Index

Indicates that this is a reference to the synthesis of either a specific compound or a group of compounds

A Acyl 2H-azirines, 676

Ab initio calculations, 34 N-Acylazoles, hydrolysis, 598
2-Acetamidopyridine N-oxide, chlorination, 269 2-Acylbenzimidazoles
, 529
2-(Acetoxyalkyl)pyridine
, 381 N-Acylbenzotriazoles, acylating agents, 599
1-Acetoxybenzo[c]furan
, 439 N-Acyl-2-cyclopropylanilines, intramolecular rearrangements, 841
N-Acetoxy-4,5-dialkylpyrid-2-thione, reaction with benzynes, 876 N-Acyl-4,5-dihydropyrroles
, 440
Acetoxydithiocin, tautomerism ,612 2-Acylfurans, reaction with xanthate derived radicals, 427
2-Acetoxyfuran, Diels–Alder reactions, 432 1-Acyl-2-heteroaryl-2,3-dihydro-4(1H)-pyridones
, 464
3-Acetoxy-3H-indole, 418 4-Acylimidazoles
, 746
Acetoxymercurioxazoles, 589 1-Acylindoles, photoisomerization, 471
3-Acetoxymercuripyridine
, 270 3-Acylindoles
, 405
Acetoxymercurithiazoles, 589 thallation, 448
3-(Acetoxymethyl)-2-(tributylstannylmethyl)furan, in formation of 3-Acyl-3H-indoles
, 471
2,3-dimethylene-2,3-dihydrofuran, 452 4-Acylindoles
, 448
2-(2-Acetoxyphenyl)pyridine
, 299 N-Acylisoquinolinium salts, 258
N-Acetylazoles, carbonyl frequencies, 184 3-Acylisoxazoles, nucleophilic ring opening, 570
5-O-Acetyl-2-O-benzoyl-3,4-O-isopropylidene-1-O-methyl derivative of 4-Acyloxy-b-lactams, are converted into 1,3-oxazin-6-ones, 752
b-L-idoseptanose, structure, 222 2(4)-Acyloxypyridines, ease of hydrolysis, 358
Acetylenes, reaction with 4-substituted thiazoles, 694 2-Acylphenylacetonitriles, cyclization, 826
2-Acetylfuran-2,4-dinitrophenylhydrazone, rotamers, 130 1-Acylpyridinium ions, 258
2-Acetyl-l-(2-hydroxyethyl)-5-nitropyrrole, base-induced cyclization, 457 as acylating agents, 377
3-Acetylpyrazoles, Willgerodt reactions, 569 1-Acylpyrroles, carbonyl frequencies in IR spectra, 119
2(3)-Acetylpyridines, asymmetric hydrogenation, 344 rearrangement in vapour phase, 471
3(4)-Acetylpyridine, reduction, 344 2-Acylpyrroles
, 389, 404
4-Acetylpyridine
, 320 reaction with allylphosphoranes, 892
8-Acetylquinoline
, 336 reaction with xanthate derived radicals, 427
N-Acetyl-5-styrylpyrazoles, Diels–Alder cycloadditions, 541 rearrangement to 3-acylpyrroles, 399
5-Acetyl-2,2,6-trimethylpyran, valence tautomerism, 83 3-Acylpyrroles
, 399, 405
Acid-catalyzed hydrogen exchange in azines, 265 N-Acyl-1,3,4,5-tetrahydro-2,1-benzoxazepines
, 836
in azoles, 504 N-Acyltetrahydropyrazoles
, 552
Acridine, 38 2-Acyltetrazoles, loss of nitrogen ,599, 780
nitration, 332 thermal decomposition, 481
nucleophilic attack, 246 Acyl thiosemicarbazides, cyclization, 775
oxidation, 271 N-Acyl-o-toluenesulfonamides, directed ortho-methyl
Acridizinium ion, [4 + 4] photocycloaddition, 313 lithiation/cyclization, 835
Acridones, 880 N-Acyl-o-toluidines, conversion to indoles, 812
9-Acridone
, 274 1-Acyl-1,2,3-triazoles, isomerisation, 598
N-Acylamidines, reaction with sodium hypochlorite, 779 rearrangement to 2-acyltriazoles, 499
2-Acylamino-6-acetyl-4(1H)-pyrimidinones, Diels–Alder reactions, 312 1(2)-(1-Adamantyl)indazoles, flash vacuum pyrolysis, 202
N-Acylamino-2-alkenylbenzenes, rearrangements, 841 4-(1-Adamantyl)pyrazole
, 506
b-Acylamino esters, thermolysis, 750 3(5)-(1-Adamantyl)pyrazole
, 506
a-Acylamino ketones, reaction with hydrazine, 782 Aldehyde azines, reaction with dimethyl acetylenedicarboxylate, 719
reaction with iminoesters to give imidazoles, 738 Aliphatic 1,2-diamines, conversion into 1,2,5-thiadiazoles, 772
reaction with phosphorus pentasulfide to give thiazoles, 738 Alizarin Green G
, 883
3-Acylamino-5-methyl-1,2,4-oxadiazole, 524 [N-(Alkane/arenesulfonyl)imino]aryliodanes, as a source of nitrenes, 655
a-Acylamino Schiff bases, reaction with phosphoryl chloride, 738 a,w-Alkanedithiols, oxidation, 732
o-(Acylamino)styrene, intramolecular iodoamintation, 799 Alkenes, cycloaddition to sulfur trioxide, 713
Acylanilines, reaction with the Vilsmeier–Haack reagent to give quino­ epoxidation, 653
lines, 818 N-Alkenylazoles, weak or moderate p-electron acceptors, 598
3-Acylanthranils, rearrangement to benzoxazinones, 570 N-Alkenylimidazoles, addition reactions, 598
Acylated 2-aminobiphenyls, cyclodehydration, 877 Alkenylindoles, 410

971
972 Index
4-Alkenyl substituted isoquinolines, 826
1-Alkenyltetrazoles, photochemical degradation, 747
N-Alkoxyamides, oxidation, 850
3-Alkoxy-2H-azirines, nucleophilic addition, 620
1-Alkoxybenzimidazoles, reaction with anionic sulfur species, 519
1-Alkoxycarbonylbenzotriazoles
, 499
(Alkoxycarbonylmethyl)ethers, reaction with arylglyoxylates, 686
N-Alkoxycarbonylpyridinium salts, reaction with organometallics, 286
reaction with titanium enolates, 288
1-Alkoxycarbonyl-pyrroles, carbonyl frequencies in IR spectra, 119
2-Alkoxy-3-hydroxyindolines
, 419
1-Alkoxy-3-methylbenzimidazolium salts, reaction with anionic
sulfur species, 519
2-Alkoxy-l-methylimidazoles, rearrangement of alkyl group, 580
1-Alkoxymethylbenzotriazoles, lithiation, 595
4-Alkoxypyrazoles, 714
2-Alkoxypyrazoliums, reactivity of side chain methyl groups, 566
2(4)-Alkoxypyridines, dealkylation, 358
flash vacuum pyrolysis to N-alkylpyridones, 250
nitration, 263
2-Alkoxypyridine N-oxides, rearrangements, 357
1-Alkoxypyridinium compounds, reaction with hydroxide ions, 382
reaction with cyanide ions, 294
Alkoxypyrimidines, rearrangements, 357
b-Alkoxyvinyl trifluoromethyl ketones, cyclocondensation with
thiosemicarbazides, 718
3-Alkyl-5-acetamidoisothiazoles, nitrosation, 508
1-Alkyl-3-acylazolium salts, powerful acylating agents, 598
N-Alkyl-2-acylpyrroles, reaction with strong anhydrous acid, 456
N-Alkyl-3-acylpyrroles
, 456
1-Alkyl-3-alkoxycarbonylisoquinolines
, 827
2-Alkyl-5-alkoxyoxazole
, 741
5-Alkylamino-1-aryltetrazoles, Dimroth rearrangement, 208
1-Alkyl-2-aminobenzimidazoles, diazotisation, 574
1-Alkylaminoindazoles, rearrange into 2-alkyl-3-aminoindazoles, 601
4-Alkylaminoindoles, rearrangement, 449
N-Alkyl-5-aminoisoquinolinium salts, ring contraction, 815
1-Alkylaminopyrazoles, rearrangement, 601
Alkylaminopyridines, nitration 263
5-Alkylamino-1,2,3,4-thiatriazoles, ring opening, 514
3-Alkyl-3-aryloxindoles, synthesis, 810
Alkylated glycolurils, X-ray structures, 156
N-Alkylation of 1,2,3-triazoles and benzotriazoles, 496
Alkylazetines, synthetic routes, 675
N-Alkyl azetidin-3-one dimethyl acetals, hydrolysis, 638
1-Alkylbenzimidazole 3-oxides, reaction with anionic sulfur species, 519
N-Alkyl-1,2-benzisothiazolin-3-one S-oxides, synthesis, 832
N-Alkylbenz[d]isoxazolium cations, base-catalyzed ring expansion, 841
2-Alkyl-1,2,4-benzotriazines, synthesis, 861
N-Alkylbenzotriazoles
, 496
oxidation, 500
1-[Alkyl(aryl)carbonylmethyl]-2-alkylpyridinium halides, Chichibabin
reactions, 892
3-Alkyl-2-(N-cyanoimino)thiazolidine 1-oxides, ring-enlargement, 785
N-Alkyl-3,3-dialkyloxaziridines, resolvability, 234
3-Alkyl-2,5-diaryl-1,4-oxathiepin-7-ones
, 769
2-Alkyl-2,3-di(t-butyl)azete, cycloaddition of nitriles, 752
1-Alkyl-1,4-dihydro-3,4-diphenyl-1,2-diazete-2-oxide
, 614
1-Alkyl-4,5-dihydroimidazoles, deprotonation, 550
1-Alkyl-4,5-dihydrotriazoles, hydrolytic decomposition, 549
Alkyl 3,5-dimethyl-4-[(1-iodo-2,2-dimethyl)propyl]pyrrole-2-carboxylate,
rotational barrier, 131
Alkyl 3,5-dimethyl-4-(1-iodoneopentyl)-1H-pyrrole-2-carboxylate, rota­
tional barrier, 131
4-Alkyl-2,6-diphenylthiopyrylium cations, reaction with methoxide ions, 279
2(3)-Alkyl five-membered heterocyles, fragmentation patterns in mass
spectrometry, 120
2-Alkyl groups in 1,3-dithiolylium ions, reaction with aldehydes, 566
2-Alkyl-5-hydroxy-1,3-benzoxazepine
, 844
a-(Alkylideneamino)nitrile, addition to methyl vinyl ketone, 663
N-(Alkylidene)-g-bromoamines, in formation of azetidines, 661
5-Alkylidene-1,4-dimethyltetrazolines, cycloadditions, 544
1-Alkylimidazoles, reaction with alkyl radicals, 533
2-Alkylimidazoles, 594
3-Alkylimidazolin-2-ones
, 580
2-Alkylindazoles, photolysis, 562
2-Alkylindoles, condensation with a,b-unsaturated ketones, 874
Alkyl indole-2-carboxylates, synthesis, 814
2-Alkyl-2H-isoindoles, synthesis, 823
2-Alkylisoquinolinium salts, synthesis, 826
2-Alkyl-3-isothiazolinones, nucleophilic attack, 511
2-Alkylisothiazolium salts, conversion to isothiazoles, 594
N-Alkyl-(p-methoxyphenyl)anilines, photocyclization to tetrahydrocarba­
zoles, 873
3-Alkyl-5-methyl-6-phenyl-3,4-dihydro-1,2,3-triazin-4-ones
, 774
N-Alkyl oxaziridines
, 707
barrier to pyramidal inversion of the nitrogen atom, 233
2-Alkyloxazoles, McLafferty rearrangement, 185
N-Alkylphenothiazines, oxidation, 314
1-Alkyl-2-phenylimidazole-4,5-dione
, 744
1-Alkyl-5-phenyltetrazoles, reaction with alkyl iodides, 493
1-Alkylpyridines, conversion to 4,40 -bipyridyl diquaternary salts, 293
2-Alkylpyridines, 285, 302
2(4)-Alkylpyridines, conversion to anions, 337
4-Alkylpyridines, reaction with benzenesulfonyl chloride, 341
1-Alkylpyridinium halides, dissociation, 376
oxidation, 276
photolysis, 251
proton loss to give N-ylides, 376
reaction with Grignard reagents, 286
rearrangements, 377
N-Alkyl-2-pyridones
, from rearrangements, 357
N-Alkylpyrimidinones
, 357
Alkylpyrroles, oxidation to maleimides, 418
N-Alkylpyrroles, fragmentation patterns in mass spectrometry, 121
N-Alkylsaccharins, synthesis, 832
Alkyl-substituted pyridines, complexes with boron Lewis acids, 261
Alkyl-substituted thiiranes, reaction with 3-chloroallyllithium, 620
Alkyl-substituted 1,2,4-triazines
, 782
3-Alkylthiazoline-2-thiones
, 582
3-Alkyl-thietane 1-oxides, deprotonation, 628
S-Alkylthiiranium salts, desulfurization, 616
5-Alkylthio 1,2,3,4-thiatriazoles, alkylation, 494
2-Alkylthiothiazoles, rearrangement, 582
N-Alkyl-1,2,4-triazoles, radical substitutions, 533
reaction with nitrenes, 532
2-Alkyltriazole 1-oxides
, 770
1-Alkyl-1,2,3-triazolines, 13C chemical shifts, 168
2-Alkyl-1,2,4-triazolo[3,4-a]pyridines, 903
Alkynes, cycloaddition with diazoalkanes and nitrile oxides, 718
reaction with nickel bisdiphenyldithiolene, 761
Alkynoic acids, reaction with thiocarbonyl compounds, 751
o-Alkynylanilines, diazotization, 832
intramolecular annulations, 805
Alkynylbenzaldimines, cyclization reactions, 826
1-Alkynylbenzotriazoles, 599
2-Alkynylbenzyl alcohols, in production of 1H-isochromenes, 826
2-Alkynylimidazole
, 590
2-Alkynylphenols, intramolecular annulations, 805
cross-coupling reactions combined with catalytic cyclization, 806
Alkynylpyridines, 371
Alkynyl-substituted trifluoroacetyltriazepines
, 786
Alkynyl sulfides, reaction with sodium sulfide, 761
Alkynylsydnones
, 591
Allinger’s MM force field, 35
Alloxan, 356
Alloxazine, structure, 53
o-Allylanilines, conversion into indulines, 802
Allyl anions, 644
1-Allyl-2-allyloxybenzenes, in ring-closing metathesis reactions to benzo­
furans, 813
2-Allylbenzaldehydes, in production of 1H-isochromenes, 826

1-Allyl-2-benzimidazolinone
, 580
Allylic alcohols, enantioselective epoxidation, 653
N-Allyl-o-haloanilines, to indoles, 809
N-Allyl-N-nitrosamides, cyclization, 718
Allyloxybenzenes, iodonium ion promoted cyclization, 819
2-Allyloxybenzimidazole, rearrangement, 580
6-Allyloxy-2-methylbenzothiazole, Claisen rearrangement, 559
4-Allyloxyquinolines, rearrangement to 3-allyl-4-quinolones, 357
o-Allylphenols, cyclization, 805
cyclization to 2,3-dihydrobenzofurans, 801
N-Allylpyidiniums, rearrangements, 378
2-Allylpyrrole, hydroboration, 451
3-Allyl-4-quinolones
, 357
4-Allylthio-3-methyl-2(3H)-pyrimidinone, thermolysis, 360
5-Allyl-4-thiouracil
, 360
1-Allyl-2-vinylindole, cyclization to pyrrolizines, 892
Alumopine, 30
Amidines, reaction with sulfur dichloride, 794
a-Amidobenzotriazoles, cyclization, 849
Amidoximes, reaction with a-haloketones, 784
t-Amine N-oxides, Meisenheimer rearrangement to monocyclic
1,2-oxazepines, 731
Aminoacetophenones, reaction with hydrazines, 770
2-Amino-3-acetylfurans, reaction with bases, 459
a-Amino acids, cyclodimerization to 2,5-dioxopiperazines, 760
4-Aminoacridine, protonation, 256
b-Aminoacylamines, cyclization to imidazolines, 741
Amino-alkylamino-1,2,5-thiadiazole 1-oxides, hydrolysis, 514
1-Aminoalkylbenzotriazoles, displacement of benzotriazole ring, 597
4-Amino-1-alkylindoles
, 449
2(3)(2-Aminoalkyl)pyrroles
, 411
2-Amino-1-aryltetrahydroindoles, diazotization, 908
2-Amino-3H-azepines
, 562
Aminoazines, as weak acids, 347
N-Aminoaziridines, 639
3-Amino-2H-azirines, nucleophilic addition, 620
N-Aminoazoles, oxidation, 600
2-Aminoazoles, tautomerism, 205
2-Aminobenzenethiol, diazotization, 858
1-Aminobenzimidazole, protonation, 600
oxidation, 601
2-Aminobenzimidazoles, oxidation, 575
3-Amino-2,1-benzisothiazole, acylation, 572
diazotization, 574
5-Aminobenzisothiazole, oxidation cleaves benzene ring, 560
3-Aminobenzofurans, tautomerism, 138
2-Aminobenzothiazole, diazotisation, 574
oxidation, 575
4(5)(6)(7)-Aminobenzothiazoles, bromination, 559
2-Aminobenzo[b]thiophene, tautomerism, 138
3-Aminobenzo[b]thiophene, thermal [2 + 2] cycloaddition reactions with
activated alkynes, 435
4-Amino-1,2,3-benzotriazine
, 860
3-Amino-1,2,3-benzotriazin-4-ones, reaction with lead tetraacetate, 379
1-Aminobenzotriazole, oxidation to benzyne, 600
4-Aminobenzotriazoles, thermal rearrangements, 571
2-Amino-1-[a-benzotriazol-1-ylmethyl]pyridinium chlorides, reaction
with aldehydes, 896
2-Aminobenzoxazole
, 516
4-Amino-1-benzylimidazole-5-carbaldehyde, reaction with 1,2-dimethyl­
hydrazine dihydrochloride and trimethyl or triethyl orthoformate, 868
4-Amino-2-t-butyl-5-nitro-1,2,3-triazole 1-oxide
, 518
3-Amino-5-t-butylpyrazole, amination, 500
2-Amino-3-chloropyrazine
, 285
5-Amino-4-(cyanoformimidoyl)imidazoles, reaction with tosyl isocyanate, 842
4-Amino-3,5-diaryl-1,2,4-triazoles, deamination, 600
3-Amino-2,3-dihydrobenzo-1,4-diazepine-2-ones, 849
cis-2-Amino-1,3a,5,7a-dihydroimidazo[4,5-b]pyridine
, 323
3-Amino-4,5-dihydropyrazole, nitrosation, 547
6-Amino-2,3-dihydro-1,3-thiazin-4(1H)-ones, base hydrolysis, 753
cis(trans)-2-Amino-4,5-dimethyl-2-thiazolines
, 745
Index 973
1-Aminodioxindoles, conversion into cinnolin-3-ones, 833
4-Amino-3,5-disubstituted pyrazoles
, 714
2-Amino-1,3-dithiolylium tetrafluoroborate
, 740
b-Amino esters, cyclocondensation to b-lactams, 662
2-Amino-3-ethoxycarbonylthiophenes, reaction with sodium ethoxide, 459
2-Aminoethanethiol, reaction with a,b-unsaturated or b-halo ketones, 767
2-Aminoethanols, reaction with b-diketones, 851
Aminoethyl-substituted b-lactams, transamidation, 766
2-Amino-20 -formyldiphenyls, intramolecular cyclization, 878
2-Aminofuran, instability, 92
3-Aminofurans, tautomerism, 138
2-Aminofuran-3-nitriles, from condensation of a-hydroxy ketones
with malononitrile, 685
b-Aminohalides, in formation of aziridines, 659
4-Amino-3-hydrazino-1,2,4-triazoline-5-thione, reaction with
aldehydes, 908
2-Aminoimidazoles
, 736
4-Aminoimidazoles
, 741
5-Aminoimidazoles, reactivity, 151
N-Amino-imidazolium salts, heating with anhydrides, 894
2-Aminoindole, tautomerism, 458
3-Aminoindoles, tautomerism, 138
1-Aminoindolizines, tautomerism, 138
2-Amino-3-iodopiperidines
, 326
Aminoisoxazoles, tautomerism investigated by IR spectra, 184
a-Amino ketones, dimerisation, 758
2-Amino-6-methoxy-3-nitropyridine
, 281
Aminomethylfurans, conversion into 3-hydroxypyridines, 701
3-Amino-2-methylfuran, relative stability, 458
2-Amino-4-methyloxazole, reaction with aldehydes, 509
2-Aminomethylsulfonamide, reaction with ethyl orthoformate, 866
2-Amino-3-methylthio-1,2,4-triazin-5(2H)-ones, 261
3-Amino-4-nitrofuroxane, reaction with butylamine, 518
2-Amino-5-nitropyridine
, 281
3-Amino-4-nitroquinoline
, 281
4-Amino-5-nitrosopyrimidines, conversion into 1,3,5-triazines, 791
Aminooxadiazoles
, 776
3-Amino-1,2,4-oxadiazoles
, 524
2-Amino-1,3,4-oxadiazoles, rearrangements, 572
(S)-(+)-6-Amino-1,3-oxazepan-4-one
, 755
2-Aminooxazoles
, 736
N-Aminooxindoles, ring expansion to cinnolines, 833
2-Aminophenol, reaction with 1,3-dibromopropane, 853
(2-Aminophenyl)acetonitrile, conversion to indoles, 812
1-o-Aminophenylimidazole, diazotisation and intramolecular
cyclization, 508
2-Aminophenyl ketone hydrazones, oxidation, 859
1-[(2-Aminophenyl)methyl]-1-phenylhydrazines, reaction with
triethyl orthoacetate, 867
1-o-Aminophenyltetrahydrobenzimidazole, azocoupling, 508
5-Amino-l-phenyltriazoles, rearrangement to 5-anilinotriazoles, 571
1-Amino-5-phenyl-1,2,3-triazolo[4,5-d]-1,2,3-triazole, oxidation, 864
3-Aminopyrazine 1-oxide, chlorination, 285
1-Aminopyrazole, oxidation, 774
rearrangement, 601
ring expansion to 1,2,3-triazines, 600
3-Aminopyrazoles
, 720
5-Aminopyrazoles
, 721
reaction as dienophiles, 538
N-Aminopyridazinotriazoles, oxidative fragmentation, 600
2-Aminopyridine
, 280, 374,
cyclocondensation with a-halo carbonyl compounds, 896
irradiation, 313
reaction with trichloromethanesulfenyl chloride, 903
reactions, 346
sulfonation, 265
4-Aminopyridine, tautomerism, 82
2(3)(4)-Aminopyridines, nitration, 263
2(4)-Aminopyridines, tautomerism, 349
Aminopyridine N-oxides, diazotization, 347
2(4)-Aminopyridine N-oxides, tautomerism, 349
974 Index

1-Aminopyridinium cation, 261 N-Aryl-b-amino alcohols, production of N-aryl aziridines, 660

acylation, sulfonylation and nitration, 379
reaction with nitrous acid, 379
1,3-dipolar cycloadditions, 894
b-Aminopyridones, conversion to diazo anhydrides, 347
2-Aminopyrimidines
, 747
4-Aminopyrimidines
, 748
5-Aminopyrimidines
, 374
N-Aminopyrroles, Diels–Alder reactions, 433
Diels–Alder reactions with activated alkynes, 441
2-Aminopyrroles, from cyanomethylenes with a-aminocarbonyl
derivatives, 685
tautomerism, 138
2(4)-Aminoquinolines
, 281
8-Aminoquinoline, protonation, 256
b-Aminosulfates, in formation of aziridines, 659
Aminotetrazoles, with bromine, 573
5-Aminotetrazoles, with nitric acid, 572
diazotisation, 574
2-Amino-1,3,4-thiadiazoles, acylation, 572
3(5)-Amino-1,2,4-thiadiazoles, acylation and sulfonation, 572
diazotisation, 575
formation of nitrosamines, 573
3-Amino-1,2,5-thiadiazole, chlorination, 505
2-Aminothiazole, diazotisation, 574
4-Aminothiazole
, 741
2-Aminothiazole-5-sulfonic acids
, 504
N-Amino-thiazolium salts, heating with anhydrides, 894
2-Aminothiazolo[3,2-b][1,2,4]thiadiazolylium bromide
, 901
2-Aminothiophenes, from a-mercapto carbonyl compounds with
malononitrile, 685
reactions of amine group, 458
3-Aminothiophene, exhibits enamine character, 458
thermal [2 + 2] cycloaddition reactions with activated alkynes, 435
3-Amino-1,2,4-triazine
, 782
3-Amino-1,2,4-triazine 2,4-dioxide, 261
3-Amino-1,2,4-triazine 2-oxide, oxidation, 261
3-Amino-1,2,4-triazin-5(2H)-one, 261
4-Aminotriazole, carboxylation, 506
1-Amino-1,2,3-triazoles
, 770
loss of nitrogen, 600
4(5)-Amino-1,2,3-triazoles, diazotization, 575
3-Amino-1-tritylpyrrole, tautomerism, 458
6-Aminouracils, direct alkylation, 269
Angeli’s rearrangement, 565
Anilinoacetic acids, cyclization, 810
o-Anilinobenzoic acid, cyclization, 880
5-Anilinotriazoles
, 571
Anionic ring contraction of cyclic acetals, 670
Anomeric effect, 35
ANRORC processes, 363
Anthranilic acids, reaction with formamidine acetate, 839
Anthranils, by cyclization of o-acylphenylhydroxylamines, 831
cleavage by base, 516
photolysis, 562
N-Arenesulfonyl-N-haloamides, as a source of nitrenes, 655
Aromatic and heteroaromatic fused pentathiepins, synthesis, 871
Aromaticity indices, of five-membered heterocycles, 127
using NMR shifts, 128
Aromaticity, of five-membered heterocycles, 126
of five-membered heterocycles with more than one heteroatom, 187
of heterocycles, 75
of tautomeric structures, 76
1-Aroyl-3-alkylperimidinium salts, reaction with hydroxide ions, 278
3-Aroyl-4-naphthylpyrrole, 687
1-Aroylpyrroles, dimerization, 428
6-Aroyl-2H-thiopyrans, alkylation on sulfur, 316
Arsinine, NICS values, 78
Artimisinin, 43
N-Arylaldimines, [4 + 2] cycloaddition with vinyl ethers, 821
1-Aryl-5-alkylthiotetrazoles, oxidation to sulfoxides, 583
5-Arylamino-1-alkyltetrazoles, 208
N-Arylaminoketones, cyclization to indoles, 808
3-Arylanthranils, thermolysis to acridones, 567
thermolysis, 880
2-Arylated 1-benzazocines, from Beckmann rearrangements, 823
N-Arylation of pyrazoles and imidazoles, 495
1-Arylazetidines
, 616
Arylazetines, synthetic routes, 675
Arylazoarylimines, cyclization, 868
2-Aryl-1,2-benzisothiazolo-3(2H)-ones, from N-aryl-2-(benzylthio)
benzamides, 831
1-Aryl-5H-2,3-benzodiazepines, synthesis, 857
1-Arylbenzotriazoles, extrusion of nitrogen, 479
photolysis, 482
pyrolysis to carbazoles, 874
1-Aryl-5-benzyltetrazoles
, 565
N-Aryl-N-(o-bromobenzyl)hydrazines, conversion to
2-aryl-2H-indazoles, 831
3-Arylcinnolin-4-amines, synthesis, 833
2-Aryl-4,5-dihydrooxazoles, cobalt-catalyzed carbonylation, 753
4-Aryl-1,4-dihydropyridine-3,5-dicarboxylates, 317
2-Aryl-4,5-diphenylthiazoles
, 738
5-Aryl-1,2,4-dithiazoline-3-thiones, conversion to 3-ones, 582
1-Aryl-2,5-di(2-thienyl)pyrroles
, 677
o-(Arylethynyl)benzene diazonium salts, cyclization to indazoles, 830
4-Aryl-3-furanols
, 686
2-Arylfurans
, 427
Arylhydrazine, mechanism of reaction with 1,3-dicarbonyl compounds, 715
Arylhydrazones, cyclization, 729
2-Arylidenaminodiphenyls, radical cyclization, 878
N-Arylimidazoles
, 496
rearrangement, 593
N-Arylimines, reaction with acrylonitrile, 378
3-Arylimino-2-indolinones, oxidation, 841
2-Aryl-2H-indazoles, synthesis, 831
2-Arylindoles
, 469, 470
Aryl isocyanates, dimerisation, 732
2-Aryl-2H-isoindoles, synthesis, 823
2-Arylisoquinolinium salts, synthesis, 826
2-Aryl-5-methanesulfonyl-1,3,4-oxadiazoles, reaction with malonate, 583
1-Aryl-3-methylpyrazoles, ozonolysis, 509
2-Aryl-3-methylpyridines
, 371
1-Aryl-5-methyltetrazoles, reaction with benzyne, 565
1-Aryl-4-nitroimidazoles
, 601
5-Aryl-1,3,4-oxadiazole-2-thiones, S-methylation, 581
2-Aryl-4-oxido-1,2,3-benzotriazinium betaine 1-oxides, synthesis, 859
N-Aryloxypyridinium salts
, 380
1-Arylpentazoles
, 794
1-Aryl-2-phenacylcyclopropanes, reaction with chlorosulfonyl isocyanate, 755
5-Aryl-2-phenyloxadiazoles
, 591
2-Arylpiperidines
, 327
Arylpyrazines
, 370
N-Arylpyrazole
, 493
1-Aryl-5-pyrazolidinones, photochemical ring contraction to b-lactams, 554
2-Arylpyridines, 285
2-Arylpyrimidines, reduction with zinc, 694
3-Arylpyrroles
, 440
3-Aryl-2,4-quinazolinediones
, 841
3-Aryl-substituted 2H-azirines, reaction with difluorocarbene, 754
2-Aryl-substituted benzo[b]thiophenes, 804
Aryl-substituted 1,2,4-triazines
, 782
1-Arylsulfonyl-1,2,3-triazoles, reversible ring opening, 484
Arylsydnones, mercuration, 507
2-Aryl-2,3,4,5-tetrahydro-1,2-diazepin-3-ones
, 729
Aryl tetrazolyl ethers, reduction, 581
N-Aryl-1,2,6-thiadiazine 1,1-dioxides
, 774
2-Aryl-1,2,3-thiadiazol-5(2H)imines
, 771
4-Arylthiazol-2(3H)-ones
, 743
N-Aryltriazole N-arylimides, isomerisation studied by NMR spectra, 166
Asymmetric synthesis of 1,2-dihydropyridines, 287
 Index 975

Atropisomers, 35 Azinethiones, reactions, 359

Azabicyclobutanonium ion, 625 Aziridinations, 655
2-Azabicyclo[2.2.0]hex-5-enes
, 768 Aziridine, 548
general synthetic routes, 799 ab initio modelling of N-inversion, 214
8-Azabicyclo[4.2.0]octa-3,5-dienones, 612 barrier to pyramidal inversion of the nitrogen atom, 233
Aza-1,3-butadiene, 672 calculated proton affinity, 214
1-Azabutadienes, reaction with enamines, 699 cleavage to dianions, 631
2-Azabutadienes, reaction with alkynes, 699 conversion into piperazine, 763
1-Aza-1,2,4,6-cycloheptatetraene
, 345 electrophilic attack on nitrogen, 614
Aza-Darzens synthesis of aziridines, 660 from oxiranes with iminophosphoranes, 669
1H-Azaheterocinyl anions, NMR spectra, 232 IR spectra, 227
Azaindoles
, 348 microwave spectra, 222
3-Aza-7-oxatricyclo[4.1.0.02,5]hept-3-enes
, 768 N-allylation, 61
15
Azepane, conformational analysis, 234 N NMR spectra, 225
Azepan-2-ones, from asymmetric Schmidt ring expansion of the reaction with bis(trimethylsilyl)acetylene, 691
4-substituted cyclohexanones, 667 reduction, 631
9a-Azaphenalene, 40 ring opening, 745
Azepines
, 702 ring opening to azomethine ylides, 668
1H-Azepines
, 702 synthetic methods, 655
theoretical studies, 216 valence tautomerism to 1,3-dipoles, 236
1H-Azepine derivatives, diene complex with (tricarbonyl)iron, 636 Aziridine-2-carboxylic acid, ring opening, 620
2H-Azepine
, 703 1H-Azirine, antiaromatic nature, 231
3H-Azepine
, 702 by carbene addition to nitriles, 674
conformations, 221 by matrix photolysis of 4H-triazoles, 675
3H-Azepin-2-one, ring inversion, 234 [4+2]cycloaddition, 632
Azete, aromatic character, 231 cycloaddition to 1,2,4,5-tetrazines, 785
theoretical studies, 215 microwave spectra, 222
by photolysis of pyridazines, 676 photolysis to nitrile ylides, 635
Azetidine
, 661 reaction with activated b-chloroalkenes, 615
barrier to ring inversion, 233 synthetic methods, 655
N-inversion, 234 theoretical calculations, 214
13
C NMR spectra, 225 2H-Azirine system, antiaromaticity relieved on protonation, 215
alkylation, 615 basicity, 215
N-chlorination, 615 general synthetic methods, 674
Azetidine derivatives, NMR spectra, 223 theoretical calculations, 214
IR spectra, 227 Azirinyl cations structures, 215
photoelectron spectroscopy, 230 Azlactones, tautomerism, 539
removal of a-protons, 629 2,20 -Azobenzimidazole
, 575
Azetidin-2-one, carbonyl frequency in IR spectra, 227 Azocane, 666
general methods of synthesis, 657, 662 Azocines
, 702
mass spectra, 229 antiaromatic character, 232
N-inversion, 234 2H-Azocinones, 612
N-protection-deprotection, 639 Azoleacetic acids, decarboxylation, 568
reaction with nucleophiles, 625 Azolecarboxylic acids, acidity, 568
Azides, cycloaddition with DMAD, 773 decarboxylation, 568
8-Azido-1-arylazonaphthalenes, photolysis or themolysis, 886 Azolediazonium salts, stability, 574
3-Azido-2-azetidinones
, 625 Azoles, 140
2-Azidocyclopentene-1-carbaldehyde, 716 acidic and basic properties, 141
3-Azidocyclopropenes, thermolysis, 691 C-lithiation by n-butyllithium, 525
5-Azido-1,4-diphenyltriazole, loss of nitrogen, 576 formation of metal complexes, 491
3-Azido-2-halopropenones, thermolysis, 717 halogenations, 504
2-Azido-3-hydroxy-1,4-diones, reaction with mesyl chloride, 717 metal salts, 532
2-Azidoimidazoles, 574 pKa values, 488
1-(2-Azidophenyl)benzimidazole, thermolysis, 895 reaction with phenyl radicals, 533
2-Azidophenyldiazoalkanes, thermolysis, 859 thermal and photochemical fragmentations, 479
2-Azidopyrazines, photochemical transformation into imidazoles, 747 Azole N-oxides, alkylation, 602
4-Azidopyridazine, photolysis, 351 deoxygenation, 602
2-Azidopyridine, 484 Azolesulfonic acids, as zwitterions, 583
structure and reactions, 350 Azolidines, 142
4-Azidopyridines, thermolysis or photolysis, 766 Azolines, 142
2-Azidopyridine N-oxides, pyrolysis, 694 Azolinimines, 575
5-Azido-1,2,3-thiadiazoles, rearrangement, 486 Azolinones, acidity, 532
Azido-1,3,5-triazines, photolysis, 351 2-Azolinones, protonation, 578
5-Azido-1,2,3-triazoles, rearrangement, 793 O-alkylation, 578
3-Azido-2-vinyl derivatives, thermolysis, 459 Azolium cations, pKa values, 148
Azines, 38 Azolium ions, formation of pseudo bases, 514
direct ring metallation, 298 hydrogen exchange reactions, 528
Azine-carboxylic acids, exist partly as betaines, 342 Azomethine ylide, 634
Azine Grignard reagents, reactions, 367 in dipolar cycloaddition reactions, 658
Azine N-oxides, reaction with dipolarophiles, 312 intramolecular dipolar cycloaddition, 669
reactions with imidoyl chlorides, 381 Azonines
, 702
976 Index

1H-Azonine, 232 1,4-Benzodiazepine N-oxides, synthesis by ring expansion of quinazoline

3-Azophenylindole, nitration, 400 N-oxides, 850
Azulene
, 289 1,4-Benzodioxanes
, 848, 849
1,5-Benzodioxepin-2-ones, synthesis, 854
5H-1,4-Benzodioxepinones, synthesis, 852
B Benzo[1,2-h:4,3-h 0 ]diquinoline, proton sponge, 255
Baeyer–Villiger oxidation, 667 Benzo-1,4-dithianes
, 848
Baldwin’s rules, 648 1,4,2,3-Benzodithiadiazines
, 865
Barbituric acid, halogenations, 267 1,3,2-Benzodithiazole-1,1,3,3-tetraoxide, fluorination, 499
preferred structure, 318 Benzodithiepanes
, 758
Becke-style hybrid functional approach B3LYP, 34 Benzodithiepin system, 845
Beckmann rearrangement, 667 1,4-Benzodithiin, reactions, 314
Benzaldehyde, conversion to styrene oxide, 654 Benzo[1,3]dithiolium tetrafluoroborate, 143
reaction with an alkyl azidoacetate, 814 1,3-Benzodithiolylium ions, reaction with trialkyl- and
Benzazepines, by transition-metal-catalyzed cyclizations, 829 triarylphosphines, 524
synthesis based on transition metal-catalyzed cyclizations, 822 Benzofuran, fragmentation patterns in mass spectrometry, 121
1,3-Benzazepinone system
, 843 reaction with dichlorocarbene, 426
Benzazetes, by thermolysis of 1,2,3-benzotriazines, 800 from o-aryloximes, 807
from 1,2,3-benzotriazines, 250 Benzo[b]furan, B3LYP/6-311+G

calculations, 97
Benzazetidines, general synthetic routes, 799 13
C-NMR spectra, 109
Benzazoles, reaction with organometallic compounds, 520 from o-aryloxyketones, 808
rearrangements, 561 halogenations, 403
Benzazolones, electrophilic substitution often occurs in the benzene orientation of substitution reactions, 397
ring, 502 reaction with bis(pinacolato)diboron, 468
1,2-Benzenedimethanethiol, reaction with methylene iodide, 845 reaction with formaldehyde, 413
1,2-Benzenedimethanol, reaction with aldehydes, 845 structure, 100
N,N-1,2-Benzene-disulfonamide anion, stability, 594 synthesis, 802, 805
Benzene oxide, theoretical studies, 216 Benzo[c]furan, B3LYP/6-311+G

calculations, 97
Benzene sulfide, theoretical studies, 216 Diels–Alder reactions, 434
1-Benzhydrylazetidine
, 661 generation and Diels–Alder reactions, 434
Benzimidazo[1,2-a]benzimidazoles, 895 Benzofuran-2-carboxylic acids
, 280
Benzimidazole
747, a-Benzo[b]furanones
, 802
acidity, 490 Benzofurazan
, 536
acylation, 498 from benzazole rearrangement, 858
aromaticity compared to imidazole, 193 photochemical cleavage, 480
decreased electron density at C-2, 146 reduction, 534
from o-amino-anilides, 836 Benzofuroxan, conversion into quinoxaline di-N-oxides, 849
Mannich reactions, 498 derivatives, studies of isomers by NMR spectra, 164
oxidation, 500 reaction with enamines, 539
reaction with acid chlorides and alkali, 513 reaction with nitrile oxides, 862
reaction with difluorocarbene, 532 reaction with secondary amines, 524
reaction with lithium aluminum hydride, 522 reduction, 536
solubility, 187 Benzo-fused azete, 231
synthesis, 643 Benzo-fused bicyclic sulfonium salts, 915
thiation with sulfur, 533 Benzo[b] heterocycles, structure, 96
Benzimidazolones, synthesis, 837 UV spectra, 114
Benzimidazol-2-one, conversion to 2-chlorobenzimidazole, 578 Benzo[c] heterocycles, ionisation potentials, 124
Benzimidazole 3-oxides, reaction with phosphorus oxychloride or sulfuryl UV spectra, 114
chloride, 519 Benzo[c,d]indoles, 886
Benzimidazole N-oxides, instability, 602 2,1-Benzoisothiazole, reaction with DMAD, 538
2H-Benzimidazole-2-spirocyclohexane, reaction with sulfur nucleophiles, Benzoisothiazolethiones, equilibrium with iminobenzodithioles, 485
560 Benzo[1,2-c][1,2,5]oxadiazoles, 15N NMR studies, 174
Benz[d]isothiazoles, from sulfenyl chlorides, 831 Benzo-1,4-oxathianes, synthesis, 848
1,2-Benzisothiazole, nitration, 559 Benzopentathiepin
, 480
1,2-Benzisothiazoline 1,1-dioxide, conformation, 196 1H-2-Benzopyran-1-carbaldehyde
, 612
1,2-Benzisoxazoles, reduced, 535 Benzopyran-4-ones, reaction with Grignard reagents, 289
ring opening, 530 Benzopyridines, reaction with organometallics, 286
2,1-Benzisoxazole, methylation, 492 Benzopyrroles pKa values, 398
Benzo[c]cinnoline, 878 Benzopyrylium cations, reaction with enolates, 289
Benzo[b]cyclohepta[d]furans, 876 Benzopyrylium ions, from ketones and o-acylphenols, 816
Benzo[b]cyclohepta[d]thiophenes, 876 2-Benzopyrylium perchlorate, reaction with hydrazine, 857
5H-Benzocyclohepten-5-one oxime, Beckmann rearrangement, 823 2-Benzopyrylium salts, reaction with vinyl ethyl ether, 306
Benzodiazepines
, 835 3,4-Benzopyrylium salts, synthesis, 826
1H-1,2-Benzodiazepines
, 835 Benzo[d,e]quinolines, 886
1H-2,3-Benzodiazepines
, 857 Benzo[c]quinolizine derivatives, 905
1,5-Benzodiazepines
, 853 Benzoselenophane, fragmentation patterns in mass spectrometry, 121
1,4-Benzodiazepine-2,5-diones
, 849 Benzotellurophane, fragmentation patterns in mass spectrometry, 121
2,4-Benzodiazepin-1,3-diones
, 844 1,2,4,5-Benzotetrazepines
, 870
1,4-Benzodiazepin-2-ones
, 853 Benzotetrazine oxides
, 864
2,4-Benzodiazepin-1-ones
, 844 Benzothiadiazepines, 869
1,3-Benzodiazepin-4-ones
, 843 1,2,4-Benzothiadiazepines
, 866
 Index 977

1,2,4-Benzothiadiazepine 1,1-dioxides
, 866 photochemical [2 + 2] cycloaddition to maleinimides, 543

1,2,5-Benzothiadiazepine 1,1-dioxide
, 867 tautomerism studied by 15N NMR spectroscopy, 175
2,1,3-Benzothiadiazines
, 860 X-ray studies, 156
4,1,2-Benzothiadiazin-3-carboxylate 4,4-dioxides
, 864 1,2,3-Benzotriazoles
, 858
1,2,3-Benzothiadiazine 1,1-dioxides
, 860 Benzotriazolylalkyl amides, 597
1,2,3-Benzothiadiazole
, 858 (Benzotriazol-1-yl)methyl ethers, reaction with Grignard reagents, 524
formation of sulfoxide, 510 (Benzotriazol-1-yl)methyl isocyanide, in pyrrole synthesis, 597
thermolysis in presence of sulfur, 480 (Benzotriazol-1-yl)oxiranes
, 595
2,1,3-Benzothiadiazole, oxidation, 559 a-(Benzotriazol-1-yl)-substituted tosylhydrazones, lithiation, 862
reductive cleavage, 523 1-(Benzotriazol-1-yl)-N-triphenylphosphoranylidenemethylamine,
1,2-Benzothiazepines
, 835 reaction with Grignard reagents, 597
1,4-Benzothiazepines
, 853 a–Benzotriazolyl-a,b-unsaturated ketones, reaction with
1,5-Benzothiazepines
, 853 hydroxylamine, 715
2,4-Benzothiazepines
, 844 Benzoxadiazepines
, 869
1,2-Benzothiazepine 1,1-dioxides, from 1,2-benzoisothiazoles, 835 1,3,5-Benzoxadiazepines
, 869
1,3-Benzothiazepin-4-one system
, 844 1,3,4-Benzoxadiazines
, 863
1,4-Benzothiazepin-5-ones
, 851 1,3,4-Benzoxadiazepin-5-ones
, 868
2,4-Benzothiazepin-5-ones
, 844 1,2,3-Benzoxadiazole, detection in matrix, 207
Benzo[c]-1,2-thiazetidine 1,1-dioxides, synthesis from sulfonic acids, 829 1,2,3-Benzoxathiazines
, 860
Benzothiazines
, 834 Benzoxathiepins, from 2H-1-benzothietes, 852
2H-1,3-Benzothiazines
, 840 from alkenylselenonium salts, 852
1,4-Benzothiazines, from 2-aminothiophenols, 847 1,2-Benzoxathiin 2,2-dioxides, from 2-acylphenols, 834
4H-1,4-Benzothiazine 1,1-dioxides
, 847 Benzoxazepines
, 842
2,1-Benzothiazine 2,2-dioxides
, 834 1,4-Benzoxazepines, prepared from o-aminophenols, 853
1,3-Benzothiazin-4-ones, from 2-acylmercaptobenzamides, 840 3,1-Benzoxazepines
, 843
Benzothiazole, from o-mercapto-anilides, 836 2,4-Benzoxazepine systems
, 844
lithiation at C(2), 525 4,1-Benzoxazepine-2,5-dione
, 850
reaction with bis(tributylstannyl)acetylene, 520 1,4-Benzoxazepin-3-ones
, 850
2,1-Benzothiazoline 2,2-dioxides, thermolysis, 552 2,3-Benzoxazepin-l-one system, 857
Benzothiazolium ions, one-electron reduction to free radicals, 534 4,1-Benzoxazepin-2-ones
, 850
Benzothiazolones
, 837 4,1-Benzoxazepin-5-one system from anthranilic acids, 851
Benzo[4,5]thieno[2,3-b]pyridines, 876 Benzoxazines, by [4 + 2] cycloadditions, 847
3H-[4,5]-Benzothieno[2,3-d]-1,2,3-triazole, site of methylation established 1,3-Benzoxazines
, 594, 841
by nuclear Overhauser effects, 164 1,4-Benzoxazines, from 2-aminophenols with 1,2-dielectrophiles, 846
2H-Benzo[b]thiete, retro-[2 + 2] ring opening, 633 1,3-Benzoxazine-2,4-diones
, 842
Benzothiinones, from thiophenols, 818 1,3-Benzoxazin-4-ones, by the cyclization of O-benzoylsalicylamides, 840
Benzothiophene, fragmentation patterns in mass spectrometry, 121 Benzoxazinones, from 3-acylanthranils, 841
oxidation to o-mercaptobenzaldehyde, 420 Benzoxazole, reaction with hydroxylamine, 516
synthesis, 805 from o-hydroxy-anilides, 836
Benzo[b]thiophene, 13C-NMR spectra, 109 Benzoxazolones
, 837
dianion, 429 1-Benzoxepanes, by Pd-catalyzed cyclization of 2-halogen-substituted
electrophilic reactions, 397 d-hydroxyalkylbenzenes, 822
from o-arylthioketones, 808 Benzoxepin
, 822
photocycloaddition reactions with DMAD, 436 3-Benzoxepin
, 829
reaction with t-butyl bromide, 411 reaction with dimethyldioxirane, 612
reduction by sodium metal, 429 Benzoxetan-2-ones
, 800
sulfonation, 401 Benzoxocines
, 823
Benzo[c]thiophene, Diels–Alder reactions, 434 2-Benzoylarenesulfonyl chlorides, reaction with amidines, 866
reaction with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate, 435 N-Benzoyl-N 0 -arylthioureas, reaction with diiodomethane, 733
structure, 100 1-Benzoylbenzazepine
, 822
synthesis, 824 3-Benzoylcinnolines, synthesis, 833
Benzo[b]thiophene S,S-dioxides, structure, 102 Benzoylcyanamide
, 531
system as a vinyl sulfone, 438 1-Benzoyl-2-cyano-1,2-dihydroquinolines, decomposition, 318
2-Benzothiopyrylium-4-olate, thermal dimers, 311 2-Benzoyl-4-cyanopyridine
, 304
1H-1,2,4-Benzotriazepines
, 865 2-Benzoyl-2-halo-2H-azirines, thermolysis, 721
1,3,4-Benzotriazepin-5-ones, 867 N-Benzoylimidazoles, IR spectra, 184
1,2,3-Benzotriazines, flash vacuum pyrolysis to benzazetes, 250 2-Benzoylimino-1,3-thiazetidine
, 733
hydrolysis, 276 1-Benzoylphthalazine, hydrolysis, 276
synthesis, 859 4-Benzoyl-1(2H)phthalazinone
, 276
thermolysis, 800 1-Benzoylpyridinium ions, with acetophenone, 290
1,2,4-Benzotriazines, 574 1-Benzoylpyrrole, dimerization, 428
1,2,3-Benzotriazin-4-ones, from 3-(carbamoylmethyl)-1-(2-alkoxycarbo­ N-Benzoyltriazoles, IR spectra, 184
nyl)phenyltriazenes, 859 1-Benzoyluracil
, 301
protonation and ring-chain tautomerisation, 253 1-Benzyl-2-aminobenzimidazole, autoxidation, 575
pyrolysis, 250 1-Benzylbenzotriazoles, reaction with boranes, 595
1,2,3-Benzotriazine 2-oxides, 260 1-Benzyl-3,5-dibromo-1,2,4-triazole, reaction with CsF, 585
1,2,4-Benzotriazine 1-oxide, 261 4-Benzyl 1,4-dihydropyran, rearrangement, 321
1,2,4-Benzotriazine 1,2,4-trioxides, synthesis, 862 1-Benzyl-2,5-dihydropyrrol-3-yl trifluoromethanesulfonate, 440
Benzotriazole, acidity, 490 1-Benzyl-4-hydroxy-1,2,3-triazole
, 586
as a useful synthetic auxiliary, 596 (Z)-4-Benzylidene-4H-3,1-benzothiazines, synthesis, 840
chlorination, 499 1-Benzylimidazole, benzylic metallation, 594
978 Index

1-Benzylindole
, 471 3,4-Bis(trifluoro-methyl)pyrrole, 439

2-Benzyloxymethyl-5-(tributylstannyl)tetrazole, coupling, 591
Benzylpenicillin potassium, structure determination, 221
N-Benzyl-2-pentyl-4-ethylpyrrole
, 680
2-Benzylpyrrole
, 426
N-Benzyl-1,4,5,6-tetrahydropyridine, coupling with alkynes, 326
3-Benzylthiazolo[3,2-a]benzimidazole
, 897
2-Benzyltriazole 1-oxide
, 770
Benzynes, reaction with imidazoles, 496
1-Biarylpyrazoles
, 593
Biaryls
, 344
Bicyclic isoxazolidines
, 326
Bicyclic 1,3,4-oxadiazinones, synthesis, 863
Bicyclic N-pyrrolylboranes
, 451
Bicyclic sulfonium ions, 915
Bicyclic systems, from isomerization of large rings via electrocyclic
reactions, 651
1,3-Bielectrophiles, reaction with enamines and enamides, 690
Biguanidines, cyclocondensation with a-oxoaldehydes, 792
reaction with lactones, 788
2,20 -Biindolyl
, 812
Binucleophiles, 643
4,4-(Biphenyl-2,2-diyl)-2,6-diphenyl-1-methyl-1,4-dihydropyridine,
spectra, 56
2-Biphenyl isocyanide, photolysis, 876
2-Biphenylsulfonyl diazomethane, photolysis, 876
1,10 -Bipyrazole, structure, 195
2,20 -Bipyridines,
372
4,40 -Bipyridine
, 304, 305
Bipyridyls, 304
4,40 -Bipyridyl diquaternary salts
, 293
4,40 -Bipyridyl
, 304
4,40 -Bipyrimidines
, 372
2,30 -Biquinolyl
, 305
Bird aromaticity indices for five-membered heterocyclic rings, 192
Bird index, for aromaticity, 35, 77
meso-Bis(acetoxymethyl)aziridine, enzymatic hydrolysis, 637
Bisadamantylidene, reaction with singlet oxygen, 712
N,N-Bis(alkoxymethyl)amines, reaction with five-membered hetero­
cycles, 415
2,20 -Bis(benzimidazole, absorption and fluorescence spectra, 195
1,2-Bis(bromomethyl)benzene, in synthesis of isoindoles, 823
4,5-Bis(bromomethyl)-3-phenylisoxazole, cycloadditions, 541
4,5-Bis(bromomethyl)-1-phenylpyrazole, generation of o-quinodi­
methanes, 541
1,2-Bis-t-butyl-3-aminopyrazolin-5-one
, 720
Bischler indole synthesis, 808
Bischler–Napieralski synthesis of 3,4-dihydroisoquinolines, 827
3,4-Bischloromethyl-2,5-diphenylfuran, 414
2,5-Bis(chloromethyl)furan, 453
Bis(12-crown-3) derivatives with dialkylmalonate spacers, sodium ion
complexation, 218
3,30 -Biselenenyls, conformation, 131
2,20 -Bis-1H-imidazole, solid state NMR studies, 167
N1,N2-Bis(mesityl)imidazolylidene–methanol complex, X-ray structure, 157
Bis(methoxycarbonyl)methylthiophene
, 472
2,2-Bis(methoxycarbonyl)thiolane
, 630
1,3-Bismethylenecyclobutane, ring strain, 231
Bismuthine, 50
Bismuthinine, NICS values, 78
N,N-Bis(phenacyl)anilines, reaction with hydrazine hydrochloride, 787
Bis(pyrazole)
, 508
1,5-Bis(silyl)pentane-1,5-diones, cyclodehydration, 688
2,6-Bis(silyl)-4H-pyrans
, 688
N,N0 -Bissuccinimide
, 328
Bistetrazolium mercury salts
, 507
Bistratamide F-I
, 739
Bis(1,2,4-triazolyl)sulfoxide
, 501
3,4-Bis(trifluoromethyl)-1,2-dithietene, 633
2,3-Bis(trifluoromethyl)-1,4-dithiins
, 633
1,4-Bis(trifluoromethyl)phthalazine
, 856
3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazine, cycloaddition to benzyne, 856
2,3-Bis(trifluoromethyl)thiophene, irradiation, 387
2,5-Bis(trifluoromethyl)thiophene, irraditation, 388
o-Bis(trimethylacetyl)-benzenes, reaction with P2S5, 824
5,6-(Bistrimethylsilyl)benzo[c]furan
, 824
1,4-Bis(trimethylsilyl)indole
, 448
3,5-Bis(a,b-unsaturated)-1,2,4-dithiazolium salts
, 778
Bi–tetrahydrofuran motifs, synthesis, 664
2,20 -Bithienyl, structure in solid and vapour phase, 131
Bi-1,2,4-triazin-5,50 -yls
, 293
1,10 -Bi-1,2,3-triazole, structure, 195
2,20 -Bi-1,2,3-triazole, structure, 195
4,40 -Bi-1,2,4-triazole, structure, 195
3-(Boc-amino)-5-methylisoxazole, direct lithiation, 526
5-(Boc-amino)-3-methylisoxazole, direct lithiation, 526
1-Boc-3-methylindazole, bromination of methyl group, 562
Boc-protected g-amino-a,b-enones, conversion to pyrroles, 679
Bohlmann bands, in IR spectra of trans-fused quinolizidine structures, 70
Bond angles of three-membered heterocycles, 218
Bond lengths and angles in heterocyclic compounds, 51
Bond lengths of three-membered heterocycles, 218
1H-Boratobenzene anion, isoelectronic structure with benzene, 30
Borepine-like, heteroatoms, 30
Borirenes, aromatic character, 231
Borsche synthesis of tetrahydrocarbazoles, 875
Boulton–Katritzky rearrangement, 152
Bradsher reaction, 306
Bridged diazonines, photoelectron spectroscopy, 230
transannular interaction of the nitrogen lone pairs, 235
Bridged ring 6H-1,2-dihydro-3-pyridones, 676
3,4-Bridged trithiapentalenes, 916
Bromamine-T, in formation of nitrenes, 656
Bromoallenes, palladium-catalyzed cyclization, 766
5-Bromobarbituric acid
, 319
3-Bromobenzo[b]furan, 403
3-Bromocarbazole
, 403
3-Bromo-4-chloropyridine, in formation of pyridynes, 362
3-Bromocoumarone, lack of reactivity, 365
Bromocyanogen, reaction with pyridine, 259
5-Bromo-2,4-dichloropyrimidine, sequential displacement, 370
3-Bromo-4,5-dicycanoisothiazole
, 722
2-Bromo-4,5-dicyano-1-methylimidazole, conversion to fluoro
compounds, 584
6-Bromo-1,4-dioxocin, 237
2-Bromoimidazoles
, 529
4-Bromoimidazole, coupling with methyl acrylate, 590
3-Bromoindole
, 403
5-Bromoindole, conversion to lithio derivative and reactions, 448
5-Bromoisoquinoline
, 332
3-Bromo-2-lithiothiophene, formation, 461
4-Bromo-7-methylbenzothiadiazole
, 559
4-Bromomethyl-2-chlorooxazole, Stille coupling, 591
2-Bromomethyl-5-methylthiophene, displacement reactions, 453
5-Bromo-1-methyltetrazole, reaction with nucleophiles, 586
5-Bromooxazoles, coupling with alkynes, 587
2-Bromo-5-phenyl-1,3,4-oxadiazole
, 575
palladium-catalyzed Suzuki cross-coupling, 591
3-Bromo-6-phenylpyridazine, metallation, 298
5-(2-Bromophenyl)tetrazole, Suzuki coupling on benzene ring, 589
b-Bromopropionate ion, cyclization, 661
5-(3-Bromopropyl)-3,3,7,7-tetramethyl[1,2,5]perhydrodithiazepine
, 787
2-Bromopyridine
, 302
conversion to pyrimidines, 753
displacement reactions, 364
2(3)(4)-Bromopyridines, metal-catalyzed coupling with amines, 373
5-Bromopyrimidine, 267
metallation, 299
palladium-catalyzed aminocarbonylation, 373
reaction with sodium amide, 362
2-Bromopyrroles
, 402

3-Bromo-2-pyrones, reaction with hydroxide ions, 280
3-Bromopyrones, formation and ring cleavage, 695
2-Bromoquinoline
, 302
conversion into 2-methylquinazoline, 363
3-Bromoquinoline
, 821
7-Bromoquinoline, coupling with ethynylpyridines, 336
5(7)-Bromoquinolines, Heck reactions with ethyl acrylate, 336
4-Bromo-5-substituted thiazoles
, 525
5-Bromo-1,2,4-thiadiazole, reduction, 587
2-Bromothiophene, reaction with excess sodamide, 461
formation of Grignard reagent, 461
3-Bromothiophene
, 461, 460, 677
coupling with 2-pyridone, 470
metallation, 420
reaction with Grignards, 467
3-Bromothiophene-2-carbaldehyde
, 466
3-Bromothiophene-2-carboxylic acid, copper-catalyzed reactions with
active methylene compounds, 460
3-Bromothiophene-4-carboxylic acid, copper-catalyzed reactions with
active methylene compounds, 460
Butane, pyrolysis with sulfur, 680
2-Butene-1,4-diones, in furan synthesis, 678
Butenolide, 414
N-(t-Butoxycarbonyl)aziridines, deprotonation, 627
N-t-Butoxycarbonyl-2-methoxypiperidine, reaction with
organozincs, 327
N-t-Butoxycarbonyl-1-phenacyl-L-histidine methyl ester, alkylation, 492
3-(t-Butylamino)-2-nitroacrylaldehyde, reaction with
ethylenediamines, 765
2-Butylaminopyridine
, 374
2-t-Butylaziridine, 15N NMR spectra 225
3-t-Butylbenzo[b]thiophene
, 411
N-t-Butyl-2-chloromethylaziridine
, 625
4-t-Butyl-3,6-dichloropyridazine
, 303
1-(t-Butyldimethylsilyl)-2-azetidinones, desilylation, 639
N-t-Butylisoindole, coupling with p-nitrobenzenediazonium
fluoroborate, 416
t-Butyl isonitrile, reaction with aldehydes, 736
4-t-Butyl-2-lithiothiazole dimer, crystal structure, 588
1-Butyl-3-methylimidazolium salts, ionic liquids, 492
1-t-Butyl-5-methylthiotetrazole, oxidation to sulfone, 583
4-n-Butylpyridine
, 286
1-t-Butylpyridinium ion, 258
1-t-Butyltetrazoles
, 496
2-t-Butylthiazole, reaction with methyl iodide, 492
2-t-Butyl-1,3-thiazolidine, conformations, 198
2-Butyne-1,4-diones, in furan synthesis, 678
C 2-Chlorofuran, nucleophilic reactions, 460
Calculated dipole moments of azole tautomers, 200
Calculated structural parameters of heterocycles, 48
Cambridge Structural Database, 51, 99
Camphor imine, oxidation, 707
Camps reaction to give 4-quinolones, 816
"-Caprolactam, conformational analysis, 234
3-(Carbamoylmethyl)-1-(2-alkoxycarbonyl)phenyltriazenes,
thermolysis, 859
Carbazole
, 479, 873
13
C-NMR spectra, 109
electrophilic substitutions go para to heteroatom, 447
fluorescence and phosphorescence, 114
1
H NMR spectra, 105
pKa, 388
structure, 101
Carbenes, in the synthesis of heterocyles, 649
Carbenoid, addition across an imine, 656
addition to a thiocarbonyl compound, 656
insertions to give b-lactams, 667
in the synthesis of heterocyles, 649
N-Carbomethoxy-1,2-dihydropyridine, Diels–Alder reactions, 324
Index 979
Carbonyl compounds, reaction with methylene equivalents, 654
reaction with chloramine or hydroxylamine-O-sulfonic acid, 707
Carbonyl-containing five-membered heterocycles, rotational
isomerism, 130
1,10 -Carbonyldi(benzotriazole)
, 499
Carbonyldiimidazole, in peptide synthesis, 598
Carbonyl groups on C(2) position of five-membered heterocycles, IR
spectra, 119
2-Carboxy-5,6-dimethoxyphenoxyacetic acid, thermolysis in acetic
anhydride, 852
1-Carboxymethoxypyridiniums, decarboxylation, 377
Carboxymethylpyridines, decarboxylation, 343
Catechol, reaction with chloroacetonitrile, 854
CC1065, antitumor antibiotic, 810
Cephalosporin, antibiotics, 212
synthetic routes, 799
Cesium fluoroxysulfate, reaction with pyridine, 285
Chelidamic acid, halogenations, 268
Chichibabin reaction, 280
of 2-aminopyridines, 698
Chiral N-alkoxycarbonylpyridinium salts, reaction with zinc enolates, 288
Chiral, nonracemic epoxides, synthesis, 653
Chiral 3-(3-oxoalkyl)indoles
, 409
Chiral 2-(3-oxoalkyl)pyrroles
, 409
Chiral pyridinium-based ionic liquids, 258
Chiral sulfides, enable high enantioselectivities and diastereoselectivities
in epoxidation, 655
Chloramine-T, in formation of nitrenes, 656
a-Chloroacetanilides, palladium-catalyzed annulations, 810
9-Chloroacridine
, 880
b-Chloroacrylates, reaction with internal alkynes, 691
3-Chloro-5-arylisoxazoles, reaction with alkoxides, 584
2-Chlorobenzimidazole
, 519, 578
2-Chlorobenzothiazole, iron-catalyzed cross-coupling reactions, 591
1-Chlorobenzotriazole
, 499
2-Chloro-5-carboethoxypyridine, metal-catalyzed coupling with aryl
Grignards, 373
Chlorocarbonylsulfenyl chloride, reaction with ureas, thioureas, and
guanidines, 779
1-Chloro-1,3-di-t-alkylurea with potassium tert-butoxide, 708
2-Chloro-4,5-dihydroimidazole, reaction with isoquinoline, 910
6-Chloro-1,2-dihydropyridines
, 325
2-Chloro-4,6-dimethoxypyrimidine, nitration, 263
6-Chloro-1,3-dimethyllumazine, reaction with 1,2-diaminoethane, 282
1-Chloro-2,2-diphenylaziridine, barrier to pyramidal inversion of the nitro­
gen atom, 233
5-Chloro-1,4-diphenyl-1,2,3-triazole, reaction with sodium cyanide, 585
1-(2-Chloroethyl)imidazolidine-2-one, hydrolysis, 899
6-Chloro-5-fluoroindole
, 804
6-Chloro-5-hydroxypyridinecarbaldehyde, reaction with methyl trimethyl­
silyl ketene acetal, 344
3-Chloroindole
, 403
4-Chloro-5-iodo-2,4-dimethoxypyrimidine, Sonogashira coupling, 371
3-Chloro-4-iodo-1,2,5-thiadiazoles
, 574
5-Chloroisoxazoles, methylation, 492
2-(Chloromethyl)azetidine, ring enlargement, 638
N-Chloro-2-methylazetidine, resolution, 234
3-Chloromethylbenzo[b]thiophene
, 414
1-Chloromethylbenzotriazole, metallation, 595
5-Chloromethylfuran-2-carbaldehyde, 679
4-Chloromethylpyrimidines, ring expansion, 755
4-Chloro-2-methylquinoline
, 354
2-Chloromethylthiazole, side-chain lithiation, 563
2-Chloromethylthiophene, displacement of chloro atom, 453
5-Chloro-2-methylthiopyrimidine, halogenation of methyl group, 360
5-Chloro-3-methylthio-1,2,4-thiadiazol-2-ium chlorides, as precursors to
thiapentalenes, 916
2-Chloro-3-nitropyridine, reaction with thiols, 364
2-Chloro-5-nitropyridine, reaction with amines in presence of acids, 363
5-Chloro-8-nitro-4(3H)-quinazolinone
, 333
980 Index

2-Chloro-1-phenacylbenzimidazole, reaction with sodium benzoate, 899 Cyanine dyes, 292

3-Chloro-2-phenylbenzo[b]thiophene, reaction with n-butyllithium, 424 o-Cyanoanilines
, 531
2-Chloro-6-phenylpyridine, lithiation, 299 2-Cyanoazetidines, hydrolysis, 638
3-Chloro-5-phenyl-1,2,4-thiadiazole, reaction with alkoxides , 585 1-Cyanobenzotriazole
, 600
4-Chloropicolinyl chloride
, 342 3-Cyano-4-carbamoyl-1,4-dihydropyridines
, 288
1-(3-Chloropropyl)benzotriazole, 595 2-Cyano-4,5-dihydro-3,1-benzoxazepine
, 843
3-Chloropropyl phenylsulfamide, cyclization, 774 2-Cyanofurans, microwave spectroscopy, 104
2-Chloropyrazine, displacement reactions, 365 2-Cyanoimidazoles
, 529
3-Chloropyrazoles
, 579 3-Cyano-5-methyl-6-acetoxyindole
, 809
3-Chloropyridazine, displacement reactions, 365 2-Cyano-3-methylindole
, 454
2-Chloropyridine
, 285 3-Cyano-2-methylpyrroles
, 459
3-Chloropyridine
, 701 Cyanooxanthrenes, 884
cross-coupling with 1-hexanethiol, 375 Cyanopyridines, in coupling reactions, 343
from pyrrole, 426 2-Cyanopyridines, with aryl Grignards, 343
2-Chloropyrimidine, stannylation, 361 3-Cyanopyidine, reduction by sodium borohydride, 295
2-Chloropyrrole
, 471 1-Cyanopyridinium bromide, 259
Chloropyrylium ions
, 355 2-Cyanopyrrole
, 592
2-Chloro-1,3,4-thiadiazole, reaction with benzylamine, 585 photochemical rearrangement to 3-cyanopyrrole, 387
5-Chloro-1,2,4-thiadiazoles
, 779 3-Cyanopyrrole
, 387
1-Chloro-1,2,4,6-thiatriazine
, 796 2-Cyanoquinoline
, 293
Chloro-1,3,5-triazines, reaction with phenylboronic acid, 368 a-Cyano-b-thioenaminones, oxidative cyclization, 717
3-Chloro-5-trichloromethyl-1,2,4-thiadiazole, reaction with antimony pen­ 2(3)-Cyanothiophenes, microwave spectroscopy, 104
tafluoride, 563 1-Cyano-1,2,3-triazole, 13C chemical shifts, 168
1-Chlorosulfinylimidazole, 603 reversible ring opening, 484
b-Chlorovinyl ketones, reaction with thioamides, 748 3-Cyano-4-trifluoromethyl-6-aryl-2(1H)-pyridones, with
Chromanones, synthesis, 820 hydrazine hydrate, 720
Chromans, synthesis, 819 Cyanuric acid, tautomerism, 81
2H-Chromenes, from ring opening of benzofurans, 822 Cyanuric chloride
, 789
irradiation, 321 Cyclam, conformations, 218
Chromium–aminocarbene complex, reaction with amides, 682 Cyclen, salvation, 217
Chromones, from phenols, 818 Cyclic sulfamidates, thermolysis to vinyl aziridines, 670
Mannich reaction, 270 Cyclization of 1,5-dicarbonyl precursors, 688
reaction with hydroxylamine, 284 of 1,5-diols, 665
Cinnoline, from o-alkenyldiazonium ions, 832 of b-haloamines, 660
mass spectra, 70 Cycloaddition, involving azomethine ylides to give pyrroles, 687
nitration, 332 involving isonitriles to give pyrroles, 687
protonation, 255 involving mesoionic oxazolium 5-oxides to give pyrroles, 687
UV spectra, 67 of alkenes with carbonyl ylides, 658
Cinnolinones, halogenations, 268 of imines with ketenes, 657
Cinnolin-3-ones, synthesis, 833 of N-sulfonylimines with alkynyl ethers to give functionalized
Cinnolones, from o-acyldiazonium ions, 832 2-azetines, 671
Clerodin, 91 [2 + 2] Cycloaddition, 644, 645
Clomipramine, 213 of aldehydes and ketenes, 657
Clopidogrel, 89 reactions of 4-dialkylamino-3-butyn-2-ones with substituted
2,4,6-Collidine, nitration, 263 phenyl isothiocyanates to thietimines, 671
Comarin, reaction wtih malonic ester, 291 [3 + 3] Cycloadditions, 643
Combes synthesis of quinolines, 819 N-(1-Cycloalkenyl)pyrroles
, 471
Complete neglect of differential overlap (CNDO), 33 Cyclobis(paraquat-p-phenylene) tetracation, in assembling supramolecu­
Concerted thermal [2 + 2] cycloadditions forming heterocycles, 644 lar structures, 84
Condensed pyridines, synthesis, 309 Cyclobuta[b]furan derivatives, thermolysis, 703
Condensed 1,2,4-triazines, synthesis, 861 Cyclodopa, 98
Conjugated heterocumulenes, act as heterodynes, 700 Cyclohexanespiro-30 -oxaziridine, 617
Conjugated mesomeric betaines, 35, 42 Cyclohexanone, reaction with chloramines, 707
Conrad–Limpach cyclization to 4-quinolones, 817 Cyclohexene episulfide
, 483
Copper-catalyzed cyclization of the thiopropargyl imines to pyrroles, 680 1,3,6-Cyclooctatriene, UV spectra, 226
Core-ionization energies, of five-membered heterocycles, 125 Cyclopentenes, ozonolysis, 731
Cornforth synthesis of oxazoles, 739 Cyclopropa[c]cinnolines, as intermediates, 835
Cotarnine
, 325 Cyclopropenyl azides, rearrangement, 774
2-Coumaranone, ring opening, 445 Cyclopropyl azides, thermal ring expansion, 675
Coumarin, bromination, 268 Cyclotrimerization of alkynes with nitriles, 700
from phenols, 818 of nitriles, 789
nitration and bromination, 333 Cytosine, fluorination, 269
reaction with hydroxide ions, 279
Cross-conjugated mesomeric betaines, 35
Crown ethers, 213 D
12-Crown-3, conformational analysis, 218 (+)-DC-81, antitumor antibiotic, 850
12-Crown-4, conformational analysis, 218 3-Deazaadenosine
, 590
18-Crown-6, as a complex with potassium ions, 213 5-Deazaflavins, 880
Cryptands, 213 Degenerate rearrangement, 35
Cryptates, mass spectra, 229 Dehydrodithizone, structure, 209
Cyanin, 43 Density functional theory (DFT), 34
 Index 981

Deoxycytidine , structure, 41 5,7-Diaryl-2-fluoro-4H-1,3-diazepines
, 754

Deoxythymidine, structure, 41 2,5-Diarylfurans
, 678
Desaurin derivatives, 734 Diarylfuroxans, irradiation, 483
Desmotropes, 35 3,5-Diarylisoxazoles, 17O NMR spectra, 175
N-Deuterio-1,2,3-triazole, microwave spectrum, 160 3,7-Diarylisoxazolines, 17O NMR spectra, 175
Dewar pyridines
, 633 2,5-Diaryl-1,3,4-oxadiazoles, reaction with thiourea, 781
by photoisomerization of pyridines, 676 1,5-Diarylpyrazoles
, 715
Dewar pyrimidines, 752 1,2-Diarylpyrroles, 677
Dewar resonance energies, 75 3,4-Diarylsydnones, photolysis, 539
of five-membered heterocycles, 126 2,5-Diaryl-1,3,4-thiadiazoles
, 781
DFT, 34 N,N0 -Diaryl ureas, reaction with paraformaldehyde, 790
calculations on tautomerism, 50 1,2-Diaza-1,3-butadienes, Diels–Alder reaction with diethyl azodicarbox­
1,3-Diacetyl-2-imidazolone, reaction with cyclopentadiene, 543 ylate, 795
2,6-Diacetylpyridine, reduction using bakers yeast, 344 Diazadienes, cycloaddition with alkenes, 724
o-Diacylbenzenes, reaction with hydrazine, 854 Diazadienium iodide, reaction with acetylenes, 700
Diacylhydrazines, dehydration, 775 2,4-Diazapentadienes, formation and cyclization, 742
Diacyl sulfones, cyclodehydration with ammonia, 761 Diazatricyclo[3.2.0.02,4]heptanes
, 730
2,5-Dialkoxy-2,5-dihydrofuran, 418, 429 3,4-Diaza-1,6,6al4 -trithiapentalene, theoretical studies, 150
Dialkylaminoborirenes, 231 Diazepam, 213
4-Dialkylamino-3-butyn-2-ones, cycloadditions with substituted phenyl Diazepines, photoelectron spectroscopy, 230
isothiocyanates to thietimines, 671 1,2-Diazepine conversion to 1,3-diazepines, 649
3-Dialkylaminoindoles
, 415 1H-1,2-Diazepines
, 730
N-Dialkylaminomethylbenzotriazoles, structure, 202 3H-1,2-Diazepines
, 729
2-Dialkylaminothiazolidine-4,5-dione bisimides
, 744 4H-1,2-Diazepine, 610, 730
Dialkylbenzo[c]furanyl derivatives, 824 1,3-Diazepines, 753
2,5-Dialkyl-3,6-diethoxypyrazine,
760 from 1,2-diazepines, 649
1,3-Dialkyl-2,3-dihydroperimidines
, 278 1,4-Diazepine rings
, 765, 768
3,6-Dialkyl-1,2-dithiin
, 727 theoretical studies, 217
4,5-Dialkyl-1,3-dithiol-2-one, by ring closure of dithiocarbonate, 742 6H-1,4-Diazepine, 610, 766
2,5-Dialkylfurans, oxidation, 418 1,4-Diazepine-5,7-diones
, 765
3,3-Dialkyl-3H-indolium salts, nitration, 447 1,3-Diazepin-2-ones
, 755
2,5-Dialkyl-1,3,4-oxadiazoles, hydrolysis, 513 Diazepin-5-ones
, 766
cis-2,6-Dialkylperhydropyrans, oxidative ring expansion, 768 1,4-Diazepin-5-ones
, 765, 766
1,3-Dialkylperimidones
, 278 1,2(3)-Diazetes, 231
2,4-Dialkylpyrrole-3,5-dicarboxylic esters, conversion to 3-substituted theoretical studies, 215
2,4-dialkylpyrroles, 677 Diazetidines microwave spectra, 222
1,4-Dialkyl-1,2,4-thiadiazol-3,5-diones
, 779 13
C NMR spectra, 225
2,3-Dialkyl-thietane 1-oxides, deprotonation, 628 1,2-Diazetidines, by cycloaddition reactions, 830
1,2(3)-Dialkyltriazolium salts, displacement of alkyl groups, 594 general method of synthesis, 708
Diallylaniline, cobalt carbonyl induced cyclization to quinolines, 821 N-inversion, 234
1,4-Diamines, reaction with carboxylic acid derivatives, 753 1,3-Diazetidines
, 732, 733
1,2-Diaminobenzenes, reaction with 1,2-dicarbonyl compounds, 845 1,2-Diazetidinones, general method of synthesis, 709
1,2-Diaminobenzimidazole, oxidation, 601 1,3-Diazetidinones
, 732
2,3-Diamino-5-t-butylpyrazole
, 500 Diazetine dioxides, 710
2,4-Diamino-6-chloropyrimidine, nitration, 264 1,2-Diazetines, reaction with ketones, 727
1,2-Diamino-3,5-dialkylpyridiniums, reaction with benzil, 907 2,20 -Diazidoazobenzene, thermolysis, 913
2,4-Diamino-6-hydrazino-5-nitrosopyrimidine, reaction with 1,1-diethoxy­ Diazines, 38
2-chloroethane, 861 alkylation, 258
1,2-Diamino-4-methylthiazole, reaction with phosgeniminium chloride, 901 protonation, 254
1,8-Diaminonaphthalene, cyclizations, 886 Diazinodiazines, 906
1,4-Diaminophthalazine
, 854 Diaziridines
, 483, 548
2,3-Diaminopyrazines
, 763 from carbonyl compounds by the Schmitz method, 707
2,6-Diaminopyridine, nitrosation, 270 slow nitrogen inversion, 234
4,6-Diaminopyrimidines
, 748 Diaziridinones, general method of synthesis, 708
5,6-Diaminopyrimidine, reaction with 1,2-dicarbonyl compounds, 845, 846 ring enlargement to pyrazolinones, 720
6,7-Diamino-5,6,7,8-tetrahydropteridine
, 282 Diazirine microwave spectra, 222
3,4-Diamino-1,2,5-thiadiazole, reaction with a-diketones, 763 photoelectron spectroscopy, 230
2,3-Diaminothiophene, stability as hydrochloride salts, 458 Diazirines, production by the Grahan procedure, 708
3,4-Diaminothiophene
, 457 Diazirinyl cations, structures, 215
exhibits enamine character, 458 Diazoacetaldehyde, from 1,2,3-oxadiazole, 207
2,4-Diaminotriazines
, 788 a-Diazoacetamides, ruthenium-catalyzed carbenoid cyclization, 667
o-Diaroylbenzenes, reaction with P2S5, 824 Diazoalkanes, cycloaddition to diazabicyclo[2.2.0]hexanes, 730
1,3-Diarylazetidin-2,4-diones
, 732 1,2-Diazocine, NMR spectra, 224
3,8-Diaryl-4,7-dichlorodiazocines, UV spectra, 226 UV spectra, 226
2,5-Diaryl derivatives of the 1,3-oxathiolylium system
, 741 1,4-Diazocines, stability, 217
3,5-Diaryl-5,6-dihydro-2H-1,3,5-oxadiazin-4(3H)-ones
, 790 Diazo compounds, cycloaddition with ketenes, 709
4,7-Diaryl-4,5-dihydro-1,3-oxazepinones
, 755 Diazomethane, transfer of methylene to carbonyl groups, 654
3,5-Diaryl-1,2,4-dithiazolium salts, reaction with nucleophiles, 518 2-(Diazomethyl)pyridine, 345
1,2-Diarylethenes containing heterocyclic ring, reversible 4-Diazo-5-phenyl-4H-1,2,3-triazole, reaction with alkenes, 541
photocyclization, 450 3-Diazopyrazole, gas-phase thermal extrusion, 573
Diarylethynes, reaction with elemental sulfur to give tetraarylthiophenes, 688 4-Diazopyrazolidine-3,5-diones, photochemical Wolff rearrangement, 709
982 Index

Diazo-substituted 1,2,3-triazoles, in regiospecific dipolar cycloaddition, 2,3-Didehydrothiophene, formation and reactions, 456
541 4,4-Dideutero Hantzsch dihydropyridine, mechanism of reduction
Diazotetrazole, preparation and pyrolysis, 574 of a-cyanocinnamates, 320
5-Diazotetrazole, thermal degradation, 481 Dieckmann reaction, in formation of heterocycles, 666
2-Diazothione tautomers, 577 Diels–Alder reaction ([4 + 2] cycloaddition), 645
1,2-Dibenzamidobenzene
, 513 to form six-membered heterocycles, 646
Dibenzo[b,e][1,4]dioxin, 43, 884 of carboxylate-substituted 2H-azirines, 890
Dibenzo[1,2]dithiins, 879 Dienyldiazoalkanes, 1,7-electrocyclization, 729
Dibenzofuran, 873 3,3-Difluoroazetidin-2-ones
, 662
derivatives, regioselective cleavage by lithium metal, 429 N0 ,N0 -Difluoro-2,20 -bipyridinium bis(tetrafluoroborate), 260
13
C-NMR spectra, 109 Difluoroethyne, formation by ring opening of fluorinated
fragmentation patterns in mass spectrometry, 122 triazines, 249
structure, 101 cis-3,5-Difluoro-1,2,4-trioxolane, conformation, 196
Dibenzo heterocycles, 1H NMR spectra, 106 Diheteropentalenes, UV spectroscopy, 115
Dibenzoselenophene, structure, 101 9,10-Dihydroacridine
, 305
Dibenzothiazepine
, 382 Dihydroalloxazine, structure, 53
Dibenzothiophene, 873 1,2-Dihydroazocines
, 703
fragmentation patterns in mass spectrometry, 122 Dihydroazoles, tautomerism, 546
structure, 101 2,3-Dihydrobenzimidazole
, 522
Dibenzothiophene S-oxide O-trimethylsilyl derivative, reaction with 2,2­ 2,5-Dihydro-1H-2,3-benzodiazepin-l-ones
, 856
dilithiobiphenyl, 439 3,5-Dihydro-4H-2,3-benzodiazepin-4-ones
, 856
5,5-Dibromobarbituric acid, loss of Br+, 319 1,5-Dihydro-3H-2,4-benzodioxepins
, 845
4,7-Dibromobenzothiadiazole, conversion to diamines, 591 3,4-Dihydro-2H-1,5-benzodioxepins
, 854
5,6-Dibromobenzotriazole
, 559 2,3-Dihydrobenzo[b]furan
, 801
2,20 -Dibromo-4,40 -dimethoxybiphenyl, metal-catalyzed amination to reductive cleavage, 441
carbazoles, 875 synthesis via photochemically-mediated cyclizations, 811
2,5-Dibromo-3,4-dinitrothiophene, reduction, 457 1,2-Dihydro-3H-benzo[e]indoles, 810
3,5-Dibromo-4-formylpyridine
, 338 2,3-Dihydrobenzoselenophenes, synthesis, 801
Dibromohydroxypyridines, monolithiation, 367 3,4-Dihydro-1,2,5-benzothiadiazepine 1,1-dioxides, synthesis, 867
3,5-Dibromo-4-picoline, oxidation, 338 Dihydrobenzothiinones, synthesis, 820
2,6-Dibromopyridine
, 302 2,3-Dihydrobenzothiophenes
, 801
3,5-Dibromo-2-pyrones, Stille couplings, 370 Dihydrobenzothiophene 1,1-dioxide, 394
2,4-Dibromoquinoline, reaction with trimethylsilylacetylene, 371 2,3-Dihydro-1H-1,3,4-benzotriazepines, 867
3,4-Dibromo-2,3,4,7-tetrahydrothiepine 1,1-dioxide
, 703 4,5-Dihydro-1H-1,3,4-benzotriazepines
, 868
2,4-Dibromothiazole, reaction with Grignard reagents, 584 4,5-Dihydro-3H-1,3,4-benzotriazepines, 867
3,4-Dibromo-N-tosylpyrrole, reaction with benzyne, 433 4,5-Dihydro-1H-1,2,5-benzotriazepin-4-ones
, 866
3,6-Di-t-butylazonin, tautomerism, 235 1,2-Dihydro-1,2,4-benzotriazines
, 861
1,2-Di-t-butyldiaziridine, resolution, 234 4,5-Dihydro-3,1-benzoxazepines
, 843
2,5-Di-t-butylfuran
, 411 Dihydro-1,4-benzoxazines, synthesis, 848
2,3-Di-t-butyl-4-mesitylazete, 236 1,2-Dihydrocinnolines, synthesis, 833
dimerisation, 632 Dihydrodiazepines
, 729, 730
2,6-Di-t-butylpyridine, protonation, 256 2,3-Dihydro-1,4-diazepines
, 765
2,7-Di-t-butylthiepin, stability, 237 5,6-Dihydro-4H-1,2-diazepines
, 728
3,4-Di-t-butylthiophene, structure, 130 1,2-Dihydro-1,2-diazete, theoretical studies, 215
3,4-Di-t-butylthiophene 1-oxide
, 394 lack of aromatic character, 231
3,4-Di-t-butyl-1-tosyliminothiophene
, 394 1,4-Dihydro-1,4-diazocine, 232, 237
2,3-Di(ethoxycarbonyl)-4-methylpyrrole
, 687 as 1,3-dienes, 633
a-Dicarbonyls, condensation with thioglycolic acid esters, 686 deprotonation, 616
1,3-Dicarbonyl compounds, reaction with amidines, 747 structure, 235
reaction with amines, 683 Dihydrodinaphthothiepin, X-ray structure determination, 222
reaction with hydrazines, 714 2,3-Dihydro-1,4-dioxane
, 762
reaction with hydroxylamine, 714 2,3-Dihydro-5H-1,4-dioxepins
, 769
1,4-Dicarbonyl compounds, reaction with hydrazines, 722 4,7-Dihydro-1,3-dioxepins
, 757
3,3-Dichloroazetidines, conversion into aziridines, 638 2,3-Dihydro-1,4-dioxins
, 760
3,4-Dichlorocinnoline, displacement reactions, 366 3,6-Dihydro-1,2-dioxin, conformations, 78
1,6-Dichloro-2,7-dihydroxy-3,8-dimethoxythianthrene
, 884 microwave spectrum, 54
4,5-Dichloro-1,2,3-dithiazolium chloride, X-ray structure, 157 conversion to furans, 695
1-(2,2-Dichloroethenyl)benzotriazole, 599 Dihydro-1,2-dithiines, by [4+2] cycloaddition reaction of 1,3-dienes with
2,2-Dichloro-1-(indol-1-yl)-1-ethanone
, 388 singlet sulfur, 725
Dichloromethylene–imine sulfonamide, reaction with 3,6-Dihydro-1,2-dithiin
, 726
N-hydroxythioamides, 777 5,6-Dihydro-1,4-dithiins
, 764
4,5-Dichloro-2-methylpyridazin-3-one, nitration, 264 2,3-Dihydrofuran, 90, 673
Dichloropyrazolinones, reaction with alkali, 544 MM2 calculations, 99
3,6-Dichloropyridazine, reaction with 2-(hydroxymethyl)-i-propyl nonplanarity, 132
radicals, 303 reaction with tetracyanoethylene, 440
2,4-Dichloroquinazoline, successive displacement reactions, 366 2,5-Dihydrofurans
, 549
2,5-Dichlorothiophene, reaction with ethyl 2-diazoacetoacetate, 425 ionisation potentials, 125
Dictyodendrin B, 687 NMR spectra, 108
Dicyandiamide, self-condensation, 788 nonplanarity, 132
2,5-Dicyano-3,6-dimethylpyrazine, reaction with hydroxyl ions, 330 4,5-Dihydrofurans, react as enol ethers, 440
(Dicyanomethylene)dithiazole, 722 2,3-Dihydroimidazoles, aromatisation, 546
 Index 983

4,5-Dihydroimidazoles, alkylation, 549 Dihydropyrimidines, stabilities, 318

dehydrogenation, 547 2,5-Dihydropyrrole, nonplanarity, 132
2,5-Dihydroimidazole N-oxides, 551 3,4-Dihydropyrroles
, 673
formation of radicals, 551 trimerisation, 440
1,3-Dihydro-2H-imidazo[4,5-c]pyridine-2-thiones
, 533 Dihydropyrrole-2,3-diones, Bayer–Villiger oxidation, 764
2,3-Dihydroimidazo[2,1-b]thiazol-5-one, 897 1H-Dihydropyrrolizines, 892
2,3-Dihydroindole
, 422, 437 3H-Dihydropyrrolizines, 892
4,7-Dihydroindole
, 448 1,2-Dihydroquinoline
, 295
1,3-Dihydro-2H-indol-2-one
, 420 Dihydroquinolin-4-imines, synthesis, 820
3,4-Dihydroisoquinolines
, 827 Dihydro-4-quinolones, synthesis, 820
aromatisation, 320 1,4-Dihydrotetrazines
, 40, 795
4,5-Dihydroisoxazoles, [2 + 2] cycloadditions with furan, 551 Dihydro-1,2,4,5-tetrazines, tautomerism, 82
formation by 1,3-dipolar cycloaddition, 551 1,4-Dihydro-1,2,4,5-tetrazines, electrochemical oxidation, 321
5,11-Dihydro-4-methyldibenzo[b,e][1,4]thiazepine
, 885 4,5-Dihydrotetrazoles, photolysis, 548
1,4-Dihydro-1-oxa-4-azaazocines, 237 5,6-Dihydro-2H-1-thia-2,4-diazin-3(4H)-ones
, 785
4,5-Dihydro-1,3,4-oxadiazines
, 784 2,5-Dihydro-1,3,4-thiadiazole derivatives, fragmentation, 549
Dihydro-1,2,4-oxadiazoles, mass spectra, 186 2,5-Dihydro-1,2,3,5-thiatriazole 1-oxides
, 794
2,3-Dihydro-1,3,4-oxadiazoles, hydrolytic ring opening, 551 Dihydro-1,4-thiazines
, 761
2,5-Dihydro-1,2,4-oxadiazoles
, 780 3,6-Dihydro-2H-1,2-thiazine 1-oxides
, 725
2,5-Dihydro-1,3,4-oxadiazoles, thermolysis, 549 3,4-Dihydrothiazine-3-thione, reaction with methyl iodide, 763
4,5-Dihydro-1,2,4-oxadiazoles, oxidation, 548 4,5-Dihydro-1,3-thiazole, reaction with dichloroacetyl chloride, 890
4,5-Dihydro-1,2,4-oxadiazol-5-ones, catalytic hydrogenation, 522 Dihydrothiepines
, 697
5,6-Dihydro-1,4-oxathiins
, 764 Dihydrothiepine 1,1-dioxides
, 703
4,7-Dihydro-1,3-oxazepin-2(3H)-ones
, 756 2,7-Dihydrothiepine 1,1-dioxide
, 703
Dihydrooxazin-2,3-diones
, 764 loss of sulfur dioxide, 608
3,6-Dihydro-2H-1,2-oxazines
351 3,6-Dihydro-2H-thiin, conformations, 78
one-atom cobalt carbonyl-mediated ring-expansion, 756 microwave spectrum, 54
4H-Dihydrooxazin-3-ones
, 763 2,3-Dihydrothiophene, nonplanarity, 132
4,5-Dihydro-1,3-oxazin-6-ones
, 753 reaction with tetracyanoethylene, 440
4,5-Dihydrooxazoles, uses in synthesis, 552 reaction with DMAD, 440
Dihydrooxepines
, 696 ring expansion, 693
4,5-Dihydrooxepines
, 697 2,5-Dihydrothiophene, 90
3,6-Dihydro-6-oxo-pyridinium-4-olates, 42 NMR spectra, 108
5,10-Dihydrophenazine, 40 3,4-Dihydrothiopyrans
, 673
3,4-Dihydrophenazin-1(2H)-ones, 882 5,6-Dihydro-4H-thiopyran-4-one, lithiation, 325
3,4-Dihydropyrans
, 673 Dihydro-1,2,4-triazines
, 782, 783
TiCl4-promoted coupling of pyruvates, 323 2,5-Dihydro-1,2,3-triazine
, 296, 297
3,6-Dihydropyrans
, 673 4,5-Dihydro-1,2,4-triazin-6-ones
, 782
conformations, 78 4,5-Dihydro-1,2,3-triazoles, phase-transfer-catalyzed oxidative
by ring-closing metathesis, 674 dehydrogenation, 548
Dihydropyran-4-ones
, 673 photodecomposition, 548
2,3-Dihydropyrazines
, 759 Di(2,3,4,5-tetramethylphenyl)borirenes, 231
2,5-Dihydropyrazines
, 758 [5,6-2H2]5,6-Dihydrouracil
, 306
4,5-Dihydropyrazoles, aromatisation, 546 2,3-Dihydroxybenzofuran, tautomerism, 136
as models of intramolecular dyotropy, 547 2,4-Dihydroxy derivatives of furan, tautomerism, 137
NMR studies, 166 2,4-Dihydroxy derivatives of thiophene, 137
pyrolysis, 548 2,8-Dihydroxy-3,7-dimethoxythianthrene
, 884
quaternisation, 551 2,3-Dihydroxyfuran, tautomerism, 136
studies of protonation by NMR spectroscopy, 167 3,4-Dihydroxyfuran, tautomerism, 137
4,5-Dihydropyrazole-3-diazonium salts
, 547 2,3-Dihydroxyindole, tautomerism, 136
Dihydropyridazines
, 727 5,6-Dihydroxyindoles, 804
1,4-Dihydropyridazine
, 309 b-Dihydroxylamines, oxidative closure, 710
from Diels–Alder reactions, 728 2,3-Dihydroxypyrrole, tautomerism, 136
4,5-Dihydropyridazine
, 309 2,3-Dihydroxythiophene, tautomerism, 136
Diels–Alder type [4 + 2] cycloadditions with 2,3-dimethyl-1,3-butadienes, 909 1,3-Diiminodihydroisoindole, in synthesis of phthalocyanines, 825
4,5-Dihydro-1H-pyrazole-1-thiocarboxamide
, 718 2,4-Diiodoimidazoles
, 504
Dihydropyridines
, 688, 693 4,5-Diiodoimidazole
, 505
oxidation, 319 Diiodomethane and methyllithium, in formation of oxiranes, 654
tautomerism, 82 2,5-Diiodomethyl-1,4-dioxane, 762
1,2(4)-Dihydropyridine, reaction with very strong bases, 322 Diketene, reaction with aqueous triethylamine to give
1,2-Dihydropyridine, 286 2,6-dimethyl-4-pyrone, 691
[2 + 2] cycloaddition with alkynes, 324 reactions, 624
[2 + 2] cycloaddition of DMAD, 703 Diketones, reaction with hydrazines in absence of solvent, 715
protonation, 322 a-Diketones, reaction with 1,2-diaminoalkanes, 759
reaction with dienophiles, 323 1,3-Diketones, reaction with hydroxylamine, 715
ring contraction, 799 Diketooximes, reaction with excess hydrazine, 714
1,4-Dihydropyridine
, 294, 288, 689 1,8-Dilithionaphthalene, reaction with sulfur, selenium, or tellurium, 886
NMR spectra, 55 1,3-Dimesitylimidazoline-2-ylidene, stability, 194
oxidative aromatisation, 320 2,5-Dimethoxy-3-alkenyl-substituted pyrazines, reaction with singlet
2,3(5)-Dihydropyridines, instability, 317 oxygen, 308
2,3-Dihydropyridinium ion
, 322 4,7-Dimethoxybenzo[c]furan, structure, 101
984 Index

[2-(2,2-Dimethoxyethyl)phenyl]hydrazine, in synthesis of 1,2-dihydrocin­ Dimethylsulfonium methylide, as methylene transfer agent, 654

nolines, 833 2,5-Dimethyl-1,3,4-thiadazole, side chain metallation, 527
3,4-Dimethoxyfuran, reaction with maleic anhydride, 431 Dimethyl 1,2,5-thiadiazole-3,4-dicarboxylate
, 618
2,6-Dimethoxypyridine, nitration, 263 2,5-Dimethylthiophene, gas electron diffraction studies, 129
[3-(Dimethylamino)-2-azaprop-2-en-1-ylidene]dimethyl ammonium 3,4-Dimethylthio-1,2,5-thiadiazole, 618
chloride
, 366 4,6-Dimethyl-1,2,3-triazine, halogenations, 268
4-Dimethylamino-5,6-dihydro-4H-1,3-thiazine
, 751 reaction with Grignard reagents, 297
6-(N,N-Dimethylamino)fulvene, reaction with thiophene sulfones, 438 4,6-Dimethyl-1,2,3-triazine 2-oxide, structure, 51
2-Dimethylaminonaphtho[b,c]oxepinium salts, 887 2,5-Dimethyltriazole 1-oxides
, 770
2-Dimethylamino-1,3,4-oxadiazole
, 777 1,4-Dimethyl-3,5,6-triphenyl-4,5-dihydro-1,2,4-triazinium iodide,
1-(4-Dimethylaminophenyl)pentazole
, 794 photolysis, 321
3(4)-Dimethylaminopyrazoles, alkylation, 572 1,3-Dimethyluracil, oxidation, 271
4-Dimethylaminopyridine, electron density in ring, 47 Dimroth rearrangement, 571
catalyzing acylation and related reactions, 259 Dimroth-type rearrangements, 557
2-Dimethylaminopyridine N-oxide, halogenations, 268 4,6-Dinitrobenzofuroxan, electrophilic behaviour, 560
cis (trans)-2,3-Dimethylaziridines, to trans- and cis-2-amino-4,5-dimethyl­ Dinitrogen pentoxide, in nitration of pyridines, 263
2-thiazolines, 745 1,4-Dinitroimidazole, reaction with methanol, 602
1,3-Dimethylbenzimidazoline
, 515 3,5-Dinitroindazole
, 559
1,3-Dimethylbenzimidazolone
, 515 1-(2,4-Dinitrophenyl)-pyrazole, reaction with hydrazine, 593
1,10-Dimethylbenzo[c]cinnoline, conversion to 1,8-dimethylbiphenylene, 1-(2,4-Dinitrophenyl)pyridinium chloride
, 258
250 reaction with amines, 283
2,3-Dimethylbenzo[b]furan, photooxygenation, 435 cis-1,2-Dinitrosoalkene, as intermediates in reactions of furoxan-oxides,
1,8-Dimethylbiphenylene, from 1,10-dimethylbenzo[c]cinnoline, 250 209
5,50 -Dimethyl-2,20 -bipyridyl
, 304 1,2-Dinitrosoarenes, as intermediates in reactions of benzofuroxans, 209
1,2-Dimethyl-3-t-butyldiaziridine, 13C NMR spectra, 225 1,2-Diols, conversion into oxiranes, 659
conformations, 230 reaction with rhodium carbenoids, 760
2-N,N-Dimethylcarboxamides of furan, pyrrole, and thiophene, rotational 1,6-Diols, dehydration to oxepanes, 665
isomerisation, 130 1,3-Dioxalanes, ring expansion, 768
1,6-Dimethyl-1,6-diazacyclodecane, monoprotonation, 235 Dioxanes
, 762
cis-2,5-Dimethyl-2,5-dihydrothiophene 1,1-dioxide, extrusion of sulfur 1,4-Dioxanes
, 765
dioxide, 441 1,5-Dioxaspiro[3.2]hexane, reaction with 1,2,3-triazole, 623
2,5-Dimethyl-3,4-dinitrofuran, structure, 130 1,3,2-Dioxathiolane S,S-dioxides
, 773
1,4-Dimethyl-3,5-dinitropyrazole, base-catalyzed reaction with aldehydes, 1,3,2-Dioxathiolane S-oxides
, 773
564 4,2-Dioxazines
, 784
2,5-Dimethyl-1,3-diphenyl-isoindole, pKa values, 398 1,2-Dioxepans, 731
3,4-Dimethyl-1,2-dithiolylium perchlorate, reaction with ammonia, 721 1,4-Dioxepin-5-ones
, 768
2,3-Dimethylene-2,3-dihydrofuran, formation and trapping, 436 Dioxepinones
, 768
reactions, 452 1,2-Dioxetan-3-ones
, 713
2,3-Dimethylene-2,3-dihydrothiophene, 451 from ketenes, 712
1,3-Dimethyl-5,6-epoxy-5,6-dihydrouracil, 271 Dioxetanes, 13C NMR spectra, 225
Dimethyl N-ethoxycarbonylthiocarbonimidate, reaction with a monosub­ UV spectra, 225
stituted hydrazine, 777 1,2-Dioxetanes, 712
1,3-Dimethyl-2-hydroxybenzimidazoline, ring open form in solid state, inherent instability, 215
515 reduction to 1,2-diols, 631
4,4-Dimethyl-4H-imidazole, rearrangement, 545 Dioximes, oxidative cyclization, 772
4,5-Dimethyl-1H-imidazole
, 545 1,2-Dioxines by [4 + 2] cycloaddition reactions of 1,3-dienes with singlet
2,3-Dimethylindole, oxidation, 419 oxygen, 725
2,6-Dimethyl-4-iodopyrimidine
, 354 1,4-Dioxin, 43, 760, 762
4,5-Dimethylisothiazole
, 721 electrophilic addition reactions, 314
3,5-Dimethylisoxazol-4-ylboronic acid, Suzuki coupling, 591 1,4-Dioxin–halocarbene adducts, 769
3,8-Dimethyl-2-methoxyazocine, 232 1,3-Dioxin-4-ones
, 750
3,5-Dimethyl-4-nitroisoxazole, different reactivity of methyl groups, 557 Dioxirane-mediated enantioselective epoxidations, 653
3,4-Dimethyl-1,2,5-oxadiazole, side chain lithiation, 563 1,4-Dioxocin, 232
3,5-Dimethyl-1,2,4-oxadiazole, differential activity of the methyl groups, UV spectra, 226
563 1,2-Dioxolane, derivatives, 1H NMR studies, 167
2-[(1,1-Dimethyl-2-oxoethyl)disulfanyl]-2-methylpropanal, reductive 2,5-Dioxopiperazines
, 760
amination with 3- bromopropylamine, 787 Dipeptides, cyclization, 739
N,N0 -Dimethyl-4-oxo-oxadiazine
, 790 Diphenylamines, reaction with carboxylic acids, 880
Dimethyloxosulfonium methylide, as methylene transfer agent, 654 3,5-Diphenyl-4-bromopyrazole, tautomerism, 200
2,5-Dimethyl-5-phenyl-2-oxazoline
, 744 6,7-Diphenyldibenzo[e,q][1,4]diazocine, reduction, 631
2,6-Dimethylpyran-4-one, irradiation to cage dimer, 313 1,2-Diphenyl-3,4-dicarboethoxy-5-fluoropyrrole
, 687
1,5-Dimethylpyrazinium-3-olate, reaction with dipolarophiles, 311 6,6-Diphenyl-1,6-dihydroimidazo[1,2-a]imidazole-3,5-dione
, 897
1,3(4)(5)-Dimethylpyrazole, coupling constants in 1H NMR, 163 1,1-Diphenyl-2,2-dimethylpropanol, acid-catalyzed rearrangement in
3,5-Dimethylpyrazole, dynamic properties in the solid state, 175 presence of sulfur trioxide, 713
tautomerism, 200 3,5-Diphenyl-1,2,4-dithiazolium perchlorate
, 778
1,2-Dimethylpyrazolium salts, base-catalyzed hydrogen exchange, 529 2,5-Diphenyldithiin, formylation, 314
Dimethylpyridine-2,3-dicarboxylate, conversion to amide, 342 Diphenyl ethers, photochemically initiated cyclization to dibenzofurans,
1,2-Dimethylpyridinium cation, reaction with benzaldehyde, 340 873
2,6-Dimethyl-4-pyrone
691 reaction with sulfur, 884
2,6-Dimethylpyrone, reaction with benzaldehyde, 339 Diphenylfurazan, flash vacuum pyrolysis, 480
2,4-Dimethylquinoline, regioselectivity of deprotonation, 337 3,5-Diphenyl-4-hydroxypyrazole, tautomerism, 204
 Index 985

4,5-Diphenyl-2H-imidazoles, migrating groups, 545 2,4-Disubstituted thiophenes, 678

reaction with singlet oxygen, 538 Disulfur dichloride, reaction with alkynes, 656
1,3-Diphenylisoindole
, 823 1,5,2,4-Dithiadiazepines, synthesis, 870
3,5-Diphenylisoxazole, hydrogenolysis, 535 1,4,2,6-Dithiadiazines, extrusion of sulfur, 314
Diphenylketene, reaction with imidazolidines
, 766 1,5-Dithia-2,4,6,8-tetrazocine system, 235
2,4-Diphenyl-1,3-oxazol-5-one, tautomerism, 206 1,5-Dithia-2,4,6,8-tetrazocines, UV spectra, 226
N-(5,5-Diphenyl-4-oxo-2-imidazolyl)glycine, lactamization, 897 Dithianes
, 762
3,5-Diphenylpyrazoline, disproportionation, 547 1,3-Dithiane, mass spectra, 72
Diphenyl sulfides, photochemically initiated cyclization to dibenzothio­ 1,4-Dithianes
, 765
phenes, 873 1,3,2,4,6-Dithiatriazine
, 796
3,6-Diphenyl-1,2,4,5-tetrazine
, 795 1,3,5-Dithiazine, 53, 789
1,5-Diphenyltetrazole, fragmentation, 838 1,4,2-Dithiazines
, 785
thermolysis, 481 Dithiazole series, cycloadditions, 558
2,5-Diphenyl-1,3,5-thiadiazin-4-one, reaction with Lawesson’s reagent, 1,2,4-Dithiazoles
, 778
355 1,2,4-Dithiazolidine ring, S-S bond cleavage, 511
4,5-Diphenyl-1,2,3-thiadiazole, photolysis, 482 1,2,4-Dithiazolidine-3,5-dione, as a nucleophilic isocyanate building
reaction with n-butyllithium, 511 block, 512
3,4-Diphenyl-1,2,5-thiadiazole 1,1-dioxide, thermolysis, 480 1,2,4-Dithiazolines
, 782
4,5-Diphenyl-1,2,3-thiadiazole trioxide, 145 1,3,2-Dithiazolium cations, reduction to stable radicals, 523
Diphenylthioketene, 482 reduction, 535
2,5-Diphenylthiophenes, structures, 102 Dithienothiophenes, 877
4,5-Diphenyl-1,2,3-triazole, amination, 500 1,3-Dithienylisothianaphthenes
, 678
1,3-Dipolar cycloaddition, 645 Dithienyls
, 467
of three-membered heterocycles, 634 Dithiepanes
, 758
to the synthesis of heterocyles, 644 1,2-Dithiepanes, 732
Dipolarophiles, 646 1,4-Dithiepanes
, 769
1,2-Di(pyrazol-1-yl)ethanes
, 497 1,3-Dithietanes
, 735
3,6-Di(pyridin-2-yl)-s-tetrazine, Diels–Alder reaction, 824 1,2-Dithietane 1,1-dioxides, synthesis, 713
4,40 -Dipyridyl
, 281 1,2-Dithietes, 713
Diradicals, 644 Dithiins
, 760
1,2-Disubstituted 4-acylimidazoles
, 746 1,2-Dithiin, non-aromaticity, 49
2,6-Disubstituted 4-aminopteridines, synthesis, 846 nucleophilic attack at sulfur followed by ring cleavage, 315
1,3-Disubstituted-arylimino-1,3-diazetidine
, 733 1,2(4)-Dithiins, loss of sulfur, 695
trans-3,4–Disubstituted azetidin-2-ones, 662 1,3-Dithiins
, 751
1,2-Disubstituted benzenes, reaction with a-haloethanal ketals, 848 1,4-Dithiins
, 760, 761, 762, 763
3,8-Disubstituted benzo[c]cinnolines, 879 electrophilic addition reactions, 314
2,3-Disubstituted benzofurans, 806 extrusion of sulfur, 314
1,3-Disubstituted-2,4-bisalkyl-1,3-diazetidine
, 733 metallation at C-2, 315
4,40 -Disubstituted-2,20 -dinitrobiphenyls, conversion to benzocinnolines, reactions on sulfur, 314
879 Dithiiranes, 13C NMR and 15N NMR spectra, 225
2,6-Disubstituted 1,4-dithiins, 761 UV spectra, 225
2,3-Disubstituted furans, 17O NMR spectra, 111 1,2-Dithiolane
, 717
2,4-Disubstituted furans, formation, 464 S-alkylation, 555
3,5-Disubstituted-4-haloisoxazoles
, 715 1,2-Dithioles, reaction with carbenes and nitrenes, 532
1,4(5)-Disubstituted imidazoles, coupling constants in 1H NMR, 163 1,2-Dithiole-3-ones
, 717
1,3-Disubstituted imidazole-2-ylidenes, stability, 194 reaction with Grignard reagents, 512
1,3-Disubstituted imidazolium salts, reaction with sodium hydride, 530 1,3-Dithiole-2-thione, reaction with diiodine studied by Raman spectro­
3,5-Disubstituted-4-isothiazolecarbonitriles
, 717 scopy, 182
3,5-Disubstituted isoxazoles
, 719 1,2-Dithiole-3-thione, 144
2,5-Disubstituted 4-methyloxazoles, bromination of methyl group, 562 1,2-Dithiolium cations, ring expansion to thiinthiones, 693
2,6-Disubstituted 4-(methylthio)pyridines
, 698 1,3-Dithiolium salts, ring expansion with sodium azide, 785
1,3-Disubstituted 6-methyluracils
, 752 1,2-Dithiolium-4-olates, tautomerism, 209
2,5-Disubstituted-1,3,4-oxadiazoles
, 482 1,3-Dithiols, oxidative cyclization, 717
2,5-Disubstituted oxazoles, 740 1,2-Dithiolylium cations, reaction with active methylene
N,N-Disubstituted pentafulven-6-amines, 292 compounds, 916
1,4-Disubstituted piperazines
, 763 1,2-Dithiolylium ions, hydrogen exchange reactions, 528
3,5-Disubstituted pyridines
, 699 ring opening, 515
2,2-Disubstituted 2H-pyrroles
, 408 Dithiolylium mesoionic systems
, 737
alkylation, 437 Dithiolylium salts
, 740
2,3-Disubstituted 4(3H)-quinazolinones, synthesis, 842 1,2-Dithiolylium salts, 581
3,4-Disubstituted quinolines, synthesis, 826 conversion into pyrazoles, pyrazolium salts, and isothiazoles, 721
3,5-Disubstituted-4-selenoisoxazoles
, 715 reaction with amines, 518
1,5-Disubstituted tetrazole
, 792 1,3-Dithiolylium salts
, 736
photolysis, 569 addition of alkoxide ions, 515
2,5-Disubstituted tetrazoles, thermolysis, 481 reaction with amines, 517
3,5-Disubstituted 1,2,4-thiadiazoles
, 781 reaction with sodium borohydride, 523
3,4-Disubstituted-1,2,5-thiadiazole 1,1-dioxides, reaction with reaction with sulfur nucleophiles at the 2-position, 519
nucleophiles, 518 1,3-Dithiolylium-4-olates, cycloaddition reactions, 538
2,4-Disubstituted 1,2,3-triazoles
, 770 Dithiophenes
, 467
3,5-Disubstituted 1,2,4-triazoles
, 777 cis-Divinyl-b-lactam, rearrangements, 697
3,4-Disubstituted thiophenes
, 694 Dopaquinone, cyclization to cyclodopa, 98
986 Index

E F
Ebalzotan, 43 Feist–Benary furan synthesis, 684
Efaroxan, 142 Fischer indole synthesis, 806
Eigenfunctions, 32 Five-membered ring systems readily available via 1,3-dipolar
Eigenvalues, 32 cycloadditions, 646
Eight-membered heterocyclics, by ring-closing metathesis, 675 Flavones, nitration, 341
nomenclature, 213 Baeyer–Villiger oxidation, 854
synthesis by ring expansion, 669 Fluorinated alkynes, formation by ring opening of fluorinated triazines, 249
Eight-membered lactones, 669 N-Fluoro-1,3,2-benzodithiazole-1,1,3,3-tetroxide, preparation and use as
Electrocyclic ring closures in the formation of six-membered fluorinating agent, 499
rings, 648 2-Fluoro-5-bromopyridine
, 349
Electron-deficient carbon double bonds, conversion to oxiranes, 654 3-Fluoro-1,3-dihydro-2H-indol-2-ones
, 403
Electron-rich alkenes, reaction with singlet oxygen, 712 trans-5-Fluoro-3,6-dihydro-1,2-oxathiin 2-oxide, 53
Elementotropy, 202 6-Fluoroindole
, 804
Empirical resonance energies, of five-membered heterocycles, 126 2-Fluoropyrazine, reaction with amides, 365
of five-membered heterocycles with more than one 2-Fluoropyridine
, 266, 285, 302
heteroatom, 191 amination, 363, 374
2-En-4-ynylamine , Pd(II)-catalyzed annulations, 680 5-Fluoropyridine-2,3-dicarboxylic acid
, 333
Enamides, reaction with 1,3-bielectrophiles, 690 N-Fluoropyridinium salts, 260
Enamines, reaction with 1,3-bielectrophiles, 690 5-Fluoro-2(1H)-pyrimidinones, 269
Enaminothiones, reacton with electron-deficient dienophiles, 671 5(6)(8)-Fluoroquinolines
, 332
6-Endo-trig closure, 648 5-Fluorouracil, structure bound to uracil phosphoribosyltransferase, 54
Epi-swainsonine, 915 1-Formylbenzotriazole
, 599
trans-Epithiocyclooctane, 656 2-Formylpyridine
, 345
Epoxidation reagents, 653 Four-membered heterocycles, bond lengths and angles, 2
Epoxides, deoxygenation, 617 IR spectra, 227
reaction with allylsilane reagents, 622 mass spectra, 227
reductive ring openings, 622 NMR spectra, 223
3,4-Epoxyalcohols, expansion to hydroxymethyloxetanes, 668 nomenclature, 211
4,5-Epoxyalcohols, valuable intermediates for the regioselective photoelectron spectroscopy, 230
synthesis of tetrahydrofurans and tetrahydropyrans, 668 ring strain, 230
Ethane-1,2-dithiol, reaction with 1,3-dihalopropanes, 769 quantum mechanical calculations, 215
N-Ethoxycarbonylazepine, reaction with dichlorocarbene, 630 X-ray diffraction studies, 218
3-Ethoxycarbonyl-2,4-dimethylpyrrole, reaction with formaldehyde, 413 Fragmentation reactions in small rings, 606
2-Ethoxycarbonylindole
, 803 Friedl€ander synthesis of quinolines, 816
a-(Ethoxycarbonyl)methylsulfonylurea, cyclization, 783 Fulgides, 450
1-Ethoxycarbonylpyridinium cations, reaction with phosphites, 284 Fully-unsaturated seven-membered heterocycles, conformations, 221
5-Ethoxy-4-methyloxazole
, 737 bond lengths, 222
Ethyl 5-acetyl-2,4-dimethyl-3-carboxylate
, 406 Functionalized azetidines
, 658
Ethyl 4-acetyl-5-methyl-3-propyl-1H-pyrrole-2-carboxylate
, 683 Functionalized 2-azetines, from cycloaddition of N-sulfonylimines with
N(6)-Ethyladenine
, 348 alkynyl ethers, 671
3-Ethylamino-1,2-benzisothiazole, Dimroth rearrangements, 571 Functionalized oxirane, reaction with nitriles, 621
Ethyl 6-aminoindole-7-carboxylate
, 804 Furan, 1,4-addition with ethoxycarbonylnitrene, 426
Ethyl diazoacetate, reaction with N-alkyl aldimines, 656 addition reactions with carbenes, 424
2-Ethyl-1,3-dioxepane
, 757 B3LYP/6-311+G

calculations, 97
1-Ethyl-3,5-diphenyl-1,2,4-triazole
, 479 by addition of benzoin to dimethyl acetylenedicarboxylate, 685
4-Ethyl-3,5-diphenyl-4H-1,2,4-triazole, rearrangement, 479 by regioselective [3 + 2] annulations, 685
Ethyl 2-formamide propionate, reaction with phosphorus conversion into thiophenes or pyrroles, 694
pentoxide, 737 electrophilic reactions on ring carbons, 395
Ethyl 2-iodothiophene-3-carboxylate
, 463 fragmentation patterns in mass spectrometry, 120
Ethyl 3-methoxy-1-methyl-1H-pyrazole-4-carboxylate, 5-lithiation, 527 from 1,4-diketones, 677
Ethylene, theoretical study of ozonolysis, 152 in photopromoted [2 + 2] cycloadditions with carbonyl compounds, 435
Ethylenediamine, reaction with 1,3-dialdehydes and irradiation with benzene, 436
1,3-diketones, 765 Gattermann aldehyde synthesis, 406
Ethyl furan-3-carboxylate, direct arylation, 469 less aromatic character, 386
Ethyl b-methylcinnamate, epoxidation reaction using a fructose-derived 2-lithiation, 677
catalyst, 653 nitration, 400
3-Ethyl-4-methylpyridine
, 698 oxidation, 417
5-Ethyl-2-methylpyridine
, 698 phenylation, 417
2-Ethyl-3-methylquinoline
, 821 photoinduced alkylation with diarylalkenes, 427
Ethyl-3-phenyl-5-methylpyrrol-2-carboxylate
, 679 reactions with aldehydes and ketones, 412
Ethyl thiophene-3-carboxylate, metallation, 463 reaction with alkenes, 411
Ethyl a-(p-tolylhydrazono)-2-furopropionate, crystal structure, 130 reaction with ammonia, 694
2-Ethynylaryl sulfides, cyclization, 806 reaction with benzynes, 434
5-Ethynyl-1-methylimidazole
, 569 reaction with chlorine and bromine, 402
Ethynyl-oxiranes, isomerisation to furans, 691 reaction with hydrogen sulfide, 694
reaction with amines gives pyrroles, 691 reaction with maleic anhydride, 431
2-Ethynyl-3-pyridinols, metal-catalyzed couplings, 354 reactions with methanolic hydrogen chloride, 422
Eumelanin, 98 reaction with singlet oxygen, 434
5-Exo-trig closure, 648 ring hydrogen atoms exchange, 399
Extended H€ uckel (EH) approximation, 33 sulfonation with pyridine–sulfur trioxide, 400
 Index 987

thermal stability, 386 2-Halo-4,5-dihydroimidazoles, generation and use, 552

Vilsmeier–Haack acylation, 406 3-Halo-1,2-dithiolyliums, displacement of halo atoms, 586
Furan-3-carbaldehydes, rotamers, 129 2-Halofurans, reaction with piperidine, 460
Furan-2-carboxaldehyde, as a diene, 431 Halogenated thiophene sulfones, increased stability, 438
production, 89 1-(w-Halogenoalkyl)-2-methylsulfonyl-5-substituted pyrrole,
Furancarboxylic acids
, 695 intramolecular radical acylation, 428
Furan-2-carboxylic acids
, 280 5-Halogeno-5-nitroimidazoles, reaction with thiolates, 584
3(2H)-Furanone, 414 b-Halohydroperoxides, dehydrohalogenation, 712
Furan-2-sulfonic acid, sulfonation, 400 4(5)-Haloimidazoles, nucleophilic displacement of halides, 584
3-(Furan-2-yl)acrylic acid, conversion to an ester of g-oxopimelic acid, 453 4-Haloisoxazoles
, 717
Furazan, 145, 771 general method of synthesis, 721
alkylation with dimethyl sulfate, 493 a-Haloketones, reaction with amides to oxazoles, 735
Furfural
, 679 reaction with amidines to imidazoles, 735
2-arylation, 469 reaction with enamines to form pyrroles, 684
reaction with 1,3-butadiene, 434 reaction with thioamides to thiazoles, 735
rotamers, 129 reaction with thiohydrazides, 785
Furfuryl alcohol, reaction with HCl, 453 5-Haloketones, reaction with substituted hydrazines, 728
Furfuryl chloride, reaction with sodium cyanide, 451 5-Halo-1-methyl-1,2,3-triazoles, reaction with amines, 585
Furfuryl halides, very reactive, 453 5-Halooxadiazoles
, 507
Furo[3,4-b]benzothiopyran-9-one
, 298 4(5)-Halooxazoles, nucleophilic displacement of halides, 584
Furo-1,2-diazepines
, 835 Halopyridines, reactivity, 360
2-Furoic acid, Birch reduction, 429 3-Halopyridines, metallation, 298
Furopyrroles, structures, 97 5-Halo-1,2,4-thiadiazoles, displacement of halo atom by nucleophiles, 585
4H-Furo[3,2-b]pyrrole-2-carboxylate, 97 2-Halo-1,3,4-thiadiazoles
, 575
Furoxan
, 145 5-Halothiazoles, reaction with methoxide, 584
Furoxan-2-oxide, interconversion to 5-oxide, 209 2-Halothiophenes, spectra, 124
Furoxan-5-oxide, interconversion to 2-oxide, 209 5-Halotriazines, 268
Furoxans
, 771 Hantzsch pyridine synthesis, to 1,4-dihydropyridines, 689
3-Furylmercury acetate
, 677 Hantzsch pyrrole synthesis, 684
2-(2-Furyl)pyrrole, conformation, 131 Harmonic oscillator model of aromaticity, 36, 77
5,5-Fused aromatic heterocycles, electron distribution, 94 Hartree–Fock calculations on sodium azole complexes, 150
HOMO energies, 96 Hassner reaction, 674
13
C-NMR spectra, 110 ‘Head-to-tail’ dimerization of thiocarbonyl compounds to 1,3-dithietanes,
Fused azirines, 890 735
Fused 1,4-benzothiazepine derivatives, synthesis, 852 Heck alkenylation of bromo- or iodopyridines, 372
Fused bicyclic pyrrolidines, 669 Hemetsberger–Knittel indole synthesis, 814
5,5-Fused heterocycles, 1H NMR spectra, 107, 162 Heptaazapentalene anion, quantum mechanical calculations, 208
cis-Fused 5-methylquinolizidinium salts
, 328 Heptaazaphenalene, stability, 47
Fused pyrans, from cyclohexan-1,3-diones, 689 Hess–Shaad resonance energies, of five-membered heterocycles, 126
Fused six-membered rings, 38 of five-membered heterocycles with more than one heteroatom, 191
Fused 1,2,4-thiadiazine 1,1-dioxides, synthesis, 864 Hetaryl-substituted 1,2,4-triazines
, 782
Heterepine/heteronorcaradiene rearrangement, 611
Heteroaromatic N-imines, 1,3-dipolar cycloaddition reactions, 378
G Heterocyclic 2,3-azidoaldehydes, reaction with hexamethyldisilathiane, 459
Gabriel synthesis of aziridines, 660 Heterocyclic a,b-quinodimethanes, 451
Gallepine, 30 [4+2] Heterocyclization reactions, 671
Gandberg modification of the Fischer synthesis, 807 Hetero-Diels–Alder reaction with iminium species, 672
Gas chromatography, of five-membered heterocycles, 126 Heteronines, 232
Gas-liquid chromatography of five-membered heterocycles with more Heteropines, 232
than one heteroatom, 187 Heteropine–heteronorcaradiene equilibrium, 237
of heterocycles, 73 Hexahydrofuro[3,4-c]furans, structures, 103
Gas phase microwave spectroscopy of five-membered heterocycles, 103 Hexahydrothiazino[2,3-a]quinoline, 649, 909
Gassman synthesis of indoles, benzo[b]furans, 808 Hexahydro-1,3,5-triazines
, 789
Gaussian basis sets, 34 Hexapyrrol-1-ylbenzene
, 389
Gewald synthesis, 680 cis-Hexatriene, reaction with sulfur dioxide, 703
Glutaconic aldehyde, 277 Hexazine, 38
Glutaconic dialdehyde, reaction with ammonia, 698 High performance liquid chromatograpy of heterocycles, 73
Gould and Jacobs cyclization to 4-quinolones, 817 Hinsberg thiophene synthesis, 686
Graebe–Ullmann synthesis of carbazoles, 874 Histidine, as a chelating agent, 491
Gramine, quaternisation and reaction with nucleophiles, 454 Hofmann–Loeffler–Freytag reaction, 663
Griseofulvin, 92 HOMA index for five-membered heterocyclic rings, 192
Guanidines, reaction with a-halo ketones to 2-aminoimidazoles, 736 HOMO energies of five-membered heterocycles, 95


D-Gulonolactam , 669 Homophthalaldehyde
, 277
reaction with ammonia, 826
H€ uckel calculations, 33
H on five-membered heterocycles, 93, 146
Haloacetylhydrazones, intramolecular cyclization, 709 on six-membered heterocycles, 45
5-Halo-aldehydes, reaction with substituted hydrazines, 728 H€ uckel’s rule, 75
b-Haloalkylhydroxylamines, conversion into oxazetidines, 710 Hydrazides, reaction with dichloromethylene-dimethyliminium
Haloazirines, 674 chloride, 777
N-Haloazoles, 499 1,2-Hydrazinedicarboxylates, reaction with 1,2-disulfenyl chlorides, 865
988 Index

Hydrazino-1,4-benzoquinones, thermolysis, 863 3-Hydroxypyridine
701,

4-Hydrazino-1-methylpyridinium salts, reactions, 350 from aminomethylfurans, 701
8-Hydrazinopyridazino[4,5-c]pyridazines, synthesis, 855 halogenations, 267
N-Hydrogen-4,5-dihydroimidazoles, side-chain deprotonation, 550 nitration, 263
a-Hydroperoxy acids, 713 orientation of electrophilic reactions, 263
2-Hydroxyacetophenone, conversion to benzo[b]furans, 813 reaction with carbon dioxide, 270
g-Hydroxy acids, spontaneous cyclization to lactones, 663 reaction with formaldehyde, 271
b-Hydroxyacylamines, cyclization to oxazolines, 741 tautomerism, 79
4-Hydroxyalkyl-1,2-oxazetidines, stereoselective synthesis, 711 Hydroxypyridine 1-oxides, 352
2-(a-Hydroxyalkyl)pyridinium salts, formation of zwitterions, 345 1-Hydroxypyridinium ions, loss of a proton, 380
3-(1-Hydroxyalkyl)pyrroles
, 435 4-Hydroxypyrimidine, tautomerism, 81
2-Hydroxyaminopyridine
, 350 3-Hydroxy-4-pyrones
, 701
1-Hydroxy-2-azetidinones, a-azidation, 625 N-Hydroxypyrroles, tautomerism, 136
1-Hydroxybenzimidazole N-oxides
, 594 3-Hydroxypyrroles, tautomerism, 135
3-Hydroxybenzofurans, tautomerism, 135 8-Hydroxyquinoline, metal complexes, 257
2-Hydroxybenzo[b]thiophene
, 464 3-Hydroxy-2-quinolones
, 821
tautomerism, 134 3-Hydroxy-1,2,5-thiadiazoles, coversion to bromo, 580
3-Hydroxybenzo[b]thiophene, tautomerism, 136 2-Hydroxythiophene, tautomerisation, 98
1-Hydroxybenzotriazole, in peptide synthesis, 603 3-Hydroxythiophene, reaction with benzaldehyde, 444
b-Hydroxy-a-cyanoenamines, reaction with trimethyl tautomerism, 136
orthoformate, 736 2-Hydroxythiophene sulfoxide
, 393
N-Hydroxy-2-cyanopyrrole
, 694 Hydroxyurea, reaction with a,b-unsaturated ketones, 787
tautomerism, 136
1-Hydroxy-2,5-dihydroimidazoles, formation of radicals, 551
1-Hydroxy-2,5-dihydroimidazole 3-oxides, tautomerisation, 551 I
5-Hydroxydihydroisoxazole
, 715 Imidazocarboxylic acids, bromodecarboxylation, 505
5-Hydroxy-1,5-dihydro-2H-pyrrol-2-one
, 417, 434 Imidazoles
, 736
4-Hydroxy-3,4-dihydro-1,2,4-triazines
, 783 acylation, 498
2-Hydroxy- 20 ,40 -dinitrodiphenylamines, cyclization, 882 N-alkylation, 496
N-(2-Hydroxyethyl)-N0 -acylhydrazines, dehydration, 784 alkylation, 494
2-(2-Hydroxyethylimino)imidazolidine, reaction with 2-chloro-1,3­ chlorination, 504
dimethylimidazolium chloride, 896 chlorosulfonation, 504
2-Hydroxyethylpyridine, dehydration, 345 carrying a substituent on nitrogen, quaternisation, 492
2-Hydroxy five-membered heterocycles, tautomerism, 134 general method of synthesis, 738
2-Hydroxyfuran, tautomerism, 92 hydroxymethylation, 508
3-Hydroxyfurans, tautomerism, 135 HMO p-electron partial charges, 146
2-Hydroxyimidazoles, tautomers, 578 2-lithiation, 525
4(5)-Hydroxyimidazoles, tautomerism, 579 Michael reactions, 497
1-Hydroxyimidazole 3-oxides, 602 N-H bond length, 160
3-Hydroxyiminoalkyl-1,2,5-oxadiazole, 486 nitrosation, 508
N-Hydroxyindoles, tautomerism, 136 orientation of electrophilic reactions, 502
2-Hydroxyindole, tautomerism, 134 pKa, 141
3-Hydroxyindoles, tautomerism, 135 quaternisation, 169
3-Hydroxyisoquinoline, tautomerism, 81 reaction with alkyl radicals, 533
4-Hydroxyisothiazoles, O-methylation and O-acylation, 580 reaction with benzynes, 496
3-Hydroxyisoxazoles, IR spectra, 184 reaction with chloroform, 532
5-Hydroxyisoxazoles, tautomerism, 579 thermodynamic stability, 192
a-Hydroxy ketones, reaction with amidines to imidazoles, 736 2H-Imidazoles, thermal rearrangement to 1H-isomers, 545
4-Hydroxy-g-lactones to b-lactams, 670 oxidation, 545
Hydroxylamine O-sulfonic acid, reaction with pyridine, 261 4H-Imidazoles
, 747
Hydroxylation of azoles, 513 rearrangements to 1H-isomers, 545
2-Hydroxyl cyclobutylidenes, rearrangements, 692 Imidazole-2-carbaldehyde, as hydrate, 569
Hydroxyl-directed epoxidations of chiral allylic alcohols, 653 deacylations, 570
2-(Hydroxymethyl)aziridines, hydrolysis, 637 2H-Imidazole 1,3-dioxides, oxidation to stable nitroxide radicals, 545
2-Hydroxymethylfuran, reaction with chlorine, 701 Imidazole N-oxides, instability, 602
5-Hydroxymethylfurfural
, 679 rearrangement, 602
Hydroxymethyloxetanes, 668 Imidazole 3-oxides, NMR spectra, 169
3-Hydroxy-5-methylpyrazole, tautomerism, 203 Imidazole-2-ylidenes, aromaticity, 195
2-Hydroxymethylpyridine
, 303 Imidazolidines, aromatisation, 553
oxidation, 345 ring-chain tautomerism, 207
2-Hydroxymethylpyrrole, reduction, 453 Imidazolines
, 142, 746
2-Hydroxymethylthiophene, reaction with HCl, 453 from phenyl-N-tosylaziridines, 745
5-Hydroxymethyluracil, 269 Imidazoline-2-thiones, tautomerism, 581
3-Hydroxy-5-phenylisothiazole, reaction with diazomethane, 579 alkylation, 581
4-Hydroxyphthalazin-1(2H)-one
, 856 reduction, 582
4-Hydroxypiperidines
, 665 2-Imidazolinones, as cyclic ureas, 578
3-Hydroxypyrazoles, tautomerism, 203 Imidazolium mesoionic systems
, 737
5-Hydroxypyrazoles, conversion to sulfates, 589 Imidazolium salts, reaction with sulfur and selenium, 534
1-Hydroxypyrazole 2-oxides, acidity, 602 Imidazolo-fused 1,3-benzodiazepin-2-ones
, 842
5-Hydroxy-2-pyridone, from pyrid-2-one, 271 Imidazolo-fused thiadiazepinedithiones, 869
Hydroxypyridines, 352 Imidazol-2-ones, 143
 Index 989

Imidazo[1,2-a]pyridines, orientation of electrophilic reactions, 502 Indolo[2,1-c]benzo[1,2,4]triazine derivatives, 908

Imidazo[4,5-c]pyridines, hydroxylation, 513 2-(Indol-1-yl)ethanols
, 389
Imidazo[2,1-b] [1,3,4]thiadiazoles, 902 Indol-1-ylmagnesium halides, conversion into 2-arylindoles, 469
Imidazo[2,1-b]thiazole-3,5-diones, 897 2-Indolylsilanols, cross coupling with aryl halides, 470
Imidazo[4,5-e]triazepines, synthesis, 868 Indophenines, 413
1-Imidoylbenzotriazoles, 599 Indoxyl, oxidation, 444
Imines, [2 + 2] cycloaddition with sulfenes, 711 Infrared spectroscopy of five-membered heterocycles, 116
Iminobenzodithioles, equilibrium with benzoisothiazolethiones, 485 Intermediate neglect of differential overlap (INDO), 33
2-Iminobenzothiazoline, reaction with acrylic acid, 575 Intramolecular condensation of b-amino acids, 662
Iminochloromethanesulfenyl chlorides, reaction with amidines, 779 Intramolecular cyclizations, in synthesis of pyrroles and furans, 682
Iminoiodanes ,in formation of nitrenes, 655 Intramolecular cycloaddition reactions, 649
Iminonitrenes, 644 Intramolecular dipolar cycloaddition reactions of azomethine ylides, 669
4-Imino-1,2-oxazetidines
, 710 Intramolecular Heck cyclization to indoles, 809
2-Imino-4-phenyl-2H-1,3-thiazinium perchlorate, base hydrolysis, 753 N-w-Iodoalkylpyridinium salts, intramolecular radical cyclizations, 303
Iminophosphoranes, in production of aziridines from oxiranes, 669 5-Iodo-2-aminopyridine
, 362
reaction with 2-azidocyclopentene-1-carbaldehyde, 716 2-Iodobenzo[b]furan
, 465
Indazole, acidity, 490 o-Iododiarylamine, cyclization tocarbazoles on treatment with Pd(OAc)2,
electrophilic substitutions on benzene rings, 559 874
from o-acylphenylhydrazines, 830 2-Iodofuran
, 402
3-lithiation, 527 Iodohydration of double bonds followed by ring closure to give oxiranes, 659
solubility, 187 1-Iodoimidazoles, 603
tautomerism, 199 2-Iodoimidazoles, Suzuki coupling, 590
Indazole carbaldehyde, 417 2(5)-Iodoimidazoles
, 504
Indazolinone, tautomerism, 204 4-Iodoimidazole
, 505
Indigo
, 92, 444 coupling with methyl acrylate, 590
Indole, acid-catalyzed condensation with 2,5-hexanedione, 874 4(5)-Iodoimidazole, benzylation, 495
acid-catalyzed dimerization, 421 2-Iodoisoquinoline
, 299
13
C-NMR spectra, 109 4-(Iodomethyl)azetidin-2-one, reaction with azide, 638
C-alkylation, 410 2-Iodo-1-methylimidazole, reaction with zinc, 590
cleavage of C(2)–C(3) bonds by oxidation, 418 5-Iodopentan-2-ol
, 442
deprotonation with butyllithium, 462 N1-(2-Iodophenyl)-N1-methylbenzene-1,2-diamine, carbonylation, 884
electrophilic reactions on ring carbons, 395 2-Iodopyridine
, 299
enzymatic carboxylation, 408 3-Iodopyridine, cross-coupling with n-butanol or isopropanol, 373
fluorescence and phosphorescence, 114 2(4)-Iodopyrimidines, alkynylation, 372
fragmentation patterns in mass spectrometry, 121 8-Iodoquinoline
, 299
pKa values, 398 2-Iodothiophene, reaction with terminal alkynes, 467
reaction with acetic anhydride, 406 5-Iodo-1,2,3-triazoles, coupling reactions, 591
reaction with benzenediazonium salts, 416 6-Iodo-4-trifluoromethylindole
, 804
reaction with benzoylhydrazones, 415 IR spectra of five-membered heterocycles with more than one hetero­
reaction with dimethyl diazomalonate, 425 atom, 179
reaction with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate, 435 of substituted pyridines, 68
reaction with electrophilic alkenes, 408 Irbesartan, crystal forms, 171
reaction with epoxides, 412 Isatin, 92, ring fission, 445
reaction with excess methyl iodide, 410 reaction with hydroxylamine, hydrazine, 445
reaction with imines, 415 reaction with Grignards, 446
reaction with oxiranes, 622 ring expansion with diazomethane, 821
reaction with N-tosylaziridines, 411 synthesis, 811
reduction in benzene ring, 448 Isatoic anhydride, reaction with amines, 842
reduction to 2,3-dihydroindole, 422 Isobenzofuran, formation of [8 + 8] photodimers, 436
reduction to cis-octahydroindole, 430 1H-Isochromenes, by cyclizations of 2-alkynylbenzyl alcohols or 2-allyl­
ring expansion with dibromocarbene, 821 benzaldehydes, 826
sulfonation, 401 Isochromylium-4-olates, photolysis, 252
synthesis via arynes, 811 Isochrysohermidin–distamycin hybrids
, 694
tautomerism, 133 Isocyanides, reaction with nitrones, 710
thermolysis to 2-phenylacetonitrile and 2-methyl- and Isoflavones, 369
3-methylbenzenecarbonitriles, 387 Isoindole, Diels–Alder reactions, 434
1H-Indoles, 1H NMR spectra, 105 oxidation, 419
3H-Indoles, acid-catalyzed isomerisation, 437 pKa values, 398
3-Indoleacetic acid, 90 tautomerism, 133
3-Indoleacetonitrile
, 454 N-(Isoindolino)aziridines
, 639
Indole-2-carboxaldehydes, from quinoline, 815 Isoquinoline, 38
Indole-(2)3-carboxylates, synthesis, 810 mercuration, 270
Indole-2-carboxylic acid, flash vacuum pyrolysis, 456 nitration with dinitrogen pentoxide, 264
IR spectrum in solid phase, 119 nitration, 332
Indole-2,3-quinodimethanes, intermolecular cycloaddition reactions, 454 oxidation to cinchomeronic and phthalic acids, 271
Indoline, 91, 430, 801 oxidation to pyridinedicarboxylic acids, 333
synthesis via photochemically mediated cyclizations, 811 reaction with 2-chloro-4,5-dihydroimidazole, 910
3H-Indolium salts, 807 reaction with dimethyl acetylenedicarboxylate, 259
Indolizine, in acid, 421 reaction with ethoxycarbonylcarbene, 302
oxidation, 419 synthesis, 826
pKa values, 398 Isoquinoline-1-carboxamides
, 318
990 Index

isoquinoline 2-oxide, synthesis, 826 3-Lithio derivative of 1-benzenesulfonylindole, instability, 462

Isoquinoline–sulfur trioxide, ring fission, 277 Litho-derivatives of indole, 462
1-Isoquinolone
, 274, 828 3-Lithio-2,5-dimethylselenophene, ring opening, 466
Isothiazole
, 717 2-Lithioimidazoles, reactions, 588
irradiation, 485 4(5)-Lithioimidazoles, rearrangements to 2-lithioderivatives, 588
orientation of electrophilic reactions, 502 2-Lithioindole, formation and reactions, 462
react with hexacarbonyls, 491 5-Lithioisothiazoles, reactions, 588
reductively desulfurized by Raney nickel, 536 2-Lithio-3-methoxypyridine
, 298
Isothiazolo-3-sulfolenes, thermolysis, 541 2-Lithio-1-methyl-5-octylpyrrole, reaction with N-fluoro-N-(phenylsulfo­
Isoxazole, synthesis by 1,3-dipolar cycloadditions, 718 nyl)benzenesulfonamide, 465
conversion to acids and nitriles, 531 3-Lithiomethyl-4-phenylsydnone
, 526
general method of synthesis, 714 2-Lithiomethylpyridine, formation and reactions, 337
halogenations, 505 2-Lithio-1-methylpyrrole, reaction with sulfur, 464
metallation leads to ring opening, 526 2-Lithiooxazoles, in equilibrium with open chain forms, 526
orientation of electrophilic reactions, 502 4-Lithio-3-phenylsydnone, reaction with copper(I) bromide, 589
rearrangements, 484 5-Lithioquinolines, coupling reactions, 336
ring contraction, 676 2-Lithiotellurophenes, formation and reactions, 462
ring opening, 530 2-Lithiothiazoles, reactions , 588
solubility, 187 3-Lithiothiophene, 677
with electron-withdrawing substituents, as dienophiles, 542 Lithium a-bromoenolates, reaction with sulfinimines, 660
Isoxazolidines, as masked 1,3-amino alcohols, 553 Local p-deficiency (LOCpD), 47
by 1,3-dipolar cycloadditions of nitrone or nitrone esters and alkenes, 719 Losartan, tautomerism, 202
reactions, 554 2,4-Lutidine, regioselectivity of deprotonation, 337
Isoxazolinones, 716 2,6-Lutidine, alkylation, 258
Isoxazolinones, general methods of synthesis, 716 nitration, 263
Isoxazolium salts, reduction, 523
Isoxazolo[3,4-d]thiazoles, 577
(b-Isoxazol-4-yl)-a,b-dehydroamino acids
, 721 M
Madelung synthesis of indole, 812
Magnetic criteria of aromaticity of five-membered heterocycles with more
J than one heteroatom, 193
Jacobson–Hugershoff synthesis, 838 Magnetic susceptibility anisotropy, in estimating aromaticity, 77
Mannich reactions, in synthesis of pyrrolidines, 663
Mass spectrometery of five-membered heterocycles with more than one
K heteroatom, 184
Ketazines, conversion into pyrroles under strongly acidic conditions, 686 Meerwein rearrangement to give benzo[b]furanones, 814
Ketenes, cycloaddition with diazo compounds, 709 Melamine
, 788
b-Keto esters, reaction with an aldehyde and ammonia, 689 Melting and boiling points of heterocycles, 73
reaction with an a-amino ketone, 683 Melting points, of five-membered heterocycles, 126
reaction with hydrazine or hydroxylamine, 716 30-Membered hexaazamacrocycle, anion recognition, 218
Ketoximes, reaction with alkynes, 686 12-Membered ring triazacycloalkanes, pKa values, 613
Knoevenagel synthesis, 685 b-Mercaptoacylamines, cyclization to thiazolines, 741
Knorr pyrrole synthesis, 683 o-Mercaptobenzaldehyde, 420
Kojic acid, 352 2-Mercaptobenzo[b]thiophene, tautomerism, 137
coupling with diazonium salts, 270 2-Mercaptobenzoylhydrazide, reaction with formaldehyde, 868
Koopmans theorem, 36 3-Mercapto derivatives of benzothiophene, 138
Kostanecki–Robinson synthesis of coumarins, 816 2-Mercapto derivatives of furan, thiophene, selenophene, and
Kuanoniamine A
, 838 pyrrole, tautomerism, 137
3-Mercapto derivatives of furan, tautomerism, 138
3-Mercapto derivatives of indole, tautomerism, 138
L 3-Mercapto derivatives of selenophene, tautomerism, 138
L’abbe rule, 541 3-Mercapto derivatives of thiophene, tautomerism, 138
b-Lactams
, 662 2-Mercapto-20 ,40 -dinitrodiphenylamines, cyclization, 882
alkylation at C(3), 627 b-Mercaptohalides, formation of thiiranes, 659
are oxygen bases. 613 2-Mercapto-1-methylpyrrole
, 443
by carbenoid insertions, 667 2(4)-Mercaptopyridine, tautomerism, 82
ring expansion to give 1,2-oxazinones, 727 5-Mercapto-1,2,3,4-thiatriazole, oxidation to disulfide, 581
Lactones, natural abundance 17O NMR spectra, 66 5-Mercapto-1,2,3-thiazoles, tautomerism, 581
Ladenburg rearrangement, 377 5-Mercaptothiazoles, tautomerism, 581
Lawesson’s reagent, in conversion of pyridines to thiopyridones, 355 Mercury(II) acetate, reaction with five-membered heterocycles, 416
Leimgruber–Batcho indole synthesis, 804 2-Mesityl-3,4-di-tert-butylazete, 231
Levulinic acid
, 453 Mesoionic compounds, Type A and Type B, 36, 143
Lipoic acid, 144 Mesoionic 5-oxidothiazolium systems, 740
a-Lithiated aryloxiranes, addition to aryl nitrones, 711 Mesoionic 4-trifluoroacetyl-1,3-oxazolium-5-olates, reaction with
2-Lithiated imidazoles, 13C chemical shifts, 170 phenylhydrazine, 720
N-Lithioaziridines, thermolysis, 635 Mesomeric betaines, 36
3-Lithiobenzo[b]furan, ring opening, 465 Metalloenamines, 637
2-Lithiobenzo[b]thiophene, conversion to 2-hydroxybenzo[b]thiophene, 464 N-Methoxy(2-arylethane)sulfonamide, reaction with
2-Lithio-1-Boc-indole, reaction with triisopropyl borate, then coupling [hydroxyl(tosyloxy)iodo]benzene, 834
reactions, 468 2-Methoxy-3H-azepines
, 562
2-Lithio-3-bromofuran
, 420 N-Methoxycarbonyl-3,4-dihydropyrrole, Vilsmeier formylation, 440

2-(Methoxycarbonyl)nicotinic acid
, 344
2-Methoxycarbonylpyrrole, flash vacuum pyrolysis, 456
3-Methoxycarbonylpyrrole, 470
4-Methoxy-dibenzo[1,4]thiazepin-2-one
, 886
4-Methoxy-2,6-dimethylpyrylium cation, displacement reactions, 356
3-Methoxyfuran, reaction with dienophiles, 431
1-Methoxyisoquinoline, rearrangement, 250
4-(Methoxymethyl)-2-methylindole
, 804
2-Methoxy-4-methylquinoline, rearrangement, 250
4(5)-Methoxy-5(4)-nitroimidazole, tautomerism, 200
2-Methoxyoxazolidines, in asymmetric formylation of various
nucleophiles, 555
o-Methoxyphenol, reaction with sulfur dichloride, 884
Methoxypyrans, 279
2-Methoxypyridine
, 301, 354
4-Methoxypyridine 1-oxide, halogenations, 268
1-Methoxypyridinium salts, ring fission, 277
2-Methoxypyrrole
, 457
3-Methoxy-1,2,3,4-tetrahydrocinnolines, synthesis, 833
2(3)-Methoxythiophene
, 460
4-Methoxy-1,2,3-triazine, lithiation, 299
2-Methyl-3-acetylpyrrole, 684
Methyl acrylate, cycloaddition with N0 -thiobenzoyl-N,N-dimethylforma­
midine, 751
10-Methylacridinium ions, formation of pseudo bases, 276
N-Methylacridinium, reaction with sodium amide, 283
2-(1-Methylallyloxy)pyridine, rearrangement, 357
5(6)-Methyl-N-alkyluracils, oxidation, 271
o-Methylaminobenzamide, reaction with ethylene oxide, 851
2-Methylaminopyrimidine
, 348
1-Methyl-2-aminopyrimidinium iodide, Dimroth rearrangement to
2-methylaminopyrimidine, 348
3-Methyl-3H-azepine, ring inversion, 234
2-Methylazines, mass spectra, 71
N-Methylaziridine, barrier to pyramidal inversion of the nitrogen
atom, 233
2-Methylaziridine, 15N NMR spectra 225
N-Methylbenzimidazole, arylation, 591
dimerisation, 532
15
N NMR studies, 173
1-Methylbenzimidazol-2-yl-silanes, reaction with acyl halides, 529
6-Methylbenzothiazole, nitration, 559
1-Methylbenzotriazole, lithiation on methyl group, 595
1(2)-Methylbenzotriazole, tautomerism, 201
1-Methyl-2-benzoyloxypyrrole
, 427
1-Methyl-3-benzyl-3-methyldiaziridine, resolution, 234
9-Methylcarbazole, pKa, 388
N-Methylcarbazole, study of protonation by NMR, 112
2-Methylchromylium, reaction with benzaldehyde, 340
2-Methyl-5-cyanobenzothiazole, bromination of methyl group, 562
2-Methyl-6-cyanobenzothiazole, bromination of methyl group, 562
2-Methyl-3-cyano-4-ethylpyrrole, 684
2-Methyl-3-cyano-5-trifluoromethylpyrrole
, 684
5-Methyl-5H-dibenzo[b,e][1,4]diazepin-11(10H)-one
, 884
1-Methyl-2,5-dibromoimidazole, to dilithium derivative, 587
10-Methyl-9(R)-9,10-dihydroacridines, oxidative aromatisation, 319
2-Methyl dihydrofuran
, 673
Methyldihydrooxepines
, 696
1-Methyl-1,2-dihydropyridine, reaction with methyl acrylate, 323
2-Methyl-4,5-dinitroimidazole
, 602
1-Methyl-2,5-dinitropyrrole, reaction with thiol anions, 447
1-Methyl-3,4-dinitropyrrole, reaction with sodium methoxide, 457
cine-substitution with secondary amines, 458
1-Methyl-2,5-diphenyl-4-styrylimidazole, oxidation, 570
3-Methyl-1,2-dithiolyliums, reaction with aldehydes, 566
3-Methyleneazetidin-2-one, conjugative addition, 638
Methylene blue, oxidation, 335
Methylenecyclobutane, ring strain, 231
3-Methylene-2,3-dihydrofuran, 456
4-Methylene-2-imidazolinones
, 744
4-Methyleneoxetan-2-one, ring strain, 231
Index 991
Methylene-substituted 2-oxetanones, reactions, 624
2(3)-Methylfuran, microwave spectroscopy, 128
5-Methylfuran-2-carboxaldehyde, bromination, 402
Methyl furan-2-carboxylate, cyclopropanation with ethyl
diazoacetate, 424
Methyl 6H-furo[2,3-b]pyrrole-5-carboxylate, 97
Methylfuroxans, reaction with alkoxides, 565
1-Methylgramine, lithiation, 448
reactions, 454
3-Methyl-4-a-hydroxypropyl-4,5-dihydroisoxazole, reductive ring
opening, 551
1-Methylimidazole, dimerization, 535
15
N NMR studies, 173
2-Methylimidazole, solid state NMR and tautomerism, 200
1-Methylimidazole-5-carbaldehyde, Wittig reactions, 569
1-Methylimidazo[1,2-a]imidazole, formylation, 509
(1-Methylimidazol-2-yl)thioglycolic acid, 897
N-Methylindole, formation of metal complexes followed by reaction with
nucleophiles, 448
study of protonation by NMR, 112
1(3)(5)-Methylindole, adiabatic ionization energies, 125
2-Methylindole, nitration in 5-position, 447
1-Methylindole-7-carbaldehyde
, 448
3-Methylindole-2-carbaldehyde
, 419
4-(3-Methylindol-1-yl)butanoic acid
, 389
N-Methylisoindole
, 824
formation of [8 + 8] photodimers, 436
Methyl isonicotinate, complex with chlorine, 260
3-Methylisothiazoles, oxidation of methyl groups, 562
Methyl 3-methyleneazetidine-1-carboxylate, epoxidation, 638
Methyl nicotinate, complex with chlorine, 260
reaction with phenyl chloroformate and reduction, 323
5-Methyl-4-nitrobenzofuroxan, rearrangement, 152
7-Methyl-4-nitrobenzofuroxan, theoretical studies of formation by
rearrangement of 5- methyl-4-nitrobenzofuroxan, 152
2-Methyl-5-nitrofuran
, 397
2-Methyl-4-nitroimidazole
, 602
Michael reactions, 497
2-Methyl-1-nitroindolizine
, 400
3(5)-Methyl-4-nitropyrazole, existence of desmotropes, 199
2-Methyloxazole, formation of side chain anion, 563
1-Methyl-2-phenylimidazole, structure, 195
1-Methyl-4-phenylimidazole, structure, 195
1-Methyl-5-phenylimidazole
, 591
5-Methyl-3-phenylisoxazole, nitration, 567
5-Methyl-3-phenyl-1,2,4-oxadiazole, reaction with benzaldehyde, 564
4-Methyl-2-phenyl-5-oxazolinone, reaction with phenylmagnesium
bromide, 520
1-Methyl-2-phenylphenanthro[9,10-d]imidazole
, 321
3-Methyl-2-phenylphenol
, 429
1-Methyl-2-phenylthioindole
, 459
1-Methyl-3-phenylthioindole, acid-catalyzed rearrangement, 459
2-Methylphthalazinium ion, reaction with hydroxide ions, 278
2-Methylphthalazin-1-one
, 278
N-Methylpiperidine, oxidation, 328
Methyl propargyl carbonate, reaction with b-ketoesters, 685
2-Methylpyran-4-ones, reaction with benzaldehyde, 339
N-Methylpyrazole, coupling constants in 1H NMR, 162
coupling constants, 173
metallation, 526
1-Methylpyrazole 2-oxide, nitration, 503
3-Methylpyridazine, reaction with aldehydes, 339
3-Methylpyridines, side-chain deprotonation, 337
1-Methylpyridinium ion, reaction with hydroxide, 276
reduction, 296
3-Methyl-pyridinium methiodides, base-catalyzed hydrogen–deuterium
exchange, 300
2-Methylpyridinium salts, formation of anhydro-bases, 340
1-Methylpyridin-4-one, base-catalyzed hydrogen–deuterium
exchange, 300
1-Methyl-2-pyridone, pyrolysis, 250
992 Index
2(4)(6)-Methylpyrimidines, reaction of methyl groups, 339
1-Methylpyrrole, chlorination, 402
copper-promoted reaction of ethyl 2-diazoacetoacetate, 425
deprotonation by n-butyllithium, 420
reaction with dimethyl acetylenedicarboxylate, 433
2-Methylpyrrolidine
, 328
4-Methylpyrylium salts, reaction with acetic anhydride, 341
2-Methylquinazoline
, 363
1-Methylquinolinium ion, formation of pseudo bases, 276
reaction with cyanide, 292
reduction, 296
4-Methyl-2-quinolone
, 817
2-Methyl-4-quinolone
, 817
2-Methyl-substituted benzo[b]thiophenes, 804
1-Methyl-1,2,3,6-tetrahydropyridine
, 296
1-Methyl-1,4,5,6-tetrahydropyridine
, 328
stability, 326
6-Methyl-2,3,4,5-tetrahydropyridine, deprotonation, 326
1-Methyl-1,2,3,4-tetrahydroquinoline
, 297
1-Methyl-2,4,4,6-tetraphenyl-1,4-dihydropyridine, spectra, 56
1-Methyltetrazol-5-yllithium, decomposition, 589
2-Methylthiazole, reacton with DMAD, 909
2-Methylthiazolium salts, reaction with dicarbonyl compounds, 907
2-Methylthiodithiolylium iodide, reduction, 536
2-Methylthiofuran, Diels–Alder reactions, 432
3-Methylthiophene, bromination or oxidation, 449
metallation, 420
2-Methylthiophene-3-carboxylic acid, dilithiation, 462
regioselective side-chain lithiation, 462
3-Methylthio-1,2,4-thiadiazole, displacement of methylthio group by
hydrazine, 583
4-Methyl-1,3,5-triazines
, 791
2-Methyltriazole 1-oxide
, 770
3-Methyl-5-tributylstannylisoxazole, ipso substitution with iodine, 505
1-Methyl-2-[(trimethylsilyl)sulfanyl]-1H-pyrrole, desilylation, 443
1-Methyl-5-trimethylsilyl-1H-1,2,4-triazole
, 510
6-Methyluracils
, 752
Methyl vinyl ethers, reaction with aziridines to give pyrrolidines, 668
Microwave-assisted Fischer indolization, 807
Microwave spectroscopy of indoles, 99
Minisci reactions, 303
Mitomycin C, 211
Mitsunobu reaction, 258, 659, 662
Modified neglect of differential overlap (MNDO), 33
Molecular mechanics, 35
Molecular Orbital PACkage (MOPAC), 34
Monocyclic rearrangements, 651
Monocyclic 1,2,3-triazines, 774
Monomethine cyanines
, 566
N-(Monosubstituted amino)pyridiniums, prototropic equilibria, 378
M€unchnones, cycloadditions, 539
1,3-dipolar cycloaddition reactions with imines, 746
Muscone, 407
N 1-Nitropyrazoles, rearrange to 4-nitropyrazoles, 601
Naphtho[1,8-c,d]dichalcogenols, 886
1H-Naphtho[1,2-d]imidazole, aromaticity, 193
Naphtho[2,3-d]imidazole, aromaticity, 193
Naphtho[2,3-d]-1,2,3-oxadiazole, valence tautomerism, 207
Naphtho[b,c]thiete
, 886
Naphtho[1,8-d,e]triazine derivatives, 886
1-Naphthyl-1,2,3-triazole, photolysis, 886
1,7-Naphthyridinium-4-olates, 42
Nascent sulfur, in preparation of thiiranes, 656
Neber rearrangement of oxime sulfonates, 674
Neglect of diatomic differential overlap (NDDO), 33
Nenitzescu indole synthesis, 802
N-Heterocyclic carbenes, 36
Nickel boride, desulfurization of benzo[b]thiophene and dibenzothio­
phene, 430
NICS value, in estimating aromaticity, 36, 78-see also Nucleus-independent
chemical shifts
Nifedipine, 40
Nine-membered heterocyclics, nomenclature, 213
Ningalin A
, 694
Nipecotic acid, spectra, 57
1,3-Nitramine nitrates
, 615
Nitration, of azoles, 503
Nitrene generation, 655
Nitriles, reaction with acylhydrazides, 777
reaction with dicyandiamide, 788
reaction with functionalized oxiranes, 621
Nitrile sulfides, 1,3-dipolar cycloaddition with nitriles, 781
formation, 480
o-Nitroanilines, reaction with dihydroxybenzenes, 882
Nitroanilinocyclohexenones, cyclization, 882
o-Nitroanilinopyridines, cylization, 882
6-Nitroanthranil, ring opening by amines, 516
N-Nitroazetidines
, 615
2-Nitrobenzaldehyde arylhydrazones, reaction with halogens, 859
2-Nitrobenzenesulfonyl chloride, reaction with w-aminoacetophenone,
867
2-Nitrobenzimidazole
, 575
Nitrobenzofuroxans, reaction with dienes, 542
4-Nitrobenzofuroxan, rearrangement, 562
1-Nitrobenzotriazole, valence tautomerism, 208
2-Nitrobenzyl triphenylphosphonium ylide, reaction with aryl
isocyanates, 831
o-Nitrobiphenyls, pyrolysis with iron(II) oxalate, 876
o-Nitrocinnamic acid, formation of 2-quinolone, 815
6-Nitrocoumarin
, 333
o-Nitrodiphenylamines, reduction, 882
2-Nitrofuran
, 400
addition of Grignard reagents, 423
5-Nitrofurfural diacetate
, 400
2-Nitroimidazoles, 574
4(5)-Nitroimidazoles, 13C chemical shifts, 171
tautomerism, 200
3-Nitroindazole
, 559
3-Nitroindoles
, 391, 400
4-Nitroisothiazoles, reduction, 576
Nitroketene dithioacetate, reaction with dibromomethane, 734
a-Nitroketoximes, dehydration, 772
3-Nitro-4-methoxypyridine, displacement of methoxy group, 356
2-Nitromethylene-1,3-dithietane
, 734
Nitrones, addition to isocyanides, 710
Nitrophenols, 292
1-(4-Nitrophenyl)azoles
, 496
1-(2-Nitrophenyl)benzimidazole, deoxygenation, 895
2-Nitrophenylhydrazones, reduction, 861
1-(2-Nitrophenyl)imidazole-2-carbaldehyde, ring closures, 569
4-Nitro-3-phenylisoxazole, thermal rearrangement, 484
4-Nitro-2-phenyloxazoles
, 484
2-Nitro-1-(phenylsulfonyl)indole, nucleophilic substitutions with eno­
lates, 423
4-Nitropyrazoles
, 601
2(4)-Nitropyridines, reactions, 349
4-Nitropyridine
, 368
2(4)-Nitropyridine N-oxides, reactions, 349
4-Nitropyridine 1-oxides, reactions, 698
N-Nitropyridiniums, as mild nitrating agents, 379
5-Nitropyrimidin-2-ones, to nitrophenols, 292
2-Nitropyrrole
, 399
reaction with chloromethyl sulfones, 423
3-Nitropyrrole
, 400, 687
5-Nitroquinoline
, 332
8-Nitroquinoline
, 332
6-Nitro-2-quinolone
, 333
6-Nitro-2,3,4,5-tetrahydro-1H-1,4-diazepines
, 765
Nitrosoarenes, addition to diphenylketene, 710
Nitroso compounds, [2 + 2] cycloaddition to alkenes, 710
 Index 993

N-Nitrosoglycine derivatives, reaction with acetic anhydride, 774 6H-1,3,5-Oxathiazines, thermally induced retro[4 + 2]-cycloconversion in
3-Nitrosoindole
, 391, 417 presence of sulfur, 782
1-Nitroso-2-naphthol, reaction with alkenes, 847 Oxathiazole, cycloaddition reactions, 538
2-Nitrosophenolates, reaction with DMAD, 847 1,2,3-Oxathiazole S-oxides
, 772
2-Nitrosopyridine, reaction with 1,3-dienes, 351 1,2,4-Oxathiazolines, thermolysis, 549
Nitrostyrenes, reduction, 804 1,3,4-Oxathiazolones, decarboxylation, 480
Nitrothiophenes, vicarious nucleophilic substitution (VNS) of 1,2-Oxathietane 2,2-dioxides
, 713,
13
hydrogen, 422 C NMR spectra, 225
2-Nitrothiophenes, reaction with carbanions, 423 1,4-Oxathiins
, 760, 762
2(3)-Nitrothiophenes, reduction by tin and HCl, 457 1,2-Oxathiin 2,2-dioxides, general method of synthesis, 726
3-Nitrothiophene
, 465 1,3-Oxathiin-6-ones
, 751
13
C-NMR spectra of five-membered heterocyles, 108 1,2-Oxathiolane derivatives, 1H NMR studies, 167
1
H-NMR spectra of five-membered heterocycles containing more than 1,2-Oxathiole, derivatives, 1H NMR studies, 167
one heteroatom, 160 1,2,4,5-Oxatriazine-3,6-diones
, 795
15
N-NMR spectra, 64 1,2,3,4-Oxatriazole derivatives
, 794
17
O-NMR spectra, 66 theoretical studies, 152
studies of azoles, 173 instability, 208
studies of five-membered heterocycles with more than one 1,4-Oxazepanes
, 767
heteroatom, 167 Oxazepines
, 767
Nomenclature of heterocyclic compounds, 31, 32 1,2-Oxazepines, 731
of heterocyclic rings, 211 1,4-Oxazepines
, 768
of three and four-membered heterocycles, 211 Oxazepinones, synthesis, 851
Nuclear Overhauser effect, in 1-substituted 1,3-Oxazepinones
, 756
1H-1,2,3-triazoles, 163 1,3-Oxazetidin-2-ones
, 733
Nucleus-independent chemical shift, in measuring aromaticity of five- 1,2-Oxazetidines, general methods of synthesis, 710
membered heterocycles, 128 2H-1,2-Oxazines, ring opening, 253
Nucleus-independent chemical shifts of five-membered heterocycles with 1,2-Oxazine derivatives, asymmetric synthesis, 649
more than one heteroatom, 151 1,2-Oxazines
, 723
Nucleus-independent chemical shift parameters, in evaluation of by Diels–Alder reactions, 724
aromaticity, 49 thermal pericyclic reactions, 322
Nucleus-independent chemical shift values of five-membered 4H-1,3-Oxazines
, 749
heterocycles, 98 deprotonation and isomerisation, 322
1,4-Oxazines
, 762, 763
1,3-Oxazinium perchlorates
, 751
O Oxazin-4-ones
, 750
cis-Octahydroindole
, 430 1,3-Oxazin-4-ones, photocycloaddition of ketene acetals, 313
Octapyrrol-1-ylnaphthalene
, 389 1,3-Oxazin-6-ones
, 750, 752
Oligopyridine, metal complexes, 257 isomerisation, 253
Optically active aziridines, 637 pyrolysis, 250
Organyl azides, decomposition to nitrenes, 655 reaction with amines, 753
Outcome of theoretical studies of heterocycles, 32 Oxazinones, general method of synthesis, 722
1-Oxa-2-azaspiro[2.5]octane, N-O cleavage, 628 1,4-Oxazinones
, 763
6-Oxa-5,8-diazabenzocycloheptenes, synthesis, 866 Oxaziridines, 653
1-Oxa-2,4-diazines
, 783, 784 barrier to pyramidal inversion of the nitrogen atom, 233
1,3,4-Oxadiazinan-2-one derivatives, reaction with bromobutyryl preparation by oxidation of imines by peracids, 707
chloride, 914 ring opening to nitrones, 236
1,3,5-Oxadiazine
, 790 Oxazocine, structure, 235
1,3,5-Oxadiazinimine
, 790 1,4-Oxazocine, as 1,3-dienes, 633
1,3,5-Oxadiazinium salts
, 790 stability, 217
conversion to 1,3,5-triazines, 791 Oxazole, conversion to imidazoles with formamide, 516
reaction with hydroxylamine, 781 deuteration, 504
Oxadiaziridines
, 769 Diels–Alder reactions, 537
Oxadiazoles, photolysis, 838 fast 2-deuteration, 528
1,2,3-Oxadiazole, impossibility to prepare, 192 formation of cycloadducts with dienophiles, to dihydropyridines, 693
1,2,4-Oxadiazoles
, 779, 781 mercuration, 507
catalytic reduction, 536 solubility, 187
mass spectra, 186 Oxazole-4-carboxylic acids, conversion into imidazoles, 746
reduction, 522 Oxazole-4,5-xylylene, formation and reactions, 542
1,2,5-Oxadiazoles, thermal and photochemical ring cleavage, 480 Oxazolidines, ring-chain tautomerism, 206
1,3,4-Oxadiazoles
, 775 Oxazolidinones, synthesis of penams, 890
intramolecular cycloadditions, 540 2-Oxazolidinones
, 742
1,2,4-Oxadiazolinone
, 777 Oxazolin-2-one, acetone-photosensitized photochemical addition to
1,3,4-Oxadiazolinones
, 509 ethylene, 543
ring opening by water, 516 Oxazolines from N-acylaziridines, 745
1,2,3-Oxadiazolium-5-olates
, 774 2-Oxazolines
, 744
3-(1,3,4-Oxadiazol-2-yl)pyridines
, 780 5(4H)-Oxazolinones
, 743
Oxaheterocinyl anions, NMR spectra, 232 Oxazolo[3,2-a]benzimidazoles, 899
1,10 -Oxalyldiimidazole, 598 2(3H)-Oxazolones, in thermal [4 + 2] cycloaddition reactions, 543
6H-1,3,5-Oxaselenaazines, rearrangements, 782 tautomerism, 206
1,3-Oxathiane, conformations, 78 Oxazolopyridines, synthesis, 837
Oxathiazines
, 775, 790 Oxazones, tendency to addition reactions, 248
994 Index

Oxepane, conformational analysis, 234 Pentazole, estimated pKa value, 146

cyclization of 1,6-diols, 665 spontaneous conversion to azides, 482
IR spectra, 227 4-Penten-1-ols, ruthenium-catalyzed oxidative cyclization, 673
Oxepins
, 702 Peracid, oxidation of alkenes, 653
diene complex with (tricarbonyl)iron, 637 2-Perfluoroalkylindoles, 426
spontaneous equilibrium with benzene oxide, 237 3-Perfluoroalkyl-1,2,4-oxadiazoles
, 517
theoretical studies, 216 5-Perfluoroalkyl-1,2,4-oxadiazoles, with hydrazine or
Oxetane, 644 hydroxylamine, 517
barrier to ring inversion, 233 2-Perfluoroalkylpyrroles, 426
cationic polymerisation, 614 Perfluoralkyl-substituted 1,3,5-triazines
, 789
general synthetic methods, 657, 663 3-Perfluoroalkylthiocoumarins
, 303
microwave spectra, 222 3-Perfluoroalkyl-1,2,4-triazoles
, 517
photoelectron spectroscopy, 230 Perfluoro-3-methyl-1-butyne, formation by ring opening of fluorinated
reaction with Grignard reagents, 623 triazines, 249
ring opening, 631 Perfluoropiperidine, 266
Oxetan-2-one, carbonyl frequency in IR spectra, 227 Perhydropyrrolo[1,2-b]isoxazoles, 900
ring strain, 231 Perimidine, 886
Oxetanones, conversion into methylene-oxetanes, 624 formation of anions and alkylation, 301
2-Oxetanone, basicity, 613 Perimidine-2-thiones, 284
general methods of synthesis, 657 Pfitzinger synthesis of quinoline-4-carboxylic acids, 816
nucleophilic reactions on, 624 N-Phenacyl-2-pyridones, cyclocondensation, 900
17
O NMR, 225 Phenanthridine, 38, 878
synthetic methods, 663 nitration, 332
4-Oxidothiazolium hydroxides
, 737 9-Phenanthridones
, 276
Oxime of 2,6-diphenylpiperidin-4-one, rearrangement, 766 1,10-Phenanthroline, 38
Oxindoles
, 802, 810 o-Phenanthroline, metal complexes, 257
synthesis via photochemically mediated cyclizations, 811 Phenazine, 38, 882
Oxirane, conversion to thiiranes by thiocyanate ion, 669 Phenazine 5,10-dioxides, 882
methods of formation, 653 Phenols, with b-keto esters give coumarins or chromones, 818
nucleophilic ring opening reactions, 621 Phenosafranine, reaction with alkali, 335
overview of reactivity, 211 Phenothiazine, 882
reaction with azides, 622 extrusion of sulfur, 877
reaction with dilute sulfuric acid, 765 oxidation to phenothiazinium salts, 315
reaction with iminophosphoranes, to give aziridines, 669 S-phenylation, 314
reduction, 631 structure, 52
valence tautomerism to 1,3-dipoles, 236 Phenothiazinium salts, tendency to addition reactions, 248
Oxirene, antiaromatic nature, 231 Phenothiazin-3-ones, 883
Oxirenes, antiaromatic character, 215 Phenoxathiin, 884
1-Oxo-2,3-dihydropyrrolizines, 891 structure, 52
Oxonin, 232 Phenoxazine, 882
3-Oxo-1,2,4-oxadiazepines
, 787 oxidation to phenoxazonium salts, 315
7-Oxo-1,2,6-oxadiazepines
, 787 structure, 52
Oxygen in rings replaced by a ring sulfur or nitrogen, 650 Phenoxazinium ions, tendency to addition reactions, 248
Phenoxazin-3-ones, 883
Phenoxyacetic acids, cyclization, 810
P Phenoxyphenyl 1,2,4-triazoles
, 779
Paal–Knorr synthesis for furans and thiophenes, 677 N-2-Phenylallylacetamide , conversion into 2,5-dimethyl-5-phenyl-2-oxa­
microwave promotion, 677 zoline, 744
Palladium(0) oxidative insertions on haloazines, 368 2-Phenylamino-5,5-di-(trifluoromethyl) 1,2,4-dithiazoline,
Palladium-mediated Stille coupling of bromopyrazines with conformation, 196
aryltributylstannanes, 370 5-Phenylaminothiatriazole, reversible rearrangement to 1-phenyl-5-mer­
Palladium-catalyzed intramolecular cyclization of imines onto alkynes to captotetrazole, 557
give indoles, 813 N-Phenylation of pyridines, 258
Paraherquamide A
, 809 Phenyl-azolones, electrophilic substitution often occurs in the benzene
Pariser–Parr–Pople (PPP) method, 33 ring, 502
Paterno–B€ uchi cycloaddition, 800 Phenyl azides, photolysis, 702
Paterno–B€ uchi reaction, 657 3-Phenyl-1,2,4,5-benzotetrazepine
, 870
Penams, synthetic routes, 890 2-Phenylbenzoxazole, dimerisation, 543
Penicillin, antibiotics, 212 2-Phenyl-4-benzoyl-1,3,4-thiadiazolium chloride, thermal rearrangement,
synthetic routes, 799 506
Pentaarylpyrroles, rotational barrier, 131 1-Phenyl-2-(2-n-butylthiophenyl)acetylene
, 424
2,2,3,4,5-Pentachloro-2H-pyrrole, 437 2-Phenyl-5-carboethoxythiazoline
, 742
N2-(6-Pentafulvenyl)formamidines
, 292 3-Phenyl-5-chlorotriazole 1-oxides, deprotonation, 527
Pentakis(pentafluoroethyl)-1-azaprismane, formation, 251 4-Phenylcinnoline
, 319
2,2,3,4,5-Pentamethyl-2H-pyrrole
, 391 4-Phenyldihydrocinnoline, disproportionation, 319
2,3,3,4,5-Pentamethyl-3H-pyrrole, isomerisation, 437 3-Phenyl-5,7-dimethoxybenzo[b]furan, formylation, 404
Pentane-1,5-diols, cyclization, 665 N-Phenyl-4,6-dimethoxycarbazole
, 875
Pentane-1,5-diones, ring closure, 698 4-Phenyl-1,2,3,5-dithiadiazolium chloride
, 794
Pentaphenyl-1,3-oxazepines
, 757 o-Phenylenediamine, reaction with 1,3-bis-carbon electrophile, 853
Pentasubstituted pyridines
, 700 reaction with nitrous acid, 858
Pentathiepinopyrroles, synthesis, 871 reaction with o-quinones, 882
Pentazine, 38 reaction with thionyl chloride, 858
 Index 995

2-Phenylethanol
, 441 Photoelectron spectroscopy and tautomerism, 73

N-(2-Phenylethynylaryl)methanethioamides, undergo 6-exo-dig Phthalamides
, 446
cyclization, 840 Phthalazines
, 854
Phenylhydrazides, conversion to oxindoles, 810 [2 + 4] cycloaddition with enamines, 307
Phenylhydrazine, reaction with mesoionic 4-trifluoroacetyl-1,3-oxazolium­ reduction, 295
5-olates, 720 Phthalic anhydride, reduction of one carbonyl, 446
1-Phenylimidazolidine, ring-chain tautomerism, 207 reaction with trimethylsilyl azide to afford 1,3-benzoxazine-2,4-diones, 842
Phenyliminooxalic acid dichloride, reaction with thioureas to Phthalide
, 446
thiazolidines, 744 Phthalimides, ring opening, 445
3-Phenylisothiazole, nitration, 567 Phthalocyanines, 825
4-Phenylisothiazole, nitration, 567 Phthalodinitrile, reaction with hydrazine, 854
1-Phenyl-5-mercaptotetrazole
, 557 o-Phthalonitrile, cyclization, 825
2-Phenyl-6-methoxyquinoline
, 821 Phthaloyl peroxide, loss of CO2, 800
2-Phenyl-4-methyl-4H-oxazolin-5-ones, reaction with imines, 746 2-Picolinamides, 299
3(5)-Phenyl-5(3)-methylpyrazole, low temperature NMR studies, 164 Picolines, nitration, 263
5-Phenyl-1,3,4-oxadiazole, hydrolysis, 531 2-Picoline
, 698
3-Phenyloxetane, reaction with phenyllithium, 623 benzylic sulfonylation, 337
2-Phenylpiperidine
, 305 reaction with acetic anhydride, 337
2-Phenyl-3-propylindole
, 807 3-Picoline, oxidation to nicotinic acid, 336
1-Phenylpyrazole, mercuration, 507 4-Picoline
, 698
metallation of phenyl ring, 593 Picolinoyl fluoride
, 342
nitration, 592 Pictet–Gams preparation of isoquinolines, 827
3(5)-Phenylpyrazole, low temperature NMR studies, 164 Pictet–Spengler synthesis of tetrahydroisoquinolines, 828
nitration in phenyl ring, 567 Piericidin
, 672
tautomerism, 200 Piloty–Robinson pyrrole synthesis, 686
a- and g-Phenylpyridines, nitration on phenyl ring, 341 Picolines, nitration, 263
2-Phenylpyridine 1-oxide, nitration, 341 Piperazine, 40
1-Phenylpyridinium cation, nitation and sulfonation, 377 Piperazines
, 762, 40
1-Phenylpyridinium-3-olate, irradiation, 311 Piperidine
, 40, 295, 297, 305,
reaction with benzyne, 311 aromatisation to pyridines, 327
4-Phenylpyrimidine-2(1H)-thione
, 753 13
C NMR spectra, 62
2-Phenylpyrrole
, 434 Polyaza-macrocycles, metal complexes, 614
Phenyl salicylates, reaction with benzamidines, 840 Polyfluorosubstituted pyrazolo[1,5-a]pyridines
, 378
3-Phenyl-5-substituted isoxazoles
, 715 Poly(pyrazol-1-yl)alkanes
, 497
1-Phenylsulfonyl-4,5-dihydropyrazole-3-diazonium tetrafluoroborate
, 547 Poly(1-pyrazolyl)borate ligands, 491
1-Phenylsulfonylindoles, reduction, 422 Polymer-supported a-silylnitrosoamides, cycloaddition with dimethyl
3-Phenylsydnone, Friedel–Crafts acylation, 506 acetylenedicarboxylate, 719
4-Phenyl-1,2,3,4-tetrahydrocinnoline
, 319 3(5)-4-Polymethylenepyrazoles, tautomerism, 200
5-Phenyl-1,2,3,4-thiatriazole, photolysis, 483 Polypyrrole, as a conducting polymer, 88
4-Phenyl-1,2-thiolylium salt, reaction with hydrazides, 721 Polythienyls
, 467
Phenyl N-tosylaziridine, reaction with acetonitrile affords imidazolines, 745 Pomeranz–Fritsch synthesis of isoquinolines, 828
1-Phenyl-1,2,4-triazole, pyrolysis, 593 Potassium N-(trifluoroboratomethyl)piperidine, 369
1-Phenyl-1,2,4-triazolium dicyanomethylide, 1,3-dipolar cycloaddition Primary amine, oxidation, 655
with dimethyl acetylenedicarboxylate, 544 Prins reaction yields 1,3-dioxanes
, 749
1-Phenyl-2-trimethylsilylacetylene, reaction with 5-bromopyrimidine, 371 Propadienethione
, 480
5-Phenyl-2-trimethylsilyltetrazole, flash vacuum pyrolysis, 481 1,3-Propanethiol, oxidation with iodine, 717
5-Phenylthiatriazole, photoloysis, 483 reaction with 1,2-dibromoethane, 769
3-Phenylthiazirine
, 483 Propargyl–allenyl anions, 644
2-Phenylthiirane, as sulfur donor, 656 Propargylamine, reation with carbon disulfide, 744
Phenylthioacetic acids, cyclization, 810 Propargylamine amides, cycloisomerization to oxazoles, 739
2-Phenylthio-5-alkylfurans, in preparation of 2,4-disubstituted Propiolactone, hydrolysis, 624
furans, 464 N-Protected 1,2-dihydropyridines, electrophilic reactions, 323
3-lithiation, 677 N-Protected-1,2,3,4-tetrahydropyridines, lithiation, 326
cis-(Phenylthio)stilbene
, 629 N-Protected 1,4,5,6-tetrahydropyridine, as an enamine, 326
2-Phenylthiophene, rearrangement, 387 Proton affinity of azoles, 490
3-Phenylthiophene,
387 Prototropic tautomerism, 36
4-Phenyltriazolinedione, as a dienophile, 543 Prototropic tautomers, in five-membered heterocycles, 133
1-Phenylurazole, reaction with diazomethane, 580 Pschorr-type cyclization of diazonium salts, 874
Phosphinine, NICS values, 78 Pseudocyanides, 292
1-Phosphorylimidazoles, 603 Pteridine
, 38, 643, 839, 845
phosphorylating agents, 603 reaction with ammonia, 282
Photochemical [2 + 2] cyclization between alkenes and carbonyl Purine, acidity, 490
compounds, 657 via Traube synthesis, 836
Photochemical cyclization of unsaturated imines to give quinolines, 819 Purine ring, anomalous numbering, 141
Photochemical isomerization of five- and six-membered rings, 649 2H-Pyran, from 1,3-diketones, 689
Photochemically initiated electrocyclizations, in formation of Pyran-2-one, 44
five-membered rings, 648 Diels–Alder reactions, 307
[2 + 2] Photocyclization of thiones to alkenes, 657 formation of unsymmetrical dimers, 312
Photocycloaddition, of benzaldehyde and trimethylsilyl cinnamyl ether, 657 irradiation, 253
[2 + 2] Photocycloadditions, 644 production of [2 + 2] photodimers, 313
Photoelectron spectra of five-membered heterocycles with more than one ring opening with hydroxide, 279
heteroatom, 186 2H-Pyran-2-ones
, 691, 692
996 Index

Pyran-4-one, 44 Pyridazino[4,5-d]pyridazines
, 855

photoisomerisation, 253 Pyridazino[4,5-d]pyridazin-1(2H)-ones
, 855
reaction with amines, 284 Pyridine, base-catalyzed hydrogen–deuterium exchange, 300
4H-Pyran-4-one, reaction with Danishefsky’s diene, 313 basicity, 245
Pyrano[3,2-b]pyrans, 13C NMR spectra, 62 catalytic hydrogenation, 305
4H-Pyrans
, 688 1
H chemical shifts, 54
13
Pyrans, aromatisation, 320 C chemical shifts, 59
2H-Pyrans, tautomerism, 82 complex with chlorine, 260
valence tautomerism, 83 complexes with metal ions, 256
Pyrantel, 89 conversion into 2-azabicyclo[2.2.0]hex-5-enes, 768
Pyrazine, 758, 759 effect of substituents on reactivity, 254
chlorination, 267 electrochemical reductions, 305
conversion to di-oxides, 261 electronic charge distribution, 45
lithiation, 299 halogenation, 246, 262, 266,
reduction, 295 halogenations and sulfonation in the 3-position, 698
o-Pyrazinediamines, reaction with glyoxal, 845 isoelectronic structure with benzene, 30
Pyrazino[2,3-d]pyridazine-5,8-dione
, 855 isotopic exchange reactions, 306
Pyrazinones
, 763 mass spectra, 70
2-(1H)-Pyrazinones
, 760 mercuration, 270
Pyrazinopyrazines
, 845 N-alkylation, 257
Pyrazole, alkylation, 494 nitration, 245
by 1,3-dipolar cycloadditions, 718 nucleophilic attack, 246
carrying a substituent on nitrogen, quaternisation, 492 nucleophilic reactions on, 272
chlorination, 504 photoisomerization to Dewar pyridines, 676
general method of synthesis, 714 reaction with acyl and sulfonyl halides and anhydrides, 258
nitration, 503 protonation, 254
orientation of electrophilic reactions, 502 reaction with alkyl radicals, 303
N-H bond length, 160 reaction with aryl and alkyllithiums, 285
reaction with 1-bromoadamantane, 506 reaction with boron, aluminum, and gallium trihalides, 261
reaction with chloroform, 532 reaction with dimethyl acetylenedicarboxylate, 259
reaction with reactive malonic acid derivatives, 912 reaction with 2,4-dinitrochlorobenzene, 258
tautomerism, 200 reaction with diphenyliodonium ions, 258
weaker base than imidazole, 148 reaction with halogens and interhalogens, 259
3H-Pyrazoles, photolysis to cyclopropenes, 545 reaction with hydroxide ions, 274
Pyrazole-3-diazonium ions, 547 reaction with hydroxylamine O-sulfonic acid, 261
2-Pyrazolines, protonation sites, 172 reaction with ozone, 271
site of protonation by 15N NMR spectroscopy, 175 reaction with phenyl radicals, 304
Pyrazolinones
, 716 reaction with Raney nickel, 304
3-Pyrazolin-5-ones, rearrangement, 485 reaction with sulfur trioxide, 261
5-Pyrazolinones, nitrosation, 508 reaction with sodium amide, 280
Pyrazolium-4-olates, 143 reaction with triplet diphenylcarbene, 302
Pyrazol-3-ones, 143 reaction with zinc or sodium to give radicals, 304
Pyrazolo[4,3-e][1,3,4]oxadiazine, ring transformation, 862 reduction, 294
Pyrazolo[1,2-a]pyrazole system, 913 reduction by organometallic hydrides, 295
cross-conjugated betaines, 912 reduction by samarium diiodide, 295
Pyrazolo[3,4-d]pyrimidines
, 538 regioselective a-lithiation, 299
Pyrazolo[3,4-d]thiazoles, 577, 838 ring fluorination, 285
3H-Pyrazolo[5,1-c]-1,2,4-triazoles, 903 sulfonation, 265
Pyridazine
, 722, 728 vapour-phase halogenations, 302
isomerization to pyrimidine, 250 3-Pyridineacetic acid, no tendency to decarboxylate, 343
photolysis to azetes, 676 Pyridine N-acylimides, thermolysis, 379
reaction with enolates, 288 Pyridine-2-carboxaldehyde, reaction with the allylindium reagent, 344
reaction with hydroxylamine O-sulfonic acid, 261 3-Pyridinecarboxaldehyde, reaction with trimethylsilyl cyanide, 344
reaction with maleic anhydride, 259 Pyridine carboxylic acids, decarboxylation, 342
reduction, 295 esterification, 342
UV spectra, 66 exist partly as betaines, 342
Pyridazine carboxylic esters, cycloaddition reactions, 307 Pyridine-2(4)diazonium ions, reactions, 347
Pyridazine-3,4-dicarbonitrile, reaction with hydrazine, 855 Pyridine-derived aminosulfonamides, reaction with urea, 864
Pyridazine-4,5-dicarbonitrile, cycloaddition reactions, 307 Pyridine–halogen complexes, dissociation, 382
Pyridazine-2,3-dicarboxylic acid derivatives, reaction with hydrazine, 855 “Pyridine-like” heteroatoms, difference to ‘pyrrole-like’ heteroatoms, 30
Pyridazine N-oxides, isomerisation, 380 Pyridine N-imides, photochemistry, 730
nitration, 264 Pyridine N-imines, 302
reaction with acetic anhydride, 280 Pyridine 1-oxide, 42
Pyridazinium-5-olate betaines, conversion to pyrimidin-4-ones, 252 base-catalyzed hydrogen–deuterium exchange, 300
3-Pyridazinones
, 723 13
C NMR shifts, 60
Pyridazinones
, 722 conversion into piperidines, 297
halogenations, 268 formation, 260
N-arylation, 375 halogenations, 268
Pyridazin-3(2H)-ones
, 723 in the Reissert–Henze reaction, 293
Pyridazino-oxazepine
, 851 irradiation, 380
Pyridazino[1,2-a]pyridazines, 914 mass spectra, 70
 Index 997

mercuration, 270 3,4-Pyridyne, 362

metallation, 298 2,3-Pyridyne N-oxide
, 362
nitration, 263, 264 Pyrimidine
, 748, 752
nucleophilic reactions on, 273 as azadienes in reactions with enamines, 307
17
O NMR spectra, 66 from pyridazine, 250
reaction with acetic anhydride, 280, 381 halogenations, 267
reaction with acyl halides and enamines, 292 isolectronic structure with benzene, 30
reaction with phosphorus oxychloride, 285 mass spectra, 70
reaction with sodium acetylide, 291 reaction with phenylmagnesium bromide, 286
reactivity, 247 Pyrimidine nitriles, nucleophilic displacement of nitrile group, 343
reduction, 380 Pyrimidine N-oxide, base-catalyzed hydrogen–deuterium exchange, 300
ring expansion, 650 Pyrimidinones, reaction with chlorotrimethylsilane, 354
sulfonation, 265 Vilsmeier–Haack reactions, 271
thioalkylation, 284 2-Pyrimidinones
, 747
Pyridine N-sulfides, 382 deuterium exchange, 266
Pyridine 1-sulfonylimides, 302 nitration, 264
Pyridinesulfonic acids, structure, 360 4-Pyrimidinones
, 747, 753
Pyridine–sulfur trioxide complex, reaction with sodium reaction with hydrazine hydrate, 781
cyclopentadienide, 289 2-Pyrimidin-2-thiones,
747
ring fission, 277 Pyrimidopyridazines, synthesis, 839
Pyridine-N-(2,4,6-trinitrophenyl)imine, nitration, 264 Pyrimidopyrimidines, synthesis, 839
Pyridinium cation, formation, 245 Pyrimidothiazinone, mass spectra, 72
electrochemical reductions, 305 5-Pyrimidylcerium dichlorides, 362
nucleophilic reactions on, 273 a,(g)-Pyrones, aminolysis, 694
reduction with sodium dithionite, 296 weak bases, 353
reaction with ketone enolates, 290 2-Pyrone, bromination, 262
Pyridinium-3-olates, 42 mass spectra, 72
as inner 1,3-dipoles, 311 4-Pyrone
, 688
photolysis, 252 mass spectra, 72
reaction with enes, dienes and trienes, 311 Pyrone-carboxylic acids, decarboxylation, 342
Pyrido[1,2-a]azepines, 911 Pyrrole, acylation, 403
Pyrido[1,2-a]azepinium system, 911 addition to alkynes, 392
Pyrido-1,2-diazepines, synthesis, 835 a-alkenylation with acetylenedicarboxylic ester, 410
Pyrido[3,4-d]pyridazine derivatives, synthesis, 855 arylation, 469
Pyrido[2,3-b]quinoxalines, 882 as a weak acid, 420
Pyrido[3,4-b]quinoxalines, 882 by addition of a-amino ketones to dimethyl
Pyrido[1,2-b][1,2,4]triazinium salts, 907 acetylenedicarboxylate, 685
Pyridones, C-alkylation, 410
IR spectra, 69 catalytic hydrogenation, 430
mass spectra, 71 electrophilic reactions on ring carbons, 396
N-arylation, 375 fragmentation patterns in mass spectrometry, 120
nucleophilic reactions on, 273 from 1,4-diketones and ammonia, 677
oxidation, 271, NMR spectra, 55 Gattermann aldehyde synthesis, 406
1
reactivity, 247 H NMR spectra, 105
structures, 41 halogenations, 401
tautomerism, 43 high degree of aromatic character, 386
weak acids, 301 libraries, 677
weak bases, 353 Mannich reactions, 414
2-Pyridone
, 274, 690 N-alkylation, 389, 390
anion formation and alkylation, 301 N-arylation, 391
conversion to chloropyridines, 354 N-arylation with arylboronic acids, 392
irradiation, 313 nitration, 399
reaction with diazomethane, 354 nitrosation, 417
2(4)-Pyridone, halogenations, 268 occurrence and isolation, 88
nitration, 264 oxidation, 417
reaction with amines, 284 photoinduced alkylation with diarylalkenes, 427
4-Pyridone
, 284, 688, 693 pKa values, 398
by condensation of nitriles with dianions of b-diketones or polymerisation in acid, 421
3-iminoketones, 690 reactions with aldehydes and ketones, 412
mercuration, 270 reaction with activated alkenes, 391
Pyridonecarboxylic acids, decarboxylation, 342 reaction with benzenediazonium salts, 416
Pyridothiazepinones, synthesis, 852 reaction with benzoylhydrazones, 415
2-Pyridylazide, 208 reaction with benzyl radicals, 426
Pyridylboronic acids
, 367 reaction with N-bromosuccinimide, 402
2-Pyridylcarbene, interconversion with phenylnitrene, 345 reaction with diazoacetic acid ester, 424
Pyridylgalactopyranoside
, 301 reaction with dichlorocarbene to give 3-chloropyridine, 701
4-Pyridylithium, reaction with gaseous dinitrogen tetroxide, 368 reaction with dichlorocarbene, 426
2-(4-Pyridyl)oxazoline, metallation, 298 reaction with dimethyl acetylenedicarboxylate, 433
1-(40 -Pyridyl)pyridinium chloride, 347 reaction with electrophilic alkenes, 408
2(4)-a-Pyridylthiazoles, bidentate chelating agents, 491 reaction with ethoxycarbonyl isothiocyanate, 408
Pyridynes
, 298 reaction with formaldehyde, 413
998 Index

Pyrrole, acylation (Continued) Quinoline N-imides, photolysis, 835

reaction with terminal aroylethynes, 409 Quinoline 1-oxides, bromination, 269
reaction with triphenylmethyl radicals, 427 photolysis, 842
ring hydrogen atoms exchange, 399 Quinoline pseudo base, disproportionation, 277
sulfonation with pyridine–sulfur trioxide, 400 5(7)(8)-Quinolinesulfonic acids
, 332
thermal stability, 386 Quinolinium ions, with ketone enolates, 290
thermolysis to (Z)- and (E)-1-cyanoprop-1-ene and 1-cyanoprop-2-ene, 386 Quinolizidine, quaternisation, 328
2-trifluoromethylation, 408 Quinolizidine–piperidine alkaloids, NMR spectra, 59
Vilsmeier–Haack reactions, 404 Quinolizinium cation, 38
Pyrrole-2-carbaldehyde, acetylation, 404 Quinolizinium ion, nucleophilic reactions on, 274
Pyrrole carboxylic acids
, 347 reaction with piperidine, 283
Pyrrole-2-carboxylic acids
, 694 2-Quinolone
, 274, 815
facile loss of carbon dioxide, 455 nitration, 264
Pyrrole-3-carboxylic acid, acidity, 455 photochemical addition of tetramethylethylene, 313
Pyrrole-2,5-dicarbaldehyde
, 405 4-Quinolone
, 816
Pyrrole Grignard reagents, 388 bromination, 268
Pyrrole[2,1-a]isoquinolines, 294 coupling with diazonium salts, 270
‘Pyrrole-like’ heteroatoms, difference to ‘pyridine-like’ heteroatoms, 30 nitration, 264
2H-Pyrrole 1-oxides, 1,3-dipolar cycloaddition with DMAD, 437 6-Quinolylalkanones
, 336
1H-Pyrrol-3(2H)-ones, C- and O-alkylation, 444 Quinolyl triflates, cross-coupling reactions with alkyl Grignard reagents, 335
Pyrrolethiols, preparation and properties, 459 Quino[7,8-h]quinoline, protonation, 255
Pyrrolidine, 90 Quinoxaline
, 845
formation of an N-nitroso derivative, 441 protonation, 255
fragmentation patterns in mass spectrometry, 122 Quinoxaline di-N-oxides
, 539
synthetic methods, 663
Pyrrolidine derivatives
, 658
Pyrrolizines, 892 R
Pyrrolo[1,2-a]azepines, 911 Radical cyclizations, 649
Pyrrolopyrazoles, 895 Ranitidine, 89
3H-Pyrrolo[1,2-b]pyrazoles, 894 Reactivity of small heterocyclic rings, 606
Pyrrolo[1,2-a]pyridine, numbering of ring atoms, 90 Reissert compounds
, 293
Pyrrolo[3,2-d]pyrimidines
, 312 deprotonation, 322
Pyrrolopyrrole, electron distribution, 94 Reissert indole synthesis, 802
1H,4H-Pyrrolo[3,2-b]pyrrole, 1H NMR spectra, 107 Resonance energy, definition, 75
Pyrrolothiadiazolines, 902 Richter method, 832
Pyrrolylacetic acids
, 694 Ring expansions of cyclic conjugated systems, 650
3-(Pyrrol-2-yl) aldehydes
, 409 Ring-chain tautomerism, 36
N-(Pyrrol-1-yl)pyridinium salts
, 379 Ring-closing metathesis, 674
1-(Pyrrol-3-yl)pyrroles, 677 in formation of indoles, 813
Pyrylium ion, isoelectronic structure with benzene, 30 Robinson–Gabriel synthesis, 737
Pyrylium-3-olate, 44 Rosindoles, 413
Pyrylium salts, one-electron reduction, 305 Rotamers, 36
reaction with amines, 701 [2]Rotaxanes, 85
reaction with hydroxide ions, 278 Rotenone, 91
reaction with hydroxylamine, 722
reaction with sodium sulfide, 284
S
Saccharin
, 832
Q N-alkylation and arylation, 498
Quinaldine, deprotonation of me group and reactions, 338 solid state studied by IR spectra, 179
Quinazoline, by the reaction of o-acylanilines with amides, 838 Salicylic hydrazide, reaction with acid chlorides, 868
nitration, 332 Salicylyl nitriles
, 531
protonation, 255 Samarium diiodide, in reduction of pyridines, 295
4-Quinazolinones, synthesis, 838 Saturated heterocyclic six-membered rings, ‘g-gauche effect’ in 13C spectra, 64
Quinazolyl-1-ols, reaction with aryl isocyanates, 866 Schmidt reaction, 667
o-Quinodimethane
, 328 Schr€odinger equation, 32
Quinoline, 38 Selenolo[3,2-b]selenophene, 17O NMR spectra, 111
amination, 281 Selenolothiophenes, UV spectroscopy, 115
electronic charge distribution, 45 Selenolo[2,3-b]thiophene, 17O NMR spectra, 111
nitration, 332 Selenophene, chloromethylation, 414
nitration with dinitrogen pentoxide, 264 electrophilic reactions on ring carbons, 395
nucleophilic attack, 246 fragmentation patterns in mass spectrometry, 120
oxidation to pyridinedicarboxylic acids, 333 from furans, 694
ozonolysis, 333 general synthesis, 686
1
phenylation, 333 H NMR spectra, 105
reaction with alkyl radicals, 303 reaction with dimethylmaleic anhydride, 435
reaction with dimethyl acetylenedicarboxylate, 259 reaction of Se with halogens, 393
reaction with sodium, 305 Selenopyrylium salts, reaction with anhydrous hydrazine, 730
reduction, 334 Semiempirical calculations, 33
via Michael addition reactions, 818 Sesamol, 144
Quinoline-2-carboxamides
, 318 Seven-membered heterocycles, by ring-closing metathesis, 675

nomenclature, 213
NMR spectra, 224
synthesis by ring expansion, 669
Seven-membered unsaturated heterocycles, UV spectra, 226
Sharpless asymmetric epoxidation, 653
Sildenafil, 40
N-(Silylmethyl)isoquinolin-1-one, 894
5-Silylmethylisoxazoles, reductive cleavage, 523
Singlet oxygen, addition to electron-rich alkenes, 712
SKF 89976A
, 756
Slater-type orbitals, 34
Sodium 2-furanylsilanolate, reaction with aryl iodides, 470
Sodium 1-methylpyrrole-3-sulfonate
, 400
Sodium salicylate, reaction with 2-chloroethanol, 852
Solubilities, of five-membered heterocycles, 126
Sonogashira reaction, 371
Spirothietanes
, 657
Spiro transition state, in epoxidation of alkenes, 653
Spirotriazolines, 544
Squamocin
, 664
2-Stannylpyrimidines, reactions, 361
Staudinger reaction, 657, 890
Stereoselective [3 + 2] annulation of allyl silanes, 658
Sterically shielded porphyrins
, 679
Stibinine, NICS values, 78
stability, 50
Stille reaction for the preparation of complex pyridine derivatives, 370
Strychnine, 91
Styrene oxide, from benzaldehyde, 654
Styryl isocyanates, cyclization to 1-isoquinolones, 828
b-Styrylthiophene
, 466
2-Substituents in 1,3-dithiolyliums, highly activated, 556
9-Substituted acridines, 880
1-Substituted 4-acylimidazoles
, 746
5-Substituted 3-acylisoxazoles
, 717
5-Substituted alkyltetrazoles, pyrolysis, 570
Substituted 3-aminofurans
, 694
N-Substituted aminopyrroles, Diels–Alder reactions, 433
Diels–Alder reactions with activated alkynes, 441
4-Substituted 2-aminothiazoles, sulfonation, 504
5-Substituted 2-amino-1,3,4-thiadiazoles
, 775
Substituted aziridines, in formation of azomethine ylides, 669
N-Substituted azoles, NMR studies, 168
2-Substituted 1,3-azoles, tautomerism, 204
4(5)-Substituted 1,3-azoles, tautomerism, 205
N-Substituted azonines, 232
N-Substituted benzimidazoles, amination, 517
direct hydroxylation, 513
lithiation in the 2-position, 525
3-Substituted benzo[b]furans, 806
Substituted 4H-3,1-benzoxazines, 841
N-Substituted 4-bromoisothiazolin-3-ones, coupling reactions, 590
o-Substituted cinnamoyl derivatives, conversion to quinolines, 815
Substituted cycloheptatriene endoperoxide, ring opening, 697
4-Substituted cyclohexanones, Schmidt ring expansion, 667
2-Substituted 1-b-cyanoethylpyrroles, Houben–Hoesch cyclization, 891
5-Substituted-4-cyanooxazoles
, 736
1-Substituted 1,2-diacylhydrazines, cyclization, 775
3-Substituted 2,4-dialkylpyrroles
, 677
6-Substituted 2,4-diamino-1,3,5-triazines
, 788
N-Substituted 4,4-diaryl-1,2-oxazetidin-3-ones, 710
Substituted 4,5-dihydroazepines
, 697
2-Substituted 1,2-dihydro-1,3-dithioles
, 521
1-Substituted dihydropyridines, aromatisation, 320
2-Substituted-1,2-dihydropyridines, irradiation, 324
N-Substituted 2,5-dimethylpyrroles, reaction with sulfuryl chloride, 871
Substituted 1,4-dioxins, thermolysis, 314
2-Substituted 4,6-diphenyl-1,3,5-triazines
, 368
2,3,4-Substituted furans, 678
a-Substituted heterocycles, vertical ionization energies, 123
Substituted hydrazines, reaction with 1,2-dihaloalkanes, 708
Index 999
Substituted 2-hydroxypyridines, tautomerism, 81
1-Substituted imidazoles
, 738
acylation, 529
quaternisation, 492
reaction with cyanogen bromide, 529
5-Substituted indoles, 15N NMR spectra, 112
3-Substituted-1H-indazoles, synthesis, 830
2-Substituted indolizines, 892
N-Substituted-3-iodoindoles, vinylation, 468
1-Substituted isoquinoline N-imides, photoreaction, 842
1-Substituted 2H-isoquinolin-3-ones, 826
3-Substituted isothiazoles, tautomerism, 203
5-Substituted isothiazoles, tautomerism, 204
3-Substituted isoxazoles, tautomerism, 203
5-Substituted isoxazoles, tautomerism, 204
1-Substituted-6-methyluracils
, 752
1-Substituted-2-nitroimidazoles
, 503
2-Substituted oxazoles
, 479
Substituted oxepines, 703
3,3-Substituted oxindoles, synthesis, 810
Substituted oxiranes, 17O NMR, 225
1-Substituted-perimidin-2-ones
, 274
3-Substituted-1-phenylpyrazol-5-ones, tautomerism, 204
Substituted 4- and 3-piperidones, 666
N-Substituted-pyrazoles, benzoylation, 506
direct lithiation, 525
3-Substituted pyrazoles, tautomerism, 203
5-Substituted pyrazoles, tautomerism, 204
3-Substituted 3H-pyrimidin-4-ones, general method of synthesis, 749
N-Substituted pyrroles, 2-lithiation, 677
rearrangements, 471
2-Substituted pyrrolidines
, 441
1-Substituted pyrrolidine 1-oxides, Meisenheimer-type
rearrangements, 727
2-Substituted quinazolines, synthesis, 841
3-Substituted b-sultams, asymmetric synthesis, 712
N(1)-Substituted tetrazoles, alkylation, 493
deuteration, 528
electrophilic iodination, 505
N(2)-Substituted tetrazoles, alkylation, 493
5-Substituted tetrazoles, tautomerism, 201
5-Substituted 1,2,3,4-thiatriazoles
, 793
Substituted thiazolo[3,2-a]benzimidazoles, 897
Substituted thiophenes, characteristic IR spectra, 117
3-Substituted thiophenes, from 3-lithiothiophene, 677
2-Substituted 4,5,6-triaminopyrimidines, reaction with
a-ketoaldoximes, 846
N-Substituted triazines
, 789
N-Substituted triazoles, 770
1-Substituted 1,2,3-triazoles, metallation, 527
oxidation, 500
2-Substituted 1,2,3-triazoles, alkylation with methyl fluorosulfonate, 493
1-Substituted 2,4,5-tribromoimidazoles, exchange reactions, 587
N-Substituted-3,4-trimethylenepyrazoles
, 716
Succinic anhydride, tautomers, 98
Sulfenes, cycloaddition with imines, 711
reaction with electron-rich alkenes, 657
Sulfinimines, reaction with lithium a-bromoenolates, 660
N-Sulfinyl- or thionitrosoarene dienophiles, cycloaddition with
dienes, 725
Sulfonation of azoles, 504
1-Sulfonylbenzotriazoles
, 604
1,10 -Sulfonyl-di(benzotriazole)
, 499
1,10 -Sulfonyldiimidazoles, 603
N-Sulfonyl-1,3,5-dioxazines
, 790
N-Sulfonylimines, cycloaddition with alkynyl ethers to give
functionalized 2-azetines, 671
N-Sulfonyl-1,3,5-oxadiazines
, 790
N-Sulfonyloxaziridines, barrier to pyramidal inversion of the nitrogen
atom, 234
N-Sulfonyl-1,3,5-triazines
, 790
1000 Index

Sulfur, reaction with an a-methylene carbonyl compound, and an 1,2,3,4-Tetrahydroquinoline
, 305

a-cyanoester, 680 5,6,7,8-Tetrahydroquinoline
, 334
d-orbitals, little role in bonding in thiadiazoles, 150 cis-1,2,3,4-Tetrahydroquinoline-2,3-dicarboxylic acids
, 552
Sulfur dichloride, reaction with alkynes, 656 Tetrahydroquinoline diones, by cascade [4 + 2] cycloaddition-acylation
Sulfur trioxide, addition to dienes, 726 reaction, 820
cycloaddition to alkenes, 713 Tetrahydroselenophene, structure, 132
Sulfur ylides, addition to imines, 656 1,2,3,6-Tetrahydro-1,2,3,4-tetrazines
, 795
as methylene transfer agents, 654 Tetrahydrothieno[2,3-d]pyrimidine-2-thiolates, reaction with
Suzuki–Miyaura reactions of pyridine systems, 368 a-bromoesters, 907
Swainsonine, 915 Tetrahydrothiin, 13C NMR spectra, 63
Swern oxidation of isopropenyl-substituted cyclopropylcarbinols, 696 Tetrahydrothiophene, 90
Sydnones, chlorination, 505 fragmentation patterns in mass spectrometry, 122
N-methyl, metallation, 526 structure, 132
thermal cycloadditions, 539 synthetic methods, 664
Tetrahydrothiopyrans
, 665
Tetramethylenediamine
, 295
T Tetramethylene dibromide, in synthesis of pyrrolidine and thiolane, 663
Tellurophene, electrophilic reactions on ring carbons, 395 1,2,4,6-Tetramethylpyridinium, nitration, 264
1
H NMR spectra, 105 1,2,3,4-Tetramethylpyrrole, methylation, 391
fragmentation patterns in mass spectrometry, 120 3,3,6,6-Tetramethyl-1,2,4,5-tetrathiane, conformations, 78
reaction of Te with halogens, 393 3,3,6,6-Tetramethyl-1,2,4,5-tetroxaane, conformations, 78
2-Tellurophenes, spectra, 124 2,3,4,5-Tetramethylthiophene, reaction with dicyanoacetylene, 436
Terminal alkynes, production of 1,4-disubstituted triazoles in 2,3,5,6-Tetraphenyl-1,4-dithiin
, 763
copper-catalyzed cycloadditions, 773 Tetraphenylhexaazaanthracene, structure, 53
Tetraarylselenophenes
, 688 Tetraphenyl-1,3-oxazepines
, 757
Tetraarylthiophenes
, 688 Tetraphenylthieno[3,4-c]thiophene, structures, 103
Tetraazamacrocycles, metal complexes, 614 Tetraphenylthiophene
, 688
pKa values, 614 Tetrasubstituted pyridazines
, 724
Tetraazapentalenes, 913 3,3,6,6-Tetrasubstituted 1,2,4,5-tetroxanes
, 796
2,3,4,5-Tetrabromopyrrole
, 402 Tetrathiafulvalenes, 144
2,3,7,8-Tetrachlorodibenzodioxin, 43 1,2,4,5-Tetrazin-3-ones, ring chain tautomerism, 83
2,3,5,6-Tetrachloro-1,4-dioxane, 762 Tetrazines, 38
Tetracyanoethylene oxide, reaction with 1,2,3-triazines, 259 protonation, 255
2,4,6,8-Tetraene, NMR spectra, 225 1,2,3,4-Tetrazine
, 544
2,3,4,5-Tetra(ethynyl)thiophene
, 467 1,2,4,5-Tetrazine, cycloaddition to 1-azirines, 785
1,2,3,4-Tetrafluorodibenzo[b,f][1,4]oxazepine
, 885 Diels–Alder reactions, 783
Tetrahydroazocinone
, 697 hydrolysis, 276
Tetrahydroazoles, aromatisation, 553 inverse electron demand Diels–Alder reactions with alkynes, 728
Tetrahydrobenzimidazoles
, 541 reaction with alkenes, 309
4,5,6,7-Tetrahydrobenzimidazole, synthesis, 643 reaction with donor-substituted carbenes, 309
Tetrahydro-3,2-benzothiazepine 3,3-dioxide
, 857 reaction with electron-rich alkenes, 728
Tetrahydrobenzothiins, synthesis, 819 ring opening, 248
Tetrahydrocarbazolones, 873 UV spectra, 67
4,5,6,7-Tetrahydro-1,2-diazepines
, 728 Tetrazole, pKa, 141
Tetrahydrofuran
, 629 HMO p-electron partial charges, 146
from diols, 663 thermolysis, 481
general methods of synthesis, 658 1H-Tetrazoles
, 793
MM2 calculations, 99 2H-Tetrazole, aromaticity, 192
reaction with n-butyllithium, 442 dipole moment, 160
structure, 132 gas phase stability, 191
synthetic methods, 664 stable complexes with metal ions, 491
2,3,5,6-Tetrahydro-imidazo[1,2-a]imidazoles, 896 Tetrazole ions as ligands for heavy metals, 491
Tetrahydroimidazo[2,1-b]oxazoles, 899 1,3(4)-Tetrazolium salts, X-ray structures, 157
2,3,5,6-Tetrahydroimidazo[1,2-d][1,2,4]thiadiazol-3-ones, 902 Tetrazolo[1,5-b]pyridazine, reduction, 523
Tetrahydroindazoles
, 541 Tetrazolopyridine, pyrolysis, 592
4,5,6,7-Tetrahydroindole
, 448 Tetrazolo[1,5-a]pyridine, flash vacuum pyrolysis, 481
1,2,3,4-Tetrahydroisoquinoline, thermal retro-Diels–Alder reaction, 328 valence tautomerism, 208
Tetrahydro-1,4-oxazin-2-ones
, 765 3-(5-Tetrazolyl)pyridines, acylation and rearrangement, 780
Tetrahydro-2H-1,2-oxazines
, 727 Tetrazolyl radicals, 510
Tetrahydrophthalazines
, 856 Thermally induced cycloreversion reactions in formation of nitrenes, 655
1,2,3,4-Tetrahydrophthalazine
, 295 3-Thia-1,5-diketones, reaction with amines, 761
Tetrahydropyran, 13C NMR spectra, 62 4H-1,2,4-Thiadiazine
, 785
spectra, 57 Thiabenzenes, oxidation, 316
2,3,4,5-Tetrahydropyridazines
, 724 Thiabenzene sulfoxides, nitration and bromination, 316
Tetrahydropyridine derivatives, synthesis by ring-closing metathesis, 674 Thiacrown ethers, 614
1,2,5,6-Tetrahydropyridines
, 294 Thiadiazepines
, 792
2,3,4,5-Tetrahydropyridines
, 673 1,3,5-Thiadiazepines
, 792
3,4,5,6-Tetrahydropyridine, as a trimer in solid phase, 326 Thiadiazines
, 789
Tetrahydropyrido[1,2-b]pyridazines, 909 1,2,6-Thiadiazines
, 774
Tetrahydropyrimidine
, 305, 752 1,3,4-Thiadiazines
, 785
Tetrahydroquinolines, 649, 819 2H-1,3,5-Thiadiazines
, 791
 Index 1001

2H-1,2,6-Thiadiazine 1-oxides, extrusion of sulfur monoxide, 316 Thiazole 2-halides, coupling reactions, 591
1,3,4-Thiadiazol-2-amines, Sandmeyer reactions, 575 reaction with azides , 584
Thiadiazoles, photolysis, 763 Thiazolidines
, 744
1,2,3-Thiadiazoles
, 770, 771 aromatisation, 553
ab initio calculations, 151 hydrolysis, 554
alkylation, 493 ring opening, 553
deuteration, 528 1,3-Thiazolidine, conformations, 198
matrix photolysis to 2-thiirenes, 675 Thiazolidine-2,5-dione
, 743
photolysis, 482 Thiazolidine-4,5-diones
, 744
rearrangement, 486 2-Thiazolines
, 744
1,2,4-Thiadiazoles
, 778 Thiazolium cations, reaction with anhydro bases, 521
ring interconversions, 557 Thiazolium salts, reaction with aldehydes, and dimethyl acetylenedicar­
1,2,5-Thiadiazole
, 314, 772 boxylate, 694
electronic structure of NSN fragment, 150 1,3-Thiazolium-4-olate, 144
reduction, 536 Thiazolo[3,2-a]benzimidazoles, 895
1,3,4-Thiadiazole
, 775, 776, 777 Thiazolo[2,3-b]pyridinium salts, 907
substituents, highly activated, 556 Thiazolo[3,2-a]pyridinium system, 899
1,2,3-Thiadiazole-4-carboxaldehydes, reaction with amines, 516 Thiazolo[5,4-d]pyrimidines, synthesis, 837
1,2,5-Thiadiazole-3,4-dicarbonitrile
, 772 Thiazolo[2,3-b]thiazolium salts, 897
1,3,4-Thiadiazole-2,5-dithione, as a spot test for bismuth, 491 2-Thiazolylthioureas, oxidation, 901
1,2,3-Thiadiazole 3-oxides, isomerisation, 602 2-Thiazolylzinc bromide, coupling with alkyl and aryl halides, 590
[1,2,5]Thiadiazole[3,4-b]pyrazines
, 763 Thiazones, tendency to addition reactions, 248
1,2,4-Thiadiazolidine, interconversion to 1,2,4-dithiazolidine, 540 Thieno-1,2-diazepines, synthesis, 835
1,2,3-Thiadiazoline
, 771 Thieno[2,3-c][1,2,5]oxadiazole N-monoxides, studies of isomers by NMR
1,2,4-Thiadiazolines
, 779 spectra, 164
Thiadiazoline 1,1-dioxides
, 518 Thieno[3,4-b]pyrrole 1,1-dioxide, reaction with DMAD, 451
1,2,4-Thiadiazolium salts, hydrolysis, 515 Thieno[3,2-d]thiazoles, synthesis, 838
reaction with amines, 518 Thienothiophene series, NICS values, 98
1
1,2,3-Thiadiazolo[4,5-d]pyridazines, synthesis, 856 H NMR spectra, 107
[1,2,4]-Thiadiazolo[2,3-a]pyridines, 901 UV spectroscopy, 115
6-Thiaellipticine
, 874 Thieno[3,4-c]thiophenes, structure, 95
2-Thianaphthylium ions, reaction with various butadienes, 915 N-(2-Thienyl)allene carboxamide, intramolecular cycloaddition, 433
Thianthrene, extrusion of sulfur, 877 2-Thienylfulgide, 450
Thianthrene, structure, 52 3-Thienyllithium, formation and reactions, 461
1,6,6al4-Thia-1,3,4,6-tetraazapentalenes, 916 2-Thienylmagnesium, reaction with vinyl halides, 466
Thiatriazines
, 796 2-(Thien-2-yl)pyrroles, conformation, 131
1,2,4,6-Thiatriazine 1,1-dioxides
, 796 reaction with tetracyanoethene, 410
1,2,3,4-Thiatriazoles
, 486 2-Thienylthioureas, reaction with bromine, 838
decomposition, 482 2-Thienyl-(tributyl)stannanes, react with chlorosulfonyl isocyanate, 465
valence tautomerism, 208 3-Thienyl-(tributyl)stannanes, react with chlorosulfonyl isocyanate, 465
1,2,3,4-Thiatriazole–thioformyl azide conversion, theoretical studies, 152 Thienylzincates, 463
1,2-Thiazepines, 731 Thiepanes, from dibromoalkanes, 666
1,3-Thiazepines
, 756 3-Thiepanone, 666
1,4-Thiazepine
, 767, 768 Thiepin, theoretical studies, 216
1,4-Thiazepin-3,7-diones
, 767 thermal instability, 237
1,2-Thiazepin-5-ones, 731 4H-Thiepinium ions, NMR spectra, 224
1,4-Thiazepin-5-one
, 767 Thietane
, 657
Thiazetidines, 13C NMR spectra, 225 barrier to ring inversion, 233
1,3-Thiazetidine
, 734 microwave spectra, 222
from primary aromatic amines, formaldehyde and hydrogen sulfide, 733 oxidation, 631
1,2-Thiazetidine 1,1-dioxides, general methods of synthesis, 711 photoelectron spectroscopy, 230
1,2-Thiazetine ring, dimensions, 221 reductive cleavage, 631
4H-Thiazine
, 763 reaction with bis(methoxycarbonyl)carbine, 630
4H-1,3-Thiazines
, 749 synthetic methods, 663
1,3-Thiazines, rearrangement, 753 Thietane rings, opening by radicals, 629
1,4-Thiazines
, 761 Thietane 1,1-dioxides
, 657
2H-1,2-Thiazines, ring opening, 253 Thietan-2-ones, reaction with amines, 625
1,3-Thiazine skeleton
, 748 Thietane S-oxide
, 631
1,4-Thiazine S,S-dioxides
, 761 Pummerer reactions, 639
Thiazinium salts, 763 Thietes, microwave spectra, 222
1,3-Thiazinium perchlorates
, 751 Thietimines, by cycloaddition reactions of 4-dialkylamino-3-butyn-2-ones
1,3-Thiazinium salts
, 748 with substituted phenyl isothiocyanates, 671
Thiazole
, 738 Thiins, aromatisation, 320
amination, 517 2H-Thiin dioxides, formation of anions, 316
coordination complexes, 491 Thiinium (thiopyrylium) ion, isoelectronic structure with benzene, 30
Diels–Alder reactions, 538 Thiinium salts
, 701
deprotonation at C(2), 526 structures, 51
desulfurization by Raney nickel, 511 Thiinium tetrafluoroborates, 13C NMR shifts, 60
oxidation, 500 Thiiranes
, 656
reaction with bis(tributylstannyl)acetylene, 520 conversion to b-chlorothioacetates, 619
reaction with DMAD, 909 desulfurization by radicals, 629
1002 Index

Thiiranes (Continued) Thiophene-2,5-dicarboxylic acid derivatives
, 686

desulfurization, 616 Thiophene 1,1-dioxides, 394
dimerisation, 765 act as dienes, 437
extrusion of sulfur, 607 as Michael acceptors, 424
NMR spectra, 223 instability, 394
oxidation, 630 Thiophene S,N-ylides, 393
photoelectron spectroscopy, 230 Thiophene-2-sulfinic acid
, 459
produced from oxiranes by thiocyanate ion, 669 Thiophene-2-sulfonic acids, properties, 459
reaction with benzyne, 629 Thiophene sulfoxide
, 393
Thiirane 1,1-dioxide, instability, 630 instability, 96
reaction with LDA, 626 Thiophene-2-thiol
, 464
X-ray diffraction studies, 218 Thiophenium bis(alkoxycarbonyl)methylides
, 393
Thiirane S-oxides, oxidation, 630 Thiophenium salts
, 393
ring opening, 627 Thiopropargyl imines, copper-catalyzed cyclization, 680
Thiirene, antiaromatic nature, 231 2H-Thiopyrans, Diels–Alder reactions, 324
as intermediate, 482 4H-Thiopyrans
, 689
extrusion of sulfur, 607 Thiopyridines, by palladium-catalyzed coupling, 375
theoretical studies, 215 4-Thiopyrones, halogenations, 268
2-Thiirenes, by matrix photolysis of 1,2,3-thiadiazole, 675 Thiopyrylium cations, reaction with aryllithiums, 272
Thiirene oxide, addition of 1,3-dipoles, 635 Thiopyrylium salts, reaction with amines, 284
a-Thioacylaminoketones, reaction with hydrazine, 782 Thiosaccharin, solid state studied by IR spectra, 179
2-Thioacyltetrazoles, loss of nitrogen, 780 Thiosemicarbazides, oxidative cyclization, 776
Thioanilides, conversion into benzothiazoles, 838 Thiosuccinimides, reaction with 1,1-diphenylethene, 657
o-Thiobenzoquinone methide, 633 b-Thioxoimines, cyclizations, 717
N 0 -Thiobenzoyl-N,N-dimethylformamidine, reaction with methyl acrylate, 751 6-Thioxo-1,2,4,5-oxatriazin-3-ones
, 795
Thiobenzoylphenylcarbene, as intermediates, 482 2-Thioxo-1,3-thiazepan-4-ones, reaction with
Thiocarbonyl compounds, reaction with diazoalkenes, 657 N,N0 -dicyclohexylcabodiimides, 734
Thiocyanate ion, converts oxiranes into thiiranes, 669 Three-centre, two-electron bonds, 150
Thioindigo
, 444 Three-membered heterocycles, bond lengths and
Thioindoxyl, oxidation, 444 angles, 211
Thioketene dimers, thermolysis, 734 IR spectra, 227
g-Thiol acids, spontaneous cyclization to thiolactones, 663 mass spectra, 227
b-Thiolactones, synthetic methods, 663 NMR spectra, 223
Thiolane, synthetic methods, 663 nomenclature, 211
Thionation of 3-N-acylamino ketones, 749 photoelectron spectroscopy, 230
Thionin, 232 quantum mechanical calculations, 214
2-Thiooxy-l,3-thiazolinyl derivatives
, 742 ring strain, 230
Thiophene, ab initio calculations, 95 X-ray diffraction studies, 218
addition reactions with carbenes, 424 Thymine, dimerisation, 313
alkylation, 393 o-Toluenediazonium salts, spontaneous cyclization, 830
by addition of a-mercapto ketones to dimethyl acetylenedicarboxylate, 685 p-Toluenesulfonylmethyl isocyanide anion, addition to a,b-unsaturated
chloromethylation, 414 ketones, 687
electrophilic reactions on ring carbons, 395 2-(p-Tolyl)pyridine
, 355
fragmentation patterns in mass spectrometry, 120 Topological charge stabilization rule, 36
Friedel–Crafts reactions, 406 Topological resonance energies, of five-membered
from the intramolecular condensation of a-thioglycolates onto adjacent heterocycles, 126
carbonyls, 685 N-Tosyl-2-allyl piperidines
, 326
high degree of aromatic character, 386 1-Tosylazetidines
, 662
ionic hydrogenation, 422 reaction with nitriles, 752
ionisation potentials, 125 N-Tosylaziridine, reaction with aniline, 620
2-lithiation, 677 4-Tosyloxycoumarins, 4-arylation, 369
MO calculations, 96 N-Tosylpyrrole, Friedel–Crafts reactions, 405
nitration, 400 N-Tosyl-substituted-g-aminoalcohols, in synthesis of azetidines, 662
occurrence, 89 N-Tosylsulfimines, conversion into 1,2-benzothiazepines, 835
o-nitrophenylation, 427 Total p-deficiency of heterocycles, 46,47
photochemical fragmentation, 387 Total p-excess, in five-membered heterocycles, 94
photoinduced alkylation with diarylalkenes, 427 Transition metal-mediated [2 + 2 + 2] cycloadditions, 700
Raney nickel desulfurization, 430 nitrene transfer reactions, 655
reactions with aldehydes and ketones, 412 2,3,5-Trialkylpyrazines
, 758
reaction with alkenes, 411 N-Trialkylsilylazoles, 603
reaction with benzynes, 434 N-Trialkylstannylazoles, 603
reaction with t-butyl bromide, 411 2,4,6-Trialkyl-1,3,5-triazines
, 789
reaction with ethoxycarbonylnitrene, 426 2,20 ,6-Triamino-60 -propylthiobiphenyl
, 878
reaction with maleic anhydride, 433 2,4,6-Triamino-s-triazine
, 345
reduction to dihydrothiophene, 430 Triaryl-N-cyanoazomethine imines, trimerization, 910
ring hydrogen atoms exchange, 399 2,3,5-Triarylfurans
, 678
sulfonation, 401 2,4,5-Triarylimidazoles
, 737
thermal stability, 386 2,4,5-Triarylimidazole anions, 510
Thiophene-3-carbaldehydes, rotamers, 129 cis-2,4,5-Triarylimidazolines
, 742
Thiophene-2-carboxylic acids, acidity, 455 3,5,6-Triaryl-1,2,4-triazines, 286
Thiophene-2,3-dicarboxylic acid anhydride, as a precursor of 1,4,7-Triazacyclodecane, structure, 218
2,3-didehydrothiophene, 456 1,5,9-Triazacyclododecane, structure, 218
 Index 1003

1,4,8-Triazacycloundecane, structure, 218 Tributylstannylallenes, reaction with (Z)-b-iodoacrylic acids, 691

Triazamacrocycles, metal complexes , 614 1-Tri-n-butylstannylbenzotriazole, coupling constants, 168
3,4,7-Triaza-2,4-norcaradienes, photochemical rearrangement, 785 5-Tributylstannylisoxazole, coupling reactions, 590
Triazapentalene derivatives, 912 (Tricarbonyl)iron complexes of 1,2-diazepines, 637
Triazaphenothiazines, 884 5-Trichloroacetyl-1,4-dihydropyridine
, 323
1,2,4-Triazepines, loss of nitrogen, 608 2-Trichloroacetylpyrrole
, 405
2H-1,2,4-Triazepines
, 785 bromination, 402
4H-1,2,4-Triazepines
, 785 Trichloromethanesulfenyl chloride, reaction with amidines
, 779
1,2,5-Triazepines
, 787 5-Trichloromethyl-1,2,4-oxadiazoles, reaction with amines, 517
1,3,5-Triazepines
, 2,4,6-Trichloropyrimidine, successive reactions, 365
Triazepinones
, 792 2,4,6-Trichloro-1,3,5-triazine, successive reactions, 366
Triazines, 38 Tricyclic Dewar pyridines, photolysis, 611
alkylation, 258 Tricyclic oxazolo[3,2-a]pyridines, 900
protonation, 255 8-Trifluoromethanesulfonyloxyquinoline, Stille coupling, 335
1,2,3-Triazine, decomposition to hydrogen cyanide, 249 5-Trifluoromethyl-3-arylpyrazoles
, 720
flash vacuum thermolysis, 249 2-Trifluoromethyl-4-formylquinolines, 821
oxidation, 260 5-Trifluoromethyl-3-hydroxypyrazoles
, 720
reaction with enamines, 308 3-Trifluoromethylsulfonyloxy-4-phenyl-1,2,5-thiadiazole, coupling
reaction with tetracyanoethylene oxide, 259 reactions, 591
1,2,4-Triazines
, 783 1-Trifluoromethylsulfonyl-1,2,3-triazole, ring-opened form, 168
in cycloaddition reactions, 308 Trifluoronitrosomethane, reaction with polyhalogenated ethylenes, 710
photochemical hydration reactions, 275 Triheterapentalenes, 915
reaction with enamines and enol ethers, 702 2,4,5-Triiodoimidazole
, 505
reaction with Grignard reagents, 286 reductive dehalogenation, 584
thermal stability, 249 Tri-isopropylsilylmethylpyridinium salts, conjugation, 52
1,3,5-Triazines
, 788, 789, 791 1,3,5-Triketones, reaction with P2S5, 916
nucleophilic reactions on, 273 Trimerization of imidates, 789
reaction with active methylene compounds, 292 of methyl isocyanate, 790
reaction with dienophiles, 309 4,5,7-Trimethylchroman
, 819
1,2,4-Triazine-5-carboxamides
, 293 2,3,5-Trimethylisoxazilium, reaction with aldehydes, 565
1,2,3-Triazine N-imines, 261 3,4,5-Trimethylpyrazole, halogenations of methyl groups, 564
reactions with DMAD, 312 1-Trimethylsilyl-2-azetidinones, desilylation, 639
1,2,4-Triazinones, ring-chain tautomerism, 83 1-Trimethylsilylbenzimidazole, migration of trimethylsilyl
1,2,3-Triazine 1-oxide, reduction, 297 group, 202
1,2,4-Triazine 1-oxides, NMR spectra, 55 2-Trimethylsilylbenzothiazole, reaction with aroyl halides, 506
1,2,4-Triazine 4-oxides
, 783 1-Trimethylsilyl-3-dimethylaminomethylindoles, fluorine-induced
Triazinium 2-dicyanomethylides, 259 reactions, 454
Triazirinyl cations, structures, 215 1-Trimethylsilylimidazole, 603
Triazoles, acidity, 489 (Trimethylsilylmethyl)(2-indolyl)zincs, 463
matrix photolysis to azirines, 675 (Trimethylsilylmethyl)(2-pyrrolyl)zincs, 463
1,2,3-Triazole
, 548, 770 2-Trimethylsilylpyridines, Hiyama cross-couplings, 371
acylation, 499 1-Trimethylsilylpyrimidinium triflate, reaction with silylated
alkylations, 487 enol ethers, 291
amination, 500 2-(Trimethylsilyl)thiazole, acylation, 530
bromination, 505 4-Trimethylsilylthiepine 1,1-dioxide
, 703
by cycloaddition, 773 1-(Trimethylsilyl)-1,2,3-triazole, reacted with halodiorganylboranes, 491
microwave spectrum, 160 2-Trimethylstannylbenzo[b]furan, ipso reactions, 400
N-alkylation, 496 9-Trimethylstannylcarbazole, bromination, 403
tautomerism, 201 1-Trimethylstannylindole, reaction with bromine, 403
2H-1,2,3-Triazole, aromatic stabilisation, 149 2(4)-Trimethylstannylthiazoles, 588
aromaticity, 192 2,4,5-Trinitroimidazole, displacement of nitro groups, 576
1H-1,2,4-Triazole, aromaticity, 191 1,3,5-Trioxanes
, 789
1,2,4-Triazole
, 775, 781, 1,2,3-Trioxolanes, MO studies, 196
gas and solid phase tautomerism, 160 2,3,6-Trioxopyridotriazines, 907
tautomerism, 201 2,4,6-Triphenylnitrobenzene
, 291
weak base, 148 Triphenyl-1,3,4,5-oxatriazine
, 795
1,2,4-Triazole carbenes, reactions, 530 Triphenylphosphine ozonide, reaction with ketenes, 712
Triazole N-carboxamides, thermolysis, 479 3,4,5-Triphenylpyrazole, 257
1,2,4-Triazoline-3-thione
, 776 2,4,6-Triphenylpyridine
, 283
1,2,4-Triazolinone
, 777 2,4,6-Triphenylpyridine N-oxide, photochemical rearrangement, 756
[1,2,3]-Triazolo[2,1-a]benzotriazoles, 912 2,4,6-Triphenylpyrylium cation, reaction with ammonia, 283
[1,2,4]-Triazolo[1,5-c][1,3]benzoxazines, 908 reaction with active methylene compounds , 291
Triazolo-fused 1,2,3,4-tetrazines, synthesis, 864 2-Triphenylsilyl-2-lithiooxirane, 626
[1,2,4]-Triazolo[1,5-a]pyridines, 901 4,5,6-Triphenyl-1,2,3-triazine, reaction with nonacarbonyldiiron, 257
1,2,4-Triazolo[3,4-a]pyridines, 544 2,4,5-Triphenyl-1,2,3-triazole 1-oxide
, 795
1,2,3-Triazolo[1,5-a]pyridine derivatives, 904 1,3,4-Triphenyl-1H-1,2,4-triazole-5-ylidene, stability, 194
[1,2,4]-Triazolo[1,5-a]pyridine 3-oxides, 901 Triple bonds, in synthesis of pyrroles and furans, 681
Tribenzo[b,d,f]oxepins, 887 Tris(dimethylamino)azete, 231
2,4,5-Tribromoimidazoles, reductive dehalogenation, 584 Tris(dimethylamino)-1,2,3-triazine, 249
2,3,5-Tribromothiophene, reductive dehalogenation, 460 Tris(3,5-dimethylpyrazol-1-yl)methane, structure, 195
2,3,4-Tri-t-butylazete, isolation, 215 2,4,6-Tris(dimorpholinomethyl)-1,3,5-triazine, 344
1004 Index

2,4,6-Tris(trichloromethyl)-s-triazine, conversion to UV spectra of five-membered heterocycles with more than one

2,4,6-triamino-s-triazine, 345 heteroatom, 177
1,3,4-Tris(trimethylsilyl)pyrrole
, 691 UV spectroscopy, in determining ionization constants, 67
Tris-trimethylsilylthiirane S,S-dioxides
, 626 in studies of tautomeric compounds, 67
2,3,4-Trisubstituted azetes
, 691 investigation of charge-transfer complex formation, 67
1,2,5-Trisubstituted imidazoles
, 525 investigation of covalent hydration, 67
2,3,5-Trisubstituted 1,3,4-oxadiazoliums
, 775 of five-membered heterocycles, 113
2,4,6-Trisubstituted 6H-1,3-oxazines
, 748
2,4,5-Trisubstituted oxazoles, 740
2,4,6-Trisubstituted pyridine derivatives
, 701 V
2,4,6-Trisubstituted pyrylium salts, reaction with hydrogen peroxide, 279 Valence tautomerism of heterocycles, 36, 83
1,3,5-Trisubstituted 1,2,4-triazoles
, 776 van Leusen pyrrole synthesis, 825
Trithiadiazepine, nucleophilic attack on sulfur atom, 618 Vinyl azides, loss of nitrogen, 674
delocalized 10p aromatic nature, 217 Vinyl aziridines, by thermolysis of cyclic sulfamidates, 670
structure, 234 2-Vinylaziridine, reaction with phenyl isothiocyanate or
1,3,5,2,4-Trithiadiazepines
, 870 4-chlorothiobenzoyl thioglycollate, 756
stability, 609 1-Vinylazoles, electrochemical reduction, 534
1,3,5-Trithiane
, 789 Vinyl benzo[b]furans, intermolecular reactions, 450
Trithiapentalenes, 143 1-Vinylbenzotriazole, flash-vacuum pyrolysis, 480
1,6,6al4-Trithiapentalenes, 916 lithiation, 595
Trithiatriazepine, delocalized 10p aromatic nature, 217 Vinylcarbenes, 644
1,3,5,2,4,6-Trithiazepine, stability, 609 cis-2-Vinylcyclopropanecarboxaldehyde, interconversion with
Tri-(2-thienyl)methyllithium, 462 2,5-dihydrooxepin, 696
1,2,3-Trithiolanes
, 773 1-Vinyl-1,2-dihydropyridines, isomerisation, 321
3-Tritylindazole
, 497 Vinyl ethers, transition-metal-catalyzed formation of 1,3-dioxepanes, 757
1(2)(3)-Tritylindazoles, flash-vacuum pyrolysis, 202 2-Vinylindoles, reaction with oxalyl chloride, 451
2-Tritylpyrrole, electrophilic substitution at the 3-position, 677 Vinylphenols, cyclization, 805
Trofimov’s pyrrole synthesis, 686 N-Vinyl pyridiniums, as Michael acceptor, 378
Tropanes
, 426 N-Vinylpyrroles
, 392
Tropinone
, 663 3-Vinylpyrrole , reaction with methyl propiolate, 449
Tryptamines, 90, 411 2-Vinylpyrrolidines, Pd(0)-catalyzed ring expansion, 755
Tryptophan, 90 5-Vinyl-1-substituted-2-aminoimidazoles, Diels–Alder cycloadditions, 541
Type A mesoionic compounds, 143 2-Vinylthietanes
, 620
Type B mesoionic compounds, 143 2-Vinylthiophene, reaction with tetrabromocyclopropene, 450

U W
Ugi four-component condensations, 723 Water solubility of heterocycles, 73
a,b-Unsaturated a-amino iminolactones
, 622 Wolff rearrangement of diazo compounds to b-lactams, 670
C(3)-Unsubstituted S-arylbenzo[b]thiophenium ions, ring opening, 421 intermediacy of oxirenes, 231
4-Unsubstituted azetidin-2-ones
, 658 to give indoles, 814
Unsaturated 1,3-benzodiazepines, synthesis, 842, Wolff ring contraction of diazopyridones, 694
Unsubstituted benzotriazole, tautomerism, 201 Woodward–Hoffmann rules, 644
Unsaturated 1,3-benzoxazepine system, system, 844
N-Unsubstituted diaziridines, oxidation, 708
N-Unsubstituted dihydropyridines, tautomerism, 317 X
N-Unsubstituted 4,5-dihydropyrroles, tautomeric equilibrium, 439 Xanthone
, 278, 880
Unsaturated 5H-1,4-dithiepin
, 769 Xanthydrol
, 278
2-Unsubstituted 1,3-dithiolylium salts, reduction, 536 Xanthylium ions, reaction with amines, 283
N-Unsubstituted-imidazoles, coupling with diazonium salts, 507 reaction with b-diketones, 291
3-Unsubstituted indolizines, 892 reaction with hydroxide ions, 278
3-Unsubstituted isoxazolium salts, loss of C(3) proton, 531 Xenon difluoride, reaction with pyridine, 266
reaction with hydrazines, 720 reaction with pyridine, 285
a,b-Unsaturated ketones, reaction with hydroxylamines, 716 Xenon hexafluoride with pyridine, 285
a,b-Unsaturated nitriles, reaction with elemental sulfur, 680 X-ray data for heterocyclic compounds, 51
N-Unsubstituted pyrazoles, from N-allyl-N-nitrosamides, 718 X-ray structures of heterocyclic compounds, 99
Michael reactions, 497 X-ray studies on penicillin and cephalosporin antibiotics, 221
N-Unsubstituted pyridones, anion formation, 248
2-Unsubstituted-4(3H)-quinazolinones, synthesis, 839
Unsubstituted 1,2,4-thiadiazole, sensitivity to alkali, 514 Y
Uracil, dimerisation, 313
Yohimbine, 90
fluorination, 269
irradiation, 275
reaction with sodium sulfide, 284
Reimer–Tiemann reaction, 270
Z
structure bound to uracil phosphoribosyltransferase, 54 Zaitsev Rule, 257
Ureas form 2-aminooxazoles, 736 Zinke reaction, 283