Synthesis of phosphorothioates using thiophosphate salts

Abstract

Reactions of O,O′-dialkyl thiophosphoric acids with alkyl halides, in the presence of a base, provide a direct synthetic route to phosphorothioates via O,O′-dialkyl thiophosphate anion formation. Studies on the reaction of ambident nucleophile ammonium O,O′-diethyl thiophosphate with benzyl halides and tosylate in different solvents show that only S-alkylation is obtained. Reaction of this ambident nucleophile with benzoyl chloride (a hard electrophile), gave the O-acylation product. A simple, efficient, and general method has been developed for the synthesis of phosphorothioates through a one-pot reaction of alkyl halides with the mixture of diethyl phosphite in the presence of triethylamine/sulfur/and acidic alumina under solvent-free conditions using microwave irradiation. © 2006Kaboudin and Farjadian; licensee Beilstein-Institut.