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Abstract
An improved high-yield Arbusov-type synthesis for diphosphorylmethanes with different substituents on both phosphorus atoms ( 4 , 5 , 7 ) by the reaction of isopropyl diphenylphosphinite or diisopropyl phenylphosphonite with diisopropyl bromomethylphosphonate ( 1 ) or isopropyl phenyl-bromomethyl-phosphinate ( 2 ), respectively, is described. 1 and 2 are available in yields of about 50% by the reaction of an excess of methylene bromide with triisopropylphosphite or diisopropyl phenylphosphonite, respectively.
The metalation of the symmetrical and unsymmetrical diphosphorylmethanes 3–8 with NaH in toluene yields the corresponding carbanionic salts 3A–8A . Their structure und reactivity are investigated by means of 31P NMR spectroscopy and Horner-reactions with benzaldehyde.
Regioselective monomethylation at the central carbon atom of 3–7 is performed using the phase-transfer technique. With exception of the phosphono-phosphinate derivative 14 , on this way the appropriate 1,1-diphosphorylethanes 13 and 15–17 are obtained in high yield.