REACTION OF POLYPEROXIDES WITH TRIPHENYLPHOSPHINE

The triphenylphosphine deoxygenation of the polyperoxides, poly(styren e peroxide), poly(methyl methacrylate peroxide), and poly(alpha-methyl styrene peroxide) proceed via the phosphorane intermediates, which in the presence of moisture hydrolyze to give the respective diols. At hi gher temperatures and under dry conditions the phosphorane decomposes into epoxide and triphenylphosphine oxide. The reaction has been studi ed by H-1-, C-13-, and P-31-NMR spectroscopy. The results obtained are consistent with a concerted insertion of the biphile, triphenylphosph ine, into the peroxy bond and this reaction pathway seems to be new as far as the chemistry of polyperoxides is concerned. Though the aim of this investigation was to test the selective deoxygenation of polyper oxide by triphenylphosphine as a method of preparing polyethers, it tu rned out to be a fruitful method of synthesis of stereospecific diols. (C) 1997 John Wiley & Sons, Inc.