A. N. Pudovik

Thiolophosphohydrides: New Reagents in the Organo-Phosphorus Synthesis

Abstract A simple and effective method has been developed for synthesizing a new type of organophosphorus compounds, thiolophosphohydrides, with the general formula R(R′S)PH based on the selective reduction of thioesters of P(III) acids by di- or trialkylstannanes. Stable S-alkylalkylthiophos-phonites and S-alkylalkyldithiophosphonites have been obtained for the first time by using the processes of oxidation and sulfurization. The functionally substituted phosphorus (111) thio derivatives have been obtained by the addition reactions of thiolophosphohydrides with compounds containing carbon-carbon and carbon-oxygen multiple bonds, with the cleavage of the P-H bonds and the preservation of P-S bonds. Factors affecting the rate of interaction, stability and the structure of additional products have been elucidated. Depending on the reaction conditions of thiolophosphohydrides with halogen containing electrophilic reagents and on the nature of the latter, the process can lead to the cleavage either of the P-H...

Synthesis of monothioesters of alkyl thiophosphonous acids

There is virtually no information available on the preparation of acid thioesters of alkyl phosphonous acids. Akamshin [i] and Ofitserov [2] have reported the intermediate formation of these compounds in the hydrolysis and acidolysis of acid chlorides and esters of alkyl thiophosphonous and alkyl dithiophosphonous acids. The unstable S-ethyl ester of phenyl thiophosphonous acid detected by 3~p NMR spectroscopy at low temperature is the only reported example of these compounds [3].

Reactions of thioesters of trivalent phosphorus acids with complex alkali-metal hydrides

Conclusions1.Thioesters of phosphinous, phosphonous, and diaminophosphorous acids react with lithium aluminum hydride to form the corresponding primary and secondary phosphines or diamides of hypophosphorous acid.2.The use of crown ethers as phase-transfer catalysts in reduction reactions of thioesters of pIII acids makes it possible to increase the rate of the process and raise the yield of the final products.