MIXED ANHYDRIDES OF DIALKYLPHOSPHINOUS ACIDS AND DIALKYL HYDROGEN PHOSPHITES, AND THE ISOMERIC MONOXIDES

Abstract
The three isomers possible for oxidized 1,1-dialkyl-2,2-dialkoxydiphosphines, R2(O)P–P(OR')2 1, R2P–O–P(OR')2 2, and R2P–P(O)(OR')2 3, have been synthesized. Irreversible transformations of 1 to 2 and 2 to 3 have been found and the rearrangement patterns, the role of electrophilic and nucleophilic catalysts are discussed. The fact that 3 is more stable than 1 is attributed to higher donor activity of the ligands attached to the four-coordinate phosphorus in 3. Acid chlorides have been shown to attack the phosphorus atom of ambident anions of trivalent phosphorus acids (the products are 1 and 3) whereas the acids proper react with the acid halides at the oxygen atom, to give 2.

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