INDEX: TABLE OF SUBSTITUTION REACTIONS OF PYRIDINES Substrates Leaving group Entering group* PAGE ELECTROPHILIC SUBSTITUTIONS Atylation and carboxylation Pyridines H .CHO, .COPh 162 Pyridine 1-oxide .COMe 162 Pyridines .C02H 163 Alkylation and substituted alkylation Pyridines H . CRa, . CH2NR2 163 .C02H .C(OH)R2 163 Deuteration and tritiation Pyridinium ions H T 164 Pyridine 1-oxides (cations) D 164 Diazo coupling Pyridines H .N2Ar 164 Halogenation Pyridines H Cl, Br, I 164-9 Pyridine !-oxide Br 169-70 Pyridines .SOaR Cl, Br 164, 166 Hydroxylation Pyridines H .O.SOaH,.OH 170 Aietalation, halogen-metal interchange Pyridines H .HgX 171 Pyridine !-oxide .HgX 171 Pyridines Br, I Li 170-1 Nitration and nitrosation Pyridines H .N02 171--4 Pyridine !-oxides .N02 174 Pyridines .NO 176 Sulphonation Pyridines H .SOaR 176-7 Pyridine 1-oxides .SOaR 177 Thiotyanation Pyridines H .SCN 178 NUCLEOPHILIC SUBSTITUTIONS AlJilation Pyridines H .COR 200 Alkylation and substituted alkylation Pyridines H alkyl, allyl 100-3 Pyridine !-oxides .c;cH, alkyl 201,203 Pyridinium ions . C: C. C02Me, alkyl 192, 203 (.CH2COMe) 204 Pyridinium ions (acyl) alkyl, (.C;C.Ph) 201 (.CH(R) .COR'}, (.CH2N02) 205 (alkoxy} alkyl 201 (acyloxy) .CH(CN) .C02Et 206 417 TABLE INDEX Substrates Leaving group Entering group PAGE Alkylation and substituted alkylation-continued Pyridines halogen alkyl 201,203 . CH(CN)Ph, . CE<(CN)Ph'} .C(CN)Ars, .C(Me2) .COsEt, .CEt. (COsEt)s, 203 . CHAr. SOsR, .CH(COsEt)s, . CEt(C02Et)s Pyridine (via pyridyne) Br .CHsCOPh 204 Pyridine !-oxides Br .CHAr:. COsEt, .CHPh.COsEt 204 Pyridinium ions halogen alkyl 203 . CH(COPh) . COCHsR, + . CH2. CsH4NEt 205 Pyridines .OMe .CH(COsEt)2 203 Pyridones :0 :CHR 201 Pyridinium ions .OR alkyl 203 Amination and substituted amination Pyridines H .NHs, .NHPh, .NHR, .NHNHR 206--8 + Pyridinium ions :N. 186,209-10 I Pyridines .NHs .NH.Csli4N 210 + Pyridinium ions :N. .NHs, .NHPh 210 .CN .NHa 210 Pyridines halogen .NH2, .NHR, .NRa 191, 210-1, 214, 216 .NHAr, .NHNHR 211, 216 + :N. 191, 212,216 I Pyridines (via pyridynes) .NHa, .NRa 214 Pyridine 1-oxides .NH2, .NR2, .NHNHa 213, 215-6 Pyridine 1-oxides (via pyridynes) .NHa 215 Pyridinium salts .NHs, .NHR, .NHAr 213 .NHNHCOPh 213 + :~. (intramolecular) Pyridines .OH, .OAr .NH2, .NHPh 218-9 .O.COMe, + • O.SOaC7H7 :N. 219 I Pyridine 1-oxides .OAr .NHR 219 Pyridinium ions .OR, .OAr .NHR 219 Pyridines .NOa .NH2, .NHR, .NRs 212-3,219 .SOsH .NHs, .NHR 219-20 Pyridine 1-oxides .SR .NHR, .NHAr 219 Pyridinium ions .SR, .SAr .NHR 219 Arylation Pyridines H .Ar 220-3 Pyridine 1-oxides .Ar 220-3 Pyridinium ions .Ar 220,223 Pyridines Br .Ph 223 Cl .Ar(intramolecular) 223-4 Modified carbonyl reactions Pyridines H .CRaOH 224-5 418 TABLE INDEX Substrates Leaving group Entering group PAGE Formation of cyanides Pyridinium ions H (.CN) 225 (1-alkoxy) H, .OMe .CN 225--B Pyridines .N2+ .CN 226 Pyridine !-oxides .N2+ .CN 226-7 Pyridines halogen .CN 227 .SOaNa(K) .CN 227 Pyridine !-oxides .SOaNa .CN 227 Halogenation Pyridines H .Cl 227--8 Pyridinium ions H (. Cl) (followed by electrophilic bromination) 228 .Cl 228-9 + Pyridines :N. halogen 229 ' .N2+ 229-30,241,397 Pyridine 1-oxides .N2+ 230 Pyridines halogen 230 Pyridinium ions halogen 180 Pyridines .OH 231-2 Pyridine 1-oxides .OH Cl 232 Pyridines .N02 halogen 232-3 Pyridine !-oxides .N02 halogen 233 Pyridines .SOaH Cl 233 Hydroxylation and substituted hydroxylation Pyridines H .OH 234 Pyridine 1-oxides H .OAc, .O.S02C7H7 234-5 Pyridinium ions H (.O.COR) 236 H (OH) (followed by oxidation to:O) 236-8 Pyridine 1-oxides .C02H .O.COPh 238 Pyridinium ions .C02H (OH) (followed by oxidation to:O) 238 + .CH2NCsHs :0 238 Pyridines .NH2, .NHMe, .NMe2, .NHN02 .OH 238--9 + :N. .OH, .OR, .OAr 239 I Pyridinium ions . NH2, .NHMe, .NMe2, .NHN02 :0 238-9 .CN .OH 239 Pyridines .N2+ .OH, .OR, .OAr 239--41 halogen . OH, . OAc, . OR, . OAr 241-7 Pyridine 1-oxides halogen .OH, .OR, .OAr 245 Pyridinium ions .OH 245 .OAc 242,379 Pyridines .OR, .OAr .OH 247--8 Pyridine 1-oxides .OR .OH 248 Pyridinium ions .OR, .OAr .OH 248 Pyridines .N02 .OH, .OR, .OAr 248 Pyridine 1-oxides .N02 .OH, .OR, .OAr 248 Pyridinium ions .N02 .OH, .OAc 248-9 Pyridines .SH .OH 249 .SOMe, .SOaH, .SOaNa .OMe, .OH, .OR 249 Sulphur-bond formation Pyridinium ions H ( .SR), (. S02H) 249 H .SR 250 419 TABLE INDEX Substrates Leaving group Entering group PAGE + Pyridines :N. .SH, .SR, .SOaH 251 .N2+ .SH, .SCN 251 halogen .SH, .SR, .S., .SOaH 251 + .SC(NHz) :NH2 251 + Pyridine 1-oxides .SC(NHz) :NH2 251 .SOaH 251 Pyridinium ions :S 251 Pyridines .OH,:O .SH, :S 251 Pyridine 1-oxides .N02 .SR, .SOaH 251 RADICAL SUBSTITUTIONS Alkylation and substituted alkylation Pyridines H . CPha, alkyl 251-2 Arylation Pyridines H .Ar 253-5 H (intramolecular) 256 Pyridine 1-oxid~ H .Ph 253 * When the entering group is in brackets the substitution is not completed but stops at the stage of addition. 420 SUBJECT INDEX (Page numbers in italics refer to Tables.) Acetone pyrrole, 72 Acylpyrroles-continued Acylpyridines, 311-6, 312-4 N-, rearrangement to C-acylpyrroles, aldehydes, 311-5, 312-3 109 alkylation, 315 Alkenylpyridines, 122; see Stilbazoles bisulphite compounds, 311 cinnolines from, 350-1 Cannizzaro reaction, 314 dihalides, 371 hydration, 311 dehydrohalogenation, 373 reactions with electrophilic additions, 349-51 cyanide, 314 of halogen hydracids, 350 diazoalkanes, 315 of halogens, 349-50 !-oxides, 312-3 ionization constants, 146 oximes, metal complexes, 315, 397 nucleophilic additions, 351-3; see Vinyl­ quaternary salts, reactions with alkali, pyridines 397 oxidation, 351 Wittig reaction, 314 reduction, 257, 266, 353 dipole moments, 124 Alkoxycarbonylpyridines, 317-9, 321-2 ionization constants, 146 Claisen reaction, 322 ketones, 313-4, 315-6 dipole moments, 124, 126 oximes, 313--4 hydrolysis, 321-2 Beckmann rearrangements, 315 and Hammett equation, 156, 322 metal complexes, 315 ionization constants, 146-7 Neher reaction, 315 !-oxides, 319 reduction, 263-4, 315 hydrolysis, 322 side chain, 314-6 reactions at nitrogen with N-, see Pyridinium ions, 1-acyl alkyl halides, kinetics, 189-90 oximes, 312-4 alkylating reagents, 180 ionization constants, 146, 397 oxidizing agents, 197 tautomerism of, 154 reduction, 257-8, 263-4 reactions stretching frequencies, carbonyl groups, at nitrogen with 142 alkylating reagents, 180 ultra-violet spectra, 139 oxidizing agents, 197 Alkoxycarbonylpyrroles, 93, 95-6 with Grignard reagents, 220 acylization, 95-96 stretching frequencies of carbonyl groups, hydrolysis, 95 142 kinetics, 110 ultra-violet spectra, 129 N-H stretching frequencies; rotational Acylpyrroles, isomerism, I 09 C-, 92-4, 93 ultra-violet spectra, 55 acidity, 62 Alkylpyridines, 121-2 acyl-group displacement in acidity, 324-31 halogenation, 78 and nitration, 80 alkylation, 325 aldehydes, 93 hydrogen exchange, 325-6 preparation by metalation, 325 Gattermann reaction, 63-4 tautomerism, 324-5 Reimer-Tiemann reaction, 63 molecular orbital theory, 330 hydrogen bonding in, 58 N-alkyl, see Pyridinium ions, !-alkyl oximes, in Beckmann rearrangement, 99 alkylation, nucleophilic, 202 preparation by amination, nucleophilic, 206-7 Roesch reaction, 64 deuteration and tritiation, Vilsmeier reaction, 64 nuclear, electrophilic, 164 salts, 61 dipole moments, 123-5 stretching frequencies, carbonyl group, halogenation, electrophilic, 58 nuclear, 165, 168, 279 ultra-violet spectra, 55 effect of aluminium chloride, 166-8 Wittig reactions with, 110 side chain, 165 421 SUBJECT INDEX Alkylpyridines-continued Alkylpyridines, side-chain reactions-continued heats of reaction, with amination, 210, 333 Lewis acids, 151 base-catalysed, see metallic derivatives methanesulphonic acid, 151 dehydrogenation, 348 infra-red spectra, 141 diazo coupling, 339 ionization constants, 145-6, 150-1 halogenation, 165, 339-40, 345 isomerization, thermal, 324 hydrogen exchange, 325-7, 397 mercuration, 171 Mannich, 332 metallic derivatives, see Grignard re­ metalation, 202, 207, 220-1, 325, 327-8 agents, Lithium, etc. metals nitration, 343 nitration, 171-2 nitrosation, 343 1-oxides, oxidation, 346-8, 397 deuteration, nuclear, 164 Willgerodt, 348 reactions with with acetic anhydride, 234, 245, 281, acrylonitrile, 332-3 340-3 aldehydes, 334-8 aldehydes, 336 amines, 343 arenesulphonyl chlorides, 210, 340 benzenesulphonyl chloride, 344 arylacetic acid anhydrides, 380 ketones, 334, 339 carboxylic acid chlorides, 343 radicals, 344-5 ketene, 343 ultra-violet spectra, 127-9 side-chain reactions, and tautomerism, 137 halogenation, 165 Alkylpyrroles, hydrogen exchange, 326, 397 C-, 52-3 sulphonation, 177 dipyrrylmethenes formed by bromina- quaternary salts (1-alkoxy), tion, 78 acidity, 328 ionization constants, 60 pyridone methides from, 328-30 metallic derivatives, 61 reactions with methyl groups in, alkali, 236, 238, 328-30 acetoxymethylation, 97 mercaptides, 250 bromination 77-8, 96, 102 side-chain reactions, chlorination (sulphuryl chloride), 78, arylation (cyanine formation), 333-4 96-7, 102 with displacement of, in nitration, 80 aldehydes, 336-7 phenylation, 97 arnines, 343-4 oxidation to ketones, 337-9 fatty acids, 97 Schiff bases, 336 maleimides, 87, 96 ozonization, 265 rearrangement by aluminium chloride, photochromotropism, 345 68 polarography, 324 salts, 61 reactions ultra-violet spectra, 54 at nitrogen, N-, rearrangement to C-, 109 oxidation, 197 Alkynylpyridines, 122; see Tolazoles with hydration, 350 acylating agents, 195 hydrogenation, 348 alkyl halides, kinetics, 188-90 ionization constants, 146 alkylating reagents, 180-1 nucleophilic additions of aryl halides,