. 63, 1268 (1985). No rnorphinan analog carrying a heteroatorn other than nitrogen at position 17 has yet been synthesized. The synthesis of the position 17 sulfur analog of the perchlorate salt of (*)-isolevorphanol is described. The strategy adopted is based on the classical Grewe synthesis of morphinans and, under narrowly defined conditions, the title compound isosulforphanol (3a) and an intermediate by-product 13 resulting from an unusual non-bridged head ring closure of l l a were obtained. The X-ray structures of both 3a and 13 were determined. Crystals of 13 (T17H210S) are monoclinic, space group P2,/a, a = 17.080(2), b = 9.372(1), c = 9.327(1) A, P = 108.67(1), V = 1414.4 A3, Z = 4. Final R = 0.034 for 2545 reflections. The crystals 2f 3a (C17H230S'. C1O4-) are orthorhombic, space group Pna2,, a = 10.934(1), b = 9.219(1), c = 17.13 l(2) A, V = 1726.8A', Z = 4. Final R = 0.053 for 1018 reflections. The C17H2'0S' molecule has been identified by this X-ray analysis as S-methyl isosulforphanol (Fig. 2). The structure of 13 is shown in Fig. 1. The stereochemical outcome of the Grewe-like synthesis is thus established as proceeding in a reversed manner when sulfur replaces the nitrogen in the final cyclization step. Preliminary pharmacological studies showed that 3a is a potent agonist in the central nervous system but a potent antagonist on the guinea-pig ileum.BERNARD BELLEAU, UGO GULINI, BARBARA GOUR-SALIN et F. R. AHMED. Can. J. Chern. 63, 1268Chern. 63, (1985. Jusqu'h maintenant, aucun analogue de la morphinane portant un hCtCroatome autre que I'azote en position 17 n'a Ct C synthCtisC. On dCcrit la synthese d'un analogue portant un atome de soufre en position 17; il stagit-du perchlorate du (+-)-isolCvorphanol. La stratCgie adoptte se base sur la synthese classique des morphinanes dCveloppCe par Grewe et, utilisant des conditions Ctroitement dCfinies, on a obtenu le cornposC isosulforphanol (3a) mentionnt dans le titre ainsi qu'un sousproduit intermediaire (13) fig. 2). La figure I illustre la structure du composC 13. On a ainsi Ctabli que le rCsultat stCrCochimique de la synthkse de Grewe est inverse lorsqu'on remplace l'azote par le soufre dans 1'Ctape finale de cyclisation. Des Ctudes pharmacologiques prkliminaires indiquent que le composC 3a est un agoniste potentiel dans le systkrne nerveux central mais un antagoniste potentiel dans I'ilCum du cochon d'inde.[Traduit par le journal]