Oxidation of E,E‐bis(3‐bromo‐1‐chloro‐1‐propen‐2‐yl) chalcogenides and use of E,E‐bis(3‐bromo‐1‐chloro‐1‐propen‐2‐yl)sulfone in heterocyclization with primary amines

Abstract

Oxidation of E,E‐bis(3‐bromo‐1‐chloro‐1‐propen‐2‐yl) sulfide and selenide with hydrogen peroxide in chloroform/acetic acid or acetic acid affords previously unknown E,E‐bis(3‐bromo‐1‐chloro‐1‐propen‐2‐yl) sulfoxide, selenoxide, and sulfone. The reaction of E,E‐bis(3‐bromo‐1‐chloro‐1‐propen‐2‐yl) sulfone with primary amines in ethanol in the presence of NaHCO3 or Na2CO3 is found to lead not only to heterocyclization but also to alcoholysis of the chloromethylidene groups in the intermediate bis(chloromethylidene) derivatives of thiomorpholine‐1,1‐dioxides to afford N‐organyl‐2(E),6(E)‐bis(ethoxymethylidene) thiomorpholine‐1,1‐dioxides as final products.

(2E,6E)‐2,6‐Bis(organylchalogenylmethylidene) substituted 1,4‐dithiane 1,1,4,4‐tetraoxides and N‐organyl thiomorpholine 1‐oxides as new S‐oxide derivatives of bis(2‐organylchalcogenylvinyl) sulfides

“…In particular, organyl‐2‐chlorovinyl sulfoxides and sulfones easily give the substitution products with retention of the parent substrate configuration upon interaction with organylthiolates and selenolates . We have found that in the reaction of bis[(1 E )‐3‐bromo‐1‐chloro‐1‐propen‐2‐yl] sulfone with primary amines in ethanol in the presence of NaHCO 3 or Na 2 CO 3 , heterocyclization is followed by the substitution with ethoxide ion of the chlorine atoms in chloromethylidene groups of the thiomorpholine 1,1‐dioxide formed as the intermediate product to afford bis‐ethoxymethylidene derivatives of thiomorpholine 1,1‐dioxides …”