149228-06-8Relevant academic research and scientific papers
ZUR SYNTHESE UND REAKTIVITAET METHYLENVERBRUECKTER DIPHOSPHORYLVERBINDUNGEN
Goebel, R.,Richter, F.,Weichmann, H.
, p. 67 - 80 (2007/10/02)
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-bromomethylphosphinate (2), respectively, is described. 1 and 2 are available in yields of about 50 percent 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 and 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.Key words: diisopropyl bromomethylphosphonate; isopropyl phenyl-bromomethylphosphinate; diphosphorylmethanes; 31P-NMR; HORNER-reactions; 1,1-diphosphorylethanes
