH3
CH3
CH3
n = 5400-8780;
m = 5,4-8,78 ,
m = 27-74 -1.
, -1
223 523 . ,
,
CH=CH2
C6 H 5
CH3
HO[SiO]m[SiO]n[SiO]kH
CH3
CH3
CH3
m:n:k=3:80:917
203 523
573 .
, ()
CH3
C2 H 5
CH3
HO [SiO]m[SiO]n[SiO]pH
C2 H 5
CH=CH2
CH3
m:n:p=91,87:8:0,03,
.
. ,
10-12
600%.
619
,
.
, :
CH3
CH2CH2CH2CN
CH3
CH3
[SiO]n[SiO]m
; [SiO]n[SiO]m
CH3
CH3
CH2CH2R
CH3

(; R = C2F5,
C3F7 )
- , , . ,
.
. , , , , .
-1 , , , . , -1, . .
16.3.2.

, - , , - () ,
.
620

.
, , :
R
Cl
H
R Cl
Si
+ H2O
O:
Si
R
Cl
H
R Cl
R
Cl
Si
+ HCl
R
OH
. :
R
R
Cl
HOSiOH
Si
R
RRSiCl
OH
R
R
R
ClSiOSiCl
R
R

.
,
: , , .
. .
4-8- .
, .
. , (
)
-, -.
H 2O
621
- . .

, 90-95%.
, .
, , , . , ,
.

.
,
(, 1) .
, .
. 16.5 . , () 22-25%.
. 16.5.
:
1:0,85
- . (
6-18 ). .
622

.
( ,
), , .
, , .
.
:2, = 1:(1,5-1,9).
(m + p)(CH3)2SiCl2 + (m + p)H2O
m = 36; p = 3035.
CH3
HO[(CH3)2SiO]p-1SiOH
CH3
[(CH3)2SiO]m + 2(m + p)HCl,

30%- , .

. 16.6.
6 3,
. 298-303 .

. 4 , ,
0,4% , 5,
2.
. 7.
623
. 16.6.
1 - ; 2 - ; 3 - ; 4 - ; 5 - ; 6 - ; 7 - ; 8 - ; 9 - .
: I ; II ; III ; IV ; V ; VI ; VII
16.3.3.

, . .

573-673
:
[(CH3)2SiO]x
[(CH3)2SiO]l + [(CH3)2SiO]m + [(CH3)2SiO]n
l + m + n = x.
624
,
,
623-673
90%. - .

.

453-473 . , (~ 60%),
(~20%), (10-15%) (~5%).
. 573-673 5-15 , Si2. ,
.
:
CH3
CH3
CH3
NaOH
m/n SiO + H2O.
HO SiO
SiOH
CH3
m-1 CH3
CH3
n

. . 87% 13% .
.

, , . ,
, .
, "", ,
625
. ( ),
, ,
.
. 16.7. ()
1 ; 2 ; 3
; 4 ; 5 ; 6 ; 7 ; 8 ; 9 .
: I ; II - ; III ; IV
; V ; VI CaCl2; VII
.
(. 16.7).
1 , (
100-150 ) 453-463 .

, . ( ) , :
SiH + KOH
SiOK + H2.
626
4, . - 9.
5.
6.
0,01% 7 .
- 8,
493 . 4 5.
. 8 ,
. , ,
.
: 1-2% , 85% , 13-14% . .
16.4.

, , .

, .
, , . , 16.2.
16.2
,
.
. ., (, ) . .,
443-444
290,4
407-408
357,0
1,3,5--1,3,5-:
d420
0,9558
-
nD20
1,3968
-
627
-
-
1,1,3,3,5--5-
1,1--3,3,5,5-
1,3,5,7--1,3,5,7-
1,1,3,5,7--3,5,7-
1,1,3,3,5,7--5,7-
1,1,3,5,5,7--3,7-
1,1,3,3,5,5,7--7-
1,1,3,3--5,5-
1,1,5,5--3,3,7,7-
1,1,3,3--5,5,7,7-
1,1,3,3,5,5--7,7-
1,1,3,3,5,5--5,5-
1,1,3,3,5,5--7,7-
1,1,5,5--3,3,7,7-
1,3,3,5,5--1--
1,3,5--1,3,5--(3,3,3)-:
-
-
438-458 (14,7)
463 (14,7)
372,5
312,5
508
1,1062
1,5397
1,0185
1,4550
361,2361,7
404-405
423 (4,9)
237
1,0805
1,5134
440-441 (68,6)
1,0602
1,4881
443-446 (68,6)
1,0636
1,4878
384-386 (68,6)
1,0163
1,4490
563-573 (9,8)
461
335-337
603-613 (9,8)
473-474
404-405
345
439-443 (78,4)
1,0623
1,4880
390 (98,0)
287
0,9555
1,4308
329 (58,8)
265
0,9583
320-322 (24,5)
0,9566
1,4092
348 (4,9)
205
1,4155
431-432 (98)
223
0,9594
1,4340
354 (29,4)
1,0173
1,4180
377 (39,2)
257,5
308,5
628
16.4.1.
, , 473-673 . , .
, , , , .

.
ZnO + Ph2SiCl2
ZnCl2 + 1/3[Ph2SiO]3 , Ph = C6H5.
96%.
CuO, PbO, Ag2O, MnO2, CuSo4, FeSo4 .
75%.
338 98%.
, (462 ).
.
, , .. .
. - ,- ():
ClRRSi(OSiRR)mCl + HO(RRSiO)nH
R
R
(SiO)m+1(SiO)n + 2HCl,
R
R
629
R, R, R, R - ; m n
- (m 0); (m + n)3.
.
, ,
.
.
16.4.2.

: - .
SiO- SiN-, .. .

.
-
1962 . . --
:
SiN
+ CO2
SiOC(O)N
-. , , -
N-:
O
RRNCOSi(3)3.
RRNH + CO2 + HNSi(3)3
, N-, .
- :
-
[RRNH2]Cl
O
HN(Si(3)3 )2/CO2
RRNCOSi(3)3,
[RRNH2]2SO4
[RRNH2]OC(O)NRR
630
- ,
RRNH + CO2 + HN(Si(3)3)2 + (3)3SiCl
RRNC(O)OSi(3)3,
-
RRNC(O)OSi(3)3 + RRNH
RRNC(O)OSi(3)3 + RRNH,
-
nRRNC(O)OSi(3)3 + ClnSiR4-n
[RRNC(O)O]nSiR4-n + n(3)3SiCl.

. ,
(25)2Si()2 523 60
373 ,
20-30 ./2, 5,15 /2.
(C6H5)2Si()2 .
, .
N-
N- :
2RO()CNHSi(3)3
423-453
(3)2SiN(R)C(O)O(CH2)3
RNCO + (CH2)3OSi(3)2,
t0
(3)2Si(CH2)3NC(O)OR
NC(O)OR
(3)2Si
Si(3)2
RO(O)CN
0
(3)2NNC(O)OR
Si(3)3
(3)3SiNCO + (3)3SiOR + RO()CNH2,
RO(3)2Si(CH2)3NCO,
t0
2RO(3)2Si(CH2)3NCO,
[(3)2NNCO]2 + (3)3SiOR,
631
NCO
t0
CH2 [NC()OR]2
Si(3)3
CH2
+ (3)3SiOR,
NCO
RRRSi(CH2)nNCO + ROSi(3)3,
RRRSi(CH2)nNC()OR
Si(3)3
n = 13.
-N-
, , .

. , ,
.
N- .

- -
RnSi(OROH)4-n, R=Alk Ar, R= Alkylen Arylen,
n = 02. -
, () :
SiO(CH2)nO-C(O)NH
SiOC6H4O-C(O)NH
. . ,
, ,
151 /2, 373 468 /2.
- . ,
Si(OCH2CH2OCH2CH2OH)4,
(3)2Si(OCH2CH2OCH2CH2OH)2,
(3)2Si(OCH2CH2OH)2,
25Si(OCH2CH2OH)3,
Si(OCH2CH2OH)4,
3Si[OSi(3)2CH2OCH2CH2OH]3
65Si[OSi(3)2CH2CH2CH2OH]3,
Si(OCH2CH2CH2CH2OH)4, -
632
, , .
, ,
.
- (. 16.2).
16.2
*.

C6H4[SiO(CH2)4OH]2
C6H4[Si(CH3)2OSi(CH3)2A]2**
O[Si(CH3)2C6H4Si(CH3)2OSi(CH3)2A]2
C6H4[CH3SiC6H5OSi(CH3)2A]2
C6H4OC6H4[Si(CH3)2OSi(CH3)2A]2
C6H4OC6H4[CH3SiC6H5OSi(CH3)2A]2

Si: 293 ,
110-5
/2
600
31,1
1,11
356
36,4
1,11
450
38,4
1,251
422
20,0
1,11
380
32,1
1,11
415,7
1,11
362,6
31,0
1,11
* () ,
** A = (CH2)3OH.

.
:
CH3
CH3
HO(CH2)nSiOSi(CH2)nOH + OCNRNCO
CH3
CH3
CH3 CH3
O
O
O(CH2)nSiOSi(CH2)nOCNRNC
, (n = 14).
x
CH3 CH3
H H
633

, .
. ,

. ,
.
-, - , , .
:
CH3
HOR[SiO]nSiROH + HO~~OH + OCN~~NCO
CH3
O
O
O
CH3 CH3 O
[OR(SiO)n~SiROCNH~~NHCO~~OCNH~~NHC]n ,
CH3 CH3
- , - .

.

, .
SiOSi
.
523
598 .
, , ,
, , , , . ,
.

. ,
634
, .
, .
, , , , - .

R R
OCN(CH2)xSi~Si (CH2)xNCO + NO(CH2)y ~ (CH2)yOH
R R
O
R R
O
CNH(CH2)xSi~Si(CH2)xNHCO(CH2)y~(CH2)yO
R R
n ,
R = Alk, Ar; x, y 1.

. , .
:
Et3N
R3Si(CH2)3NCO + R3COOH 293 ; Et2O
R3Si(CH2)3NCOOOCR3.

,
, .
635

,

. ,
. ,
-
:
RRNC(O)OCH2CH=CH2 + HSiRnX3-n
X = OR, Cl; n = 1 3.
RRNC(O)O(CH2)3SiRnX3-n,

Si- , =
N.
, (AllNCO AllOH ) , - N:
HOROH + OCNCH2CH=CH2
CH2=CHCH2NHC(O)O ~ OC(O)NHCH2CH=CH2 ,
OCN ~ NCO + OHCH2-CH=CH2
CH2=CHCH2OC(O)NH ~ NHC(O)OCH2CH=CH2

Si-.
() - :
nOCN ~ NCO + mHOROH + (n-m+2)HOCH2CH=CH2

CH2=CHCH2O(O)CNH ~ ~ NHCO(O)CH2CH=CH2 + (RO)3SiH
,-[(RO)3Si]2,
R = 3, 25, Alk; n = 2 3.
636
, , .
2,2-(4-), 9,9-(4), 2,2-(4-), (4--3,5), 1,1-(4-) :
HO
O
OCO
O H
n
CH2=CHCH2NH C O
O
+ 2OCNCH2CH=CH2
O
OCO
O
n
O C N-HCH2CH=CH2
O
.
.

,

, :
(3)3Si(CH2)3OC(O)Cl + NH3
(3)3Si(CH2)3OC(O)NH2.

:
(RO)xR3-xSi(C6H4)y(CH2)mX
MOCN
(RO)xR3-xSi(C6H4)y(CH2)mNHC(O)OR,
R, R = Alk, Ar; M = K, Na; X = Cl, Br; = 13.

.
- , , ,
637
228 221
230 273 :
Et3N
ClC(O)ORSi(3)2OSi(3)2ROC(O)Cl + NH3[(CR2)4N3]mH
{C(O)ORSi(3)2OSi(3)2ROC(O)N3[(CH2)4N3]m}x,
ClC(O)ORSi(3)2OSi(3)2ROC(O)Cl + H2NNH2
[C(O)ORSi(3)2OSi(3)2ROC(O)NHHN]x,
R = CH2, (CH2)3, (CH2)2OCH2, (CH2)3C6H4; = 2, 3; m = 1, 2.

:
mHN
NH
CH3
CH3
mClC(O)O(CH2)2OCH2SiO[SiO]nCH2O(CH2)2OC(O)Cl
-HCl
CH3 CH3
CH3 CH3
C(O)O(CH2)2OCH2SiO[SiO]nCH2O(CH2)2OC(O) N N
CH3 CH3
m
,
.
,-() ,
l :
(3)3SiN(R)[(CH2)n(R)N]mSi(3)3 +
+ ClOC(O)RSi(3)2OSi(3)2ROC(O)Cl
{OC(O)RSi(3)2OSi(3)2ROC(O)N[(CH2)nN(R)]m}x.
.
16.5. -
638

. (1), (2), (3),
( 4), (5) (6) :
CH3
CH3
CH3
;
CCH2 ;
SiO ;
SiCH3
CH3
CH3
CH3
n
n
n
1
CHCH2
H3CSiCH3
;
2
CH3
CH2=CHSiCH2CH=CH2 ;
3
CH3
C=C
n
CH3
Si(CH3)3
CH3
n
4
5
6
(4) . ,
.
.

( )
( 2 )

..
-
( )
2
2N2

2 + N2
2 + 4
2 +

, -
639
N2 + 2 .
. ( ):
Mg + 2=Cl
CH2=CH-MgCl.
:
2=-gCl + (CH3)3SiCl
CH2=CH-Si(CH3)3 + MgCl2.

. . 328-329 99,9%.
, .
,
:
1. , , ;
2. - (2-4)
;
3. -
( , ).

:
Mg + C2H5Br
C2H5MgBr,
MgBrCCR + 26,
C2H5MgBr + CHCR
R2RSiCCR + MgBrCl.
MgBrCCR + R2RSiCl
40
70%.
:
- ;
-
( );
- .
640
313-343 K.
. 16.8.
. 16.8. ( )
1 ; 2, 3, 16 ; 4-7 ; 8 ; 9 ; 10-15 ; 17 - .
: I ; II 25Br; III - 25MgBr;
IV ; V ; VI ; VII ; VIII ; IX ; X ; XI ; XII ; XIII -; XIV ; XV ; XVI ; XVII ; XVIII

- () - .

1, , - . , (0,3% (.)
). 333-353 .
.
318-323 . 7 8, 10-15. 12-14
70%, 70-90% 90-98% . -
641
8 . - 7
16, 17 . , .
- - , .
. .. .. .
642
17

. , , -, -, - .
, , ,
600 , . : , , , . , .

, .
17.1.
17.1.1.
. Na2S Na2SO4 1073-1273 . Na2SO4 : H2, CH4, CO .
Na2SO4
Na2S + 4H2O.
[H]
823-873 ;
.
Na2S H2S :
H2S + 2NaOH
Na2S + 2H2O.
Na2Sn (n = 25) Na2Sm (m = 39)
Na2S.
Na2S + 3S
Na2S4.
643
, :
n ClRCl + n Na2Sx
[RSx]n + 2n NaCl (x = 15).
Na2S4, 1,2-.
:
n Na2S4 + n ClCH2CH2Cl
[CH2CH2SSSS]n
+ n NaCl.
:
n ClArCl + n Na2Sx
[ArSx]n + 2n NaCl (x = 15).
n- (1,4-).

1,2- 1,4-.
17.1.2. 1,2-
1,2- ClCH2 CH2Cl - ; . . 356,5 , . . 237,5 .
1,2- :
1.
[FeCl3]
ClCH2CH2Cl.
CH2=CH2 + Cl2
2.
C2H6 + 2Cl2
ClCH2CH2Cl + 2HCl.
3.
,
HCCH + 2HCl + 0,5O2
ClCH2CH2Cl + H2O.
644
4. (AlCl3/NaCl/FeCl3)
ClCH2CH2Cl.
CCH + 2HCl
5.
, SbCl5
C2H5Cl + Cl2
ClCH2CH2Cl + HCl.
6. 1,2-
BrCH2CH2Br + SbCl5
ClCH2CH2Cl + SbCl3Br2.
7. , ,
ClCH2CH2Cl + 2H2O.
HOCH2CH2OH + 2HCl
8.
2CH2N2 + ZnCl2
ClCH2CH2Cl + N2 + Zn.
1,2- : - - .
. 5.
17.1.3. n-
n- ClC6C4Cl . ; . . - 326,5 , .
. - 327,0 , .. 447,5 .
n-:
1.
- 1,4- :
+ 2Cl2
[FeCl3]
Cl
Cl
+ 2HCl.
2. n- n- :
Cl
NO2
H2
-H2O
Cl
NH2
HNO3; HCl
-H2O
645
+
N=N
Cl
Cl-
[Cu2Cl2]
-N2
Cl
Cl
1,4- 1,2 ,
.
, , .
4,4-, . :
O
O
Cl +
Cl
_S
OArO-
O-Ar-O
, , . ,
-.
4,4 :
1. , 50%
Cl
S O2
Cl
+ 2HOSO2Cl
Cl
+ 2HCl + H2SO4 .
2. n-
:
SO2Cl
Cl
Cl
-HCl
S O2
Cl
Cl
3. n,n- :
Cl
Cl
+ H2O2
Cl
S O2
Cl
646
17.2. ()
(R2P=N)n , P=N-, .

, , - ,
, , , ..,
.

.
:
n H4Cl + nPCl5
(NPCl2)n + 4HCl.
.
(NPCl2)3,
387 . (NPCl2)4, c . . 401 ,
.
, , , l3P=(NPCl2)n=NPCl4).
. , ,
, .
. . 17.1 . ,
.
17.1.
d420, / . .,
(NHCl2)3
(NPCl2)4
(NPCl2)5
1,98103
2,18103
-
387
396,5
313,5-314
(NPCI2)6
(NPCl2)7
d420, /3
, .,
363-364
255
647
. 17.1.
1, 2 ; 3 ; 4 ; 5, 11, 17, 20 ; 6
; 7 ; 8, 13 -; 9, 12, 21 ; 10, 19 ; 14, 15
;
16 ; 18 -; 22 ;
23
.
: I ; II ; III PCl5 NH4Cl; IV ; V HCl; VI
; VII ; VIII ; IX

, .. . ,
7-8 . ,

(NPCl2)nHCl3, n = 1020.
648
.
-, , , ,

,
, .
. 17.1.
: ; , .

(. . 381-387 ) ,
. , .

.
,
.

. 223 [NP(NH2)2]3.
- , .
, , , .

,
.
Cl
Cl
-P=N-
2nROM
R
-P=N-
n
n
R=OAlk OAlkF , O - ; .
649
17.3.
, . ,
,

. .
60- ,
1962 . , , 10
, , , . : -, - .
- :
Li
Li
B10H10Li2
650
, ,
-.
- ,
. Li- , , , -. , -- ,
, - .
--, -- .
- 743-773 -. - 923-973
- ( 10%), . - -, -, Li--.
, , 1,7-- , : , , , . 1,7- .
B10H14
HC
CH
HC
C6H5N(CH3)2
CH3COOCH2C
CCH2COOCH3 + B10H14
C6H5N(CH3)2
CH
CH3COOCH2C
B10H10
CCH2COOCH3
B10H10
450C
CH3OH
HCB10H10CH
HOCH2C 0 CCH2OH
C4H9Li
B10H10
LiCB10H10CLi
450C
CO2
HOCH2CB10H10CCH2OH
HOOCCB10H10CCOOH
H2SO4
PCl5
CrO3
HOOCCB10H10CCOOH
ClOCCB10H10CCOCl
PCl5
()-- - 1,7-- - -
651
,
- .
, ,
,
"".
()-- ()-- :
HC
CH
B10H10
C4H9Li
LiC
CLi
(CH3)2SiCl2
B10H10
Cl(CH3)2SiC CSi(CH3)2Cl
o
B10H10
310-350C
Cl(CH3)2SiCB10H10CSi(CH3)2Cl
_ HCl
CH3OH
CH3O(CH3)2SiCB10H10CSi(CH3)2OCH3
_ CH Cl (CH3)2SiCl2. FeCl3
3
ClSi(CH3)2CB10H10CSi(CH3)2Cl
CH3
CH3
CH3
SiCB10H10CSi O
CH3
CH3
SiCB10H10CSi O Si O
CH3
100
CH3
CH3
CH3
CH3
200
[Cl(CH3)2Si]2O . FeCl3
CH3
CH3
CH3
CH3
SiCB10H10CSi O Si O Si O
CH3
CH3
CH3
CH3
300
.
1980- 1990- , , .
652
, , , , , ..
,
.
(B4C) . , B10H12L2 (L ). 1960- , .
;
, , () , . , , , , , .
B4C/SiC
"", (-), :
CH3
LiC
C C
CLi
CH3
CH3
Cl Si O Si C B10H10 C Si O Si Cl
CH3
CH3
CH3
C
CH3
C C
CH3
CH3
CH3
CH3
CH3
C Si O Si C B10H10 C Si O Si
CH3
CH3
CH3
CH3
n
"
"

, , ,
.
653
- :
BCl3
RNH2. BCl2
RNH3Cl
HCl
Cl
R
3 RNH2. BCl2
6 Me3N
Cl
B
N
R
N
B
.
6 Me3N3 HCl
Cl
1960- .
17.4.
, ,
: ,
,
,
,
, - , . , , , , .
, , ,
. , .
CH
(1)
N
CH
HC
N
1
(2) 1
NH2
C
N
H2N
H2N C
N
C CH2-RCH
C
NH2
C
N
O-CH2
O-CH2
NH2
CH2-O
CH2-O
N
CHR-CH2 C
N
C NH2
C
NH2
15 - - .
654
R = -2- -(3)2- , 3,9-2,4,8,10-(5,5) .
17.4.1.

, :
, , ..
, . ,
, . , : , , ..

, -, - , -, -, S- N- . () 500 .
:
1.
2 NH2
C-OH
H2N
H2N
NH2 , 500
H2N
NH2
N
X
N
X
NH2
= O, S, NH.
2. H2N
NH2 2HCl
X-H
H2N
O
O
, 500
+ HOCRCOH
N
X
= O, S, NH.
N
X
NH2
655
R=
;
SO2
Z = O, CH=CH, C().
3.
2 NH2
C-OH
H2N
H2N
NH2 2HCl
H-X
X-H
500
NH2
= O, NH.

, .
2,5-(-)-1,3,4-
H2N
O1
N4
NH2
2 NO2
COCl
NO2
NO2
H2NNH2
NO2
CONHNHCO
POCl3
-2
H2, Ni
O
C
NO2
H2N
O
C
NH2
656
4,4-(-)-2,2-
3
4'
H2N
N 2' 2 N 4
C C
HC
NH2
CH
:
2
COCH2Br
NO2
N
NO2
HC
C C
S S
+ NH2CCNH2
H2
N
C
H2N
NO2
CH
C C
HC
CH
5,5-(-)-2,2-(1,3,4-)
1
O
H2N
C C
N N
NH2
:
NO2
COCl
NO2
+ NH2NHCOCONHNH2
NO2 P2O5, 530 K
CO-NH-NH-COO-NH-NH-CO
-2
O
NO2
C C
O
H2N
NO2
C C
NH2
H2
NH2
657
5,5'-(-)-2,2-(1,3,4-)
O
H2N
C C
NH2
:
2
COCl
NO2
+ NH2NHCOCONHNH2
NO2
CO-NH-NH-CO-CO-NH-NH-CO
NO2
O
NO2
C C
N N
O
H2N
P2O5, 530 K
H2, Ni
NO2
C C
NH2
17.4.2. -
3--4 , N,N-(2--5-).
() 400 2,2---(5). :
O
HO-C
NH2
Cl-C
C-Cl
OH
O
HO-C
O
O
NH-C-C 6H4-C-NH
OH
O
HO-C
N
O
O
C-OH
HO
N
O
O
C-OH
, 500
658
.
, :
O
C
O
Cl C
O
O
O
C
O
O
T. . 509-510
C
O
C
O
H-O C
O
C Cl
O
C O-H
T. . 655-656
C
O
C
O
O
C
O
Cl C
O
C Cl
N
C
T. . 459-461
O
H-O C
O
C
O
C O-H
T. . 680-681
C
O
,
O
HO-C
HO-C
O
N N
O
R C
N N
O
O
C-OH
C
n
C-OH
O
R , , n = 01,
659
.
N
C
OC
O
N
C Ar
O
OC
N
C
N
C
CO
O
n O
CO
n = 01, r = -64; n-64; 6464; 64(3)264; 6464,

.
17.4.3.
NH
R1
R2
R1 = C64, R2 = 3-65; 3265 . 1972

. - , .
, , .
17.4.4.
,
OH
R
NH-CO-CH=CH-C=N
R = , 3, 1, - d,l
2:1 390-440 .
.

.
660
17.4.5.
- "" "", " " ().
- .
. .
N,N-
O
O
C
C
NRN
C
C
O
O
,
R - , Alkylen, Arylen, Aralkylen Alkarylen
. . . 600-800 , , , .
,
R - (, , ,
-, - .)
Y
O
O Y
C
C
NRN
C
C
X
O
O X
R = Alkylen, Arylen, Aralkylen ; X Y = H, 3, Cl .
,
CO
CO
R2
NRN
R1 ,
CO
CO
R, R1 R2 ,
CO
CO
HN
CO
HN
CO
CO
CO
NH
CO
CO
NH
661
CO
CO
HN
HN
HN
CO
CO
CO
CO
CO
CO
NH
HN
CO
CO
CO
CO
CO
CO
CO
CO
CO
NH
NH
NH
CO
HN
HN
CO
CO
CO
CO
CO
NH
CO
NH
Z .
, .
17.5.
, , .
,
, , - .
. , ,
, ,
,
, , . , ,
( ) (),
, , , .
.
. ( ) ,
.
662

. -
, , .
. , , 10-1210-10 1-1 10171022 /,
.

(, ) . , ~ 923 ,
.
. ,
, - , -,
.
.

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

. , () , ()
() .
()
, -
663
.
.
- . , -,
nV-
, ,
.
,
.
( ), ( , -) , -.
: , . .
: , , - -
CH2=CHY
MXn
-
CH2=CH
Z- M+Xn-1
CH2=CHL
CH2=CH
,
MXn
nV-
MXn
, n ; ; Y, Z L .
: , ,
.
17.5.1. , -
-, , -
664
(
2=-MgBr .),
( ) , .

CH2=CCH3
COOCH2SnR3,
CH2=CHLi, CH2=CNa, (CH2=CH2)2Hg .

, - . , , .
:
PhCH=CHMgBr,
(PhCH=CH)2Hg,
Ph3 SnCH=CHPh.

- -
. (IV)
H2C C CH2
H
TiCl2
C2H5
VIII .
, . Ni2+
Pd2+, :
CH=CH2
M(PEt3)2X
( M = Ni, Pd;
X = Cl, Br, I, NCS, NCO, CN, NO2).
-, :
665
CH2
CH
(M = Pt, Pd;
R = Et, Bu;
X = Cl, Br, CN, Ph).
M(PR3)2X
,
, .
17.5.2.
, - ,
.
.
, . ,

.
-
(), ()
, () M(OH)n
:
CH2=CHCOOH
M(OCOCH=CH2)n
M(CO3)n/2xM(OH)nyH2O
:
Ca(OCOCH=CH)2
Zn(OCOCH=CH)2
Pb(OCOCH=CH)2 .

. Ca, Ba Pb . .
.
, , , 1 .
, b, , .
666
, (3),, , .
. , . ,
.
. ,
b
, , .
17.5.3. ,
-

d-( f-)
IVA- VIIA VIII n- ( nV-), , , , . ,
, ( ).
,
- , .

. ,

.
():
Zn(4-)2Cl2, Ti(4-)2Cl2, Zn(4-)2J2, Co(4-)2Cl2.
17.5.4. -
() -
. , , - , . -
.
"-" : , , , . -
667
d .
:
H
C CH2
CO
Cr
NO
CO
CH=CH2
Cr
CO
CO
CO
()
CH3
Fe(CO)3
CH2OCCH CH2
-
, , ,
.
1955 .,
.
. . :
1. :
CH=CH2
CH2=CHC6H5 + (NH3)3Cr(CO)3
Cr
CO
CO
+ 3NH3.
CO
2. (469 ). ,
.
CH=CH2
Cr + CH2=CHC6H5 + L
,
,
L = PF3, CO.
CrL3
668
-, ,
.
CH2=CH-COOCH2
Cr(CO)3
- .
. ,
. ,
, , , .. , ()
.
669

.. 204-206
,
.......................................... ................................................................................447
................................................ ........................................................................ 443-446
............................................. ................................................................................443
493, 503
...503
...... .253, 254

............................................. ........................................................................252, 253
..263-268
665
..269-280
...269
.... 242-252
.................................................. ................................................................ 255-257, 268
............................................ ................................................244, 254, 445, 446, 450
, .............. ........................................................................ 242-252
...................................... 242, 262, 269, 445-446
........................................... ................................................................................393
....................................... ................................................................................286
................................................ ................................................................ 258-260, 526
................................................ ................................247, 250
, .
..47-56
N- .229
N- 231
.......................................................................................................610
, . 561
...54-56
, .. . 220
. .31
.......... ................................................................................280
...31
...280, 546
. .486
................................. ........................................................................ 546-548
, ...283
.. 392
..386, 391
670
.. 638
...339-340
N- ..228
..285, 527
................................................. ......................................... .. 199, 285, 343-344
.................................... .......................................................................... 197
, ..284-286
.499
-.358
, .. .526
, 298
n- 492
- , 253
, .629
-, .484
-
230
............................................. ......................................... .
505-506
412-415, 430, 431, 435, 439, 440, 447-460, 463-466, 496, 499
..368-372
368, 373-378, 436-437, 486
379-380
..
253
.304-305
..298-300, 309-311
.372-378
..366, 372
..404, 413,414
............................... ................................................................................490
.......... .........................................................................512,513
............................................... ................................................................................513
............................................ ........................................................................ 412-415
, .495
, ..495
, ..494
, .495
, 485
, .. 287
, .293
......................................................................................................................... 123,126
671
-.................... ................................................................................486
............................................... ..........................................................................72, 250
............................................ ................................................................ 251, 298-300

298-300, 306
.490
................. ...................... ................................................................................235

....................................... ................................................................224, 229, 235
...................... ................................................................................257
............................. ................................................................................611
............................... ........................................................................ 206-207
............................... .................................................................176, 180,191
........................................... ................................................................127, 194, 250
........................................... ..................................................................................99
................ ........................................................................ 643-644
........................................ ................................................................................611
.....................4, 127, 159-162, 185,189, 194, 195, 206, 207, 224, 238, 243, 249-251,
253, 257, 267, 286-288, 296-298, 306, 307, 390, 391, 459, 611
N-422
, ..238
..159-161
................................................ ................................................................................540
......................... ................................................................ 537, 544-546
................ ................................................................................270
................................................ ................................................................................298
............................................. ................................................................................239
..159
, ..281
................................................ ................................................................................579
................ ................................................................................213
..499
3- 3--N-
233
, .214
................................................ ................................................................................493
............................................. ................................................................................503
, 659
20, 27, 28
.................................................... ............................................................................ 30-34
................................................ ................................................................................. 28
................. ............................................................................ 35-39
, ............................. ................................................................................659
........................................ ....................................................................... 576-578

.......................................... ........................................................................ 404-409
672
..406-408
.405-406
...408-409
.............................................. ................................................................................404
................................................ ................................................ 369, 370, 401, 584-588
................................................ ............................................................................... 348
............................................. ................................................................................489
.......................................... ........................................................................ 644-645
, 573
(-)(5,4-d)-, 466
2,5-(-)-1,3,4-,
655
2,5-(-)-1,3,4-, ..464, 655
4,4-(-)-2,2-,
..465,656
5,5-(-)-2,2-(1,3,4-), .465, 656
2,2-(4-)..541
2,4-(,--4-)-.541
2,2-(-), 469
472, 660, 661
, .535-537

535-550
.552
...537-538
..539-541
-,- ...548
550
537-550
.535-537
.538
...543-545
551
S
..556-558
.550,551
....552
.551
...499
, .517
, .588-590
-1,3..32
..393-394
................................ ........................................................................444, 449
........................ ........................................................................ 442-443
.................................. ........................................................................ 442-443
................................................ ........................................................................ 123-135
118-123, 217-218, 444, 449, 459
673
................................................... ................................................................................118
.......................................... ........................................................................432, 460
...195-197, 394, 444
.................................. ..........................................................................32, 217
................................ ................................................................................460
-, 123-131
................................................ ........................................................................ 370-371

............ ........................................................................ 129-131
................................................ ......................................................................30, 33, 86
.................................................... ............................................................................31, 33
. 127-129
..131-133
-1,3
................................................ ................................................................................525
............................................. ................................................................................238
-1,4,
................................................ ........................................................................ 389-398
............................................. .........................................................................224,389
-
.......................................... ..................................................................................98
................................................ ................................................................................173
................................................ .............................................................................95,96
83, 84
............................................................................................................163,164
................................................................................................................127-135
105-107
...371, 372
5-(-2--4)-2, ....170
-1,4,
...224,389
127
. 126, 127, 389-398
-
......................................... ........................................................................224, 435
................................................ ................................................................................397
................................................ ................................................................................427
............................................. ........................................................................400, 427
294-311
.................................................. ................................................................................297
................................................ ................................................................ 287, 296-311
............................................ ............................................................................... 295
.............................................. ................................................................................297
. .
294
674
............................................... ................................................................................237
................................................ ............................................................................... 250
..194
4--1,3136
.250
. 240, 562
, ...207
................................................ ........................................................................ 191-192

...191
.............................................................. ...................................................286-293
N-.228-234
, ................. ........................................................................237, 238

, ................ ................................................................................240
, ..... ........................................................................ 238-240
, 238
5--2-. .220
, .236
2-.223
........220-223
.........220-221
220-221
2- 4-222-223
N-
................................................ ........................................................................ 223-228
............................................. ................................................................................223
, 235, 236
, .639
, ...612, 613
, ...239
, 205-206
.179-190, 250
..179, 180
2--5-. 222, 223
28
.................................................... ............................................................................ 78-80

................................................ .......................................................... 34, 66, 67, 78-80
, .......................... ......................................................................30, 34, 80
675
.68-70
, ...71,73
..71
..60-63
........... ............................................................................ 63-66
........................... ............................................................................60, 61
" " ......................... ............................................................................ 66-68
, .73
..66
-, 567
-, .294
-1,4, ...167
1,6-516
..447-450
. 440,447
................................................ ........................................................................ 516-517

...516
-1,6, ..449
, .628,629
, 469
, ..208
..493, 503
.503
...49-51
.51,52
.51
..51
52
, 417
1--2--3, 239
251, 252
.568
-, 253
N-(2-) ............................................233
, 281-282
N-(-)
227
N-(-)..227
..509-601, 611, 612
176,177
, .581-583
-1,3, .139,140
, .633
, ..561
676
.285, 526,527
............................................. ................................................................................341
.............................................. ..................................................................................28
............................. ..................................................................................29
..47
...49
......................................................................................................................44
..46
.. 176-178
..491
,....636, 637, 644
505
5,5(n-)2,2-(1,3,4-), ...657
, 488-491, 500-502
4,4-, ..493
4,4-, ..493-494
, ..................................463-464
4,4-,
.459,460
4,4-,
1,4-, ......................................................... 458-459
3,3,4,4- , .................................................486
-2,2,3,3- , ...............................................481, 482
-2,26,6- , 483
-2,3,5,6- ..482
-3,3,4,4- , .......................................................484
-1,4,5,8- , ........................................................485
-2,3,6,7- , ........................................................486
-3,4,9,10- , ................................................ 487-488
476-477
.475-481
472,473
2,2,3,3- .......... ................................................................................481
2,3,5,6- ........... ................................................................................482
, . -1,3
4,4-..556-557
1,4-
................................................ ................................................................................398
............................................. ................................................................................398
-, .558
............................................ ................................................................................499
................................................ ........................................................................ 506-523
677
............................................. ........................................................................ 496-500

.505
4,4-, ..468
, .468
, ....359
4,4--1,3132-133, 136,137,130-143
.................................................. ................................................................................622
................................................ ........................................................................603, 612
2,6-, .380
, 359
, ..347, 398
........................................... ................................................................................579
, ......................... ................................................................................216
..603
, ...624
...239
, ..438
, .500-505
, 501-505
.................................. ................................................................................510
................................................ ................................................................................508
4,4-, . S
..383-398
............................................. .........................................................................566,567
..............................................................566,567
, .632-634
, ..528
,
632-634
-, 525,526
.................................................. ........................................................................ 620-623

.............. ................................................................................614
..616-617
N,N-, ..520
N,N-, ..521
, 234
, ..510
, .494
................................................ ........................................................................ 552-556

............................................. ........................................................................ 552-553
4,4-, ..512
511
4,4-,
678
.556

, .
, ..559
.. . 644,645
, .194
1.1--1-, .. .207
n,n.
.. ..645
4,4-
................................................ ................................................................................557
.............................................. ........................................................................ 556-557
-
209
1,2-..199
1,2-
.183-185
................................................ ........................................................................ 643-644
, .414
..111,137,166
..427
.. 116
, 517
................................................ ........................................................................ 474-481

................................................ ........................................................................ 473-474
............................................. ................................................................................473
.....145-147
.98
................................................ ................................................................................262
............................................................................................................................ .97-99
........................................................................................................144, 262, 274-277
..108
. 145
..135-142
, 277
...36, 43, 46,47, 56, 99
150-152
..149
.........150-152
..162,163
.146

111
....145
679
.153
.135-146
..136
162
, . .238-240
-, ...548-549
, ...216, 578
54-56
, ........505
..634-637
3--1,2-..481
................................................ ................................................................................429
............................................. ........................................................................400, 429
................................................ ........................................................................ 401-427

............................................. ................................................................................400
, , ..403
, .
, ..430-431
, ..229
................................................ ........................................................................ 591-593

............................................. ................................................................ 499, 591-592
.............................................. ................................................................................595
-359
.636
, 649-653
, 96
.............................................. ................................................................................241
- ............................ .........................................................................122,123
................................ ................................................................................619
..122
, .......... ................................................................................331
.......................................... ........................................................................ 617-619
. .123-127
................................. ................................................................................619
, ................. ................................................................................193
, ........ ............................................................................... 197
, ....................... ................................................................................331
--................... ................................................................................123
.297
............................................. ................................................................268, 297, 422
..................... ................................................................................215
680
.260
.
..440-443
400, 439, 440, 443, 447
..382
382, 400
.349
.244, 255-261
...255
253
263-266
N-(6-).516
7-, ............. ........................................................................ 427-428
- . ................................................................................455
-. ................................................................................455
- ..... ................................................................................455
- .... ................................................................................455
9-
429
.429
, , .......................................................................400
11-
430-431
............................ ........................................................................400, 429
- ........... ................................................................................454
-........... ................................................................................454
-(-) .. ................................................................................454
-(-).. ................................................................................454
-(-) ......... ................................................................................454
-(-)......... ................................................................................455
- ............... ................................................................................454
, , .............................................................................400
-(-)............................................................................455
................................................ ................................................................................348
423
2,2-(n-) 469
, .......... ........................................................................ 430-431
459
.............................. ................................................................................460
4,4-, ........................................................................ 467-469
4,4-, ................................................................. 468-469
681
379-380
.379
380
, ............................ ................................................................................463
..277
....278
214
214
, ....................... ................................................................................378
...............................................................................................................261
262, 263
...263-266, 274
, ........................ ........................................................................ 487-488
-2,6-
............................................. ........................................................................ 380-381
........................................... ................................................................................380
, .......................... ................................................................................382
, ....................... ................................................................................382
, .................. ................................................................................241
459
.458
, ...400
..243, 249-252, 444, 449

...........................................................................................................269-270
.347-361
518
-2,5-, .. ........................................................................ 381-382
- ........................................... ........................................................................347, 358
.296, 300-303, 309, 310

.......................................................................296, 300-302, 306-307, 309
260
, ........ ........................................................................ 430-431
, ......... ................................................................................482
..378-380
..378
, ............. ................................................................................645
.................................................. ................................................................................595
-,
682
..438
.438
, .............................................................................424
, ............................ ................................................................................227
(-), ........................................................... 551-552

, ..............................................................................462
, ..................... ........................................................................ 657-659
. 440
-, , ............. ................................................................................518
, ................. ........................................................................ 657-659
, ..34, 35
..34, 35
.74-77
598-599, 602-605
...35-39
...39-41
..39-40
28, 29
..30
, .. 598, 602-605, 610, 615
, 603-605
..636, 637

................................................599
.................. ................................................................................598
......................................... ........................................................................ 598-599
..596-641
.596-601
, ...596-598
.
629-637
.636
................................................ ........................................................................457, 518

............................................. ................................................................................400
.......................................... ................................................................................519
................................................ ........................................................................ 518-519
...348
........................... .............................................................................46,47
.......................................... ............................................................................37, 43
-, ........................ ................................................................................457
-
..486
.363, 373, 375-378
........................................... ......................................................... 363-364, 366-367
683
-, ............................... ................................................................ 347, 349-361

.458, 518
, .
..........576
, .400, 432
..432-434
, 28, 29
, .
430
................................................ ........................................................................ 594-595
.593,594,653
................................................ ................................................................................281
............................................. ........................................................................ 270-271
, ................................... ................................................................................271
......................................................................................................................... 269-282
269
,
262-263, 273, 274
.273
, -
................................................ ........................................................................ 663-665
, - 666
, ..665-666
-, .666-668
72
173
270
............................................. ............................................................................ 71-73
................................................ ..................................................................................60
, ..443
, .519-520
.................................. ...............................................................304, 309, 310,

................................................ ................................................................................304
........................ ........................................................................ 279-280

................................. ........................................................................ 546-548
3--1,3139, 145-146
2--1...146
3--1.97, 146
2--2...146
3--2--1
. . 139
684
3--1--3..139
3--3--1 139
, ..612
..250
603, 612, 613
515
, .520
....169
, ...269-280
2--1155
2--2.....................................................................................................................155-159
4--1, 101
, .222
, ..430-431
-, . 217, 218
-, 375
, .. 603
, ..611
4--4-, .359
4--4-, . 359
, . 71
4-, .71
2-, ..71
5-, ..71
..603
, ...603, 605-607, 614, 622, 623
, 44
44
2--5-, 220-221
-..66,72,90
, 517
653-661
...649-653
649
, ............. ........................................................................ 661-668
............................. ........................................................................ 654-657
.653
, ...................... .......................................................................... 81-117
, ...508
, ..517
, 201, 206
, .
, .466
,
389
, .414
685
, .
, 642-643
.348
................................................ ................................................................................373
, 519
, ..525
................................................. ............................................................................27, 28
............................................. ............................................................................27, 56
-, 489
-491
-.491
-, ...466
-, 465
.......................................... ................................................................ 404, 514-515

........................ ........................................................................ 515-516
................................................ ........................................................................ 513-514
-, .465
, ...426
- ..490
, .463
..403
, ...117
- .564-565
, .
, ..419, 420
......................................................................................................................282
, ...614, 615
, .616
, .601
....................... ........................................................................ 612-613

.601-607
.............................. ................................................................................613
...................... ........................................................................ 614-615
, .223
-.162-163
, ..506-507
.624-626
1,1-..433-434
..208
207, 208
...207
686
, 466
, ...483
137
, ..223
, .71
.0, 34, 127
-................ ..................................................................................34
.............................. ............................................................................33, 34
-
................................................ ........................................................................ 434-439
................... ................................................................................224
224-227, 281, 400
, ........................ ........................................................................454, 455

............................... ........................................................................399, 400
-4
434-435
...434
-6,6........................................... ................................................................................400
6, ........................... ........................................................................453, 456
-7, ....................... ........................................................................400, 427
-8.............................................. ................................................................................400
-8,6........................................... ........................................................................400, 457
-9.............................................. ................................................................................400
-11............................................ ........................................................................400, 429
-12 400
. 399, 400
.453, 455
433
.434
, ..529
............................................. ............................................................................81, 82
........................................... ............................................................................81, 82
............................................. ................................................................................311
, ................. ................................................................................311
, , ..........................................................................312
, .228
, 223
.638
.597
637-638
.648
..637-638
687
.470-472
.470-472
................................................ ........................................................................ 531-535

.531-533
("").651
................................................ ........................................................................ 649-653
............................................. ........................................................................ 649-654
(--) 652
-, .. ........................................................................ 590-591
- ...................... ........................................................................ 637-641
..................................... ........................................................................ 642-643
-, .......... ................................................................................569
241
, .269
-4-1, 82
, ............................. ........................................................................113, 114
, ...81, 82
, ..524
.596
................................................ ........................................................................596, 597

............................................. ........................................................................596, 597
596, 597
.596
, ..646
, 528-530
c 331
637-638
597
..209

................................................ ................................................................................642
............................................. ................................................................................643
, ..343, 344
, 343, 344
..597
..638, 639
................................................ ........................................................................ 496-500

.............................................. ........................................................................497, 498
, .338
, ..643
................................................ ................................................................................316
............................................. ................................................................................316
688
, 193
, ..81
, ..327
346, 347
........................................ ................................................................................313
313-315, 536-537
, , , ........................................................ 313-315, 524
.347, 348
..347, 348
, .348
...................................... ............................................................................ 91-95

................................................. ........................................................................ 333-336
..................... ................................................................................252
............................................. ........................................................................ 246-249
-1,2
................................................ ........................................................................ 386-389
.............................................. ................................................................................386
...169
..90-94
- 113
...... ........................................................................391, 396
........................... ................................................................................277
............................................ ........................................100, 102, 105, 111, 153, 154
..100
....................... ................................................................108, 109, 113
........................ ........................................................................ 278-279
................................................ ......................... 247, 248, 257-258, 333-337, 443, 527
.................... ................................................................ 243, 246-249
... 90-95
.. 153-159, 252, 388
..217, 336-337
................................................................................391,396
................................................ ........................................................................ 387-389

............................................. ................................................................................386
388
, ..387
............................................... ........................................................................ 386-388

................................................ ................................................................ 216, 331-338
............................................. ................................................................................331
..337-338
-
...............................................................................................................................260-261
689
63-66
..635-636
.....630
....630
, ...71, 558-559
, .26, 27, 41-49
, ...614
620
N-, .519-521
.610-612
N-, .630-631
522
-, .629-630
...
522
-
113, 163-164, 386, 388,389
.46,51
.. 113
. 366
...361-366
...395-397
.285-286
284-285, 339, 392,393
.. . 339
-, .................. ................................................................................273
, . 123.
316-323
....................................................................................................... 316-321
................................................................................................ 321-322
.....................................................................................................322,323
304
....................................... ................................................................................283
........................... ................................................................................284
...283-284
390
390
........................................ .............................................................................89,90
690
..123
.123,124
..90
-
90
............................. .........................................................................292,293
............................. .........................................................................139,140
, ..216
, , 213-219
, ..437-438
345
................................................ ........................................................................ 344-345

343-344
, 462
393
........................................... ................................................................................126
.442
..207-208
, ...................................................................................................615-616
, ..506
, ..509
................................................ ................................................................ 488, 507-511

.............................. ................................................................................508
................... ................................................................................235
....................... ................................................................................235
.................................. ........................................................................ 366-367
........... ................................................................................468
................................................ ..................................363-364, 405, 422-424, 464-466
................................................ ..................................................................... 28, 30, 35
............................................. ........................................................ 348, 364-366, 508
-, 468
.. 653
, ..517
, ...583
2,2,4--1,3, ..525
603, 612
3,3,3-..209
209
..603
, 288-289
691
, .
....36, 44, 45
43
..42
.42, 44
43, 46
.. . ...43
.30, 46, 49
35, 43
35, 49
..35
.54-56
49
..43, 47
..36
..36
47, 49
...28, 32, 34, 42, 43, 47, 49, 56
176-177
177
..46, 56
.35-41
...46
.....47
..200-204
...................................................................................................171-173
... . 162-165
............................... ........................................................................ 123-170
............................. ........................................................................ 118-123
.54-56
228
........................................ ..................................................................................67
. 47
47
46
..46, 47
..35
324-326
173-175
....30-34
.199-205
692
171- 176
.162-165
.123-170
..118-123
. 54-56
..228
...67
. 47
...47
.46
. 46,47
.35
................................................................................................... .. 324-326
...173-175
. 30-34
. 199-205
..171-176
()
...611
.99-117
...................................................................................... 83, 86, 99-108
...................................................................... 92, 108-112
................................................................................................99-107
............................................................... 35, 107-113
......................................................................................................... 82-99
........................................................................................82,83
.............................. 44,45
. 41-43
.. 41, 44
.... 43,45
.. 35
.30,32
. 113-117
, 60,68
.60,63
.66, 90, 91
..77-78
.60-62, 66-68
..253, 267, 280, 309, 310
693
............................................ ............................................................................ 60-68

....................................... ............................................................................ 68-71
............................................. ................................................................................367
........................... ........................................................................ 566-567
...570-572
, ......................................................................................298-304
..499
, ..467
, .. 546, 547
-, 489-493
................................................ ................................................................................338
............................................. ................................................................................338
- -, .. 488, 489
, 215
, .613
612
, .610
, .554
, ..213
................................................ .................................................................. 65, 569-588

...575-584
.574-575
.........................................................................573
.......................................... .........................................................401, 411,412, 442
........................ ........................................................................ 537-544
............................. ................................................................................549
.................................. ........................................................................ 546-548
.................. ................................................................................557
- ........ .........................................................................548,549
.................. ........................................................................ 546-548
....... .........................................................................555,556
2--1 .
549
....556
2--1 549
....................................... ........................................................................ 553-555
588-590
549
542
.................................. ................................................................................385
........................ ........................................................................ 511-513
................................................ ......................................................... 223-226, 316-326
............................................. ................................................ 225, 268, 316, 390-391
...................................... ................................................................................390
694
..390
2-.222
490
N---490
................................................ .........................................................................509,510
............................................. ................................................................ 553-555, 557
................................................ ........................................................................ 646-649

............................................. ................................................................................646
, 646
.210-211
................................... ................................................................................211
..................................... ................................................................................210
.................................. ................................................................................191

.............................................. ........................................................................202, 203
.................... ................................................................................202
................................ ........................................................................203, 204
.204-206
........................... ................................................................................199
............................. ................................................................................199
..393
, .393
, .
, .494
, ..461-463

574
..
574

645
n- 645
, . 644.
193-197
............................................. ................................................................................193
..193
2--1, ..549
.620
, ..646
, .
-, 214
N-(-{), 228
, ..270
695
700, .244, 250, 269, 270

, .444
.............................................. ................................................................................403
...................................... ........................................................................426, 427
................................................ .......................................... 402, 409-411,428, 441-442
................................................ ........................................................................ 405-409
..404
...................................... ................................................................ 411, 415-416

................................................ ........................................................................ 401-402
................................................ ........................................................................ 415-416
....... ................................................................................416
............................................ ................................................................................416
................................................ .........................................................................402,403
........................................ .................................................................401,402, 404
................................................ ................................................................................411
............................................. ........................................................................ 433-434
.......................................... ........................................................................ 419-422

..417-420
, 110
2-(1-)--1...410
..416
, ..416
404
.................................................. ........................................................................414, 415
................................................. ........................................................................413, 414
2--1.410
.......................................... ................................................................................416
................................................ ................................................................................416
..
.460
1,5,9-
.......................................... ................................................................................432
................................................ ........................................................................432, 460
..
460
................................................ ........................................................................ 564-568

559-564
, 567-568
-1,5, ..167
, .113-117
-5---2--5-170
, ..34
, 115-117
696
................................................ ........................................................614, 615, 628, 629

.............................. ........................................................................626, 627
, 429
................................ ................................................................................527
................................................ .........................................197,199, 285, 341, 343, 527
339-341
.340
.......................................... ........................................................................201, 205

.......................................... ........................................................................ 170-173
.................................. ........................................................................188, 189
, .
...................................... ................................................................................214
................................................ ................................................................ 215, 307-308
................................................ ........................................................................214, 348
608-609
................................. ................................................................................385
.................................. ........................................................................ 327-329
........................................... ..................................................................96, 102, 104
....................... ................................................................................216
................................................ ...............................................................242, 329, 330
261
.................................. ................................................................................173
................................................ ................................................................. 30-34, 86-89
............................................. ........................ 159, 242, 252, 302, 303, 327-330, 612
........................................ ........................................................................ 427-428
.......................................... ........................................................................180, 643
.......................................... ................................................................................111
.......................................... ................................................................................207
252
................................................ ........................................................................ 383-386

............................................. ........................................................................383, 644
............................................... ........................................................................ 383-384

................................ ................................................................................385
................................................ ........................................................................ 327-330
228, 242-246, 327
, , 327-329, 384
... ............................................... .................................................................244, 260,267

.. 244, 245
697
..242-244
................................................ ........................................................ 287, 298, 305-307

.............................................. ........................................................................ 308-309
...169
235, 236
, ..602-603, 607-608
, 236
, ..339, 340
..339
--
........................... ................................................................................392
................................................ ................................................................................392
.............................................. ................................................................................393
, ....310
..347
--, .46
-
- -, 215

.289-293
............................. ........................................................................289, 290
...294,295
, ..565, 566
698
CONTENTS
PREFACE
INTRODUCTION
20
23
Part I
BASIC TECHNOLOGICAL PROCESSES
OF MANUFACTURING BASIC MATERIALS
IN THE SYNTHESIS OF MONOMERS
Chapter 1. Refining processes... 26
1.1. Thermal destruction processes..
1.1.1. Atmospheric-vacuum oil refining...
1.1.2. Visbreaking..
1.1.3. Thermal cracking..
1.1.4. Thermal contact cracking
1.1.5. Pyrolysis of oil raw material
Chemistry of basic pyrolysis process
General aspects of the process technology
Other methods of pyrolysis
1.1.6. Coking.
1.2. Catalytic processes
1.2.1. Catalytic cracking
Basic material and target products
Cracking catalysts
1.2.3. Catalytic reforming.
Transformations of six-membered cycloalkanes..
Transformations of five-membered cycloalkanes.
Transformations of alkanes
Transformations of aromatic hydrocarbons ..
1.2.3. Hydrocracking .
General aspects of the process technology
1.2.4. Alkylation processes
1.2.5. Isomerization of alkanes..
1.3. Structure of the present-day refinery
27
27
28
28
30
30
30
32
34
34
35
35
39
39
41
43
43
44
46
47
49
49
50
54
56
56
699
Chapter 2. Coal and gas processing processes
60
2.1. Gasification of coal..

2.1.3. Autothermal processes
2.1.4. Gasification in pseudofluidized layer. Manufacture of carbon oxide.
2.1.5 Hydrogenation of coal
2.2. Processing of natural and casing-head gases and lease condensate ..
2.2.1. Processing of natural gas
2.2.2. Processing of lease condensate..
2.3. Chemical backgrounds of manufacture of hydrogen
2.3.1. Catalytic steam conversion of hydrocarbons..
2.3.2. Catalytic conversion of carbon oxide..
2.3.3. General aspects of hydrogen manufacture technology
60
63
66
68
71
71
73
74
74
77
79
Part II
MONOMERS FOR POLYMERIZATION POLYMERS
Chapter 3. Olefin monomers
81
3.1. Lower olefins 82

3.1.3. Basic material in the manufacture of lower olefins. 83
3.1.4. Manufacture of ethylene.. 86
High-temperature dehydrogenation of ethane 87
Manufacture of ethylene from methane. 87
Manufacture of ethylene from methanol 88
Dehydration of ethanol.. 89
3.1.3. Manufacture of propylene 90
Isolation of propylene from refinery and cracking gases.. 90
Isolation of propylene from the products
f Fischer-Tropsch synthesis 90
Thermal dehydrogenation of propane 92
Catalytic dehydrogenation of propane and other lower alkanes (Oleflex
process).. 92
3.1.4. Manufacture of 1-butene.. 95
Isolation of 1-butene from hydrocarbon fractions C4 95
Catalytic dimerization of ethylene. 96
3.1.5. Manufacture of isobutylene. 97
Isolation of isobutylene from hydrocarbon fractions 4 97
700
Dehydrogenation of isobutene... 98
Isomerization of 1-butene.. 99
Synthesis of isobutylene from acetone.. 99
3.2. Higher olefins 99
3.2.1. Manufacture of higher olefins by dimerization and codimerization of olefins
99
Cationic dimerization of olefins
100
Anionic dimerization of olefins 101
Dimerization in the presence of organometallic catalysts 102
Coordination-catalytic dimerization and codimerization of olefins103
Dimerization of n-butenes 105
Codimerization of propylene and n-butenes 105
3.2.2. Disproportionation of olefins 108
3.2.3. Dimerization and disproportionation of olefins in a single technological
process 110
Synthesis of isopentenes from ethylene 110
Manufacture of isopentenes from propylene 111
Manufacture of isopentenes and higher olefins from ethylene,
propylene, and their mixtures 112
3.2.4. Manufacture of higher olefins from synthesis gas.. 113
3.2.5. Manufacture of cycloolefins .. 113
Synthesis of cyclopenten. 115
Synthesis of cyclohexent. 116
Synthesis of nonbornene 117
Chapter 4. Diene monomers 118

4.1. 1,3-Butadiene..
4.1.1. Lebedevs method
4.1.2. Ostromyslenskys method..
4.1.3. Manufacture of butadiene from acetylene..
Synthesis of butadiene via aldol (the aldol method)
Synthesis of butadiene via butynediol.
Synthesis of butadiene via dimerization of acetylene..
Pyrolysis of hydrocarbon raw material ...
4.1.4. Industrial methods for the manufacture of butadiene
from butane or 1-butene
Dehydrogenation of 4-5 hydrocarbons to olefins
Oxidative dehydrogenation of butane and butanes.
One-step dehydrogenation of butane to butadiene..
122
123
123
124
124
126
127
127
127
129
129
131
701
Isolation of butadiene.. 133

4.2.Isoprene135
4.2.1wo-step manufacture of isoprene from isobutylene and formaldehyde136
Reaction mechanism 137
Transformation of 1,3-glycols into dioxanes... 139
Formation of isopentene alcohols 139
Transformation of 4,4-dimethyl-1,3-dioxane into isoprene 140
4.2.2. Manufacture of isoprene from isobutylene and formaldehyde via 3-methyl1,3-butanediol (MBD)... ..143
4.2.3. Manufacture of isoprene from isobutylene and methylal.. 145
4.2.4. Manufacture of isoprene by dehydrogenation of hydrocarbons 5 146
Two-step dehydrogenation of isopentane to isoprene 146
One-step dehydrogenation of isopentane to isoprene 149
Two-step oxidative dehydrogenation of isopentane to isoprene.. 150
4.2.5. Manufacture of isoprene from propylene.. 153
Dimerization of propylene 153
Isomerization of 2-methyl-1-pentene to 2-methyl-2-pentene . 155
Cracking of 2-methyl-2-pentene . 156
Synthesis of isoprene from ethylene and propylene 159
4.2.6. Manufacture of isoprene from acetylene and acetone 159
4.2.7. Manufacture of isoprene by liquid-phase oxidation of hydrocarbons 162
4.2.8. Manufacture of isoprene from 2-butenes and synthesis gas.. 163
4.3. Diene monomers for the manufacture of ethylene-propylene-diene rubbers 165
4.3.1. Manufacture of nonconjugated dienes.. 166
Synthesis of dicyclopentadiene 166
Synthesis of 1,4-hexadiene.. 167
Synthesis of 1,5-cyclooctadiene.. 167
4.3.2. Manufacture of norbornene derivatives. 168
Synthesis of ethylidenenorbornene.. 168
Synthesis of methylenenorbornene.. 169
Synthesis of propenylnorbornene. 169
Synthesis of 5-(buten-2-yl-4)-2-norbornene. 170
Synthesis of cyclopentadienyl-5-endo-norbornen-2-yl-5-methan 170
Chapter 5. Halogen-containing monomers 171

5.1. Chlorine-containing monomers.. 171
5.1.3 . Theoretical backgrounds of hydrocarbon chlorination. 171
702
5.1.4 . Oxidative chlorination.. 173

5.1.5 Hydrochlorination.. 176
5.1.4. Dehydrochlorination 176
5.1.5. Manufacture of chloroorganic compounds 177
Gas-phase chlorination of hydrocarbons and chlorine derivatives 177
Liquid-phase chlorination of hydrocarbons. 178
Gas-phase decomposition of chlorine derivatives .. 179
5.1.6. Manufacture of vinyl chloride 180
Balanced method of vinyl chloride synthesis from ethylene .. 181
One-step of vinyl chloride synthesis from ethylene (Staffer proc.)185
Two-step synthesis of vinyl chloride from ethylene 186
Synthesis of vinyl chloride from ethane.. 187
Hydrochlorination of acetylene 189
5.1.7. Manufacture of vinylidene chloride 191
5.1.8. Manufacture of chloroprene 193
Preparative methods of obtaining chloroprene193
Industrial methods for the synthesis of chloroprene. 194
5.1.9. Manufacture of epichlorohydrin 197
5.2. Fluorine-containing monomers 199
5.2.1. Theoretical backgrounds of fluorination processes 199
5.2.2. Mechanism of fluorination reactions.. 200
5.2.3. Methods of fluorination of alkanes 201
Metal fluoride process . 202
Cryogenic fluorination. 202
Electrochemical fluorination 203
5.2.4. Fluorinating agents. 204
Molecular fluorine 204
Hypofluorites 204
Hydrogen fluoride 205
5.2.5. Manufacture of vinyl fluoride 206
5.2.6. Manufacture of vinylidene fluoride .. 207
5.2.7. Manufacture of perfluoro-derivatives of hydrocarbons. 207
Synthesis of tetrafluoroethylene.. 207
Synthesis of hexafluorobutadiene 208
Synthesis of perfluoroallenes.. 209
5.2.8. Manufacture of other fluoro-derivatives of hydrocarbons 209
Synthesis of trifluorochloroethylene 209
Synthesis of sym-dichlorodifluoroethylene. 209
Synthesis of 3,3,3-trifluoropropylene.. 209
5.2.9. Manufacture of chladones (freons) 210
703
Chapter 6. Vinylic monomers with aromatic and heterocyclic substituents.. 212

6.1. Styrene and its derivatives 212
6.1.1. Manufacture of styrene . 212
Preparative methods of obtaining styrene 213
Industrial methods for the manufacture of styrene . 214
6.1.2. Manufacture of -methylstyrene 218
6.2. Vinylpyridines. 219
6.2.1. General aspects of basic methods for the synthesis of vinylpyridines 221
6.2.2. Industrial methods for the manufacture of vinylpyridines 221
Synthesis of 2-methyl-5-vinylpyridine 220
Synthesis of 2- and 4-vinylpyridines and 2-vinyl-5-ethylpyridine 222
6.3. N-Vinylpyrrolidinone ... 223
6.3.1. Direct vinylation of -pyrrolidinone by acetylene. 224
6.3.2. Indirect vinylation of -pyrrolidinone ... 226
6.4. N-vinylcarbazole . 228
6.4.1. Manufacture of N-vinylcarbazole through vinylation by acetylene 229
6.4.2. Manufacture of N-vinylcarbazole by the vinyl exchange reaction 230
6.4.3. Manufacture of N-vinylcarbazoles by multi-step processes. 231
Decomposition of N-(2-hydroxyethyl)carbazole 231
Decomposition of 1-substituted N-ethylcarbazoles. 233
6.5. Other vinylic monomers.. 234
6.5.1. Manufacture of ethylidenenorbornene 234
6.5.2. Manufacture of vinyl toluene. 235
6.5.3. Manufacture of vinyl ketones 236
Synthesis of vinyl methyl ketone 236
Synthesis of isopropenyl methyl ketone. 238
Synthesis of vinyl phenyl ketone 239
Synthesis of vinylene carbonate. 239
Chapter 7. Acrylic monomers. 241

7.1. Acrylonitrile 242
7.1.1Synthesis of acrylonitrile via ethylene oxide and ethylene cyanohydrin243
7.1.2. Oxidative ammonolysis of propylene 246
7.1.3. Synthesis of acrylonitrile from acetylene and prussic acid .. 249
7.1.4. Synthesis of acrylonitrile via acetaldehyde and hydroxynitryl. 251
704
7.1.5. Synthesis of acrylonitrile from propylene and nitrogen oxides 252

7.1.6. Synthesis of acrylonitrile by direct interaction of ethylene, prussic acid, and
oxygen 252
7.1.7. Oxidative ammonolysis of propane.. 252
7.2. Acrylamide. 252
7.2.1. Preparative methods of obtaining acrylamide... 253
7.2.2. Industrial methods for the manufacture of acrylamide 254
7.3. Acrylic acid ... 255
7.3.1. Hydrolysis of acrylonitrile 255
7.3.2. Hydrocarboxylation of acetylene. 257
7.3.3. Vapor-phase oxidation of propylene 257
7.3.4. Hydrolysis of ethylene cyanohydrin 260
7.3.5. Hydrolysis of -propiolactone 260
7.3.6. Oxidative carbonylation of ethylene 261
7.4. Methacrylic acid ..
261
7.4.1. Gas-phase oxidation of isobutylene. 262
7.4.2. Oxidation of methacrolein .. 262
7.4.3. Gas-phase oxidation of methacrolein.. 263
7.5. Acrylates... 263
7.5.1. Manufacture of acrylates by esterification of acrylic
and methacrylic acids .. 263
Esterification by alcohols in the presence of sulfuric acid 263
Esterification by alcohols in the presence of ion-exchange resins 264
Esterification by olefins 265
7.5.2. Manufacture of acrylates via transesterification. 265
Transesterification in the presence of acidic catalysts.. 265
Transesterification in the presence of ion-exchange resins..
266
Transesterification in the presence other transesterification
catalysts.. 266
7.5.3. Manufacture of acrylates from ethylene cyanohydrin.. 266
7.5.4. Manufacture of acrylates from acetylene by the Reppe reaction.. 267
BASF process. 267
Rom and Haas process 267
7.5.5. Manufacture of acrylates from ketene and formal 268
7.5.6. Manufacture of acrylates from acrylonitrile. 268
7.6. Methacrylates. 269
7.6.1. Manufacture of methacrylate from acetone and cyanohydrin.. 269
Synthesis of cyanohydrin (prussic acid). 269
Condensation of acetone and prussic acid . 270
Synthesis of methacrylamide sulfate.. 270
705
Hydrolysis or esterification of methacrylamide sulfate .

Commercial realization of the process
7.6.2. Manufacture of methyl methacrylate from tert-butyl alcohol
Oxidation of tert-butyl alcohol to methacrolein .
Oxidation of methacrolein to methacroleinic acid..
Esterification of methacrylic acid to methyl methacrylate..
7.6.4. Manufacture of methyl methacrylate from isobutylene
7.6.5. New methods for the synthesis of methyl methacrylate
Synthesis of methyl methacrylate via isobutyraldehyde.
Carbomethoxylation of propylene...
Carbomethoxylation of methylacetylene
Methoxycarbonylation of allene and methylacetylene-allene
Fraction
7.6.5. Manufacture of other alkyl methacrylates.
Synthesis of methacrylamide..
Synthesis of hydroxyethyl methacrylate.
7.7. Oligoetheracrylates.
271
272
273
273
273
274
274
277
277
278
279
Chapter 8. Alcohols and vinyl ethers.
283
8.1. Polyvinyl and polyallyl alcohols

8.2. Backgrounds of vinylation processes
8.3. Vinyl ethers
8.3.1. Manufacture of vinyl ethers by vinylation of alcohols.
Vinylation of alcohols under atmospheric pressure
Vinylation of alcohols under elevated pressure .
Other methods for the synthesis of vinyl ethers.
8.4. Vinyl esters. Vinyl acetate.
Synthesis of vinyl acetate from acetylene and acetic acid..
Synthesis of vinyl acetate from acetaldehyde
and acetic anhydride
Synthesis of vinyl acetate from ethylene and acetic acid
Synthesis of vinyl acetate from alternative sources
8.5 Derivatives of polyvinyl alcohol polyvinylacetals
284
286
289
290
290
292
293
294
296
Chapter 9.Monomers for polyethers.
313
280
281
281
281
282
298
300
304
311
9.1. Formaldehyde. 316

9.1.1 Mechanism and catalysts of oxidative dehydrogenation of methanol 316
Mechanism of oxidative dehydrogenation of methanol.. 316
706
Catalysts of oxidative dehydrogenation of methanol..

General aspects of the technology of oxidative
dehydrogenation of methanol..
9.1.2. Manufacture of formaldehyde
Synthesis of formaldehyde with oxide catalysts.
Oxidation of natural gas and lower alkanes
9.2. Ethylene oxide ..
9.2.1. Manufacture of ethylene oxide via ethylene chlorohydrin.
9.2.2. Direct oxidation of ethylene
9.3. Propylene oxide
9.3.1 Manufacture of propylene oxide by direct oxidation with oxygen..
Oxidation of propane..
Noncatalytic liquid-phase oxidation of propylene..
Catalytic liquid-phase oxidation of propylene
Liquid-phase oxidation of propylene by peroxides.
Epoxidation of propylene
9.3.2. Manufacture of propylene oxide by oxidation
of propylene via propylene chlorohydrin
9.4. Phenylene oxide..
9.5. Allyl glycidyl .
9.6. Epichlorohydrin .
Manufacture of epichlorohydrin from glycerol..
Manufacture of epichlorohydrin from allyl chloride..
9.7. Sulfones.
321
322
323
323
324
327
327
329
331
333
333
333
334
334
336
337
338
339
340
341
342
343
Part III
MONOMERS FOR POLYCONDENSATION POLYMERS
Chapter 10. Monomers for polyesters
10.1. Terephthalic acid and dimethyl terephthalate..
10.1.1. Du Pont process..
10.1.2. Witten process
10.1.3. Amoco process...
Mechanism of p-xylene oxidation..
Intermediate and side products in oxidation of p-xylene
to terephthalic acid .
Technology of manufacture of terephthalic acid
10.1.4. One-step VNIPIM process..
10.1.5. Manufacture of aromatic and heterocyclic carboxylic
acids by thermal transformation of their alkali salts...
346
347
349
350
351
351
358
360
361
361
707
Transformations of alkali salts. 362

Synthesis of terephthalic acid from toluene and xylenes. 363
10.1.6. Mitsubishi process 366
10.1.7. Manufacture of terephthalic acid from coal. 367
10.2. Maleic anhydride... 368
10.2.1. Manufacture of maleic anhydride by gas-phase oxidation
of benzene 368
10.2.3. Manufacture of maleic anhydride by oxidation of butane.. 370
10.2.3. Manufacture of maleic anhydride by oxidation of n-butenes. 371
10.2.4. Isolation of maleic anhydride as a side product in
the manufacture of phthalic anhydride 372
10.3. Phthalic anhydride. 372
10.3.1. Vapor-phase oxidation of o-xylene or naphthalene. 374
10.3.3. Liqid-phase oxidation of o-xylene or naphthalene.. 375
10.3.3. VNIIOS process.. 375
10.4. Fumaric acid. 378
10.5. Dichloromaleic and dichlorofumaric acids and their derivatives. 379
10.5.1. Manufacture of dichloromaleic acid and its anhydride 379
10.5.2. Manufacture of dichlorofumaric acid and its anhydride.. 380
10.6. 2,6-Naphthalenedicarboxylic acid. 380
10.7. Thiophene-2,5-dicarboxylic acid.. 381
10.8. Azelaic acid.. 382
10.9. Diols. 383
10.9.1. Manufacture ethylene glycol.. 383
Hydration of ethylene oxide 383
Other methods for the synthesis of ethylene glycol 384
10.9.2. Manufacture of 1,2-propanediol.. 386
Hydration of propylene oxide. 386
Other methods for the synthesis of 1,2-propanediol .. 388
10.9.3 Manufacture of 1,4-butanediol. 389
Synthesis of 1,4-butanediol from acetylene and formaldehyde.. 390
Synthesis of 1,4-butanediol from propylene.. 391
Synthesis of 1,4-butanediol from renewable raw material
(Cvaker Oatz process).. 393
Propylene of 1,4-butanediol by acetoxylation
of butadiene (Mitsubishi process). 393
Synthesis of 1,4-butanediol through chlorination
of butadiene ( Soda process).. 394
Synthesis of 1,4-butanediol through hydroformylation
of allyl alcohol (urare process) 395
708
10.9.4. Manufacture of 1,4-dimethylcyclohexane..
398
Chapter 11. Monomers for polyamides
399
11.1. Monomers for polymerization polyamides .

11.1.1. Manufacture of caprolactam...
Methods for the synthesis of caprolactam..
Main stages in the synthesis of caprolactam .
Synthesis of caprolactam from toluene..
Photochemical synthesis of caprolactam
11.1.2. Manufacture of valerolactam..
11.1.3. Manufacture of 7-aminoheptanoic acid..
11.1.4. Manufacture of caprilolactam.
11.1.5. Manufacture of 9-aminopelargonic acid
11.1.6. Manufacture of 11-aminoundecanoic acid..
11.1.7. Manufacture of laurolactam.
Trimerization of butadiene..
Heamisher Huls process..
Uber process
11.1.8. Manufacture of -pyrrolidinone..
Amination of -butyrolactone..
Noncatalytic synthesis of -pyrrolidinone..
Reductive amination of maleic anhydride...
Other methods for the synthesis of -pyrrolidinone
11.2. Monomers for polycondensation polyamides derived from dicarboxylic
acids and diamines.
11.2.1 Manufacture of adipic acid
Synthesis of adipic acid from cyclohexane..
Synthesis of adipic acid from tetrahydrofurane
Synthesis of adipic acid from phenol..
Other industrial methods for the synthesis of adipic acid
11.2.2. Manufacture of adiponitrile
Synthesis of adiponitrile from adipic acid
Synthesis of adiponitrile from butadiene.
Synthesis of adiponitrile from acrylonitrile
by electrochemical method..
Catalytic dimerization of acrylonitrile.
400
401
401
405
422
426
427
427
429
429
429
432
432
433
433
434
435
435
436
437
439
440
441
442
442
442
443
443
444
445
446
709
11.2.3. Manufacture of hexamethylenediamine. 447

Synthesis of hxamethylenediamine from adipic acid. 447
Synthesis of hxamethylenediamine via 1,6-hexanediol. 449
Synthesis of hxamethylenediamine from butadiene.. 449
Dimerization of acrylonitrile... 450
11.2.4 Manufacture of other monomers for the synthesis of polyamides .. 450
11.2.5. Manufacture of m-xylylenediamine 457
Bromination of xylene. 457
Oxidative ammonolysis 458
11.3. Monomers for other fiber-forming polyamides 458
11.3.1. Manufacture of fiber-forming polyamides based on suberic
acid and 1,4-diaminomethylcyclohexane.. 458
Synthesis of suberic acid . 459
Synthesis of 1,4-diaminomethylcyclohexane.. 459
11.3.2. Manufacture of fiber-forming polyamides based on
decanedicarboxylic acid and 4,4-diaminodicyclohexylmethane. 459
Synthesis of decanedicarboxylic acid.. 460
Synthesis of 4,4-diaminodicyclohexylmethane.. 460
11.4. Monomers for fully aromatic polyamides. 461
11.4.1. Manufacture of aromatic acid chlorides.. 461
Synthesis of acid chlorides from xylenes 461
Thionyl method... 462
11.4.2. Manufacture of monomers for fiber-forming polyamides by polycondensation of 4,4-diaminodiphenyl sulfone. .. 463
11.4.3. Manufacture of 2,5-bis-(p-aminophenyl)-1,3,4-oxadiazole. 464
11.4.4.Manufacture of 5,5-bis(m-aminophenyl)-2,2-bis(1,3,4-oxadiazolyl)465
11.4.5. Manufacture of 4,4-bis-(p-aminophenyl)-2,2-dithiazole 465
11.4.6. Manufacture of bis-(m-aminophenyl)-thiazolo(5,4-d)thiazole 466
11.4.7. Manufacture of monomers for polyamides based on
piperazine and diacids. 466
Synthesis of piperazine 466
Synthesis of 4,4-diphenyldicarboxylic acid. 467
Chapter 12. Monomers for polyimides..
470
12.1. Pyromellitic dianhydride.. 472

12.1.1. Manufacture of durene 473
12.1.2. Manufacture of pyromellitic dianhydride... 475
12.2. Diphenyltetracarboxylic dianhydrides.. 481
710
12.2.1. Manufacture of 2,2,3,3-diphenyltetracarboxylic dianhydride

12.2.2. Manufacture of 2,3,5,6-diphenyltetracarboxylic dianhydride..
12.2.3. Manufacture of 2,2,6,6-diphenyltetracarboxylic dianhydride
12.2.4. Manufacture of 3,3,4,4-diphenyltetracarboxylic dianhydride ..
12.3. Naphthalenetetracarboxylic dianhydrides.
12.3.1. Manufacture of 1,4,5,8-naphthalenetetracarboxylic dianhydride
12.3.2. Manufacture of 2,3,6,7-naphthalenetetracarboxylic dianhydride
12.4. Benzophenone- and perylenetetracarboxylic dianhydrides...
12.4.1. Manufacture of 3,3,4,4-benzophenonetetracarboxylic dianhydride
12.4.2. Manufacture of 3,4,9,10-perylenetetracarboxylic dianhydride
12.5. Aromatic diamines.
12.5.1. Manufacture of o- and m-phenylenediamines..
12.5.2. Manufacture of p-phenylenediamine
12.5.3. Manufacture of benzidine.
12.5.4. Manufacture of 4,4-diaminodiphenylmethane
12.5.5. Manufacture of 4,4-diaminodiphenyl oxide
12.6. Aniline derivatives.
12.6.1. Manufacture of anilinophthalein...
12.6.2. Manufacture of anilinofluorene
12.6.3. Manufacture of anilinoanthrone
481
482
483
484
485
485
486
486
486
487
488
488
489
493
493
493
494
494
495
495
Chapter 13. Monomers for polyurethanes. 496

13.1 Diamines.
13.1.1 Manufacture of diamines by reduction of dinitriles..
13.1.2 Manufacture of diamines by reduction of aromatic
dinitro compounds
Reduction of dinitro compounds by metals in acidic medium
Reduction of dinitro compounds by metals in alkaline medium..
Reduction of nitro compounds by sulfides ..
Catalytic reduction of dinitro compounds
13.2 Diisocyanates and isocyanates
13.2.1 Phosgenftion of amines.
13.2.2 Curtius, Hofmann and Lossen rearrangements.
13.2.3 Manufacture of tolylene diisocyanates.
Reduction of dinitrotoluenes to tolylenediamine.
Phosgenation of tolylenediamine
Synthesis of phosgene.
Other industrial methods for the manufacture of
tolylene diisocyanates..
500
500
501
502
503
504
504
505
506
506
508
509
509
509
510
711
13.2.4 Manufacture of 4,4-diphenylmethane diisocyanate

Condensation of aniline with formaldehyde
Synthesis of aniline..
13.2.5. Manufacture of other diisocyanates..
13.2.6 Synthesis of isocyanates using organosilicon compounds
Phosgenation of N-silylamines.
Thermolysis of N-silylurethanes.....
Thermolysis of -silylurethanes .
13.3 Polyols and polyethers
13.3.1 Manufacture of -diols..
13.3.2. Manufacture of glycerol...
13.3.3. Manufacture of arylaliphatic diols ..
13.3.4. Manufacture of monomers for poly(ether polyols)..
511
512
513
516
519
519
522
522
524
525
526
528
528
Chapter 14. Monomers for polycarbonates..
531
14.1 Bisphenols.
14.1.1 Manufacture of bisphenol A.
Condensation of phenol with acetone.
Condensation of phenol with acetone in the presence
of ion-exchange resins
Synthesis of bisphenol A from phenol and methylacetylene
or allene..
Synthesis of bisphenol A from phenol and
p-isopropenylphenol
Synthesis of bisphenol A from phenol and 2-chloropropene-1
Methods of purification of bisphenol A .
14.1.2 Manufacture of halogen-substituted bisphenols...
Synthesis of tetrachlorobisphenol A...
Synthesis of tetrabromobisphenol A..
14.2 Diphenyl carbonate
14.2.1 Manufacture of diphenyl carbonate by phosgenation of phenols.
14.2.2. Manufacture of diphenyl carbonate by
interaction of phenol with
carbon tetrachloride..
14.3 Bisphenol S.
14.4 Resorcinol...
14.5 Cyclocarbonates..
14.5.1. Manufacture of cyclocarbonates from -oxides...
14.5.2. Manufacture of cyclocarbonates from chlorohydrin ethers .
14.5.3. Manufacture of cyclocarbonates from diols.
535
537
537
544
546
548
549
550
550
551
552
552
553
555
556
558
559
564
565
566
712
14.5.4. Manufacture of multifunctional cyclocarbonates. 567

Chapter 15. Monomers for phenol- and amino-aldehyde polymers 569
15.1. Monomers for phenol-aldehyde polymers.
15.1.1. Manufacture of phenols
Isolation of phenols from the products of coal processing..
Isolation of phenols from the products of oil refining.
Synthesis of phenols via sulfonation of benzene.
Alkaline hydrolysis of chlorobenzene (Dow Chemical method)..
Rachig modified method (Hooker Chem process)
Cumene method
Oxidation of benzene ..
15.1.2. Manufacture of bromophenols and their derivatives antipyrenes..
15.2. Monomers for carbamido-aldehyde polymers.
15.2.1. Manufacture of carbamide..
15.2.2. Manufacture of melamine...
569
569
570
573
573
574
574
575
584
588
590
591
593
Chapter 16. Organosilicon monomers
596
16.1. Methods of obtaining organosilicon monomers 598

16.1.1. Organomagnesium synthesis .. 598
16.1.2. Direct synthesis... 598
16.1.3. Dehydrocondensation of silicon hydrides with hydrocarbons 599
16.1.4. Condensation of silicon hydrides with halogen-derivatives... 599
16.1.5. Hydrosilylation 599
16.2. Organochlorosilanes. 601
16.2.1. Manufacture of methyl- and ethylchlorosilanes by direct synthesis 602
Synthesis of silicon-copper contact mass 603
Synthesis of methylchlorosilanes. 605
Synthesis of ethylchlorosilane .. 607
Synthesis of ethyldichlorosilane . 608
Synthesis of diethyldichlorosilane... 609
Synthesis of phenylchlorosilanes. 610
16.2.2. Manufacture of organochlorosilanes by thermocatalytic silylation 610
Synthesis of methylphenyldichlorosilane 611
Hydrosilylation of unsaturated compounds. 611
High-temperature condensation method.. 612
16.2.3.Manufacture of organochlorosilanes by disproportionation reactions 612
16.2.4. Pyrolytic methods for the synthesis of organochlorosilanes 613
16.2.5. Manufacture of organosilicon monomers by chemical
713
transformations of organochlorosilanes 614

16.2.6. Manufacture of tetrachlorosilane.. 615
16.2.7. Purification of diorganodichlorosilanes .. 616
16.3. Monomers for siloxane rubbers. 617
16.3.1. Manufacture of siloxane rubbers . 617
16.3.2. Manufacture of siloxane monomers by hydrolysis of
diorganodichlorosilanes... 619
General aspects of hydrolysis of diorganodichlorosilanes . 620
Industrial methods for the hydrolysis of
diorganodichlorosilanes.. 621
16.3.3. Other methods of obtaining siloxane monomers . 623
Thermal rearrangement of linear polysiloxanes... 623
Catalytic rearrangement of linear polysiloxanes.. 624
16.4. Monomers for modified siloxane rubbers. 626
16.4.1. Manufacture of hexaorganocyclotrisiloxanes.. 628
16.4.2. Manufacture of organosilicon urethanes.. 629
Synthesis of O-silylurethanes.. 629
Synthesis of N-silylurethanes.. 630
Synthesis of urethanes from glycoxysilanes.... 631
Synthesis of carbofunctional organosilicon diols 632
Synthesis of products of condensation of organosilicon
isocyanates with hydroxyl-containing compounds. 634
Synthesis of monomers for organosilicon polyurethanes
prepared by hydrosilylation reaction 635
Synthesis of monomers for organosilicon polyurethanes
prepared from organosilicon bis(chloroformates) 636
16.5. Monomers for polysilicohydrocarbons permselective polymers 637
Chapter 17. Other organoelement monomers 642

17.1. Monomers for sulfur-containing polymers ..
17.1.1. Manufacture of sodium sulfide and polysulfides.
17.1.2. Manufacture of 1,2-dichloroethane
17.1.3. Manufacture of p-dichlorobenzene.
17.2. Phosphazenes (phosphonitriles)
17.3. Boron-containing monomers
17.4. Nitrogen-containing monomers
17.4.1. Manufacture of monomers with azole cycles .
Synthesis of 2,5-bis(p-aminopheny)-1,3,4-oxadiazole
Synthesis of 4,4-bis(p-aminophenyl)-2,2-dithiazole.
642
642
643
643
646
649
653
654
655
656
714
Synthesis of 5,5-di(m-aminophenyl)-2,2-bis(1,3,4-oxadiazolyl)
Synthesis of 5,5-di(p-aminophenyl)-2,2-bis(1,3,4-oxadiazolyl)..
17.4.2. Manufacture of di- and tetracarboxylic acids..
17.4.3. Manufacture of benzimidazoles..
17.4.4. Manufacture of benzoxazoles..
17.4.5. Manufacture of bis(maleimides)..
17.5. Metal-containing monomers and the related polymers
17.5.1. Manufacture of monomers containing covalently bound metals.
Synthesis of unsaturated nontransition-metal
organometallic monomers
Synthesis of unsaturated nontransition-metal
organometallic monomers
17.5.2. Manufacture of ionic metal-containing monomers
17.5.3. Manufacture of etal-containing monomers containing
coordinatively bound metals..
17.5.4 Manufacture of -tipe metal-containing monomers
Subject index
656
657
657
659
659
660
661
663
664
664
665
666
666
670
715

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