Photochemical and thermal transformations of azomethine imines

The thermal and photochemical fragmentations of a few bisazoalkenes have been investigated. 2-Phenyl-4,5-disubstituted-1, 2,3-triazoles were obtained both in the thermolysis and photolysis of 1, 2-bisphenylazo-(4, 4′-dichloro) stilbene, 1, 2-bisphenylazo(4, 4′-dimethoxy)stilbene, 1, 2-bisphenylazocyclohexene and o-(phenylazo) phenyldiazocyanide. Both 2, 3-bisphenylazo-2-butene and 1, 2-bisphenylazoethylene failed to undergo either photolysis or thermolysis in the expected manner. However, 2, 3-bisphenylazo-2-butene underwent an acid-catalysed valence isomerisation to anhydro 1-phenylimino-2-phenyl-4, 5-dimethyl-1, 2, 3-trizolium hydroxide, which on photolysis gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. The same iminotriazolium intermediate gave a cycloadduct, 2, 6-diphenyl-3, 3a-dimethyl-4, 5-dicarbomethoxypyrazolino [2.3.c][1.2.3] triazole, on treatment with dimethyl acetylenedicarboxylate, whereas treatment with carbon disulphide gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. Both photolysis and thermolysis of C-biphenylene-N^α(4-chlorophenyl)-N^β-cyanoazomethine imine gave 9-fluorenone-N- (4-chlorophenyl) anil. Photolysis of 1, 2-bisphenylazoacenaphthylene in methanol gave acenaphthenequinone monophenylhydrazone.     

Reactions of cyclammonium cations

The reaction of 1,2-diaminopyridinium salts with -dicarbonyl compounds or -halogeno ketones forms pyrido[1,2-b][1,2,4]triazinium salts. A methyl group present in position 2 of one of these salts condenses with aldehydes, giving styryl derivatives and reacts with orthoesters to give cyanines.For Communication XXII, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1266–1270, September, 1973.     

The role of electronic factors in reagents in controlling thestereochemistry of arylsulfenyl chlorides addition

For a series of substituted arylsulfenyl chlorides the stereochemistry of Ad_E-reactions with a series of substituted Z- and E-β-deuterostyrenes has been elucidated. Non-stereospecific reaction was observed only for the pair 2,4-dinitrobenzenesulfenyl chloride-p-methoxystyrene; for all the other reactants the reaction proceeded in a strictly stereospecific manner.     

Investigation of the reduction of methylenequinones by methods of polarography and EPR spectroscopy

Conclusions The polarographic reduction of certain methylenequinones was studied, and the mechanism of the reduction was investigated by the method of EPR spectroscopy.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1656–1658, July, 1970.     

EPR spectra of halogenonitromethane anion radicals

Conclusions It was deduced that fluorine is in a -combined state in the anion radicals we studied; this was based on an analysis of the EPR spectra of a series of fluoronitroalkane anion radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 458–460, February, 1969.In conclusion, the authors express their appreciation to A. A. Fainzil'berg for his interest in our work.     

Mechanism of Dehydrobromination of 1,2-Dibromo-1-phenylethane under Conditions of Phase-Transfer Catalysis

Selective dehydrobromination of 1,2-dibromo-1-phenylethane to -bromostyrene was effected under conditions of phase-transfer catalysis in systems containing KOH, toluene, and tetraalkylammonium bromides. The high selectivity of the catalytic systems originates from stabilization by lipophilic cation of the phase-transfer catalyst of a E1cb-like transition state in the E2 mechanism. In the presence of a catalytic amount of lipophilic alcohols, phenylacetylene was obtained. Substrate activation by alcohol molecules is explained by enhancement of the acceptor power of halogen atoms due to solvation and by increased mobility of hydrogen atoms.