Synthesis of tris(organylthioethyl)phosphines and their derivatives on the basis of the reaction of phosphine with vinyl sulfides
Phosphine generated from the red phosphorus in the system KOH-H2O-toluene adds regio- and chemoselectively to vinyl sulfides under radical initiation conditions with the formation of tris(2-organylthioethyl) phosphines, which are easily oxidized by elemental sulfur and selenium to the corresponding phosphine sulfides and phosphine selenides in 54-78% yield. The obtained adducts are split when treated with sodium amide in THF to give trivinylphosphine and trivinylphosphine chalcogenides.
Chernysheva,Mikhailenko,Gusarova,Fedorov,Trofimov
p. 470 - 473
(2011/06/22)
Highly atom-economic one-pot formation of three different C-P bonds: General synthesis of acyclic tertiary phosphine sulfides
The reaction of benzothiadiphosphole 1 with an equimolar mixture of R 1MgBr and R2MgBr gave intermediate A′, which, after only 4-5 min, was treated with an equimolar amount of R3MgBr, giving the asymmetric phosphine PR1R2R3 in 45% overall yield (75-80% yield when R1 = R2 and 85-90% yield when R1 = R2 = R3) and the byproduct 6 in 90% yield. The treatment of 6 with PCl3 quantitatively regenerates the starting reagent 1. Treatment of the phosphines with elemental sulfur gave the corresponding sulfides.