Reactions of (1,3,3-Trichloro-2,2,4,4-tetramethylcyclobutyl)sulfenyl Chloride with Some S- and O-Nucleophiles

Abstract

The sterically crowded 3,3-trichloro-2,2,4,4-tetramethylcyclobutanethione (2c) easily reacts with phosphorus pentachloride in CCl₄ yielding the relatively stable (1,3,3-trichloro-2,2,4,4-tetramethylcyclobutyl)sulfenyl chloride (3c). The reactions of 3c with benzylsulfane (4) and thiocamphor (5) occur with elimination of HCl leading to the unsymmetrical disulfanes 6 and 9. In the case of the sulfenates 10 and 12, which are formed as intermediates in the reactions of 3c with propargyl and allyl alcohol, respectively, the subsequent [2,3]-sigmatropic rearrangement yields the corresponding sulfoxides 11 and 13.

Keywords:

• Diorganyldisulfanes
• oxygen nucleophiles
• sigmatropic rearrangements
• sulfenyl chlorides
• sulfur nucleophiles

Dedicated to Professor Marian Mikołajczyk, CBMiM PAN in Łódź, Poland, on the occasion of his 70th birthday.

The authors thank the Rector of the University of Łódź for a grant (G. M. and M. W.) and F. Hoffmann-La Roche AG, Basel for generous support (H. H.).