Reaction of gaseous hydrogen fluoride with aluminium and its compounds

The reaction of metallic aluminium surfaces, aluminium oxides, hydrated oxides and sulphate with gaseous anhydrous hydrogen fluoride was studied at 470°C and pressures between 10 and 100 torr. The complementary analytical techniques of X-ray induced photoelectron spectra, X-ray and electron diffraction, and electron microscopy were used for identifying the (frequently unexpected) products.     

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.     

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.     

Synthesis of 1,2-Divinyloxypropenes from Glycerol and Acetylene in the Superbasic System CsF-NaOH-DMSO

Russian Journal of Organic Chemistry -     

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.