Index

alumina trimerisation 1\0 activity 235 acetal formation 94 fluorination and catalytic activity of 234 acid 525 in CFC destruction 239 acrylamide aluminium chloride route to 9 in Diels-Alder reactions 108 acrylics in dry synthesis 212 reprocessing of 449 in Ibuprofen manufacture 54 acrylonitrile aluminium fluoride route to II as a fluorination catalyst 226 acylation 92, 93 of phenols 425 oxidation of 287 regioselective 529 as a solvent 436 using Envirocats 535 amine oxides addition-cyclisation III preparation of 284 addition reactions 105 amines adipic acid oxidation of 284 route to 9 anions adsorption on surfaces 226 solvation of 424 agrochemicals antimony fluoride chirality of 203 in fluorinations 236 single isomer 204 aromatic compounds AIBN electrochemical oxidation of 389 manufacture of 288 aromatic substitution reactions alcohols alkylation 91 oxidation of 186, 275 bromination 89 aldehydes chlorination 89 oxidation of 278 halogenation 295 aldol condensations 97 nitration 90 alkylaromatics PTC in 124 oxidation of 281, 539 sulphonylation 91 alkylations waste from 8 at carbon 127 at nitrogen 35, 93, 122 methods for removal 312 at oxygen 122 arsine at sulphur 122 electrochemical generation of 408 catalytic two phase reactions 432 arylation 93 effect of solvents 428 asymmetric alkylation in liquid sulphur dioxide 435 using polymers 172 of aromatic compounds 91 asymmetric catalysis 217 PTC catalysed 122 industrial 218 using Hiinig's base 35 using polymer supported catalysts 171 using nafion 178 auxiliary reagents 34, 57 alkyl reagents azo coupling reactions 125 use of sonochemistry with 338 allyl alcohol batch processes 20, 41 route to 6 batch vs continuous processes 41 546 INDEX

BATNEEC 68, 83 in asymmetric synthesis 217 batteries in batch vs continuous processes 42 recycling of 374 in bleaching 305 Bayer ketazine process 287 in effluent treatment 299 Bayer-Villiger reaction 278 in hydrometallurgy 308 Beckmann rearrangements 9 530 in finishing 308 benzodioxepination III phase transfer 116 benzophenones recovery of from 375 production of 534, 539 shape selective 88 benzoylations 534 solid 87 benzylations 537 supported 86 benzylbiphenyls catalytic cracker 453 production of 538 catalytic two phase reactions 432 biodegradable polymers 457 cations biological decontamination solvation of 423 using electrochemistry 395 cavitation 328 using ultrasound 348 CEFIC (European Chemical Industry biological methods Council) of waste treatment 489 environmental protection guidelines 3 bipolar membranes 403 initiatives 14 bisphenol A cementation 378 manufacture 180 CFCs 222 bleaching 297, 304 catalytic decomposition 238 borohydride in ozone depletion 223 supported 165 replacements 224 BPEO 68 chemical decontamination bromination 89 using ultrasound 349 in liquid sulphur dioxide 435 chemical libraries 167 PTC in 124 chemolysis bromine of polymers 454 electrochemical regeneration of 381 chiral Bnmsted acids 172 3-bromothiophene chiral catalysts 138, 217 electro synthesis of 411 chiral drugs 202, 524 BS 7750 81 chiral Lewis acids 192 chirality cadmium link with biological activity 20 I of 463 chirality pool 205, 209 carbon monoxide chloride oxidation of 516 electrochemical oxidation of 393 capital expenditure chlor-alkali industry on environmental protection 78 waste reduction in 4 carbanion reactions chlorinated compounds from catalytic two phase reactions 432 destruction of using ultrasound 349 carbene reactions electrochemical oxidation of 393 using PTC 120, 130 chlorination of 89 Caro's acid 255,279,285,301,308,310 allylic 109 caprolactam PTC in 124 manufacture of 287 regioselective 89 catalysis chlorine in chemical manufacture 522 as an oxidant 248 catalysts electrochemical production of 395 activation by ultrasound 340 chlorine dioxide as auxiliary reagents 34 manufacture of 409 characterisation of 241 chlorofluorocarbons see CFCs for CFC alternatives 225 chlorohydrin route for CFC destruction 238 in epoxidation 272 in organonitrogen oxidation 285 chromia in aromatic hydroxylation 280 as a catalyst 228, 240 INDEX 547

supported 229 cyanation chromium effect of ultrasound 343 electrochemical treatment of 486 cyanides chemistry 309 treatment of 301, 378 chromium liquors cyclisation reactions electrochemical treatment of 380 on polymers 157, 165 chromium reagents cycloaddition reactions 108 for oxidations 276 toxicity of 467 diazotisation cilastatin in carbon dioxide 436 routes to 56 degradeable polymers 456 clayfen 90, 109 dehydrochlorination clays catalysis of 235 in acylations 92, 93 dehydrogenation in aldol condensations 97 effect of ultrasound 341 in alkylations 91 dendrimers in Diels-Alder reactions 108 as PTCs 137 in Fischer-Indole synthesis 92 as supports 194 in Friedel-Crafts reactions 537 depolymerisation 452 in hydrosilylations 100 deracemisation 214 in ketone protections III desulphurisation 383 in nitrations 90 dextran in oxidations 102 degradation of 335 clayzic 537 dielectric constants 420 cleaner protection Diels-Alder reactions 108 definition 4 chiral catalysts for 172 initiatives 13 in carbon dioxide 436 using catalysts 522 use in sonochemistry in 339 clean synthesis dimethylsulphoxide electrochemical methods 406 disposal of 438 initiatives in 14 recovery of 438 use of catalysts for 86, 116, 522 dinitrogen pentoxide use of polymers for 146 manufacture of 409 coal dioxins 455 compounds of 514 dioxiranes 258 mining and use of effect chemicals 62 diphenylmethane production of 537 catalyst in fluorination 228 dipolar aprotic solvents 419 separation of using hydrogen peroxide recovery of 438 310 dismutation COD in CFC synthesis 229, 233 of metals 467 L-DOPA reduction of 303 route to 218 colour removal 303 drugs complexing agents chirality of 202 biological production of 494 for metals 469 effect chemicals condensation polymers for cleaner technologies 59 reprocessing of 449 effluent treatment 298 continuous vs. batch processes 41 electrochemical ion exchange 376 electrochemical membranes 386 extraction of using peroxides 310 electrochemical reduction 394 costs electrochemical synthesis 406 of waste generation 24 electrochemistry 360 cradle-to-grave-to-cradle 39 in inorganic synthesis 406 cross-linked polymers 145 in membrane processes 397 crown ethers 117 in waste clean up 482 supported 175 use in effluent treatment 378 548 INDEX electrochemistry contd esterifications use in metal recovery 365 using Envirocats 94 use with sonochemistry 344 using Hiinig's base 36 electrodialysis 397, 487 using supported reagents 94 electrodeposition 365 etching solutions electrode potential 363 treatment of 373 electrodes ethylene oxide polymer films on 195 route to 9 electroflotation 397 extraction processes electrohydrolysis 400 using ultrasound 351 electroplating extractive reactions 429 use of ultrasound in 344 electro sorption 397 Fenton's reagent 254, 277, 301, 303, 391 electrosynthesis 406 fermentation 208 indirect 412 fine chemicals industry 32 inorganic 407 Fischer-Indole synthesis 92 organic 411 flow systems with ultrasound 345 for ultrasonics 353 eliminations 96 flue gas desulphurisation 383 emulsions fluidised bed electrode 369 production by ultrasound 334 fluorides use of in catalysis 342 in CFC alternative synthesis 227, 236 energy removal of 397 recovery from waste gasification 456 supported 93, 106, 109, 110, 241, 540 recovery from by waste incineration fluorinated surfaces 178, 241 455 fluorination 110 Envirocats 55, 529 catalysts 239 enviro-cell 370 catalytic 226 environmental audits 66, 80, 82 in making CFC alternatives 226 environmental legislation 66 of supports 178 and enantiopurity 202 using PTC 123 associated costs 78 using antimony species 236 comparisons 73, 78 fluorodenitration 123 European 69 Friedel-Crafts reactions 54, 531 for drugs 202 using Envirocats 531 UK 67 using hydrogen fluoride as solvent 436 US 71 using Nafion 178 Environmental Protection Act 67 using sulphur dioxide as solvent 435 environmental risk using ultrasound 343 insurance costs 79 Fries rearrangement 98 lending policies 80 enzymes as catalysts 208, 523 gaseous effluents enantiomers 215 electrochemical treatment of 378 immobilisation 216 gasification of polymers 456 in fine chemical manufacturing 525 glyphosphate in peracid oxidations 257 manufacture of 288 epoxidations routes to 55 of alkenes 190 gold Sharpless 218 recovery of 309, 313 using Payne's system 258 good housekeeping 20, 51 using peroxygens 269 Grignard reagents using porphyrins 260 use of ultrasound with 335 using PTC 262 using selenium dioxide 263 halogenations epoxides using hydrogen peroxide 259, 294 reduction of 100 halogen exchange reactions ring opening 95, Ill, 274 aromatic fluorination 123 ESBO manufacture 269 in CFC-alternative synthesis 227 INDEX 549 halons safety aspects 265 alternatives for 224 stabilisation 265 reduction of 222 hydrogen sulphide haloorganics treatment of 386 treatment of 303 hydrolysis hard-soft concept 490 effects of solvents 425, 430 heterogeneous catalysis enhancement using ultrasound 342 in CFC-alternative synthesis 225 in supercritical water 514 PTC 127 hydrometallurgy 308 using inorganic supported reagents hydroquinones 86 routes to 7 using organic supported reagents 141 heteropolyacids preparation of 287 in oxidations 280 hydroxylation 259 HCFCs 225 aromatic 280 HFCs 225 HMIP 68 ibuprofen housekeeping 51 routes to 54 Hovione incineration of waste 445, 455 waste minimisation 'total approach' initiatives methods 46 for cleaner processes 13 Honig's base 34 integrated pollution control 67 hydrazine integrated processes 193 preparation of 287 iodinations 296 hydrochlorofluorocarbons (H CFCs) ion exchange membranes 399 as CFC alternatives 224 ion exchange catalytic routes to 225 columns 479 hydrofluorocarbons (HFCs) in waste clean up 474 as CFC alternatives 224 selective 480 catalytic routes to 225 with electrodeposition 375 hydrogenation iron asymmetric 218 catalysis using 254 of polymers 454 complexation of 490 using polymer supported catalysts 185 removal of using peroxides 311 using ultrasound 340 reoxidation of 311 hydrogen fluoride toxicity of 467 as a Friedel-Crafts catalyst 54 isomerisations 97 as a solvent 435 enantioselective 218 for acid catalysis 436 in CFC alternative syntheses 226 ketones properties of 226 oxidation of 278 hydrogenolysis S-ketoprofen catalytic 231 route to 216 of CFCs 231 Kolbe reaction 345 hydrogen peroxide 247 chemistry 251 legislation 66, 67,69, 71,463 in alcohol oxidations 276 Lewis acids 280 in aldehyde oxidations 278 lithium diisopropylamide (LDA) in alkylaromatic oxidations 284 use of ultrasound with 338 in ammonia oxidation 287 in aromatic hydroxylations 280 macroporous resins 149 in effluent treatment 298 manganese in epoxide reactions 275 recovery of using peroxides 311 in halogenations 259, 294 marketing 22, 57 in organonitrogen oxidations 284 mass balance in a chemical process 28 in organosulphur oxidations 288 medical diagnostic kits 143 in product purification 296 membranes manufacture 247 bipolar 403 550 INDEX membranes contd natural resources 18 electrochemical 397 National Environmental Protection Act in reactions 195 (US) 71 use in metal clean up 498 mercury separation of 311 toxicity of 463, 467 nitrogen compounds metal carbonyls treatment of 300 use of sonochemistry with 339 nitrogen oxides metal finishing 308 treatment of 385 metal ions see also metals and metal salts nitrosamines recovery from mixtures 372,400 formation of 284 recovery or recycling by electrochemical nitration 90 methods 365 nitric acid recovery using sonoelectrochemistry 350 as an oxidant 249 metallocenes nitroxides as catalysts 54 I in alcohol oxidations 277 metals nucleophilic substitutions see also aromatic biological treatment of 490 substitution reactions chemistry of 466 effect of solvents on 419 complexation agents for 469 in liquid ammonia 437 electrochemistry and 482 PTe in 119 extraction of 309 integrated treatment of 501 oligoesters natural occurrence of 465 preparation on polymers 165 oxidation of 309 oligopeptide synthesis 141, 166 recovery of 36, 462 onium compounds solvent extraction of 495 as catalysts 177 of 462 optically active compounds metal salts industrial manufacture 218 precipitation of 470 synthesis of 201 preparation of via electrochemistry organic electro synthesis 411 407 organic waste methacrylic acid electrochemical treatment of 389 routes to 48 organometallic catalysts 2 I 7 MIBK organometallic reactions synthesis of 180 use of ultrasound in 335 Michael reactions 106 organonitrogen compounds microbes oxidation of 284 immobilisation 492 organosulphur compounds use in clean up 492 oxidation of 288 microbial synthesis 207 oxidants 248 molecular sieves 87 oxidations 101 see also zeolites electrochemical 390 use in oxidations 103 in industry 539 molybdenum in supercritical water 516 catalysis of epoxidation 270 of alcohols 186,275 recovery of 314 of aldehydes 278 supported 190 of alkylaromatics 282, 540 monoliths of ammonia 287 as supports 194 of aromatics 280 Montreal protocol 223 of ketones 278 MTBE process 179 of organonitrogens 284 municipal solid waste 442 of organosulphurs 288 mustard gas relative costs of reagents 248 destruction of 291 stoichiometric 539 using electrochemically generated S-naproxen mediators 413 routes to 210 using Envirocats 540 INDEX 551

using hydrogen peroxide and metals 260 industrial applications 173 using polymer supported catalysts 186, in halogenation 294 195 in peroxide chemistry 262 using TS-I 261 mechanism 118 Wacker 187 rates 128 oxidation potentials reaction types 118 of various oxidants 254 supported 125, 173 oxidation states phenolic wastes of metals 468 treatment of 30 I, 518 oxygen phenols in oxidations 248 destruction of using ultrasound 350 singlet form 255 electrochemical oxidation of 390 ozone photochemistry electrochemical generation 391 with sonochemistry in waste destruction in bleaching 307 350 use in waste treatment 391 photodegradable polymers 458 ozone layer photoelectrochemical oxidation 396 depletion 223 pickling of metals 313 packaging of chemicals 20 recycling of 442 paired synthesis 409 use of 441 palladium supported 180, 185, 187 capture of 491 effect of ultrasound on 341 polyalkenes in CFC chemistry 232 reprocessing of 451 paper production use of effect chemicals in 59 chemolysis of 454 Payne's system 259, 285 monomer for 536 PCBs reprocessing of 451 electrochemical treatment of 394 polybenzimidazoles penicillin preparation of 161 oxidation of 289 use as support 188, 190 peptides polyesters synthesis on polymers 166 chemolysis of 454 peracids reprocessing of 450 in aldehyde oxidations 278 Polyhipe® 167 in amine oxidations 286 polyimides in bleaching 307 preparation of 160 in epoxidations 269 polymeric protecting groups 144, 166 in ketone oxidations 279 polymeric reagents 144, 164 in organosulphur oxidations 289 polymerisation in oxidations 256 electrochemical/ultrasound 346 mechanism of reaction 270 polymers perhalogenocarbons as catalyst supports 141 minimisation in stratosphere 222 as ion exchange resins 476 peroxygen species breakdown using ultrasound 335 in oxidations 255 cross-linked 145 personnel degradable 456 involved in waste minimisation 52 depolymerisation of 452 PET energy recovery from 455 reprocessing of 449 for removal of metals 499 phase transfer catalysis 116, 432 preparation using PTC 135 advantages and disadvantages 118 pyrolysis of 452 and use of ultrasound 342 recycling of 351, 440 choice of solvent 133 reuse of 454 costs 118 thermal reprocessing of 447 gas-solid 17 5 thermo-oxidatively stable 157 importance of water 134 polymer supported catalysts 170 552 INDEX polymer supported dipolar aprotic solvents supercritical fluid treatment of 519 175 polymer supported reagents 151 effect of ultrasound 340 acidic 177 raw materials 17 advantages and disadvantages 145 Raschig process 287 industrial applications 178 reaction pathway in PTC 126, 173 modification of 343 in synthesis 164 reactors preparation 155 ultrasonic 352 reuse of 172, 189 rearrangements 97 polymer supported sulphonic acids 176 recycled paper polymer supported transition metal bleaching of 307 complexes 183 recycling polymer supports 143 of byproducts 56 modification of 155 of plastics 442 physical characteristics 150 of polymers 351 structure 149 reductions synthesis 147 in liquid ammonia 437 thermo-oxidatively stable 157 using polymer supported reagents 165 polyoxometallate species regioselectivity as catalysts in oxidations 262 effect of solvents 428 polystyrene responsible care 2, 75, 81 pyrolysis of 453 reverse osmosis 497 reprocessing of 449 resolution of racemates 206, 213 polystyrene sulphonic acid 476 rhodium poly thiophene in asymmetric catalysts 218 preparation using sonochemistry 347 supported 184, 186 porphyrins Rieke metal powders 337 as catalyst 104, 260, 272 rotating electrode cells 368 porous solids rotaxanes as catalysts 87 in PTC 137 as supports 87 rubber acceleration effect of ultrasound 341 manufacture of 293 Pourbaix diagrams 362 ruthenium precipitation techniques supported 195 for removing metal waste 470 primary recycling 452 Schiff base complexes process 27 supported 187 development 30 secondary recycling 446 flow diagrams 29 selenium dioxide product purification as a catalyst 263 using hydrogen peroxide 296 sellenides propylene oxide synthesis of 347 routes to 8 sewage sludge public image treatment of 518 of the chemical industry I Sharpless asymmetric synthesis 218 pulp and paper bleaching 304 Simmons-Smith reaction PVC use of sonochemistry in 337 pyrolysis of 453 solid catalysts see also supported reagents; reprocessing of 448 zeolite; heterogeneous catalysis in industry 526 use of ultrasound with 333 quality assurance 80 solid phase synthesis inorganic based 86 radicals organic based 141 from sonochemical reactions 333, 348 solid supports radioactive waste inorganic 86 electrochemical treatment of 488 organic 141 INDEX 553 solvation 417 supercritical water 504 of inorganic ions 422 corrosion problems with 519 solvatochromic parameters 422 properties of 508 solvent extraction reactions in 514 of metals 495 use in treatment of waste 504 solvent parameters 419 supported organic layer catalysts 235 solvents 417 supported reagents as catalysts 133 as PTCs 127 effects on reaction rates 417, 424 effect of ultrasound 342 importance in PTC 133 in alcohol oxidations 277 in metal recovery 469 in asymmetric synthesis 172 recovery 45, 48, 437 in CFC destruction 239 replacement of 116 industrial applications 178, 529, 540 selection of 417 inorganic based 86 supercritica1 504 in reducing toxicity 465 supported 175 macro porous 149 sonochemistry 328 polymer based 141 in catalyst activation 340 polymer vs. inorganic support 142 in chemical synthesis 333 reuse of 172, 192 in polymer recycling 351 in wastewater treatment 347 tantalum pentafluoride large scale 352 in fluorinations 238 with electrochemistry 345 tellurides sonoelectrochemistry 344 synthesis of 347 in waste treatment 350 terephthalic acid solvolysis reactions routes to 186 effect of solvent 426 tertiary recycling 445 enhancement using ultrasound 334 textile printing sound use of effect chemicals 62 in chemistry 329 thermal analysis 159, 188, 191 sources of water 6, 10 thioacetalisation 11 0 sterilisation thi ocyana tes of waste 394 electrochemical treatment of 378 of water 394 thiols Strecker synthesis 343 oxidation of 291,299 sulphides tin biological treatment of 490 polymer supported 165 sulphides recovery of 373 oxidation of 289 titanium catalysis 218 sulphonation in liquid sulphur dioxide 435 oxidation using electrochemically sulphonic acid catalysts 176 generated mediators 413 sulphonylations 91, 536 total approach sulphur compounds to waste minimisation 46 electrochemical treatment 381 toxic materials treatment of 299 treatment of 504 sulphur dioxide toxic organic compounds as a solvent 434 treatment of 301, 504 oxidation of 382 toxic reagents reduction of 385 manipulation via supports 164 sulphuric acid transducers 329 as a solvent 434 transition metal complexes in acetone cyanohydrin process 49 supported 183 supercritical fluids 505 triphase catalysis 125 chemistry using 508 TS-molecular sieves chromatography using 508 in amine oxidations 286 extraction using 508 in ammonia oxidation 287 use in clean-up 496 in aromatic hydroxylations 280 554 INDEX

TS-molecular sieves contd wastewater in epoxidations 272 biological treatment of 492 in oxidations 104, 261 dehalogenation of 394 tungsten organic contaminated 390 catalysis of epoxidations 271 treatment of 347, 365, 390 catalysis of oxidations 277 use of electrodeposition and ion exchange recovery of 314 with 376 supported 195 water two phase reaction systems 429 biological treatment of 492 desalination of 399 Ullman coupling reactions role in PTC 134 enhancement using ultrasound 336 sonification of 348 ultrafiltration 497 use of 53 ultrasound 329 Water Resources Act 68 see also sonochemistry wet air oxidation 519 uranium recovery of 313, 314,490,493 xylene production of 529 vanadium recovery of 315 zeolites 87 vinyl polymers in acetaldehyde trimerisation 110 reprocessing of 448 in acetal formation 94 in acylation 92, 93 Wacker oxidation 187 in additions 105 waste see also individual types, e.g. in alkylations 91,93 polymers, metals in CFC destruction 239 biological methods for treatment of 489 in Diels-Alder reactions 108 calorific value of 445 in eliminations 96 clean up 470 in epoxide ring opening 96 disposal of 23 in esterifications 94 electrochemical treatment of 361, 482 in Fischer-Indole synthesis 92 incineration of 445 in halogenations 89 integrated treatment of 501 in industrial processes 526 recovery of energy from 455 in isomerisations 97 recovery of metals from 462 in liquid phase reactions 527 treatment of 47 in nitrations 90 treatment using supercritical water 504 in oxidations 103, 280 ultrafiltration treatment of 499 in rearrangements 98 use of microbes with 492 in reductions 99 waste minimisation selectivity using 527 cost-benefit ratio 22 use as ion exchange matrices 476 definition of 3 factors 18 zirconia history of 4 in CFC destruction 238 strategy for 32 zirconium total approach 46 purification of 315