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2002

2
547 + 678
24.2 + 24.7
37
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... .: : /, 2002.-696
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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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663-683
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443-493
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578-618
343-363
573-593

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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.
Basic material and target products
Transformations of six-membered cycloalkanes..
Transformations of five-membered cycloalkanes.
Transformations of alkanes
Transformations of aromatic hydrocarbons ..
1.2.3. Hydrocracking .
Basic material and target products
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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