synopsisPoly[alkylene bis(oxyc!arbonyl) disulfides] have been prepared for the first time by the reductive Goupling of alkylene bis(oxycarbonylsulfeny1 chlorides). Potassium iodide and a variety of transition metals or their salts were employed as reducing agents. Of these potassium iodide and cuprous chloride gave the best results. Pyrolysis, desulfurization, and thiol-indud fragmentation of the polymers have been studied. Homologous polymers, i.e., monosulfide polymer, trisulfide polymer, and tetrasulfide polymer, have been also synthesized. Monosulfide and disulfide polymers were highly crystalline solids. Trisuliide polymer was a white solid with a low degree of crystallinity. These polymers were soluble in chloroform and dichloromethane. Tetrasulfide polymer was a crystalline yellow solid and was soluble only in HMPA.
RESULTS AND DISCUSSION
Reductive Coupling of Alkylene Bis(oxycarbonylsdfeny1 Chlorides)Alkylene bis(oxycarbonylsulfeny1 chlorides) (I) were prepared by the reaction of chlorocarbonylsulfenyl chloride with diols as previously described [eq. (l)]." 3317 0 1972 by John Wiley & Sons, Inc. 3318 KOBAYASHI AND FUJISAWA ClCSCl + HO(CH2),0H -C1SCO(CH2),0CSC1 (1) II 0 11 0 I1 0 I a , m = 4 b , m = 6Compounds Ia and Ib are relatively stable at room temperature and therefore might be handled more easily than alkylene bis(sulfeny1 chlorides) .' en Reductive coupling of I proceeds according to eq. (2).
IIa, m = 4 b , m = 6Polymer formation was performed by stirring a mixture of I and an excess of reducing agent at room temperature. As reducing agents, potassium iodide and a variety of transition metals or their salts were employed.