94839-53-9Relevant academic research and scientific papers
Reactions of dimethyl polysulfides with organomagnesium reagents
Clark, Peter D.,Mann, Russell S.,Lesage, Kevin L.
, p. 29 - 33 (2007/10/02)
Reactions of a mixture of dimethyl polysulfides (DMPS, CH3SxCH3, x = 3 - 8) with methyl- and phenylmagnesium halides are described.The type of product obtained was dependent on the molar ratio of DMPS to Grignard reagent.When a 6:1 methyl-Grignard to DMPS ratio was used, methanethiol and dimethyl sulfide were the major products obtained after acidification of the reaction mixture.Lesser quantities of methyl-Grignard favored the formation of dimethyl sulfide, dimethyl disulfide, and H2S.Experiments with a 6:1 phenylmagnesium bromide to DMPS ratio produced benzenethiol and phenylmethyl sulfide as major products after acidification.No methanethiol was observed in these experiments.Mixtures of phenylmethyl mono-, di- and trisulfides and H2S were obtained with a 3:1 Grignard/DMPS molar ratio.From a mechanistic viewpoint, product distributions obtained from reaction of Grignard reagents with DMPS can be explained by the formation of magnesium thiolates that are most readily stabilized by adjacent structures.Experiments using phenyl Grignard reagent in limited supply suggested that the internal sulfur atoms of the polysulfide chains were more reactive.
Formation of Stable Aryldisulphide Ions in Dimethylacetamide from the Reaction of Sulphur with Thiolate Ions
Benaichouche, Meriem,Bosser, Gerard,Paris, Jacky,Auger, Jacques,Plichon, Vincent
, p. 31 - 36 (2007/10/02)
The conditions for the formation of aryldisulphide ions, RS2- during the direct reaction of sulphur with thiolate ions RS- have been studied by the use of spectroelectrochemistry in dimethylacetamide.The series of derivatives examined was R = p-tolyl (1), phenyl (2), 8-quinolyl (3), 2- and 4-pyridyl (4), (5), N-oxido 4-pyridyl (6), 2- and 4-nitrophenyl (7), (8), and 2-(5-nitropyridyl) (9).Sulphur reaction leads to RS2- ions and preceded the oxidation to diaryldisulphide RS2R and polysulphide ions Sx-.With derivatives (1)-(3), both reactions are successive and practically stoicheiometric, while for derivatives containing electron-withdrawing groups (6)-(9), the equilibrium constants have been measured.Analysis of the reaction products by methylation of several solutions of thiolate ions in the presence of sulphur confirmed the possibility of obtaining aryldisulphide ions stabilized in aprotic dipolar media.
