The interaction of trimethylsilyl esters of trivalent organophosphorus acids containing PH and POSiMe 3 fragments in the presence of trimethylsilyl trifluoromethanesulfonate as catalyst is proposed as a convenient method for the synthesis of new trimethylsilyl esters of aminomethylenebisorganophosphorus acids with three and four coordinated phosphorus. Also the new functionalized derivatives of the aminomethylenebisphosphinic acids with substituted hydroxymethyl moieties are synthesized, and some properties of the obtained compounds are presented. C 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:355-360, 2013; View this article online at wileyonlinelibrary.com.

The interaction of trimethylsilyl esters of trivalent organophosphorus acids containing PH and POSiMe3 groups with hydrochlorides of ethoxymethylene imines is a convenient method for the synthesis of new trimethylsilyl esters of N‐unsubstituted aminomethylenebisorganophosphorus acids with three and four coordinated phosphorus. Also trimethylsilyl trifluoromethanesulfonate as effective catalyst is used for the similar interaction of hydrochlorides of ethoxymethylene imines with tris(trimethylsilyl)phosphite. The corresponding bisorganophosphorus acids and their derivatives are presented.

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