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Cyclopropylolefine 2 bilden mit p-Nitrophenylazid (1a) in der Hitze Δ1-Triazoline 3. Enolather 4 reagieren mit 1a bei 50°C in Abhangigkeit von ihrer Struktur und der Reaktionszeit zu Δ1-Triazolinen 3d–f und/oder N-(p-Nitrophenyl)imidsaureestern 5d–i, wahrend mit Tosylazid (1b) bereits bei Raumtemperatur N-Tosylimidsaureester 6 entstehen. – Die Umsetzung von 4 mit 1 uber primar entstehende 1-Triazoline 3 und deren Folgereaktionen wird in Abhangigkeit von Substituenten und Reaktionsbedingungen diskutiert. Die Weiterreaktion von 3 kann uber das Zwitterion I erfolgen, wobei N2 um so leichter abgespalten wird, je besser das hierbei entstehende Carbokation II stabilisiert ist. Enol Ethers, XII1). – Reactions of Cyclopropylolefins and Enol Ethers with Organic Azides Δ1-Triazolines 3 are formed from cyclopropylolefins 2 and p-nitrophenylazide (1a). Enol ethers 4 react with 1a at 50°C to yield either Δ1-triazolines 3d–f and/or N-(p-nitrophenyl)-imidic esters 5a–i, while reaction with tosyl azide(1b) at room temperature affords N-tosylimidic esters 6. - Reaction of 4 with 1 primarily yields Δ1-triazolines 3; the secondary reactions of 3 are discussed in terms of substituent effects and reaction conditions. Elimination of N2 from 3 may proceed via the zwitterion I. This reaction becomes easier the better the resulting carbocation II is stabilized.

The reaction of the chloromagnesium salt of benzophenone imine with tosyl azide gives a mixture of diphenyldiazomethane and of N-tosyl benzophenone imine. Similarly, diazofluorene was formed from the chloromagnesium salt of fluorenone imine and tosyl azide. The lithium salt of benzophenone imine underwent dimerization in solvents such as ether and tetrahydrofuran. The reaction of this dimeric dianion with tosyl azide and with methyl iodide is discussed. Evidence for the structure of the azide formed from dimeric anion and tosyl azide is presented.

The conversion of anions of aliphatic and aromatic primary amines to the corresponding azides by the diazo transfer reaction with tosyl azide is reported. Anions of amides do not give the acyl azides while those of hydrazones are converted to the diazoalkanes presumably via the corresponding N-azidimes. The mechanisms of these transormations are discussed.

Die N.N′-disubstituierten 1.5-Benzodiazepin-dione 1 reagieren nicht mit HNO2 oder Alkylnitriten. Ihre Na-Salze 6 lassen sich hingegen mit Brom, Chloramin und Tosylazid leicht umsetzen. Aus den mit Tosylazid aus 6 oder durch Diazotierung der 3-Amino-1.5-benzodiazepindione 3 dargestellten 3-Diazo-Verbindungen 12 erhalt man 3-Halogen-, 3-Hydroxy-, 3-Alkoxy-und 3-Acetoxy-1.5-benzodiazepin-2.4-dione. Die Salze 6 ergeben bei der Acylierung mit Benzoylchlorid die Benzoyloxybenzyliden-1.5-benzodiazepin-dione vom Typ 14. Benzodiazepines with Psychotropic Activity, VI1). – Reactions of N,N′-Disubstituted 1,5-Benzodiazepine-2.4-diones in Position 3 Whereas N,N′-disubstituted 1,5-benzodiazepinediones 1 do not react with HNO2 or alkyl nitrites, their sodium salts 6 easily react with bromine, chloroamine and tosyl azide. The 3-diazo compounds 12 obtained from 6 with tosyl azide or by diazotization of 3-amino-1,5-benzodiazepinediones 3 yield 3-halo-, 3-hydroxy-, 3-alkoxy- and 3-acetoxy-1,5-benzodiazepinediones. With benzoyl chloride 6 yields benzoyloxybenzylidene-1,5-benzodiazepinediones of type 14.

5,6,7,8,9,10-Hexahydrocyclohept[b]indole reacts with tosyl azide to form 6,7,8,9,10,10a-hexahydro-10a-p-tolylsulphonylaminocyclohept[b]indole (VII; n= 5) in poor yield and its N-methyl derivative yields 1-methyl-2′-p-tolylsulphonylamino-2-p-tolysulphonyliminoindole-3-spirocyclohexane (VIII; n= 4), 2,3,4,5,6,7-hexahydro-1-methyl-7-p-tolylsulphonylamino-12-p-tolylsulphonylimino-2,7-methano-1H-1-benzazepine (XI), 5-methyl-5,6,6a,7,8,9,10,10a-octahydro-10a-p-tolylsulphonylamino-6-p-tolylsulphonyliminophenanthridine (XI), and 5,6,7,8,9,10-hexahydro-5-methyl-10-p-tolylsulphonyliminocyclohept[b]indole (XXI). No 1 : 1 reaction products were isolated.6,7,8,9,10,11-Hexahydro-5H-cyclo-oct[b]indole and its N-methyl derivative react in a similar manner to their lower homologues, although the NH derivative reacts smoothly in high yield, in contrast to its lower homologue.

1,3-Dimethylindole reacts with arylsulphonyl azides forming 1,3-dimethyl-2-arylsulphonylaminoindoles. The compounds exist in solution as both the aminoindole and iminoindoline forms. The reaction of 1-benzyl-3-methyl-indole is similar but 1-methyl-3-phenylindole is less reactive and yielded crystalline material with only one azide. 1,3-Dimethylindole and 3-methylindole react with tosyl azide in the presence of pyridine forming compounds which contain two tolylsulphonyl groups.

3-Methylindole reacts readily in pyridine solution with p-chloro- and with p-nitro-benzenesulphonyl azides to give 1 : 2 reaction products; from the reactions between p-nitrobenzenesulphonyl azide and 3-methylindole in acetic acid solution a 1 : 1 reaction product has been isolated. Similar reactions of ethyl 1-methylindole-2-carboxylate yield ethyl 3-arylsulphonylaminoindole-2-carboxylates and these compounds, on hydrolysis and decarboxylation, give 3-arylsulphonylamino-1-methylindoles.The properties of the product obtained by treating indole with tosyl azide can be adequately explained in terms of a tautomeric mixture of amino and imino forms of the former.

The nature of the product formed by treating 1-p-tolylsulphonylaminotetrahydrocarbazole with acid has been determined. 9-Methyl-4a-p-tolylsulphonylamino-2,3,4,4a-tetrahydrocarbazole has been isolated and shown to be an intermediate in the reaction of tosyl azide with 9-methyltetrahydrocarbazole. Good yields of cyclopentenoquinolines may be obtained by carrying out these reactions under basic conditions.The products formed by heating 4a-arylsulphonylaminotetrahydrocarbazoles have been characterised, the effect of substituents at the 1-position on the nature of the product obtained when tetrahydrocarbazoles react with azides has been studied, and the kinetics of the acid-catalysed rearrangement of 1-methyl-3-p-tolylsulphonyliminoindoline-2-spirocyclopentane have been examined.

3-Ethyl-2-methylindole reacted with tosyl azide forming 3-ethyl-2-methyl-3-p-tolylsulphonylamino-3H-indole in good yield; 3-methyl-2-phenylindole formed the analogous compound in moderate yield; and 2-ethyl-3-methylindole formed 2-ethyl-3-methyl-3-p-tolylsulphonylamino-3H-indole in very poor yield. The other products of this reaction were separated and characterised. The reaction of 3-ethyl-1,2-dimethylindole with tosyl azide was similar to that reported1 for 1,2,3-trimethylindole. In contrast the reaction of 2-ethyl-1,3-dimethylindole with the azide yielded a large number of products. 1,2,3,4-Tetrahydrocyclopent[b]indole and its N-methyl derivative react rapidly with tosyl azide.Some of the indoles were treated with p-chlorobenzenesulphonyl azide to provide further examples of this type of reaction.