The method of axial: equatorial rate ratios has been applied to the study of themechanism offormation of sulfenes via the reaction of alkanesulfonyl chlorides with base. The axial trans-2-decalinsulfonyl chloride (6) and the equatorial trans-2-decalinsulfonyl chloride (8) were synthesized. The axial sulfonyl chloride 6 was found to react 71 times faster than the equatorial epimer 8 with triethylamine in the presence of aniline at -25", a reaction which evidently proceeds via the sulfene 7. With water at 50" without added base (a reaction believed to take place by direct attack on the sulfur atom) 8 reacts about 14 times faster than 6. It is concluded that the formation of the sulfene 7 from 6 by the action of triethylamine cannot take place by a mechanism involving a slow SN2 reaction followed by a fast bimolecular elimination, and that the most likely route for 6, and other alkanesulfonyl chlorides as well, is the E2 reaction.La mkthode des rapports de vitesse axia1:Cquatorial a kt6 utilisee pour Btudier le mecanisme de la formation des sulf6nes via la reaction des chlorures d'alkanesulfonyles avec une base. Le chlorure de la trans-2-decalinsulfonyle axiale (6) et le chlorure de la trans-2-dCcalinsulfonyle Cquatoriale (8) ont et6 synthttists. Le chlorure de sulfonyle axial 6 reagit 71 fois plus vite que 1'6pimere equatorial 8 avec la triethylamine en presence d'aniline a -25" (reaction qui se fait via le sulfene 7). Dans I'eau a 50°, sans I'adjonction d'une base, (reaction supposke se faire par une attaque directe sur l'atome de soufre) le compose 8 reagit environ 14 fois plus vite que le compose 6. Ces rksultats prouvent que la formation du sulfene 7 a partir de 6, par I'action de la triethylamine, ne peut se faire par un mecanisme impliquant une reaction SN2 lente suivie d'une elimination bimoleculaire rapide. A partir du compose 6, et d'autres chlorures d'alkanesulfonyle, le mecanisme le plus probable est celui faisant intervenir une reaction E2.
Die relativen Geschwindigkeiten der Dehydrohalogenierung des axialen Sulfonylchlorids (Ia) und seines Epimeren (Ib) mit basischen Reagenzien, die zur Bildung der Sulfen‐Stufe (III) führt, werden zur Untersuchung des Mechanismus dieser Reaktion ermittelt.
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