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Isolation of butadiene………………………………………….. 133 4.2.Isoprene…………………………………………………………………………135 4.2.1Тwo-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-methyl- 1,3-butanediol (MBD)……………………………………... ………..143
4.2.3.Manufacture of isoprene from isobutylene and methylal………….. 145
4.2.4. Manufacture of isoprene by dehydrogenation of hydrocarbons С5… |
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 |
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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
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5.1.4. Oxidative chlorination…………………………………………….. 173
5.1.5Hydrochlorination………………………………………………….. 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 chloroprene……………………193
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 |
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Synthesis of 3,3,3-trifluoropropylene………………………….. |
209 |
5.2.9. Manufacture of chladones (freons)………………………………… |
210 |
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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 |
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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 |
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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 |
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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 ………. 271
Commercial realization of the process………………………… |
272 |
7.6.2. Manufacture of methyl methacrylate from tert-butyl alcohol……… |
273 |
Oxidation of tert-butyl alcohol to methacrolein ………………. 273 Oxidation of methacrolein to methacroleinic acid…………….. 273 Esterification of methacrylic acid to methyl methacrylate…….. 274
7.6.4. Manufacture of methyl methacrylate from isobutylene…………… |
274 |
7.6.5. New methods for the synthesis of methyl methacrylate…………… |
277 |
Synthesis of methyl methacrylate via isobutyraldehyde………. 277 |
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Carbomethoxylation of propylene……………………………... |
278 |
Carbomethoxylation of methylacetylene……………………… |
279 |
Methoxycarbonylation of allene and methylacetylene-allene |
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Fraction………………………………………………………… |
280 |
7.6.5. Manufacture of other alkyl methacrylates…………………………. 281 |
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Synthesis of methacrylamide………………………………….. |
281 |
Synthesis of hydroxyethyl methacrylate………………………. 281 |
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7.7. Oligoetheracrylates…………………………………………………………. |
282 |
Chapter 8. Alcohols and vinyl ethers…………………………………………. 283
8.1. Polyvinyl and polyallyl alcohols…………………………………………… |
284 |
8.2. Backgrounds of vinylation processes ……………………………………… |
286 |
8.3. Vinyl ethers………………………………………………………………… |
289 |
8.3.1. Manufacture of vinyl ethers by vinylation of alcohols……………. 290 |
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Vinylation of alcohols under atmospheric pressure…………… |
290 |
Vinylation of alcohols under elevated pressure ………………. 292 |
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Other methods for the synthesis of vinyl ethers…………….… |
293 |
8.4. Vinyl esters. Vinyl acetate…………………………………………………. 294 Synthesis of vinyl acetate from acetylene and acetic acid…….. 296
Synthesis of vinyl acetate from acetaldehyde |
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and acetic anhydride…………………………………………… |
298 |
Synthesis of vinyl acetate from ethylene and acetic acid……… |
300 |
Synthesis of vinyl acetate from alternative sources…………… |
304 |
8.5 Derivatives of polyvinyl alcohol – polyvinylacetals………………………… |
311 |
Chapter 9.Monomers for polyethers…………………………………………. 313
9.1. Formaldehyde………………………………………………………………. |
316 |
9.1.1 Mechanism and catalysts of oxidative dehydrogenation of methanol |
316 |
Mechanism of oxidative dehydrogenation of methanol……….. |
316 |
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 |
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10.9.3 Manufacture of 1,4-butanediol……………………………………. |
389 |
Synthesis of 1,4-butanediol from acetylene and formaldehyde.. 390 |
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Synthesis of 1,4-butanediol from propylene………………….. |
391 |
Synthesis of 1,4-butanediol from renewable raw material |
|
(Cvaker Oatz process)……………………………………….. 393 |
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Propylene of 1,4-butanediol by acetoxylation |
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of butadiene (Mitsubishi process)……………………………. 393 |
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Synthesis of 1,4-butanediol through chlorination |
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of butadiene (Тоуо Soda process)…………………………….. 394 |
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Synthesis of 1,4-butanediol through hydroformylation |
|
of allyl alcohol (Кurare process)……………………………… |
395 |
708
10.9.4. Manufacture of 1,4-dimethylcyclohexane……………………….. |
398 |
Chapter 11. Monomers for polyamides……………………………………… |
399 |
11.1. Monomers for polymerization polyamides …………………………….… |
400 |
11.1.1. Manufacture of caprolactam……………………………………... |
401 |
Methods for the synthesis of caprolactam…………………….. |
401 |
Main stages in the synthesis of caprolactam …………………. 405 Synthesis of caprolactam from toluene……………………….. 422 Photochemical synthesis of caprolactam……………………… 426
11.1.2.Manufacture of valerolactam…………………………………….. 427
11.1.3.Manufacture of 7-aminoheptanoic acid………………………….. 427
11.1.4.Manufacture of caprilolactam……………………………………. 429
11.1.5. Manufacture of 9-aminopelargonic acid ………………………… 429
11.1.6.Manufacture of 11-aminoundecanoic acid……………………….. 429
11.1.7.Manufacture of laurolactam………………………………………. 432 Trimerization of butadiene…………………………………….. 432 Heamisher Huls process……………………………………….. 433 Uber process…………………………………………………… 433
11.1.8.Manufacture of -pyrrolidinone………………………………….. 434 Amination of -butyrolactone………………………………….. 435
Noncatalytic synthesis of -pyrrolidinone…………………….. 435 Reductive amination of maleic anhydride……………………... 436 Other methods for the synthesis of -pyrrolidinone…………… 437
11.2.Monomers for polycondensation polyamides derived from dicarboxylic
acids and diamines…………………………………………………………. 439
11.2.1 Manufacture of adipic acid………………………………………… |
440 |
Synthesis of adipic acid from cyclohexane…………………….. 441 |
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Synthesis of adipic acid from tetrahydrofurane……………… |
442 |
Synthesis of adipic acid from phenol………………………….. 442 |
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Other industrial methods for the synthesis of adipic acid……… |
442 |
11.2.2. Manufacture of adiponitrile………………………………………… |
443 |
Synthesis of adiponitrile from adipic acid……………………… |
443 |
Synthesis of adiponitrile from butadiene………………………. 444 |
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Synthesis of adiponitrile from acrylonitrile |
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by electrochemical method…………………………………….. |
445 |
Catalytic dimerization of acrylonitrile…………………………. 446
709
11.2.3. Manufacture of hexamethylenediamine……………………………. 447 Synthesis of hеxamethylenediamine from adipic acid…………. 447 Synthesis of hеxamethylenediamine via 1,6-hexanediol………. 449 Synthesis of hеxamethylenediamine 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…… 481
12.2.2.Manufacture of 2,3,5,6-diphenyltetracarboxylic dianhydride…….. 482
12.2.3.Manufacture of 2,2 ,6,6 -diphenyltetracarboxylic dianhydride …… 483
12.2.4.Manufacture of 3,3 ,4,4 -diphenyltetracarboxylic dianhydride ….. 484
12.3.Naphthalenetetracarboxylic dianhydrides…………………………………. 485
12.3.1.Manufacture of 1,4,5,8-naphthalenetetracarboxylic dianhydride … 485
12.3.2.Manufacture of 2,3,6,7-naphthalenetetracarboxylic dianhydride … 486
12.4.Benzophenoneand perylenetetracarboxylic dianhydrides………………... 486
12.4.1.Manufacture of 3,3 ,4,4 -benzophenonetetracarboxylic dianhydride 486
12.4.2.Manufacture of 3,4,9,10-perylenetetracarboxylic dianhydride …… 487
12.5.Aromatic diamines…………………………………………………………. 488
12.5.1.Manufacture of o- and m-phenylenediamines…………………….. 488
12.5.2.Manufacture of p-phenylenediamine……………………………… 489
12.5.3.Manufacture of benzidine…………………………………………. 493
12.5.4.Manufacture of 4,4’-diaminodiphenylmethane…………………… 493
12.5.5.Manufacture of 4,4 -diaminodiphenyl oxide……………………… 493
12.6.Aniline derivatives…………………………………………………………. 494
12.6.1.Manufacture of anilinophthalein…………………………………... 494
12.6.2.Manufacture of anilinofluorene…………………………………… 495
12.6.3.Manufacture of anilinoanthrone…………………………………… 495
Chapter 13. Monomers for polyurethanes……………………………………. 496
13.1 Diamines……………………………………………………………………. 500
13.1.1Manufacture of diamines by reduction of dinitriles…………………….. 500
13.1.2Manufacture of diamines by reduction of aromatic
dinitro compounds………………………………………………… 501
Reduction of dinitro compounds by metals in acidic medium… 502 Reduction of dinitro compounds by metals in alkaline medium.. 503 Reduction of nitro compounds by sulfides …………………….. 504 Catalytic reduction of dinitro compounds……………………… 504
13.2Diisocyanates and isocyanates……………………………………………… 505
13.2.1Phosgenftion of amines……………………………………………. 506
13.2.2Curtius, Hofmann and Lossen rearrangements……………………. 506
13.2.3Manufacture of tolylene diisocyanates……………………………. 508 Reduction of dinitrotoluenes to tolylenediamine………………. 509 Phosgenation of tolylenediamine ……………………………… 509 Synthesis of phosgene…………………………………………. 509 Other industrial methods for the manufacture of
tolylene diisocyanates………………………………………….. 510