3058-46-6

In this article, we have presented a novel and efficient method for the direct synthesis of unsymmetrical sulfides through the copper(I)-catalyzed cross-coupling of 2-nitro benzenesulfonamides with thiols in the presence of catalytic amount of CuI in DMF as solvent at 100 °C. In addition, the products were obtained in high to excellent yields. More importantly, the novel system showed the primary 2-nitro benzenesulfonamides as a new coupling partner and regioselectively promoted C–S bond-forming transformations through the cleavage of Ar–SO2NH2 bonds.

A novel copper-catalyzed decarboxylative methylthiolation of arenecarboxylate salts has been realized using DMSO as the methylthiolation source. Various potassium aryl carboxylates underwent decarboxylative methylthiolation under air to furnish the corresponding aryl methyl thioethers in moderate to excellent yields. The reaction tolerated a wide variety of functional groups. Notably, the synthesis of ethylthioethers was also successfully achieved directly from diethyl sulfoxide under similar reaction conditions.

A study was conducted to demonstrate the transition-metal-catalyzed synthesis of aryl sulfides by decarboxylative C-S cross-couplings. Coupling reaction of 2-nitrobenzoic acid with 1-octanethiol were carried in the presence of different combinations of tr

The relative rates of nucleophilic substitution (SN2) of alkyl halides by aromatic thiolates ArS- and aryldisulphide ions ArS2- have been studied in dimethylacetamide by UV-visible spectrophotometry for Ar = 4-nitrophenyl (1), 2-nitrophenyl (2), and 8-quinolyl (3).Rate constants are relative to the rate constants for benzenethiolate ions (4), studied as reference.With Ar = (1), the reaction rate for disulphide ions is ten times higher than that for monosulphide ions stabilized by the elevated delocalization of their charge.With Ar = (2) and (3), the reactivity of disulphide ions is higher than that of the corresponding thiolates.Our study is consistent with the uncomplicated introduction of a disulphide bond into various substrates from aryldisulphide ions stabilized in aprotic dipolar media.

Syntheses of the alkyl, cycloalkyl and aryl 2-aminophenyl sulfones 10 were achieved by oxidation of the corresponding 2-nitrophenyl sulfides 7 to the 2-nitrophenyl sulfones 9 followed by ethanolic Bechamp-reduction.The sulfides 7 in turn were obtained by either reactions of 2-nitro-thiophenol (8) with the appropriate alkyl and cycloalkyl halides or of 2-chloro-nitrobenzene (5) with the relevant thiols.Condensation of 2-nitrobenzenesulfinic acid (3) with bromoacetic acid in aqueous alkaline solution led - presumably via 2-nitrophenylsulfonylacetic acid (4) - to methyl2-nitrophenyl sulfone (1), reduction of which gave 2-aminophenyl methyl sulfone (2).Treatment of 2-aminothiophenol (11) with t-butyl alcohol in aqueous sulfuric acid gave 2-aminophenyl t-butyl sulfide (12), which was acetylated to o-t-butylthio-acetanilide (13).Oxidation of the latter to o-t-butylsulfonyl-acetanilide (14) followed by hydrolysis led to 2-aminophenyl t-butyl sulfone (15).