Novel carbonaceous coupling products containing sulphur

Abstract

The coupling of alkali ethynides with CSCl2, SOCl2, or SO2Cl2 results in new carbonaceous polymeric products; their structures were studied by FTIR and XPS spectra, and the assumptions on reaction mechanism were made with respect to the found elemental composition and model calculations. These macromolecular products, obtained in the yields of 80–92%, contain chlorine in the chain terminals, and alkyne sequences along with inserted C=S, S=O or SO2 groups. These inserted sulphur groups contribute to the stability of alkyne sequences as evidenced by FTIR spectra. Soluble thioketone iPr3SiC≡C–CS–C≡CSiiPr3 (2) prepared by similar coupling of iPr3SiC≡CLi (1) with CSCl2 in the yield of 72%, was considered as a support of the suggested coupling mechanism. Similarly monomolecular sulfoxide iPr3SiC≡C–SO–C≡CSiiPr3 (3) was prepared by coupling of iPr3SiC≡CLi (1) with SOCl2 in the yield 75%.