Synthetic reactions using dithiophosphate derivatives

Abstract

Various types of dithiophospyoric acids and their salts, have been synthesized. It was found that dithiphosphates can be converted into the corresponding S-alkyl ester and S-silyl ester by nucleophilic reaction with alkyl halids and halosilane. It has been found that alkali metal dithiphosphates or pyridinium dithiphosphates react with 2-halo-1-methyl-pyridinium iodide to give trithiopyrophosphates. The present procedure is much more convenient and effective potasim dithiophosphates instead of the sodim salts provide analogues yields of trithiopyrophosphates. Cyclic 0,0-dialkyl trithiopyrophospates have been prepared by the reaction of alkali metal dithiophosphates with 2-bromo-1-methyl pyridinium iodide. By the exchange of anion dithiophosphates, intermediate state which is in turn converted into stable molecules, cyclictrithiopyrophosphates. Dithiophosphoro acidic salts reacts with bromine to give exclusively phosphorothiono bromidates. In the course of a study converning dry metalic salts of cyclic dithiophosphoric acids. it has beem found that silver dithiophosphates react with bromine to give the corresponding cyclic dialkyl phosphorothionobromidates via cyclic dialkoxy thioxaphosphoranesulfenyl bromides. The procedure is very easy and the starting dithophosphates can be obtained in almost quantitative yields. The present method was successfully applied to various cyclic dialkylphosphorothionobromidates which are important materials in synthesis of many organophosphorus chemistry. Cyclic bis(dialkoxythiophosphoryl) disulfides by the reaction of dithiophodphoric acids of their salts with halogen of tellurium chlorides. Bromine, odine of tellurium chloride in aprotic solvent at temperature ranging from-78 C to $\theta$ C reacts with dithiophosphoric acids or their salts to give bis(dislkoxythiophosphoryl) disulfides in good yields. The esterification of dithiophosphates with diazonium salts was performed. Advantages of the method include higher yield, greate...