Subject Ilndex

Absorption peaks of azomethine group

-Absorption spectra, of azomcthinc

Acctals, reaction with amino groups

Acetone, polarographic dctcrminations

-\cctophenonc, addition reactions

Acetylacctone, nuclear magnetic rcs-

-4cetylcne see also Alkynes and C=C

Acid catalysis, of quinonediimides 704

Acid chlorides, catalytic effect of dimethylformamidc on formation 637

Actinometre 586 Acyl halidcs 307 Addition, see also Cycloaddition

565

group 565

i 9

160

262, 263

onance (proton) 176

bond bond lengths 3

lY3-dipolar 624 to azomethine group 255-293 to quinonediirnides 701

of alcohols 709 of hydrogen chloride 708 of mercaptans 710 of organic acids 709

to quinoneimides, of benzenesul- phinic acid 710

to unsaturatcd centres of carbenes 299 of nitrenes 299

diimides 704 1,4-Addition-elimination of quinone-

1,2-Addition of quinonediimides 705 Aldehydes

aromatic, addition reactions 264, 265

test for, using thiobarbituric acid 150

condensation, with amines 64-69 with N,N-dialkylhydrazines 73 with o-quinonimines 666

conversion to Schiff bases and imines 98

Aldehydes-cont. enolic forms 80 Gattermann synthesis 650 interchange reaction, with hydra-

preparation 627,628,640,641,648

N-alkyl, .yn-anli isomerizations

N-aryl, qn-anti isomerizations

u-chlorochloraldimine 322 double, infrared spectra 169 halogenztion 605 infrarcd spectroscopy 163-167 reaction with nitrilimines 314

zones 82 with imines 82

Aldimines 163-167, 351, 352

364-373

364-373

Aldokctenes 305 Aldol condensation 65, 96 of nitrones 71

Aldoses 74 Adoximes 349

conversion to 1,2,4-triazoles 31 5 halogenation 607 N-phenylformaldoxime 3 15

cycloaddition rcactions 299, 300 dimerization 299 epoxidation 304

Alkoxy groups, displacements 334-

o-Alkylations of amides 103, 105 s-Alkylations of thioamidcs 105 Alkyl halides, addition reactions 259,

Alkylidenebisamines, reaction with

Alkyllithium, addition reactions 271,

Alkyl- 1-pyrrolines, ultraviolet absorp-

Alkynes 300 see also Acetylenes and C=C bond ethoxyalkyncs, pyrolysis 306

Alkenes 299, 300

346

260

quinonimines 723

272

tion spectra 182

Allenes 303 Ally1 cleavage 173 Amide oximes, electrolytic reduction

559

775

The Chemistry of the carbon-nitrogen double bond Edited by Saul Patai

Copyright 0 1970 by John Wiley & Sons Ltd. All rights reserved.

776 Subject Index

Amides, o-alkylation 103, 105 chlorination cyclization 1C.5, 106 reactions, with nitriles 322

6 1 1 , 6 12

with phasgene 602 with phosphorus pentahalides

with thionyl chloride GO2

Amidic amino groups, condensation with carbonyl group 77

Amidines 308, 353-355,468 cyclic, electrolytic reduction 539,

electrolytic reduction 538, 539 electronic spectra 200 formation

632

602, 604

tautomerization 103-1 Ob

540

from imidoyl halides

from isocyanates 1 15 from isonitriles 1 13 from phenylhydrazones 454

rearrangements 455 Amidochlorides 328, 605, 607, 610,

626 dealkylation of N,N-dialkyl 608

Amidofluorides, structure 61 5 Amidohalides 600

infrared spectra 616 structure 610, 615

Amidoximes 633 Aminals, carbalkoxy 32 1 Amines 95

6 19-62 1 ,

as catalysts for cyclization 722 chlorination 611, 612 condensation reactions, with aldc-

hydes 64-69

conversion to azomethines 83 dehydrogenation 1 17-120 eliminations from, oxidative 12 1

reductive 12 1 interaction with trihalomethyl func-

tions 649 oxidation 117-120

electrolytic 531, 532 primary, aromatic, nitrosation 7 15

condensation reactions 6 4 6 7 preparation 277 reaction with quinonimines 723

reaction with a,/3 uraaturated ke-

secondary, condensation reactions

with ketones 64-69

tones 66

68. 69

Amines-cont. substituted, conversion to azome-

a-Amino acid esters, azomethines thines 121

from 209 configuration 209 N-neopentyiidene derivatives, opt

cal rotatory dispersion 2 10

azomethines from 209 conifigurations, assignment 2 12 derivatives 208-214 Schiff bases of 66 syntheses 287

Aminoazetidinones 307

a-Amino acids 119

2-Aminobenzy1ideneiminey complexes

Amino compounds, interchange of

Amino groups, displacements 349-

248, 249

C=N bonds with 81,82

35 1 reactions, with acetals 79

with amidic carbonyl groups 77 with esteric carbonyl groups 77 with ketals 79

a-Amino ketones, formation by re- arrangement, of N,N-dichloro-s- alkylamines 450

of quaternary hydrazonium salts

thermal rearrangement 452 a-Amino ketoximes, fragmentation

Amino steroids 224 derivatives 208

a-Aminosulphonic acid 258 Ammonia, condensation reactions 67,

N-Amylideneamylamine 157 Amylimine 157 Analysis, by infrared spectroscopy

by mass spectrometry 170-175 by nuclear magnetic resonance 176 by polarography 157-162 qualitative, by chemical methods

quantitative, by acidimetric titra-

by chemical methods 150-157 by hydrolytic methods 156, 157

Angular momentum 15 Aniline 315

reaction with quinonediimides 706 Anilines, formation of dyes from

45 1

425

68

162-170

150

tion methods 150-156

preparation, general synthetic method 266 669

Subject Index 777

.411il-nitrone product ratio 84 Anils 82, 301

benzophenone anil 306 p-benzoquinone monoanil 307 formation, from Grignard reagents

from nitroso compounds 83 Anisotropic effect. of phenylimino

group 382 .4nisotropy, magnetic, of oximido

group 388 Anomalous curves 203 Anthrone, imines of 716 Anthroquinonemonoxime, Beckmann

rearrangement 714 N-Arenesulphonyl benzaldimine, ad-

dition of ketene diaminals 309 N-Aroyldiarylamine, formation by

rearrangement of aryl imidate

Arylsulphonyl groups 308 Asymmetric synthesis, steric course

Asymmetric transamination, hydro-

Atisine 218 Atomic integrals, Coulomb exchange

108

439

288

genolytic 289

tYPe 2727 exchange one-centre Coulomb 27 two-ccntre Coulomb . 27

Atomic orbitals, of nitrogen 6 Atomization, heat of 5 4-Azacholest-4-ene 2 18 6-Azacholesterol 2 I5 kctidines 309 Azetidinone 306 Azetines 309 Azides 97

decomposition 126, 128 reaction with ylids 99

conversion to hydrazones 82 cyclic, electrolytic reduction 541,

formation from hydrazine 72

Azines 192, 468

542

electrolytic reduction 541, 542 formation 96

from azo compounds 120 from diazo compounds 98 from hydrazines 7 1, 120 from hydrazones 82 from secondary carbinylamines

118 nja-anti isomerizations 392-399 isomers 398

Azircnes 97 Aziridines, preparation 300

dichloro-. formztion 301 3,3-dichloro- 1 ,2,2-triphenylY forma-

tion 301 monochloro-, preparation 302

as reaction intermediate 548

Aziridinium salts 303 Azirine 219

Azobenzcne, elcctronic spectrum

Azolactones see Oxazoloncs Azomethine derivatives, half-wave

49

potentials 535 Azomethine group, additions to 255-

293 x electrons of 10-24 spectral properties 565, 566

Azomethine imines 316, 317 N-alkoxy 316

Azomethines, aliphatic, unconjugated,

alkylalkyl, mass spectrometry 170 analysis, by infrared spectroscopy

170- 1 75

electronic spectra 183

162-1 70 by mass spectrometry by n.m.r. spectroscopy 176 by polarography 157- 162 qualitative chemical methods

quantitative chemical methods

acidimetric titration methods

in glacial acetic acid 152, 153

via high frequency non- aqueous titrations 156

hydrolytic methods 156, 157 bisulphite 156, 157 2,4-dinitrophenylhydrazine

hydroxylamine 157 aromatic, substitucnt effects, polar-

150

150-157

150-156

156

oaraphic studies 161 - - aryl, optical dissymraetry effects

22 1-228 bathochromic shifts 177 circular dichroism 18 1-23 I conjugated, electronic spectra 188-

191 U.V. absorption 187-202

cyclic 2 14-220 optical dissymmetry effects 220

formation, by C=C bond cleavage withamines 83

778 Subject Index

Azomethines-cont. formation, by photochemical reac-

tions 126-129 by rearrangements 126- 129 effect of u.v. irradiation 65 from amines 95, 117, 119

substituted, by elimination 12 1- 124

from azides 97 from gem-dihalidcs 81 from isocyanates 1 15 from nitrones 82 from X-nitrosamidcs 128 from N-nitroso amines 128 through ylids 98

halogenated and non-halogenated, determination by titration 155

syn and anti isomers 66 microscopic identification 150 of sterically hindered ketones 82 of vanillins 177 optical rotatory dispersion 181 -

photochemical properties, including

preparation, electrochemical 5 17-

quenching effects 177 reduction, electrolytic 533-559

23 1

fluorescence 177

533

stereochemistry of hydrogenation 285-293

substituted, electronic spcctra 198-

tautornerism 183 thermochromic effects 177 ultraviolet absorption 182-202 unconjugatcd, protonation 186

20 1

ultraviolet absorption 182-187 Azomethine ylids 316, 317 Azomethinium salts 68 4-Azoxyphenol 7 14

Barton reaction 128 Base catalysis, in quinonediimine

sulphonation 697 of quinonediimides 704 phosphate dependence 697

Basicity, of coupler anion, reactivity dependenceon 692

Bathochromic shift 165, 177 Beckmann fragmentation 416-430 of a-amino ketoximes 425-428 of oximes, a-disubstituted 423

a-trisubstituted 41 7-422 of a-oximino ketones 423-425

Bcckmann products, from fragmenta-

Beckmann rearrangement 127, 408-

experimental conditions 409-41 3 intermolecularity 42 1 mechanism 430-439 of anthroquinonemonoxime 714 of benzoquinoncmonoxime 713 of oximes 70, 106 retention of configuration 121

tior.-recombination 42 1

439, 647, 648

Bcnzalaniline, addition of dichloro- carbenc 301

electronic spcctrum 49 Benzalazine, test for 150 Bcnzalbispiperidine, reaction with re-

tenequinoniininc 723 Benzaldehydc, reaction with retenc-

quinonimine 722 Bcnzamidine, reaction with N-phenyl-

benzhydrazidic chloridc 3 15 Benzcne, bond lengths 3 Bcnzimidoyl benzoates 445

rearrangcmcnt to imides 404, 445 Benzisoxazoloncs, as couplers 670 N-Benzohydrylideneaniline, photo-

Benzonitrile oxide, addition of hydro- rropy. 178

gen chloride 317 clectrolytic reduction 522

Benzophenone, anil 306 polarographic reduction 158

imine 187 oximes, picryl c:hers of p-substi-

tuted, rearrangement 43 I p-Benzoquinonc, diimines 664

Benzoquinoncmonoxime, Beckmann

tautomerism with p-nitrosophenol

monoanil 307 monoiminc 664

rearrangement 7 13

71 1 Benzothiazole 316 Benzo-1 ,2,4-triazincy electrolytic re-

Benzoyl cyanide, addition rcactions

N-Benzoylphosphorimidic trichloride

N-Benzyl a-amino acids 282 N-Benzylidenealkylamines, U.V. spec-

N-Benzylideneaniline 155 photoisomerizations 367 phototropy 177, 178

duction 530

264

603

t rum 187

Subject Index 7 79

N-Eenzylidcneaniline-conr. polarographic reduction 158 test for 150

N-Benzylideneanilincs, conformation 187, 188

structure 366 substituted, mass spcctromctry 170

(2 ) - ( + )-N-Benzylidene-a-benzylethyl- A‘-Benzylidene-n-butylamine 155

reaction with rctenequinonimine

Bcnzylidenc-f-butylamine 236 fluorination 606

N-Bcnzylidcne-n-hcxylaminc 155 N-Benzylidcne-ZO-a-(s)-3/%-hydroxy-

(2)-( + )-A’-Benzylidenc-u-phenylethyl-

N,N’-Biisoimides, rearrangement 446 Biphcnylenekctenc 305 1 ,Z-Bis( benzylidencamino) ethane

Bischler-Napicralsky reaction 106 Bisulphite method, azomethine analy-

sis 156, 157 Bond energies 2, 5, 6

cs!culation of 6 Bond lcngths, in acetylene 3

in benzene 3 inethanc 3 in ethylene 3

Bromide ion 302 N- (2-Butylactylidene) -3-butylactyl-

aminc 157 N-Butylamine, catalytic effcct in for-

mation of 2-phenylretcnoxazolc 722

606, 618

157

amine 221

722

5a-prcgnane 22 1

amine 221

155

N-(t-Buty1)-benziniidoyl fluoride

N-n-Butylbutylidcneamine 5, 155,

ultraviolet absorption spectrum 182

N-n-Butylethylidenamine 5 N-n-Butylideneaniline 155, 157 Butylimine 157 N-n-Butylpropylidenamine 5

(+)-Camphor oxine 230

Carbencs, addition to unsaturated

dichloro-, addition to benzalaniline

benzoate 230

centres 299

30 1

Carbobenzoxy groups 308 Carbodiimides 634

clcctronic spcctra 201 formation 99, 124

by rearrangement of imidyl azides

from iminophosgcnes 81 from iminophosphoranes 102

275,276

anism 79

454

Carbon, heat of sublimation 5 Carbon monoxide, addition reactions

Carbonyl-amino condensation, rnech-

Carbonyl compounds 98 interchange of C=N bonds with

reactions with isocyanates 115 Carbonyl group 1 -see also Condensa-

amidic and esteric, reaction with

condensations with amidic amino

reactions with hydrazinc 71

82, 83

tion

amino groups 77, 78

groups 77

Carboxylic acid chloride, addition reactions 265, 266

Catalytic effect, of dimethyl form- amide on acid chloride formation 637

of methanol on triazolinc formation 310

Catalytic paraineter 485 C=C bond, additions 95-98

cleavage, with amines 83 photoaddition of N-nitrosamine 90

C=C bond. see DISO Acetylenes and Alkynes

of irninophosphoranes 102 Chapman rearrangement 439-447

additions 95-98

intramolecular 440 mechanism 440,441 of imidates, acyl 445, 446

alkyl 443, 444 to diphenylamines 441

Chelate intermediate 292 Chlorimido acid esters, stereoisomers

N-Chlorimincs, configurational as-

N-p-Chlorobenzylidenc-n-hexylamine

3-Chloro-6-diazocyclohesadienone

402

signment 400 stereoisomers 400

155

713

780 Subject Indes

Chloroform 301 A'-Chloroketimines, rearrangements

2-Chloro-4-nitrodiphenylsulphone, re-

Chloro substituents, displacements

N-Chlorovinylamidines 61 9 Cinnolines, electrolytic reduction

Circular dichroism 202

45 1

actions with nucleophiles 676

328-331

525-527

of azomethines 181-231 terms and definitions 203

C-N bond, cycloaddition reactions

formation, through ylids 98-103 with carbonyl compounds 98 with isocyanatcs 99, 100 with nitroso compounds 100,

299-326

101 infrared stretching frequency 2 interchange 81-83

ionic character 20 nomenclature 466468 quantum chemical aspects 6-37 stretching frequencies 37

of aromatic Schiff bases 164

with amino compounds 81, 82 with carbonyl compounds 82,83

Co (11) compleses 245 Co (111) complexes 246 Complex formation, equilibrium con-

Complexes, hydrogen-bonded 239 stant 239

inner 715 of 2-aminobenzylideneiminc 248,

of Co (11) 245 of Co (111) 246 of Cu (11) 247 of glyosime 250, 251 of 2-hydroxyacetophenonimine

of Ni (11) 242 o f P d (11) 243 of phenanthrenequinonemonoxime

of salicylaldimine 240-248 of salicylalcioxime 242 of Zn (11) 243 transition state, change in free

energy 694 with metals 239

249

248

715

Concerted reaction 300 Concurchine 2 19

Condensation reaction-see also C=O group, Coupling, Couplers, H y - drazones, and Schiff bases

carbonyl-amino, mechanism 79 diazonium salt-methylcne 91-95 nitroso-methylene 83-85 of aldehydes with amines 64-69 or carbonyl groups with amidic

of ketones with amines 64-69 of o-quinonimines with aldehydes

Configurational assignrncnts 394 by n.m.r. correlation 388

from infrared correlation 377 of A'-chlorimines 400 o fDNP 393

of phenyl hydrazones 395

amino groups 77

666

empirical 388

Configurational stability, of N-per- fluoroalkylketimines 378

Configuration interaction 25 Configurations of oximcs, q n and anti

retention during Beckmann rc- arrangement 42 1

Conformation of benzylidene anilines

Conjugated molecules, linear 3 Copper, as catalyst in ethyl diazo-

acetate decomposition 303 Correlation problem 25 Cotton effect 203 Coulomb integrals 1 1

atomic, exchange type 27' one-centre 27 two-centre 27

molecular 26 Coupler anion 687

basicity, effect on reactivity 692 Couplers 669-67 1

active methylenc compounds 669 benzisoxazolones 670 indazolones 670 methine type 671 phenolic type 671 pyrazolones 670

elementary rate constants 691 in study of mechanism of nuclm-

philic reactions 687 with anilincs 669

70

187, 188

Coupling 669-672, 687-695

leading to indoamine dyes 669 leading to indoaniline dyes 669

Cu (11) complexes 247

Subject Index 78 1

Cyanates 116 Cyclization 587-590

amines as catalysts for 722 of amides 105, 106

Cycloadditions, 1,3-dipolnr 299,6."-6,

of carbon-nitrogen double bonds

to alkenes 300 to imines 300

647

299-326

1,3-Cyclohexadiene 3 19 Cyclohexanone, polarographic deter-

minations 160 pyrrolidine immonium salt 302

N-Cyclohexylideneaniline, U.V. spec-

N-Cyclohexylidene-n-butylamine 1 83 N-Cyclohesylidenecyclohexylamine

183 Cyclopentadiene, addition with N-

tosyl chloralimine 3 19 N-Cyclopentylidene-n-butylamine

tautomerism 207 N-Cyclopentylidene-L-tyrosine e thy!

ester 228

Deamination 694

imincs 668

trum 187

basic, of N,N-dialkylquinonedi-

kinetics 680 of quinonediimines 668

rate of, salt effect on 678 structural effect 681, 682

of quinonemonoimines 668 rate constants 684 summary of reaction schemes 686,

687 Decarboxylation 92

Decker alkylation method 259 N-Decylidencdccylaminc 157 Dehydrogenation of amines 117-120 Diacylamines 604, 635-637 N,N-Dialkylhydrazines, condensation,

with aldehydes 73

nitrosativc 86, 88, 92

with ketones 73 Diaziridines 300 w-Diazoacetophenones 305 Diazoalkanes 3 10-3 14

coupling with diazonium salts 95 electrolytic reduction 551

conversion to azines 98 reaction with nitroso compounds

Diazocompounds 127

101

Diazoketones, photolytic decomposi-

Diazomethane, reactions, with im-

Diazonium salt-methylene condensa-

Diazonium salts, coupling, with diazo-

Dicarbene, conversion to allenes 303 N, N-Dichloro-s-alkylamines,

rearrangement to =-amino ketones 450

tion 305

monium salts 303 with 4-nitrophcnols 7 16

tions 91-95

alkanes 95 with nitroalkanes 94

Dichloroformoxime, formation 607 Dichloromcthide anion, stereoselect-

ivity of addition 302 Diels-Alder reaction 299

of quinondiimine of quinonimine 718, 719

7 18, 7 19

Dienes 3 19-32 1 gem-Dihalides 8 1 2,6-Dihalobenzoquinone chloroimide

3,4-Dihydroisoquinoline 3 14 Dihydropyridines 645 a-Diketones 74

/3-Diketones, reaction with hydrazinc

y-Dikctones, reaction with hydrazine

Dimerization 589, 590 Dimcthylamine borane 283 Dimethyl anilinomalcate, conversion

to tetrahydropyridines 318 2,3-Dimethyl-l,3-butadiene, addition

with N-tosyl chloralimine 319 Dimethyl formamide, diethyl acetal of

322 catalytic effect, on acid chloride

725

conversion to osazones 74

72

72

formation 637 N,N-Dimethylhydrazones 230, 23 1 2.4-Dinitrophenylhydrazine method,

azomethine analysis 156 2,4-Dinitrophcnylhydrazones, config-

urational assignments 393 rates of s y n - m f i ; isomerizations 395 stereoisomers 393

Diphenylamincs, from Chapman re- arrangement of imidates 441

2,2-Diphenyl-2-anilino-l, 1,l -trichloro-

Diphenyldiazomethanc 31 1 Diphenylketiminc 236

ethane 301

782 Subject Index

Diphenylmcthylene aniline 301 1 ,5-DiphcnyltetrazoleY conversion to

diphcnylnitrilimine 314

2, 4, 5, 244

formation 634 1 ,5-Diphenyl-A2- 1,2,3-triazoline 3 10 Dipole momcnts Displacements, of alkoxy groups 334-

346 of amino groups 349-351 of chloro substituents 328-334 of hydrogen 348, 349, 351 of hydrosy group 351 of thioalkoxy groups 346-348

azo, formation 670, 679 formation by displacement 67 1 indarnine 669 indoaniline 669 indonaphthol 668

Dycs 669

Ehrlich-Sachs rcaction 83 Electrochemical preparation of azo-

Electrode potential 506 Electrolytic oxidation-sce oxidation

Electrolytic reaction, control of 507-

methine compounds 517-533

electrolytic

513 factors influencing 513, 514

electrode material 514 electrolytc 514 p H 514

electrolytic Electrolytic reduction-see Reduction,

Electron affinities 16 Electronegativity 13 Electronic charge densities 12 Electronic spectra 184

of azomethincs, conjugated 188- 191

substituted 198-201 unconjugated, aliphatic 183

solvent effects 187, 197 Electrons, lone pair 8 p-Electrons, ‘equivalent,’ of nitrogen

x Electrons 10

u Electrons 31-36 Electrosynthesis, optimal conditions

Elimination reactions of imidoyl

Enaminc 95, 96, 320

atom 7

of azomethine group 10-24

515

halides 623-626

structure 167

Enolic forms, fixation in thioamides 107

of aldchydes 80 ofketones 80

Epoxidation of alkcnes 304 Equilibrium constants 470

for complex formation 239 Equilibrium for ‘semiquinone’ for-

Eschweiler reaction 283, 284 Ethane, bond lengths 3 Ethyl acetimidate 3 15 Ethyl 3-aziilinocinnamate 303 N-Ethylbutylidenaminc 5 N-(2-Ethylbutylidene)-2-ethylbutyl-

2-E thy1 bu tylirnine 157 Ethyldiazoacctatc, copper catalysed

decomposition 303 Ethylene, bond lcngths 3 Ethylene oxide 302 2-kthylhesylimine 157 N-Ethylideneaniline 157 Ethyliminc 157

polymer 157 Ethyl 2,4-pentadicnoate 320 2-Ethyl- 1-piperideine 320

Flow apparatus, for study of quinone-

Fluorescence 177, 178 N-Fluorimincs, sgn and anti isomers

N-Fluoroamidofluorides, dehalogena-

Formimidoyl chloride 65 1 Fragmentation, of a-amino ketoximes

of p-toluenc sulphonate esters of

Fragmentation-recombination 423 leading to Beckmsnn products 42 1

Free-radical nitrosations 89 Friedel-Crafts reactions 640, 643 Fulminatcs, additions 114-1 16

Gattcrmann aldehyde synthesis 650 Gibbs reaction 725 Glyosime complexes 250, 251 Goeppert-Mayer and Sklar approxi-

Grignard reagents, addition reactions

niation 688

amine 157

diimine reactions 675

400

tion 608

42 5

ketoxirnes 428

mations 27

266-27 1 four centre mechanism 269 with isonitriles 112

Subject

Grignard reagents-conl. with nitriles 1 13 convcrsion to anils 108

Guanidines 322, 468 electronic spectra 200, 201 rearrangements 455

Haliminrs 468 ~~

N-Halimincs, syn-nnfi isomerization 399-402

K-Haloamidcs. reaction with tri-

A'-Haloguanidines, rearrangements

a-Haloketones, conversion to hydra-

Hamrnett parameters 483 Hcat of atomization 5 Heat of sublimation of carbon Hcterocyclic systems, from irnidoyl

halides 642 Hctcrodienes 32 1-323 Hoesch ketonc synthesis 650 Hoesch synthesis 113 Huckcl method 10-18 Huckcl molecular orbital theory re-

Hund's rule 7 Hybridcs, digonal 7

phenylphosphine 652

455

zones and osazoncs 75

5

lated to quinoncdiimines 674

tetrahedral 7 trigonal 7

Hybridization, of nitrogen atom 6-

Hydrazidic chlorides 3 14 10

N-carbethoxy benzhydrazidic chlo-

N-phenylbenzhydrazidic chloride ride 316

315 Hydrazidines 468 Hydrazines, electrolytic oxidation

532

with @-diketones 72 with y-diketones 72

Hydrazones 82, 323,467 acylatcd, electrolytic reduction

conversion to azincs 82 cyclic, acylated, clectrolytic re-

formation from p-halo-ketones

reactions, with carbonyl group 71

543,554

duction 546-550

and hydrazine 72 electrolytic reduction 543-544 electronic spectra 199 formation 81, 9!, 123

Indcx 783

Hydrazones-coni. formation by oxidation 120

from azines 82 from a-haloketones 75 from hydrazinc 71 from a-hydroxyketones 74 from oximes 82 via diazenes 127

syn-anti isomcrization 392-399 rcarrangemcnts 454,455 substitutcd, formation from sub-

thiobenzoyl hydrazones, electrolytic

Hydrobenzamidc, as necessary inter- mcdintc in 2-phenylphenanthrox- azolc formation 72 1

stituted liydrazincs 73

reduction 550, 551

Hydrogen ahstraction 590-592 Hydrogcnation, catalytic 276-279

of azomethine compounds, stereo-

reactions 276-293 chemistry- 285-293

Hydrogcn bond 43 Hydrogen-bonded compkxcs 239 Hydrogen bonding 195, 196

intramolecular 165 Hydrogcn cyanidc. addition reactions

256-258 Hydrogcn displacements 348, 349,

Ilydrogenolytic asymmctric transami-

Hydrogen sulphide, addition reactions

Hydrolysis, dependence on ste'ric and electronic features 630, 631

35 1

nation 289

2 60-2 62

of irnidoyl chlorides 629-631 ofimines 726 of iminolactones 493-501 of nitrosophenol 715, 716 of Schiff bases 468-492

of A2 thiazolincs 501, 502 Hydroxamic acids, alkyl 346

electrolytic reduction 558, 559 syn and anii isomers 403

Hydrosimic acid chiorides 333, 334 2-Hydroxyacetopherionimine com-

4-Hydroxybenzaldoxime, icst for 150 N- (m-Hydroxybenzy1idenc)aniline

N-(o-Hydroxybcnzy1idenc)anilinc

kinetic data 476

plexes 248

196

196 pliototropy 177

784 Subject Index

N- (P-Hydroxybenzy1idene)aniline 196

phototropy 178 N-(o-Hydroxybenzy1idene)-j+

Hydroxy group, displacement 35 1 a-Hydroxyimincs, rearrangements

a-Hydroxyketones 74, 77 Hydroxylamine method of azomethine

Hydroxylamines, electrolytic oxida-

Hypochlorite and phenol, test for

Imidates 322, 468, 649

naphthylamine, phototropy 177, 178

452, 454 thermal 453

analysis 157

tion 532, 533

Schiff bases 150

acyl, Chapman rearrangement

alkyl 334-345, 352, 353

intermolecular 443 thermal 443

allyl, intramolccular mechanism of thermal rearrangement 444

aryl, rearrangement to N-aroyl- diarylamine 439

Chapman rearrangement to di- phenylamines 441

conversion to I ,2,4-osadiazoles 3 17 electrolytic reduction 538 electronic spectra 20 I formation 80, 103, 109

445, 446

444 rearrangement, Chapman 443,

from imidoyl halides 631 from rearrangement of benzi-

midoyl benzoates 404 syn-anti isomerization 402-405

formation from imidoyl halides Imidazolcs 723

621, 622 Imides, formation by rearrangement

Imidic acids 598 Imidic csters-see Imidates Imidoates-see Imidates Imidocarbonatcs, rcarrangcments

Imidothio esters, electrolytic reduction

Imidoyl halides 597-656 as reactive intermediates 647-656 bromides 600

of benzimidoyl benzoates 445

447

538

Imidoyl halides-cutit. chlorides 319, 323, 328-333, 600

tronic features 630, 631 elimination reactions 623-626 fluorides 600 Friedel-Crafts reactions 640, 641 geometrical isomerism 6 17,6 18 halide exchange 629 hydrolysis 629-63 1 infrared spectra 61 5-6 17 in heterocyclic synthesis 642-647 mechanism of formation 605 nomenclature 599

N-bcnzenesulphon ylbenzimidoyl

N-(t-butyl) benzimidoyl fluoride

N-(n-butyl)-2-ethylhexanimidoyl

chloroisonitrosoacctone 599 1,3,3,4,5,6,7-hcptachloroiso-

N-methylbenzimidoyl chloride

N-phenylbenzimidoyl chloride

N-phenyltrichloroacetimidoy 1

A'- (p-tolyl) isobu tyrimidoyl

2,3,3-trichloro-l-piperideine 599 nucleophilic substitution 628 N-phenylbcnzimidoyl chloride 600 physical properties 614-618 preparation 601-613

hydrolysis 629-63 1 dependence on steric and elec-

chloride 599

599

chloride 599

indolenine 599

599

599

chloridc 599

chloride 599

from amidcs 601-606 from amidohalidcs 607. 608 from diazotates 6 I3 from difluoroamine 6 I 3 from imidates 6 12 from isonitriles 608, 609 from isothiocyanates 613 from kctcnimines 613 from nitrilcs 609-6 1 1 from oximes G 13 from thioamides 613 from trichloroacctamides 6 13 from trichloronitrosomethane

reactions, with alcohols 631, 632 613

with amidines 633 with amines 632 with carbanion reagents 638-640

Subject Index 785

Imidoyl halides-cotit. reactions,

with carboxylic acids 635-637 with hydrazines 634 with hydrazoic acid 634 with hydrogen cyanide 635 with hydrogcn sulphide 637,638 with hydroxylamines 633 with phenols with phosphiles 638 with thioacids 637, 638 with thiols 637, 638 with urcthitncs 633

reduction 627, 628 salt formation 626, 627 self condensation structure 6 14 substitution at thc a,-carbon atom

Tmidyl azides, rcarrangemcnt to car- bodiimides 454

Imidyl chlorides-see Imidoyl halidcs Iminazoles-see Imidazoles Jmines 108, 467

N-alkyl 316 N-aryl 316

. azomethine 316, 317 chrysenequinone imine 3 18 cycloadditions 300 formation, from amines 119

63 1 , 632

6 18, 6 19

64 1

from iminophosphoranes 98 from ketones 67

group theorctical treatment 45 hexaflioroacctone imine 31 3 hydrolysis 726 interchange, to form nitrones 82

with carbonyl compounds 8 2 of anthrone 7 16 ozonolysis 3 18 phenantliraquinone imine 3 18 preparation, by addition of Grig-

stability 300 Iminiumion 437 as insertion product 437

I minocarbonates isomcrization, syn-

rates of 402

nard reagents to nitriles 112

anti 402-405

Imino chlorides-see Imidoyl halides Imino ethers-see Imidates Imino group, anisotropy effect of

phenylimino group 382 Iminolactones, hydrolysis 493-501 Iminophosgcnrs--see Isonitrile diha-

lides

Iminophosphorancs 99 addition to triple bond 102 conversion, to carbodiimides 102

to Schiff bases and imines 98 Imino sulphonates 319 Iminothiocarbonates, isomcriza tion

Immonium salts 1 14 404

formation 83, 103, 119, 122 reaction with diazomcthane 303

Indazolones, as couplcrs 670 Indicator yellow 194 Infrared corrclations, for configura-

Infrared spectra, in analysis 162-

tional assignments 377

170

empirical 377

of aldimincs 163-IS7 of imidoyl halides 6 15-6 17

Infrared stretching frequency of C=N

Inscrtion product, iminium ion

Interatomic distances 2 Intermediates 690

bond 2

43 7

in quinonediimine-sulphite reaction 695

protonated, in sulphonation of N,N- dimethylquinonediiminc

Intermolecularity, during Beckmann

Internuclear distances 2-4 Intramolecular hydrogen bonding-

sce Hydrogen bonding Ionic character, of C=N bond Ionization potentials of valence state

16 N-Isobutylbutylidenamine 5 Isocyanates 99

698

rearrangement 42 1

20

acyl 322 addition reactions 114-1 16 phenylisocyanate rcaction with ni-

reactions with imines 309 thioacyl 322 thiobenzoyl 323

Isoimides 635-637 Isomerism, gcometrical, of azome-

thines 207 of imidoylhalides 617, 618 of oximes 228-230

troalkanes 3 17

in osimes, x-ray diffraction studies 385

syn-anti 167

786 Subject Indes

Lsomcrization, cis-tram 574582 of iminocarbonates 404 of iminothiocarbonates 404 photochemical, of osime ethers 392

photo-, of N-benzylideneanilinc

rate, cffcct of substitucnts OR

of iminocarbonatcs 402

of aldimincs, N-alkyl 364-373 N-aryl 364-373

of azincs 392-399 of N-halimines 399402 of hydrazones 392-399 of imidatcs 402-405 of iminocarbonates 402-405 of ketimines. N-alkyl 373-383

N-aryl 373-383 of oximc ethers 383-392 of oximes 383-392 rate, effect ofsubstitucnts on 369

ofDNP's 396

of oxinies 390

367

381 377,

syn-anti, mechanisms 405-408

thermal, of oxime ethers 392 ofoximcs 390

81 Isomers, syn-anli, of azomethines 66,

of N-fl uorimines 400 of hydroxamic acids 403

addition 113, 114 conversion to imidoyl halides 608,

dihalides 609 reaction with Grignard reagents

Isonitriles 467

609

I13 Isooctopine 289 N-Isopropylbntylidenamine 5 N-Isopropylideneisopropylaminc 157 Isoquinoline 3 16 Isorhodopsin 194 Isothiocyanates, electrolytic reduction

Isothioureas 468

Isoureas 468

540 phenylisothiocyanate 309

s-alkyl 347, 348

o-alkyl 345, 346

JappKlingemann reaction 92, 91

Ketals, reaction with amino groups 79

Ketene diaminals, addition to N- arenesulphonyl benzaldiminc 309

Ketene dimcrs, reaction with imixics 305

Ketcnes, alkyl 305 p-chlorophenyl ketcne 306 conversion to 8-lactams 305 N, N-diacylaminokctenes, formation

cliphenyl- 305 moiioaryl 305 p-nitrophenylkctenc 306 phenylkctene 306

Ketenimines, formation 6 19 from N-alkylamidcs 123 from azo compounds 129 from imidoyl halides 623, 624 from isocyanates 100 from ketenes 98 from phosphoranes 102

Ketimincs 70, 82, 351, 352 N-alkyl, syn-anti isomerization

N-aryl, syn-anti isomerization 373-

N-chloroketimines, rearrangements

double, infrared spectra 169 N-perf3 uoroalkyl, configurational

potentiometric titration 155 reaction with nitrile oxides 318

Ketoketenes, cycloaddition 305 Ketoncs 82

307

773-383

383

45 1

stability 378

condensatitma, wiih amines 64-69 with N, N-dialkylhydrazines

73 conversion, to Schiff bases and

imines 98

,%diketones 70 enolic forms 80 Hoesch synthesis 650 sterically hindered, azomethines of

ap-unsaturated 66, 70

to scmicarbazones 74

82

Ketoses 74 Ketoximes, a-amino, Beckmann frag-

#-toluene sulphonate esters, frag-

Kinetic data, for hydrolysis of Schiff

Kinetics, of dcamination 680

mentation 425-428

mentation 428

bases 476

Subject

Krohnkc reaction 85, 101 k s 4 - versus total phosphatc 696

fl-Lactams, formation from ketcnes 305

3-monosubstituted 305 Leuckart reaction 283 Lewis acids 709 Lewis base 235 Lithium aluminium hydride 28 I Lithium dichloromcthanc 302 Lithium, metallic, addition reactions

272, 273

Magnesium-magnesium iodide mis-

Maleic anhydride, addition reactions ture 273

266 Mass spectrornctric method of analysis

170-175 Melamine, C=N bond length 3 (-)-Menthone oxinic 230 Mercaptoindophenol, attempted prep-

Mesoionic oxazolones 307 iMetal chelate, intermediate cyclic

compound 2 8 i Metal complexes 44, 239 Metarhodopsin I 194 Metarhodopsin I1 193 Methane-sulphinic acid 314 Methanol, catalytic effect on tria-

Methine couplers 671 (-)-Mcthone oximc acctate 230 N-pMethoxybenzylidine-benzylaminc

N4-#-Methoxybcnzylidene-sulphathia-

N-p-Methoxychlorobenzylidene-

N-Methyl-a-amino acid 282 4-Methyl-4-azaandro-5-cn- 1 7-/3-01-

N-Methylbenzaldimine 31 7 a-Methylbenzylimine 157 ( + )-3-Methylcyclopentanone 205 Methylenebismorpholinc, rcaction

with retencquinonimine 723 Methylene compounds as couplers

669 a-Methylmercaptobenzalaniline 307 N-Methyimethylenimine 5 ( +)-1-Methyl-3-phenylpropyla~ne

aration 725

zoline formation 3 I0

155

zole 155

benzylamine 155

acetate 218

22 1

Index 787

Microscopic identification of azo-

MO-LCAG calculations 582 Molecular amplitude 205 Molccular corc integrals 26 Molecular ellipticity 202 Molecular integrals, Coulomb 26

Molecular orbital discussion of nitro- sophenol quinoncmonoxime tautomeric equilibrium 7 16, 717

methincs 150

exchange 26

Molecular rotation 202

Neber rearrangement 447-452

N-Neopentylidcnc-alkylamines 183 N-Neopentylidene-s-butylamine 207 Ni (11) complexes 242 Nitrcnes, addition to unsaturated.

mechanism 448450

cenircs 299 inkxlediatcs, rearrangements

though 126-128 Nitrile imines 646 Nitrile oxides 114-1 16,317, 318,646

acetonitrile oxide 3 17 aromatic 318 propionitrile oxidc 3 17

addition 108

cyclization, quinonimines as inter-

interaction with hydrogen halides

reaction with acyl halides 61 1

1,3-dipolar cycloadditions 625

C-carbethoxy-N-phenyl- 3 15 diphenyl, formation, from 1,s-

from the hydrazidic chloride 314

Nitrilcs 300

of Grignard reagent 112

mediates 719, 720

600, 609-6 1 1 , 649-652

Nitrile ylids 624, 646

Nitrilimines 314-316

diphenyl tetrazole 314

Nitrilium salts 610 N-alkyl 436 formation 627 infrared spectra 616 intermediates 434

Nitrimines, electronic spectra 20 I Nitroalkanes 95-see nlso Nitro-com-

pounds addition reactions 273, 274 coupling with diazonium salts 94 reaction with phenylisocyanate

317

7aa Subject Index

Ni troalkanes-cont. a-substituted, elcctrolytic reduction

in-Nitrobenzaldazine, test Tor 150 Nitro compounds-see also Nitro-

5 18-520

alkanes electrolytic reduction, of aliphatic

518. 519 of aromatic 520, 521 of a,/3 unsaturated 518

7

reduction 124, 125 Nitrogen atom, ‘equivalent’# electrons

ground term 7 hybrides 7 hybridization 6-10 lone pair of electrons 8 spin 7

Nitroiic acids, formation 87 Nitrones 71, 79, 129

aldol condensation 7 1 convcrsior. t.9 azomethines 82 electronic spectra 198 formation 83, 96, 100, 101

pounds 101

rearrangement 583-585 p-Nicro-N-(/.J-nitrobenzylidcne)

4-Nitrophenols, reactions with diazo-

p-Nitrophenyl azide, reaction with p -

N-Nitrosamine, photoaddition to

c-Nitrosation, leading to oxiincs 85-

from diazo and nitroso com-

from imines 82

aniline 310

methane 716

nitrostyrene 310

C=C bond 90

91 mechanism 88, 89

Nitrosations, a t tertiary carbons 87, 88

free-radical 89 of primary and secondary carbons

86,87 of primary aromatic amines photochemical 89 trans 90, 91 with decarboxylation 88

7 I5

Nitrosative decarboxylation 86, 92 Nitroso compounds, conversion to

anils 83 electrolytic reduction 518-52 1 reactions, with ylids 100

with diazo compounds 101 c-Nitroso compounds 88

Nitroso-methylcne condensations 83-

Nitrosophcnols, hydrolysis 7 15 tautomerism, with quinonemon-

molecular orbital discussion 7 16,

#-Nitrosophenol, tautomerism with benzoquinonemonoxime 7 1 1

j-Nitrostyrene, reaction with p-nitro- phenyl azidc 310

Nuclear magnetic resonance 176 correlations for configurational as-

Nuclcophiles, reaction with 2-chloro-

Nucleophilic addition 672

85

oximes 666

717

signment 388 empirical 388

4-nitro-diphenylsulphone 676

of quinonediimines, orientation

to imines 304 to quinonediimines 675-700

674

Nucleophilic attack, of trichloro-

Nucleophilic substitution, of imidoyl methyl anion 301

halides 628

Olefins-see Alkenes Opsin 193 Optical dissymmetry effects 202-

see also Optical rotatory dispersion and Circular dichroism

cyclic 220

-aralkylamines 227

230

of azomethines 181

of N-salicylidene derivatives 222

Optical rotatory dispersion 202.207,

ofazomethincs 181-231 of N-neopentylidene derivatives of

a-amino acid esters 210 terms and definitions 205

Orbital electronegativities 16 Organoaluminium compounds, di-

ethyl aluminium chloride and iodide 3 12

Orientation in nucleophilic addition of quinonediimines 674

Ortho esters, conversion to imidoates 80

Osazones 74

Oscillator strengths 3 1 Out-of-plane motions 46 Overlap integrals 4, 1 1

formation from o-halokctones 75

Subject Index 789

1 ,2,4Oxadiazoles, formation from imidates 317

1,3,4-0xadiazoles 645 Oxazirancs 304 Oxaziridines 583

OxazoIes, formation from o-quinon-

preferential formation from quinon- imines and primary amines 723

Oxazolones 105 mesoionic 307

electrolytic reduction 53 1

imines 666

Oxidation, electrolytic, of amines 53 1. 532 of h')ldrazines 532 of hydroxylamines 532, 533 of 2,4,6-tri-t-butylaniline 533

of amines 1 17-120 ofp-phenylenediamincs 667

Oxidative eliminations, from amines

Oxime ethers 323

121 "-Oxides 582-586

isomerization, syn-anti 383-392 photochemical 392 thermal 392

Oximes 39,467 Beckmann fragmentation, of a-

disubstituted 423 of a-trisubstituted 417-422

benzophenone, p-substituted, picryl ethers of 431

a-chloro- 3 17 circular dichroism 230 configurations, syn and anti 70 conversion to hydrazones 82 electrolytic reduction 55 1-554 of acylated oximes 556 of alkylated oximcs 554, 555

electronic spectra 198 formation 69, 81

by Barton reaction 128 by oxidation, of amines 119

of hydroxylamines 120 by reduction of nitro compounds

from 8-nitroso nitro compounds

via C-nitrosations 85-91 isomerism, geometrical 228-230

x-ray diffraction studies 385 isomerization, syn-anti 383-392

photochemical 390 thermal 390

reaction with diazomethane 31 3

124

129

Oximido group, magnetic anisotropy 388

u-Oxiniino ketones, Beckmann frag- mentation 423-425

Oxindoles, N-substituted 302 Ozonolysis of imines 3 18

Pariser-Parr-Pople metliod 20 Pauli exclusion principle 7, 24 Pd (XI) complexes 243 Penicillin 306 Peracetate ion 304 N-Perfluoroalkylkctimincs, configura-

tional stability 378 Perlluorohydrazine, addition to vinyl

fluoride 618 Peroxy acids 304 Phenanthrenequinonemonoxime, in-

Pb.enanthridine 3 16 Phenol and hypochlorite, test for

Phenolic couplers 67 1 Phenylacetic acid ester, addition re-

actions 263, 264 1 -Phenyl-5-p-chIorophenyl-A2- 1,2,3-

triazoline 310 2-Phcnyl-5,6-dihydro-1,3-thiazine 308 P-Phenylenediamines, oxidation 667

Phenylhydrazones, autoxidation 202

ner comp:exss 7 15

SchifT bases 150

unsubstituted 683

configurational stability 395 conversion to amidines 454 stereoisomers 393

Phenylimino group, anisotropic effect

N-Phenyliminophosgene 323 ( - )-a-Phenylneopentylamine 226 2-Phenylphenanthroxa~ole~ formation,

hydrobenzamidc and quinonimine intermediates in 72 1

( - )-cr-Phenyl-n-propylamine 226 pH of solution versus dependence of

Phosphate, in general base catalysis

382

rate of reaction 69

697 total, versus ks0j- 696

Phosphoranes, addition reactions 274, 275

conversion to ketenimines 102 Photoaddition to C=C bond 90 Photochemical isomerization--Jec

Photochemical reactions, formation of Isomerization

azomethines 126-1 29

790 Subject Indcs

Photochemical nitrosation-see Nitro- sation

Photochemical properties 177, 178

Photochemical reaction of quinone- diiminc- N,N'-diosides 724

Photochromism 566-570, 592 Photoisomerization-see Isomcrization Phototropy, of N-benzohydrylidene-

aniline 178 of N-bcnzylidcneaniline 177, 178 of N-(o-hydroxybcnzy1idenc)-

of N- (0-h yd rosy bcnz ylidcne) -

of N-(a-hydroxybcnzylidenc)-B-

of salicylideneaniline 177

aniline 177

aniline 178

naphthylamine 177, 178

Phthalazincs, electrolytic reduction 527, 528

Picryl ethers, of @-substituted benzo- phenonc oximes, rearrangement 43 1

Pigments, indicator ycllow 194

Pinncr reaction 109, 113 I-Piperideincs 2 14, 2 16 Piperidinedioncs 305 Polarographic method of analysis

visual purple 193

157-162 determination, of acetone 160

of cyclohcxanonc 160

tion Polarographic reduction-see Reduc-

Polarography 157- I62 kinetic waves 534 of quinoneoximes 7 17 of N-salicylideneaniline 159 studies of substitucnt effects in

aromatic azomethincs 16 I Potassium t-butoxidc 301 5a-Pregnan-3-onc oxime 230 5p-Pregnan-3-one osime 230 Prelog rule 292 N-n-Propylbutylidenaminc 5 Protonation of azornethines, conjuga-

ted 192 unconjugated 186

Prototropic shifts 126 I-Pyrazolines 3 10 Pyrazolones, as couplers 670 Pyridazines, electrolytic reduction

Pyridine 316 523--525

uItraviolet snectrum 187 ' - -~ - -

Pyridoxal derivatives, of o-hydrosy- arylidcne Schiff bases 194

Pyrimidines, electrolytic rcduction 528, 529

ultraviolet spcctrum 187 Pyrrolidinc immonium salt of cyclo-

hcxanonc 302

Quantum chcmical aspects, of C=N bond 6-37

Quaternary hydrazonium salts, re- arrangements to a-amino ketones 45 1

Quenching cffccts I77 Quinazolines 643 Quinolines 316, 643

Quinoncdiimidcs 666 from imidoyl halides 622

addition 701 of alcohols 709 of hydrogen chloride 708 of mercaptans 710 of organic acids 709

l72-additiori and loss of sulphona-

analogy to deamination of qui-

174-addition-climination reactions

catalysis, acidic 704 basic 704

reaction with aniline 706 reduction 701 transamination 706

niide 705

noncdiimines 705

704

Quinoncdiimincs, addition of aryl- sulphinic acids 673

analogy to sulphonation of qui-

intermcdiatcs 683

deamination 668

noncdiimides 705

with spiro structure 68s N,N-dialkyl 666

basic dcamination 668 N,N-dimethyl, sulphonation 697 reaction with sulphite anion 673

Diels-Alder reaction N,N'-dioxides 724-726

7 18, 7 19

photochemical reaction 724 preparation 724

general base-catalysis 697 instability, in acidic media 667

in alkaline media 667 in neutral media 667

nucleophilic reactions, addition 672, 675-700

Subject Indes 79 1

Quinonediimincs-coirt. orientation, prediction by HMO

theory 674 mechanism 687 reactions, flow apparatus I'or study

of ti75 mechanisms 664 product distribution 677 with sulphitc 695

intermediates 695 reactive spccics 695

reaction sites 676 structure, effect on rate of dcamina-

tion 681, 682 unsubstituted, rcaction with sul-

phite 698 Quinoneimides 700-7 1 1

addition of bcnzenesulphinic acid 710

Quinonemonoimines, deamination 668

Quinonemonoximes, tautomerisni with

equilibrium, molecular orbital dis- nitrosophenols 666

cussion 716, 717 Quinoneosimcs, inner complexes

715 polarography 7 17 preparation by hydrolysis of nitro-

sophenol 715 Quinonc sulphenimine, formation

725 Quinonimine intermediate, in for-

mation of 2-phenylphenanthrox- azole 721

Quinonimines, Diels-Alder reaction 718, 719

intermediates in nitrile cyclization

reaction, with alkylidenebisamines 719, 720

723 with primary amines 723

aldehydes 666 o-Quinonimines, condensation with

Raman frequencies 38 Rate constants 679, 680

composite 680 elementary 680

of deamination reactions 684 for coupling 691

Rate of rcaction, dependence versus p H of solution 69

Reactive species 679, 688

Rearrangemcnt-see also specific re-

dependence on nature and position

formation of azomcthines by 126-

in C=N bond 408-455 intermolecular, of alkyl imidates

or amidines 455 of aryl imidate to N-aroyldiaryl-

aminc 439 of benzimidoyl bcnzoatcs to imides

404, 445 of .V,T,"-biisoimidcs 446 of N-chlorokctimines 45 1 of N,N-dichloro-s-alkylamines to

u-amino ketones 450 of guanidincs 455 of N-haloguanidines 455 of hydrazones 454,455 of a-hydrosyimines 452-454 of imidocarbonates 447 of imidyl azidcs to carbodiimides

454 of picryl ethers of fi-substituted

benzophenonc osimes 43 1 of quaternary hydrazonium salts to

u-amino ketones 451 rates, efFect ofsolvent variation 439 through nitrene intermediates 126-

Rcduction, electrochemical, of cam-

arrangements

of substituents 440

129

443

128

phor oxime 553 stcreoselectivity 553

of acid derivatives 52 1-523 of amidines 538. 539

cyclic 539, 540 of azines 541, 542

cyclic 542,543 of azomethine compounds 533-

of benzonitrile oxide 522 of benzo-1,2,4-triazinc 530 of cinnolines 525-527 of diazoalkancs 55 1 of3,6-diphenylpyridazine 523 of hydrazones 543, 544

acylatcd 544-546 cyclic acylated 546-550 thiobenzoyl 550, 551

of hydroxamic acids 558, 559 of imidic esters 538 of imidothio esters 536

electrolytic 284

559

792 Subject

Rcduction-cotit. clectrolytic--coril.

of isothiocyanates 540 of nitroalkancs, a-halogcnatcd

5!8 dihalogcnatcd 5 I9 a-substituted 518-520

aliphatic 517-518 aromatic 520-52 1 a,/3-unsaturatcd 518

mcnohalogenatcd 520

of nitro compounds 517-52 1

of nitrosoalkanes, dihalogenatcd

af nitroso compounds of oxazidirines 53 1 of oximes 551-554

acylated 556 alkylated 554-556 amide 559

520

5 17-52 1

of phthalazinrs 527, 528 of pyridazines 523-525 of pyrimidines 528-530 of Schiff bases 536, 537 of semicarbazones 544 of tetrazolium salts of thiosemicarbazones 544

of nitro compounds 124, 125 of pseudo-nitroles 520 of quinonediimidcs 701

polarographic, of benzophenonc

530, 53 1

of imidoyl halides 627, 628

anil 158 of benzylideneanilinc 158

12 1

using metals 279-28 1 Reductive eliminztions, from amincs

Resonance integral 11 Resonance, steric inhibition 312 Resorcylaldoxime, tcst for 150 Rctenequinonimine, reactions, with

benzalbispiperidine 723 with benzaldchyde 722 with bcnzylidenc-n-butylaminc

with methylenebismorpholine 723 Retenoxazole, formation, from me-

thylene bismorpholine and rc- tenequinoniminc 723

722

2-phenylretenoxazole, formation from retenequinonimine, and benzalbispipcridine 723

and benzaldehyde 722 and benzylidene-n-butylamine

722

Indrs

Retinal 193 N-Retinylidenemcthylamine 194 Rhodopsin 193 Ring addition, of hydrogen chloride to

Rings, five mcmbered quinoncdiimides 708

3 10-3 18 four mcmbcrcd 305-309 sis membcrcd 3 18-323 threc membcrcd 300-305

Salicylaldimine 240 complcscs 240-248

Salicylaldoxime 240 complexes 242

Salicylazine, test for 150 N-Salicylidencalkylamines 52 Salicylideneaniline hydrochloride

N-Salicylideneanilines 44 166

n.m.r. studies 197 phototropy 177 polarography of 159

N-Salicylidene-aralkylamines, optical

(S)-( + )-N-Salicylidene-s-butylamine N-Salicylidene derivatives 224, 225

dissymmetry effects 227

224

of aliphatic amincs, optical dis- symmetry cffects 222

amine 226

methyl ester 224

(5’)-N-Salicylidene-diphenylcthyl-

N-Salicylidene-D-phcnylalanine

N-Salicylidcne-o-toluidincs 178, 197 Salt effect, on rate ofdeamination 678 Schiff bases 64, 118, 310, 348, 349- . see also Condensation

aromatic, C=N bond strctching frcqucncies 164

o-hydroxy 55 attack by semicarbazide 74 cyclization 587-590 electrolytic reduction 536, 537 formation 98

from azidcs 99 hydrolysis 468-492

kinetic dat.5 476 o-hydroxyarylidcnc Schiff bases

of a-amino acids 66 of frans- 1,2-diaminocyclopropane

of pyridine-2-aldehydc 173 titration, in acetonitrilc 154

194

175

in chloroform 153

Subject Indes 793

Schrodinger equation 7 Self-consistent-field (SCF) method 27 Semicarbazidc, attack on Schiff bases

Scmicarbazones 74, 81, 108, 467 74

elcctrolytic reduction 544 elcctroiiic spectra 200 formation from ketones 74

disrnutation equilibria 678 formation, equilibrium of 688

Semiquinone 667

Slater atomic orbitals 4 Slater determinants 25 Sodium borohydride 281-283 Sodium hydrogen sulphite, addition

Sodium, metallic, addition reactions

Solvent effects 225, 228 Solvent variation, effcct on rearrange-

ment rates 439 Spectral properties, of azomethine

gFoup 565, 566 Spin, in nitrogen atom 7 Spiro structure, of intermediate i n

quinonediimine dcamination 683

reactions 258, 259

272, 273

Stephen reduction 648, 649 Stereochemistry, of hydrogenation of

azomethine compounds 285-293 Stercoisomers, of chlorimido acid

esters 402 of N-chlorimines 400 of 2,4-dinitrophenylhydrazone 393 of a phenylhydrazone 393

Stereoselectivity, of dichloromethide

Sterically controlled reaction for a-

Steric course, of asymmetric synthesis

Steric inhibition of resonance 312 Steroidal alkaloids 222, 224 Steroidal ketones, azomethines from

206 Sticglitz rearrangement 127 Stilbene 49 Stretching frequencies, of C=K bond

37

anion addition 302

amino acid synthesis 287

288, 292

in aromatic Schiff bases 164 Substituent effect 380 Substituents, chloro, displacement;

effects of nature and position on re- 328-334

arrangement 440

Sugars 75 Sulphinic acids, aryl 673 Sulphitc anion, reactions, with N,N-

dialkylquinonediimincs 673

unsubstituted 698 Sulphonamidc, loss during 1,2-ad-

dition to quinoncdiimides 705 Sulphonation of N,N-dimethylqui-

nonediiminc 697 Sulphur trioxidc 322

Tautomeric cquilibrium, NH/OH 54 benzoquinonemonoximejp-nitroso-

with quinonediimines 695

phenol 711 ni troiophenol/quinonemonoxime

716. 717 - - - I -

Tautomcrism 197, 570-572 in substituted imines 300 of azomethincs 183 of N-cyclopentylidene-n-butylamine

of quinoncmonosimes with nitroso-

phenol-o-quinonoid 196 Tautomerization 303

of amides 103-108 w-Tcchnique 20 Testosterone oximc 230 Tetrahydropyridincs 3 18 Tetramethylethylene 302 3,3,4,4-Tetraphenyl-2-azetidinone,

207

phenols 666

formation from diphenylketenc 305

Tetrazolium salts, electrolytic rc- duction 530, 531

Thermal isomcrization-see Isomeri- zation

Thermal rearrangement, of imidates, alkyl 443 ally1 444

intramolecular mechanism 444 of a-amino ketones 452 of a-hydroxyimincs 453

Thermochromic effects 177 Thermodynamic parameters 480 2-Thiazolinc 306 A2 Thiazolines, hydrolysis Thioalkoxy groups, displacements

Thioamides, S-alkylations 105 fixation of enolic forms 107

Thiobarbituric acid, test for aromatic

Thioestcrs 638

5 10, 502

346-348

aldehydes 150

794 Subject Inclcx

Thioimidates 110 alk;d 346, 347

Thiols, addition reactions 260-262 Thiosemicarbazones, electrolytic re-

duction 544 elcctronic spectra 200

Thioureas 322 Transamination 194

hydrogenolytic asymmetric 289 of quinonediimidcs 706

Transitions, n--> n* 47, 187, 202, 205, 214

T-+T* 47, 187 n 4 0 * 47 (J-+o* 47

Transition state comp!exes, change in

Transni trosa t ions-see Nit rosat ions s-Triazines 32 1 Triazole 314 1,2,4-Triazolc-4-oside, formation 3 I5 1,2,4-Triazoles 3 15, 644

1,3,5-triphenyl-, 315 1 -Triazolines 3 10 1 ,2,3-Triazolines 3 10

4,4bis(trifluoromethyl)- 3 I3 N-mcthoxy- 3 13

lY2,4-Triazolines 3 10 2,4,6-Tri-t-butylaniline, clectrolytic

oxidation 533 Trichloroacetate anion 302 Trichloromcthyl anion, nucleophilic

Trihaloacetic acid, addition reactiorj

2,4,4-Trimcthyl- 1-pyrrolinc 185 Trioxazolidines 3 18 fi-Toluene sulphonate esters of

ketoximes, fragmentation 428 N-Tosyl butyl glyoxylaldimine 3 19

free energy 694

attack 301

2 64

N-Tosyl chloraliminc 319 N-Tosyl fl uoralimine 3 19

Ultraviolet absorption of azomethines 182-202

Urcas 322 Uretidinethionc 309 Uretidinoncs, formation from iso-

Valence-bond structures 19 Valcncc state 15

cyanates 309

electron affinities 16 ionization potentials 16

Vanillins, azomethines of 177 Vcatchine 2 18 Verazinc 184,2 17 Vilsmeier-Haak synthesis 65 1 Vision, chemistry of 193 Visual purple 193 Vitamin A 627 .~

von Braun degradation 608, 653-656

623,

mechanism of 654-656

Whcland’s formula 23

X-ray diffraction studies of isomerism

Ylids, azomethine

in osimes 385

3 16, 3 17 conversion to Schiff bases 99 formation of C-N bonds 98-103 reaction with ni troso compounds

100 Ynamincs 309

623, 624

Zn (11) complex 243

formation from imidoyl halides