Some Unsymmetrical Aryl Sulfides¹

Abstract

Dunning, under whose direction this work has been carried out* He is also indebted to Drs* Du M e 2 , Vanden Bosche, Broughton, Drake, Haring and White for their valuable instruction* Special thanks are due Professor M* R* Thompson for his assistance in the pharma cological studies of the compounds, and Dr* David I. Macht and Mr. Irvin LaBuff, of Hynson, Westcott and Dunning, Inc., for their assistance in the toxicological and bacteriological examination of the compounds* The author desires to acknowledge his thanks to Dr. H. A. B. Dunning for the generous grant of funds which has made this work possible, and for the unlimited use of the laboratories of Hynson, Westcott and Dunning, Inc.

The Sulfenic Acids and their Derivatives.

“…It was suggested that the formation of the sulfide involved rearrangement, accompanied by acetylation, of XVII to XVIII. , o-and m-cresols, catechol, thymol, and the naphthols reacted readily with aromatic sulfenyl chlorides to give hydroxy sulfides(28,29,64,106,109,113,114). The reactions are similar to those which occur with dimethylaniline, and the products obtained may be exemplified by structures XIX to XXII.…”

“…C6H6MgBr + ArSCl -+ C6H6SAr + MgBrCl (29) The reaction was suggested as a suitable method for the preparation of unsymmetrical organic sulfides.…”

“…At least superficially, the above reactions of sulfenyl halides appear similar to the coupling reactions of phenols with diazonium salts. Various other examples of sulfide formation by the reaction of sulfenyl halides with phenols are included in the papers of Zincke and also of Foss and coworkers (28,29). Such reactions serve as suitable preparative methods for the hydroxy sulfides.…”

Some New Methods for Preparing Bunte Salts

“…This was chlorinated to the sulfenyl chloride which, however, was a liquid and was not obtained in a pure state. It had been prepared but not isolated before and had been subjected in a crude state to reactions with phenols (7). In order to be sure that the crude chlorination product really contained the desired 3-nitrobenzenesulfenyl chloride, we treated it with N, N-dimethylaniline and obtained a 73.3 % yield of the compound: in a reasonably pure state.…”