REACTIONS OF TRIADS S8-KOH-DMSO, Se8-KOH-DMSO, Te-KOH-HMPA WITH ACETYLENES

Article abstract of DOI:10.1016/0040-4020(82)80214-7

A new general approach to anionic transformations of acetylenes using superbasic media has been developed.It allows series of new reactions which are not undergone by acetylene under conventional conditions.The triads S8-KOH-dimethylsulfoxide (DMSO), Se8-KOH-DMSO, Te-KOH-hexamethyl-phosphorictriamide (HMPA) are proposed as new effective reagents for the preparation of unsaturated compounds of sulfur, selenium and tellurium.A series of reactions of acetylene with sulfur, selenium and tellurium proceeding in DMSO or HMPA in the presence of alkali and water at 80-120 deg C leading to divinyl sulfide, divinyl selenide and divinyl telluride in 25-80percent yields have been found.Thiophen, di-1-(1,3-butadienyl) sulfide, 1-vinyl-2-thiabicyclo<3.2.0>hept-3-ene, and dihydrothiophen have been obtained by the reaction of vinylacetylene with sulfur.The reaction of vinylacetylene with selenium affords selenophen, di-1-(1,3-butadienyl) selenide, 1-vinyl-2-selenabicyclo<3.2.0>hept-3-ene, methyl (1-(1,3-butadienyl) sulfide, and methylthiomethyl 1-(1,3-butadienyl) selenide, vinyl 1-(1,3-butadienyl) sulfide and methylthiomethyl 1-(1,3-butadienyl) selenide (the latter two with DMSO participation).The reaction of vinylacetylene with tellurium gives mainly di-1-(1,3-butadienyl) telluride.A series of reactions between DMSO and selenium leading to dimethyl sulfide, dimethyl sulfoselenide, and methylthiomethyl selenide have been observed.