Alkyl- and arylthiodediazoniations of dry arenediazonium o-benzenedisulfonimides. Efficient and safe modifications of the stadler and ziegler reactions to prepare alkyl aryl and diaryl sulfides

J Org Chem. 2000 Sep 8;65(18):5600-8. doi: 10.1021/jo0003347.

Abstract

The reaction between dry arenediazonium o-benzenedisulfonimides 1 and sodium thiolates in anhydrous methanol represents an efficient and safe procedure, of general validity, for the preparation of unfunctionalized or variously functionalized alkyl aryl and diaryl sulfides. As a rule, the reaction temperature was maintained at 0-5 degrees C for the alkylthiodediazoniations and at room temperature (20-25 degrees C) for the arylthiodediazoniations. The sulfide yields are generally high; of the 63 considered examples, 43 gave yields greater than 80% and 13 were between 70% and 80%. Lower yields were obtained only when sterically hindered diazonium salts or thiols were used. A good amount of the o-benzenedisulfonimide (8) was always recovered from the reactions and could be reused to prepare salts 1. The copious experimental data collected in homogeneous conditions have offered several starting points for the study of the mechanism of these reactions.