Amines: Synthesis, Properties and Applications Stephen A

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Index

acetamide 206 amino group 259 Acetamiprid 299 aminoguanine 290 acetanilide 93, 95, 111 2-amino imidazole 141 acetone hydrazone 178 aminolaevulinic acid, ␦ 199 acetophenone 60 2-amino-1-methylethylbenzene 39 acetylation 92, 127 2-aminophenol 101, 103, 315 acetyl choline 274 3-aminophenol 101, 104, 316 Acid Red 304 4-aminophenol 100, 283, 316 acridine 110, 122, 316 aminophenols 100 Acrolein Process 156 aminopiperidine 242 acrylonitrile 46 3-aminopropanol 131 acylamphoglycinates 282 3-aminopropyl halides 131, 132 acylamphopropionates 282 2-aminopyrazine 158 acylation 102, 114, 251 2-aminopyridine 144, 316 adenine 159, 276 3-aminopyridine 316 S-adenoylmethionine 63 4-aminopyridine 316 adiponitrile 67 4-aminopyridine-N-oxide 155 adrenaline 258, 273 4-aminosalicyclic acid 104 ADT 262 aminotriazines 296 aerozine 289 aminyl radicals 115 agmatine 63, 260 amitrole 297 agrochemicals 246, 290 Amitryptyline 269 Aldimorph 60, 293 ammines 188, 232 aliphatic amines 33, 232 Ammon 18 alkylamines 49, 269 ammonia 1, 10, 11, 12, 14, 15, 17, 18, 19, 20, 22, 23, alkylation 94, 102, 113, 207, 208, 251 26, 28, 34, 35, 43, 44, 52, 53, 56, 65, 124, 127, N-alkylbenzylamine 132 135, 169, 171, 172, 173, 175, 177, 178, 184, Alper Reaction 317 189, 190, 260, 274, 278, 284, 309, 310, 312 Amadori Rearrangement 259 Ammonium (town) 18 amides 39, 49, 92, 236 ammonium azide 19 amidol 100 ammonium chloride 175 aminating agents 186 ammonium ﬂuoride 171 amination 36, 39, 80, 148, 193 ammonium mucate 133 amine halides 170 ammonium oleate 284 amine oxides 235, 245, 246, 247, 249, 282 ammonium picrate salts 220 amine protection 235 ammonolysis 21, 22, 35, 140, 152, 165, 166 amino acids 187, 215, 235, 252, 255, 257, 258, 260 n-amyl amine 315 2-aminobiphenyl 316 analysis methods 220, 224 4-aminobiphenyl 316 anilazine 293 3-amino-5-t-butyl-isoxazole 187 aniline 29, 71, 73, 74, 94, 98, 99, 100, 109, 111, ␥-aminobutyric acid (GABA) 258 115, 184, 210, 212, 221, 229, 240, 301, 309, 4-aminodiphenylamine 111, 116 315 2-aminoethanol 124 anisidine 102

361

362 Index

anthranilic acid 206 Basfungin 66 anti-cancer agents 129, 189, 274 Béchamp Reaction 76, 319 anti-cracking agents 115 Beckmann Rearrangement 82, 84, 123, 166, 319 anti-fungal agents 142 Bénary Reaction 319 anti-Markovnikov Addition 39 Benefin 295 anti-oxidants 114 Benomyl 293 anti-ozonants 115, 116 benzalaxyl 291, 292 antipyrene 142 benzamide 112 anti-tumour agents 64 benzamorf 60 Antracol 66 Benzidine Rearrangement arginine 63, 197, 255, 258, 259, 260 benzene 72, 228 arginine-141 (in DNA) 256, 258, 260 benzimidazole 104, 144, 148, 293 arginine decarboxylase 63 benzopyrazole 144, 148 aromatic amines 85, 232 benzoquinone 106 arylamines 71 benzotriazole 104, 144, 148 Asinger Thiazole Synthesis 317 benzoxazole 99 aspargine amide 233 N-benzoylamides 236 aspartic acid 160 benzylamine 221, 315 aspergillic acid 158 1-benzyl-4-piperidone 61 ATP 262 Bergbau–Bayer Process 177 atracurium 163 Bergmann Azalactone Synthesis 320 atrazine 295 Bergmann Degradation 320 auxin 144, 147, 298 Bernthsen Acridine Synthesis 320 2-azabicyclo[2.2.0]hexadiene 154 betaines 52, 54, 281 azaconazole 293 Betti Reaction 320 azalactone 257 1,1’-biaziridine 128 azamycin (2-nitroimidazole) 141 Biginelli Reaction 321 azepine 165 biotin 140 azepan-2-one 165 biphenyls 87 azetidine 38, 119, 130, 132, 138, 166, 232 bipyridine 191 azetidine-2-carboxylic acid 132 Birch Reduction 20 azetidin-2-one 132 Birkeland, Kristian 8, 9, 12 azides 40, 82, 90, 182 Bischler Indole Synthesis 145 azines 180 Bischler–MöhlauIndole Synthesis 321 azine dyes 92, 226, 227, 300 Bischler–Napieralski Reaction 321 aziridine 30, 37, 48, 55, 57, 59, 119, 123, 124, 125, Bismarck Brown 105 128, 130, 138, 190, 232, 277, 278, 309, 310, biurea 289 311, 312 blood–brain barrier 272, 278 aziridinium cation 123 blood plasma 271, 272, 278 azirines 122, 123, 125 blowing agents 289 azirinylium cation 122 Blum Aziridine Synthesis 321 azocine 167 BOC 58, 61, 215 azodicarbonamide 289 BOC-hydrazide 184 azo dyes 91, 92, 213, 223, 226, 227, 300, 303 Bohr effect 197 azo ferredoxin 6 Borsche–Dreschel Cyclization 321 azoles 139, 232, 293 Bosalid 293 azomethane 35 Bosch, Karl 11, 12 azonine 164 Bosch–Meiser Urea Process 322 azones 180 Boyland Synthesis 322 azote 3 Brandi–Guarna Rearrangement 322 azulene 154 bread, ‘from air’ 11 Brederick Imidazole Synthesis 322 B-band 226 bromamine 171 Baeyer–Drewson Indole Synthesis 144, 145, 318 bromamine-T 125 Baeyer Pyridine Synthesis 318 2-bromo-CBZ 239 Bailey Cycloaddition 318 2-bromoethylamine 124, 190 Bamberger Benzotriazine Synthesis 318 3-bromoquinoline 162 Bamberger Imidazole Cleavage 319 Brown Hydroboration 39, 188, 322 barbituric acid 161 von Brown Reaction 322 Bart Reaction 89 Bucherer–Bergs Reaction 323 BASF 9, 11, 12, 303 Bucherer Carbazole Synthesis 323

Index 363

Bucherer–Curtius–Schlotterbeck Reaction 323 chloroﬂuoroamine 171 Bucherer Reaction 80, 81, 100, 323 Chlormequat 297, 300 Buchwald Method 82, 84 2-chloro-5-hydroxymethylpyridine 299 Bupidine 61 1-chloromethylnaphthalene 210 Busulfan 276 chlorophyll 139, 194, 195, 197, 200 Buprimate 293 3-chloropyridine 136, 153 butathiofos 299 Chloroquine 163, 269 Butralin 295 chlorotriazine 294, 295 n-butylamine 221 chlorprazophos 299 t-butylamine 34, 37 chlorpyrifos 157, 299 sec-butylamine 292, 293 choline 45, 275 N-t-butyl-3-chloroazetidine 132 Chrysoidine 304 n-butyl cyanide 209 chryzoplus 299 butyl lithium 32 Ciamician–Dennstedt Reaction 325 butyl toluenediamine (BTDA) 108 CI pigment blue-15-3 285 CI pigment red-184 285 cadaverine 33, 62, 63, 67 CI pigment yellow-13 285 Cadogan–Cameron-Woods Cyclization 323 cis-platin 189 calcium cyanamide 9, 37 citalopram 274 cafenstrazole 297 citric-acid cycle 260, 261 Camps Quinoline Synthesis 324 Clemmensen Reaction 181 Cannizzaro Reaction 136 Cliodinate 298 caprolactam 1, 165, 166 Clopyralid 298 catalysts 191 Clothianidin 299 caramelization 259 Clotrimazole 293 carbamazepine 167 clozapine 60 Carbamorph 60, 293, 294 CNS drugs 273, 274 carbamoyl phosphate 160 cocoamidopropyl betaine 281, 283 carbazole 110, 216 cocoamine 50 Carbenazim 293 Colour Index 300, 303 carbon dioxide 45 Combes Synthesis 98, 325 carbon disulphide 45, 114, 127 conazole 293 carboplatin 189, 190 Conrad–Limpach Synthesis 98, 163, 325 carboxamides 43 Cope Elimination 48, 249, 325 carboxybenzoyl chloride (CBZ-Cl) 237 Cope–Mamloc–Wolfenstein Synthesis 326 carboxybenzoyl 58, 61, 235, 236, 237, 245 Cornforth Rearrangement 326 carotenoid biosynthesis 297, 298 corrin 139, 194, 198 Cavendish, Henry 3, 7 corrosion inhibitors 55, 265, 267, 268 cefoperazone 60 cosmetics 278 cellulose 304 coupling reactions 91 cetyl ammonium chloride 278 Craig Reaction 326 cetyl trimethyl ammonium chloride (CTMAC) 278, credazine 298 283 crimidine 299 Chapman Reaction 112, 324 critical micelle concentration 247 Chaptal, Jean-Antoine 3 Crookes, Sir William 7 chemotherapy 123 Curtius Reaction (Rearrangement) 40, 82, 182, 326 Chichibabin Pyridine Synthesis 324 Cyanamide Process ix, 8, 9, 10, 14 Chichibabin Reaction 162, 324 N-cyanoamidine 299 chlorambucil 276, 277 2-cyanoaniline chloramidation 171 cyanogen bromide 74, 127 chloramine 21, 77, 170, 171, 172, 173, 174, 176 cyclic imines 267 chloramine-T 125 cyclohexylamine 34, 72, 315 chloranil 220, 221 cyclohexylethylamine 115 Chloridazon 298 cyclophosphamide 276, 277 4-chloro-1-aminobutane 37 Cymoxanil 292 2-chloroaniline 315 Cypendazole 293 3-chloroaniline 315 Cyperquat 297 4-chloroaniline 315 cysteine 256 2-chloro-4,6-dihydroxy-1,3,5-triazine 296 cytidine triphosphate 160 3-chlorodiphenylamine 112 cytochrome C 200 2-chloroethylamine 37, 126 cystochrome P450 293

364 Index

cytochrome 200 2,2-dimethylaziridine 126 cytosine 157, 159, 276 dimethylcocoamine N-oxide 283 dimethyldiazirine 130 Dakin–West Rearrangement 326 dimethyldipropylene triamine 66 Davidson Oxazole Synthesis 327 dimethyldodecylamine N-oxide 247, 282, 283 dealkylation 47 N,N-dimethylethylamino group 269 deamination 188, 258 dimethylformamide 93 Debacarb 293 N,N-dimethylhydrazine 173 decylamine 34 2,6-dimethyl-4-nitroaniline 74 dehydroabietylamine 268 3,5-dimethyl-4-nitroaniline 74 DelépineReaction 38, 68, 210, 327 3,3-dimethyl-2-phenylazirine 122, 123 DemjanovRearrangement 327 1,1-dimethylpiperidinium chloride 300 Dewar pyridine 154 dimethylpyridines 43, 93 diallylamine 50 dimethylsulphate 66 diamines 62, 104, 241, 267 Dimidazon 298 1,4-diaminonaphthalene 106 Dimroth Rearrangement 327 2,3-diaminophenothiazine 104 N,N’-di-␤-naphthyl-p-phenylene diamine (BNPD) 1,3-diaminopropane 63, 64, 66 115 2,4-diaminotoluene 106 dinitramine 295 diarylamines 109, 110 dinitroanilines 294, 295 diazepam 167, 271, 274 dinitrogen tetroxide 288 diazine 169 dinitrotoluenes 107 diazirenes 129, 130 Dinotefuran 299 diaziridines 129 dipentachlorophenylamine 110 diazoate ion 86 diphenylamine 109, 112, 113, 116, 221, 293, 316 diazobicyclo[3.4.0]nonane (DBN) 33 N,N-diphenylethylene diamine 116 diazobicyclo[5.4.0]undecane (DBU) 33 diphenylmethylamine 315 diazo compounds 47, 48, 85, 90, 102, 109, 211, 223, N,N’-diphenylthiourea 94 232, 305 dipole moment 246, 254 diazo dyes 303 diphenylnitrogen radical 113 diazomethane 48 Diquat 157, 297 Di-BOC (di-t-butyl dicarbonate) 215, 235, 239, 240, dissociation 270 245 Dithiopyr 298 2,3-dibromo-N-propylphenylsulphonamide 130 DNA 160, 190 dibutylamines 50 Dodicin 292 dicetyldimethylammonium chloride 279 Doebner Reaction 327 dichlomezine 293 Doebner–Miller Reaction 163, 328 dichloroamine 171, 172, 174 dolobid 87 Diels–Alder Reaction 133, 135, 152, 166, 191 dopamine 258, 274 Diethamquat 297 Dow Aziridine Process 124 diethylamine 32, 34, 50, 312, 315 drug master files 233 diethylaminopropylamine 66 Duff Reaction 68, 328 diethylazodicarbonate (DEAD) 35 duodenum 272 diethylcarbamazine 59 diethylene triamine 64, 280 Ehrlich–Sachs Reaction 328 N,N-diethylphenylamine 247 Einhorn–Brunner Reaction 328 Difenoquat 297 Electric Arc Process ix, 8, 9, 10, 14 difluoroamine 171 electrostatic maxima 312 difluoroaniline 87 Emdes Degradation 328 dihydrazides 182 Emdes Method 162, 163 dihydrogenated tallow dimethylammonium chloride emetine 163 279 Emmert Reaction 329 2,5-dihydropyrrole 139 enamines 45, 60 diisopropylazodicarbonate 35 endrazoline 61 diisopropylethylamine 43, 50, 93, 215, 243 enols 92 dimethomorph 60 epoxides 45 Dimethothiazine 269 EPSP synthase 298 dimethylamine 29, 123, 138, 173, 207, 278, 315 ergosterol 293 dimethylaminopropylamine (DMAPA) 281 Eschweiler–Clark Methylation Reaction 68, 329 N,N-dimethylaniline 34, 43, 72, 93, 94, 95, 221, 316 Esproquin 163 2,6-dimethylaniline 291 ester quaternaries 279

Index 365

Ethirimol 293 Gattermann Reaction 87, 88, 332 1-ethoxycarbonylazepine 165 GC/MS 224 ethoxylated quaternary amines (ethoquats) 279 gibberellin 300 Ethoxyquin 293 glucose ester conjugates 291, 298 Ethyclozate 299 glutamate 261 ethylamine 34, 49, 127, 221, 310, 312, 315 glutamine 261 N-ethyl aniline 74, 316 glutamine amide 233 ethylene diamine 34, 62, 64, 65, 190, 208, 280, 315 glycerides 53 ethylene diamine tetraacetic acid (EDTA) 65, 177, 248 glycine 199, 298 ethylene immonium ion 276 glycine conjugate 297 ethylene oxide 22, 52, 54, 108 N-glycoside 259 Ethyl Red 162 glyoxal 218 2-ethylhexylamine 50 Glyphosate 298 N-ethyl piperidine 240 GMO crops 17 Eyde, Samuel 8 Gomberg–Bachman Reaction 87, 332 Gould–Jacobs Quinoline Synthesis 332 fabric softeners 54, 279 Gouy–Chapman diffuse layer 266 famotine 163 Graebe–Ullmann Synthesis 332 fatty alkylamine oxides 247 Graham Diaziridine Synthesis 129, 332 fatty amines 50 grain boundary corrosion 265 fatty nitriles 52 gramine 147 fenamidone 293 Griess Deamination 333 fenpropimorph 60 Griess Diazotization 85 fentanyl 61 Grignard Reagents 137 fermizone 293 Gro␤–Eschenmoser Fragmentation 333 fertilizer 1, 5, 7, 16, 262 guanidine 256 Fick’s Law 272 guanido 259 Figaron 300 guanine 159, 276, 291 Finegan Tetrazole Synthesis 329 guanine N-7 276 Fischer–Hepp Reaction 97, 329 guano 7, 262 Fischer Indole Synthesis 145, 216, 330 Guareschi–Thorpe Reaction 151, 333 Fischer Oxazole 330 Guazatine 292 Fischer Phenylhydrazone Synthesis 330 Gutknect Pyrazine Synthesis 333 Fischer Phenylhydrazone and Osazone Reaction 330 flotation agents 54 Haber–Bosch Process ix, 9, 12, 14, 15, 17, 274 fluazinim 294 Haber, Fritz 11, 12, 275 Flucarbazone 297 haem 196, 256 Flumorph 60, 293 haemoglobin 139, 194, 195, 196 N-9-fluorenylmethoxycarbonyl group 215, 254 hair dyes 283 N-9-(fluorenylmethoxycarbonyl)succinimide Halcon Process 80 (Fmoc-ONSu) 215, 235, 242, 243, 244, 245 Haloxydine 298 fluorodichloramine 171 haloperidol 61 fluoxetine 273 Hassner Azirine Synthesis 334 fluphenazine 60 Hantzsch Pyridine Synthesis 151, 333 fluspiriline 61 Hantzsch Pyrrole Synthesis 134, 334 folic acid 158 Helmholtz plane 265, 266, 267, 269 Forster Reaction 330 hematin 195 Friedel–Crafts Reaction 98, 137, 152, 153, 182, 250 Henderson–Hasslebach Equation 270 Friedlander Quinoline Synthesis 98, 163, 330 herbicides 290, 294 Fuberidazole 293 Herz Reaction 334 fungicides 65, 292, 293 Herzig–Meyer Determination 334 furalaxyl 291, 292 heterocyclic amines 119, 216, 228, 230 Heumann–Pfleger Indigo Process 305, 335 Gabriel–Colman Rearrangement 331 hexaconazole 293 Gabriel–Heine Aziridine Isomerization 331 hexafluorophosphoric acid 88 Gabriel Marckwald Reaction 331 hexamethylene tetramine 210, 268, 316 Gabriel Primary Amine Synthesis 331 hexamethylethylene diamine 34, 67, 165 Gabriel Pyrimidine Synthesis 161 hexamethylethylene tetramine 64, 67 Gabriel Reaction 37, 40, 57, 124 Hilbert–Johnson Reaction 335 gandolinium 3 Hinsberg Oxindole Synthesis 335 Gastaldi Synthesis 331 Hinsberg Test 44, 221, 222, 335

366 Index

histamine 258, 260 Isopropalin 295 histidine 140, 196, 200, 215, 255, 256, 258, 260 isoquinoline 22, 121, 162, 163, 228, 316 Hoch–Campbell Aziridine Synthesis 336 isoquinoliniuim 268 Hofmann Amination Reaction 37, 336 isosurface electronic charges 309 Hofmann, August W. 33, 41, 62, 75 isoxazoles 187 Hofmann Degradation 37, 39, 82, 334, 336 Hofmann Isocyanide Synthesis 336 Japp–Klingemann Reaction 92, 242, 337 Hofmann–Löffler–Freytag Reaction 336 Japp Oxazole Synthesis 337 Hofmann–Martius Reaction 14, 96, 336 Jourdan Diphenylamine Synthesis 337 HOMO 27, 28 Houben–Hoesch Process 137 K-band 226 Huang–Minlon Modification 181 Kaiser–Johnson–Middleton Dinitrile Hückel’s Aromaticity Rule 119, 133, 164, 194 Cyclization 337 Huisgen Tetrazole Rearrangement 337 Kaluza Synthesis 337 hydrazides 22, 183, 232 Kametani Oxidation 338 hydrazine 21, 79, 91, 96, 130, 132, 143, 157, 169, 173, Kellogg Process 14 176, 178, 185, 242, 259, 288, 315 keratin 283 hydrazine chloride 289 ketazine 178 hydrazine hydrate 176, 177 ketene 102 hydrazine sulphate 178 ␣-ketoglutarate 261 hydrazoic acid 35, 83, 169 ketosamine 259 hydrazones 91, 92, 180, 181, 184 Kishner Cyclopropane Synthesis 338 hydrogenation 238 Knoop–Osterlin Amino Acid Synthesis 338 hydrogen peroxide 185, 247 Knorr, Ludwig 142 hydroxylamine 22, 138, 169, 174, 185, 186, 240, 245, Knorr Pyrazole Synthesis 338 248, 250 Knorr Pyrrole Synthesis 134, 338 hydroxylamine hydrochloride 138, 186 Knorr Quinoline Synthesis 339 hydroxylamine-O-sulphonic acid 186, 187 Kolbe Schmidt Reaction 136 hydroxylamine sulphate 186 König Benzoxazine Synthesis 339 1-hydroxybenzotriazole 148, 149, 184 Kresze Amination Reaction 339 4-hydroxyproline 139 Kröhnke Aldehyde Synthesis 339 3-hydroxypyridine 153 Krystallin 74 hypergolic fuels 288 Kvaener Process 166 hypusine 64 ␤-lactams 30, 55, 132 ifosamine 276 lactones 22, 23 imidaloprid 299 Ladenburg Rearrangement 339 imidazole 65, 121, 139, 140, 141, 143, 228, 256, 280, lake 304 293, 312, 313, 319 Langmuir adsorption isotherm 268 imine 143, 232 Lavoisier, Antoine 3 Iminoctadine 292 lead tetra-acetate 183 imipramine 167 Le Chatelier, Henri 11 immonium ion 259 Lehmstedt–TãnãsescuReaction 340 indene 22 Leibig, Justus von 7 indigo dye 219, 305 Leimgruber–Batcho Indole Synthesis 340 indigotin 219, 305, 306 lepidine 162 indole 22, 144, 216, 228, 241, 252, 257, 316 Leuckart Reaction 53, 61 indole-3-acetic acid 147, 299 Leuckart–Wallach Procedure 36, 58, 340 indole-3-carbaldehyde 146 leuco dyes 287 indolizine 144, 147, 252 Leuna ix, x, 12, 13 indol-3-yl acetate 260 Lewis Acid/Base 2, 267 4-indol-3-yl-butyric acid 299 Liebermann Nitroso Reaction 95, 221, 223, 224 infra-red spectroscopy 225 lipid 270 ionic character of bonds 19 lithiation 128, 153 ␣-iron 15 lithium 44, 48 iron oxide 15 lithium diamide 252 isocyanates 41, 82 Lossen Rearrangement 82, 83, 340 isocyanides 48 Lwowski Reagent 82, 85, 126 isocyanide reaction 47 lycopene cyclase 297 isodiazote ion 86 lysine 255, 258 isoindole 121, 144, 147 lysinyl pyridoxamine phosphate 258

Index 367

MacDonald Porphyrin Synthesis 340 Michael Addition 52, 57, 60, 131, 191 MacFadyen–Stevens Reaction 341 Michaelis Phosphonylation Reaction 342 macrocyclic ligands 194 microtubule assembly (of plants) 298 Madelung Reaction 145, 341 Mignonac Reaction 342 Maillard Reaction 246, 259 minaprin 60 Makusza Susbstitution 340 Minischi Substitution 342 maleic hydrazide 290, 291 mitoclomine 276, 277 maleimide 138 Mitsunobu Reaction 35, 82, 84 malondialdehyde 184 Mittesch, Alwin 11 Malthus, Thomas R. 7 molecular orbital coefﬁcients 26 Mannich Reaction 44, 52, 114, 138, 147, 268, 341 molsidomine 60 mannomustine 276, 277 monoarylamines 74 Martinet Dioxindole Reaction 342 monoastral fast G 286 mauvine 301, 302 monoastral fast blue BS 286 mebhydroline 61 monoazo dyes 303 mechlorethamine 277 monochlorobenzene 212 mechloroethane (mustine) 276 monoisopropylamine 50 Meclofenoxat 269 monomethylethylenediamine 241 Mecorbinzid 293 monomethylhydrazine (MMH) 288 Meerwien Reaction 90 mordanting 304 Meﬂoquinine 163 Morfamquat 297 Meissenheimer Rearrangement 250, 342 morphine 163, 273 Meissner Effect 203 morpholine 55, 56, 58, 60, 243, 289, 293, 315 melatonin 261 mustard gas 275 melphalan 276, 277 myelosuppression 276, 277 melting points 221 myoglobin 194, 196 Menshutkin Reaction 37, 342 mepiquat 300 NADPH 262 mescaline 273 naphtha 14 mesidine 209 1-naphthaldehyde 210 metal amines 232 naphthalene 228 metalaxyl 291, 292 naphthylamines 100, 315 metalloporphyrins 195, 232 naphthaquinone 106 metanillic acid 101 Neber Reaction 122, 343 Methadone 269 Nenitzsecu Indole Synthesis 145, 343 methionine 200 Nernst, Walther H. 11 methoxythiotriazines 296 neurine 45 methoxytriazines 296 niacin 156 methylamine 34, 38, 71, 206, 310, 315 nicotinamide 156 2-methylaniline 99 nicotinamide adenine dinucleotide (NAD) 156 3-methylaniline 32 nicotinamide adenine dinucleotide phosphate (NADP) 4-methylaniline 32 156 N-methylaniline 74, 93, 94, 95, 221, 316 nicotine 156, 273 methylation 280 nicotinic acid 156 2-methylbenzoxazole 103 nicotinoid insecticides 298 5-methylcytosine 159 Niementowski Quinazoline Synthesis 343 N-methyl,N-ethylaniline 316 Niementowski Quinoline Synthesis 343 N-methylformilanilide 93 nithiazine 299 3-methylindole 144 nitration 75, 99, 217 N-methylmorpholine oxide 252 nitrene 169 Methyl Orange 91, 213, 304 nitrenpyram 299 N-methylphenylamine 154 nitric acid 20 N-methylpiperidine 29, 240 nitride ion 192, 193 N-methylpiperidine oxide 249, 251 nitrido 232 2-methylpropane 25 nitriles 36, 89, 187, 232 2-methylpyridine 148 nitroalkanes 38, 53 3-methylpyridine 156 nitroamines 245 N-methylpyridinium salts 152 2-nitroaniline 214, 226 methyl-m-xylidene 209 3-nitroaniline 226 metol 100 4-nitroaniline 221, 226 metribuzin 290, 291 2-nitrobenzaldehyde 219

368 Index

nitrobenzene 152, 210 Passerini Condensation 344 nitroguanines 299 PBN 116 nitrogen 2, 3, 4, 5, 14 Pechiny–Ugine–Kuhlman Process 177, 178 nitrogen, properties 232 Pechman Pyrazole Synthesis 344 nitrogen fixation 14, 192, 233 Pellizzari Reaction 344 nitrogen lone pair 134 penems 30 nitrogen mustard gas 275, 276, 277 penny lilac postage stamp 302 nitrogen trichloride 172, 174, 175 pentaerythritol 68 nitrogen trifluoride 309, 310, 311, 312 pentamethylenediamine hydrochloride 151 nitrogen trifluoride oxide 171 pentazole 170 nitrogen triple bond 192, 193 pentylamine 34, 209 nitrogenase 6 peptides 215, 235, 236, 239, 242, 253, 254 3-nitroindole 146 Perkin, William H. 301 nitromethylene group 299 perphenazine 60 4-nitropyridine N-oxide 155, 218 pesticides 298 5-nitropyrimidine 161 pethidine 61 2-nitropyrrole 137 Petrenko–Kritschenko Piperidone Synthesis 345 N-nitrosoamines 95 Pfitzinger Synthesis 163, 345 N-nitroso compounds 95, 112, 248 pharmaceuticals 246, 269, 274 N-nitrosodiphenylamine 112 phenazine 303 4-nitroso-N,N-dimethylaniline 207 phenazone 139 nitrosyl chloride 128 Phenglutarimide 269 nitrous acid 86 phenmetrazin 60 nitryl chloride 171 phenothiazine 59, 303 NMR 20, 133, 228, 232 phenoxazine 303 NMR (1H) 229, 230 phenylarsonic acid 89 NMR (13C) 231 phenylbutazone 142 NMR (14N) 232, 233 phenylenediamines (general) 295 NMR (15N) 232 1,2-phenylenediamine 104, 105, 214, 216, 218, non-steroidal anti-inflammatory agents 142 221 noradrenaline 274 1,3-phenylenediamine 104 Norsk Hydro x, 8, 9 1,4-phenylenediamine 105, 115, 283, 287, 291 Nottoden x, 8, 9, 10 phenyldiazonium chloride 212 Nylon x, 67, 165, 233 phenylethylamine 273 phenylhydrazine 184, 217 octylamine 34, 50 phenylhydroxylamine 101 ODPA 116 phenylisothiocyanate 94 oleum 100, 187 N-phenyl-␤-naphthylamine 111 oleyl amine 50 phenylpenatazole 170 Olin Modification 178 N-phenylpyridinium chloride 154 Oppau 12, 14 phorphobilinogen 199 ornithine 62, 63, 255, 257, 258, 259, phosgene 46, 65, 93, 94, 107, 182, 237, 239, 242 260 photography 286 ornithine decarboxylase 64 photosynthesis 295 orotic acid 160 photosystem I 297 Orton Rearrangement 77, 97, 343 photosystem II 295 osazones 184 phthalimide 22, 35, 84, 206 osmium 11 phthalocyanines 147, 189, 202, 226, 286 Ostwald Synthesis 20 Picloram 298 oxidation 46, 99, 265 Pictet–Gams Isoquinoline Synthesis 345 oximes 187 Pictet–Hubert Reaction 345 oxindole 144 Pictet–Spengler Reaction 61, 346 ozonolysis 22 pilocarpine alkaloids 140 Piloty–Robinson Synthesis 346 Paal–Knorr Pyrrole Synthesis 134, 344 Pinacyanol 162 Padwa Pyrrolidine Synthesis 344 Pinner Triazine Synthesis 346 PAN 116 piperacillin 60 papaverine 163 piperazine 55, 56, 58, 59, 128, 158, 221 paracetamol 103 piperazine dihydrochloride 65 Paraquat 157, 297 piperidine 28, 55, 57, 67, 221, 243, 315 paroxetene 273 piperidone 51, 55, 58, 61, 273

Index 369

piperylon 61 pyrrole 119, 120, 121, 133, 134, 135, 136, 138, 141, Piria Reaction 346 181, 228, 232, 238, 310 pirimiphos 299 pyrrole-2-aldehyde 136, 137, 200 pKa/pKb 31, 71, 74, 77, 127, 247, 270, 312, 315, pyrrole-2-sulphonate 137 316 pyrrolidine 37, 67 Polonovski Reaction 347 pyrrolidinone 138 polyamines 62, 64 pyrryl magnesium bromide 137 polyazo dyes 303 polyurethane 106 Q-bands 195, 228 Pomerantz–Fritsch Reaction 347 quaternary ammonium salts 213, 232, 251, 294 porphyrin 139, 189, 194, 195, 201 Queen Elizabeth I 262 potassium 20 Queen Victoria 302 potassium pyrrole 136 quinaldine 162 praziquantel 59 quinazoline 22 Priestley, Joseph R. 18 quinine 163, 273 primaquine 163 quinoline 98, 119, 162, 221, 228, 293, 316 prochlorperazine 60 quinoline-8-sulphonic acid 162 prodiamine 295 quinolinium ion 268 Prochloraz 293 quinolizinium ion 162, 164 proline 139, 237 quinones 103 Promazine 269 quinonimines 284 Promethiazine 269 quinoxaline 104, 218, 295 Prometon 296 Quinoxyphen 293 propellants 288 propoxy carbazone 297 Raschig Process 21, 169, 173, 174, 176, 178, 184, 186 propylamine 34 receptors 273, 274 protecting groups 236 reduction 75, 76, 78, 79, 207, 208, 210, 214, 251 Pschor Reaction 87 Reimer–Tieman Reaction 136 Pudovik Reaction 347 Reissert Indole Synthesis 145, 347 puppy urine 262 Reissert Reaction 347 putrescine 33, 62, 63, 67 reprography 284 pyrazine 121, 157, 228 riboﬂavin 158 pyrazole 121, 139, 143, 183 von Richter Cinnoline Synthesis 348 pyrazolone 288 Riehm Quinoline Synthesis 348 pyrazolopyrimidine 299 ring-opening reactions 126 pyrazolotriazole 288 ring strain 124, 131 ␤-pyrazol-1-ylamine 142 Ritter Reaction 37, 53, 348 Pyrichlor 298 Rjuken 8, 9 pyridate 298 Robinson–Schopf Reaction 348 pyridazine 157, 184, 228, 242, 294, 298 rocket propellants 176, 179, 288 pyridazine N-oxide 157 Rose Amine D 268 pyridazinone 293 Rosenmund–Braun Reaction 348 pyridine 102, 119, 120, 121, 141, 150, 151, 153, 155, Rothenmund Reaction 349 187, 191, 200, 221, 227, 228, 232, 291, 293, Rowe Rearrangement 349 294, 298, 299, 312, 313, 316 rubber accelerators 115 2-pyridine carboxamide 297 Runge, Friedlieb F. 133, 301 2-pyridine carboxylic acid 297 Rutherford, Daniel 3 pyridine carboxylic acids (general) 298 pyridine N-oxide 120, 154, 155, 217, 246, 250, 251 safranine(s) 303 pyridine-3-sulphonic acid 153 Saltmen ligand 193, 194 pyridone 153 saltpetre 7, 14 pyridoxal phosphate 258 Sandmeyer Diphenylurea Isatin Synthesis 349 pyridoxamine 258 Sandmeyer Isonitrosoacetanilide Isatin Synthesis 349 pyridoxine 273 Sandmeyer Reaction 87, 212, 350 pyridylmethylamines 299 Scheele, Carl W. 3 Pyrimethanil 293 Schieman Reaction 88, 350 pyrimidine 121, 157, 159, 160, 293, 298, 299 Schiener Aziridine Synthesis 129, 350 pyrimidine bases 159 Schiff Bases 44, 61, 241, 257, 258 pyrimidone 293 Schmidt Degradation 82, 83, 84, 350 Pyrindinitril 293 Schmitz Diaziridine Synthesis 129, 350 Pyroxychlor 293 Schoenherr’s Arc Furnace 9

370 Index

Schotten–Baumann Reaction 47, 215, 237, 242 Swedish magnetite 11 Schroeder–Grundmann Reaction 351 synergol 299 Schweizer Rearrangement 351 synthetic methods 205 Schweizer Synthesis 351 SDPA 116 tallow amine 50 second law of thermodynamics 269 tamoxifen 269 semicarbazide 180, 290 tartrazine 142 Semmler–Wolf Reaction 351 tepa 277 Seradix 299 Terbutrin 296 serine conjugate 297 tertiary amines 248 serotonin 8, 144, 261, 274 tetrahydropyrrole 139 shampoo 281 tetramethylammonium hydroxide 213 Sharpless, K. Barry 42 1,2,3,4-tetrahydrocarbazole 217 Sheverdina–Kocheshkov Amination 351 tetrahydroisoquinoline 59 Shibasaki Cyclization 352 N,N,N’,N’-tetramethylethylenediamine 34, 48, 64, 65, simazine 295 208, 243 Sisler Process 177, 178 N,N,N’,N’-tetramethylpropylenediamine 66 skatole 144 tetramin 128 Skraup Quinoline Synthesis 98, 162, 163, 352 N,N,N’,N’-tetraphenylethylenediamine 114 small intestine 272 N,N,N’,N’,-tetraphenyl hydrazine 113 Smiles Rearrangement 352 tetrapyrrole system 194 sodium 20, 95, 113 tetrasulphur tetranitride 202, 203 sodium arsenite 89 tetrazane 169 sodium azide 170, 203 tetrazete 169 sodium pyrrole 136 tetrazine 169 Sommelet–Hauser Reaction 352 tetrazole 170 Soret Band 194, 195, 228 Thiabendazole 293, 294 soya amine 50 thiacloprid 299 specific impulse 289 Thiamethoxam 299 spectroscopy 220 thiocyanates 94 spermidine 33, 63, 260 N-thionylaniline 135 spermine 62, 63, 260 thiophosgene 93 Spike 290 thiosemicarbazide 290 Staedel–Ringheimer Pyrazine Synthesis 352 thiotepa 129, 276, 277 Staudinger Reaction 353 thiothixene 60 stearyl benzylammonium chloride 279 Thorpe Reaction 354 steric factors 227 thymine 157, 159 Stern potential 267 Tiazopyr 298 sterol 293 Tiemann Rearrangement 354 StolléSynthesis 353 Timmis Pteridine Synthesis 354 Stork Reaction 60, 353 tinoridine 61 Strecker Aldehydes 259 titanous chloride 71, 77 Strecker Reaction 255, 259, 353 toiletries 278, 294 Strecker Degradation 354 toluene diamines 106, 107, 108 substitution reactions 250 m-toluene diisocyanate 106 succinaldehyde dioxime 138 4-toluylene diamine 283 succinimide 136, 243 tolyl triazole 109 Sulfentrazole 297 tosyl hydrazide 183, 184 sulphacytine 157 transamination 261 sulphanilic acid 100, 221 Traube Purine Synthesis 355 sulphapyridine 43, 44 3,4,5-triamino-1,1,1-trifluorotoluene 295 sulphobetaines 281 trialkylammonium peroxide 248 sulphonamide drugs 44 triarylamines 116 sulphonation 100 Triasulfuron 296 sulphondiazine 157 triazane 169, 295 sulphur–mustard gas 275 triazine 291, 296 sulphur–nitrogen compounds 202 triazinium chloride 173 sulphur trioxide 100 triazinylsulphonylurea 296 superconductivity 202 triazo dyes 303 surfactant(s) 246, 278 triazoles 122, 293, 294, 296 Suzuki Reduction 354 triazoxide 293

Index 371

tribenzylamine 315 urethane 182 tributyltin azide 170 uroprophyrinogen III 199 tricetylammonium chloride 279 urotropine 67 trichloroamine 1, 39, 171 2,4,6-trichloroaniline 315 vaccines 124, 129 trichlorotriazine 304 van der Waals energy/complexes 19, 117 tridemorph 60, 293 Van Slyke Determination 356 tri-n-butylamine 28, 315 Vilsmeier–Haack Reaction 138, 146, tributylamine N-oxide 246 356 triethylamine 28, 50, 221, 237, 239, 247, 284, 315 visible spectroscopy 225 triethylbenzylammonium chloride 240 vitamins 119 triethylene tetramine 280 vitamin B1 159 trifluoroamine 171, 232 vitamin B2 159 trifluorphenazine 60 vitamin B6 157, 258 Trifluoralin 295 vitamin B12 139, 140, 194, 195, 198, 200 trimethoprim 157 Voight Amination 357 trimethylamine 25, 26, 28, 34, 243, 247, 315 von Braun Reaction 162 trimethylamine N-oxide 252 vulcanization accelerators 45, 50 2,4,6-trimethylaniline 96 2,2,4-trimethyl-1,2-dihydroquinoline (TMDHQ) 98 Walden Inversion 127 trimethylpyridine 45 Wallach Rearrangement 357 Trimipramine 269 Watanabe Cyclization 357 triphenylamine 74, 116, 316 water gas 12 triphenylphosphine 74, 84 water gas shift reaction 12 tri-n-propylamine 28 Wencker Aziridine Synthesis 124, 357 tris-(2,12-methoxyethoxyethyl)amine 240 Werner, Alfred 189 Tröger’s (amine) Base 27, 30 Westphal Condensation 357 Trost Ligand 191, 192 Whiffen Process 178 tryptamine 144, 261 Widman–Stoemer Synthesis 358 trytophan 144, 146, 156, 241, 255, 257, 258, 260, 261, Willgerodt–Kindler Reaction 58, 358 299 Wittig Reaction 61 ␤-tubuline 293 Wöhler Urea Synthesis 358 tubocurramine 163 Wolf–Kischner Reaction 180, 181, 182, 358 Tyrian Purple 305 Wolff Rearrangement 358 world population 15 ubiquinol oxidase 293 uniconazole 294 zeta potential 267 unsymmetrical dimethyl hydrazine (UDMH) 288 zinc pyrithionate 157 urazole 289 Zinin Rearrangement 359 Urech Hydantoin Synthesis 356 Zinner Hydroxylamine Synthesis 359