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.