The roles of hetero atoms in solvolytic reactions—II: Transannular participation by neighbouring sulphur atom

Esters of sulphur-containing 5- and 6-membered heterocycles, tetrahydro-3- and 4-thiopyranol and their 3- and 4-methyl, phenyl derivatives, and tetrahydro-2-thiophenemethanol, were synthesized. The solvolysis of β-thioesters in 80% aqueous acetone resulted in strong transannular S-participation and the products of solvolysis substantiated formation of bicyclic episulphonium ion intermediates. Such participation is considered to be present even in a tertiary system. On the other hand, γ-thioesters were solvolysed without any transannular S-participation,     

Synthesis of halogenoazoles

On reaction with halogens, organolithium and organomagnesium derivatives of azoles are converted into halogenoazoles. Halogen derivatives of N-substituted imidazoles, benzimidazoles, and indazoles have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1109–1111, August, 1973.     

The activation energy as guiding factor in the fragmentation of substituted diphenylmethanes

The mass spectra of a series of substituted diphenylmethanes were obtained. The mass spectral features were compared with those of the corresponding 1,2 diphenylethanes and discussed in terms of the factors which influence the electron-impact fragmentation. In the series examined, it is shown that the activation energy is the most important factor in determining cracking patterns. The meaning of the averaged rate constants is criticised.     

An ESR study of some organic complexes of tetravalent vanadium

ESR results are reported for solutions and glasses containing vanadyl diethyldithiophosphate, vanadyl and vanadium diethyldithiocarbamates, and vanadium butylxanthogenate. Comparison with compounds of known structure gives the structures of these complexes.