Synthesis of Tetrathiophosphates from White Phosphorus

Comprehensive Summary,A transition-metal-free one-pot direct synthesis of tetrathiophosphates(R^(1)S)_(2)P(S)SR^(2) from white phosphorus(P_(4)),through intermediate sodium alkyltetrathiophosphates(R^(1)S)_(2)P(S)SNa,is presented.In the presence of NaSH,various disulfides such as diaryl disulfidbges and dialkyl disulfides are easily coupled with P_(4) to give sodium alkyltetrathiophosphates(R^(1)S)_(2)P(S)SNa in almost quantitative yield,which react with alkyl halides in one pot to generate(R^(1)S)_(2)P(S)SR2.Furthermore,S-(2-cyanoethyl)-substituted tetrathiophosphates(R^(1)S)_(2)P(S)SCH_(2)CH_(2)CN are successfully designed as a kind of tetrathiophosphorylation reagent to react with diaryl iodonium salts involving deprotection-dealkylation process.