First synthesis of S,S-dialkyl difluorophosphonodithioates and difluorophosphonotrithioates

Several dialkyl difluoromethylphosphonodithioates and difluoromethylphosphonotrithioates have been prepared from difluoromethylphosphonyl dichloride and two equivalents of alkanethiols under basic conditions. Treatment of these species with LDA at low temperatures mainly resulted in decomposition, and to the low-yield isolation of difluorophosphinates or phosphine oxides, thus reflecting the lability of the P–S bond. The desired difluorophosphonodithioates and difluorophosphonotrithioates can be efficiently prepared by reversing the sequence of reactions.