ANODIC OXIDATION OF 1,n-HALO(ALKYLTHIO)ALKANES AND 1,n-CHLORO(ALKYLSULFINYL)ALKANES

Abstract

Anodic oxidation of 1,n-halo(alkylthio)alkanes [X-(CH₂)_n-S-R, X = Cl, Br, I] and l,nhalo(alkylsulfinyl)alkanes [Cl-(CH₂)_n-S(O)-R] was studied by cyclic voltammetry in anhydrous acetonitrile and by controlled potential electrolyses. The ease of sulfur oxidation was not affected by the alkyl substituents R or the number of methylene groups n in compounds with n > 2. The oxidation of the 1,2-halo(alkylthio)ethanes (n = 2) occurred at slightly higher potentials. The peak potentials decreased slightly in the order Cl > Br > I which is probably due to the electronegativity of the halogen atoms. The investigated anodic oxidation was shown to be a two electron irreversible process. Electrolyses in aqueous acetronitrile led to the corresponding sulfoxides and sulfones in good yields.     

Bicyclische Diiodtrichalcogenatetraphosphaheptane

Bicyclic Diiodine Trichalcogenatetetraphosphaheptanes Two isomers of each of β-P₄S₂SeI₂ and β-P₄SSe₂I₂ have been identified by ³¹P-NMR spectroscopy. They were prepared by the reaction of P₄S_3–nSe_n with I₂ in CS₂. Systematic changes in chemical shifts and in coupling constants with the alterations in molecular geometry, as sulfur was replaced by selenium, are reported.