H. Kuroda, I. Tomita, T. Endo
Nov 1, 1997
Citations
0
Influential Citations
19
Citations
Journal
Polymer
Abstract
Abstract A novel polyaddition of terminal acetylenes bearing electron-withdrawing groups with dithiols, via a phosphine-catalysed double conjugate addition, is described. From the model reaction of methyl propiolate (1) with benzylmercaptan in the presence of tri-n-butylphosphine catalyst, the corresponding dithioacetal was obtained in high yield when the reaction was carried out under higher concentrations of the catalyst and the reactants. By using aliphatic dithiols having a rigid spacer [i.e. p-xylene-α,α′-dithiol (5)], the polyaddition of 1 took place smoothly to yield a polymer (6) bearing dithioacetal moieties in the main chain in 84% yield, whose Mn and Mw/Mn were estimated to be 8100 and 1.29, respectively. Further, the polymer (8) having dithioacetal moieties was also obtained quantitatively by the polyaddition of an ynone (7) with 5.