STRUCTURE AND THERMAL-DECOMPOSITION OF SOME 5-(CYCLOHEXYLOXY)THIANTHRENIUMYL PERCHLORATES

Five sets of cis- and trans-substituted cyclohexanols were used for re action with thianthrene cation radical perchlorate, namely, cis- and t rans-cyclohexane-1,2-diol, cis- and trans-2-methyl-, 3-methyl-, and 4- methylcyclohexanol, and cis,cis-and trans,trans-3,5-dimethylcyclohexan ol. Reaction in CH2-Cl-2 solution and precipitation with ether gave th e corresponding crystalline 5-(cyclohexyloxy)thianthreniumyl perchlora te salts. The configuration of each salt in CDCl3 was shown by H-1 and C-13 NMR spectroscopy to correspond with the configuration of the cyc lohexanol from which it was made. X-ray Ortep diagrams of four of the salts confirmed the structure deduced from NMR spectroscopy. In the NM R, inequivalence of the H-1 and C-13 signals from the thianthreniumyl 4- and 6-, 1- and 9-, 2- and 8-, and 3- and 7-positions was found when the 1'-position of the cyclohexyl ring was stereogenic. In the four O rtep diagrams, the orientation of the S-O bond was psuedoaxial. Therma l decomposition of the salts made from the monosubstituted cyclohexano ls at 100 degrees C in CH3CN solution gave products consistent with th e assigned structures.