70413-90-0

Upstream product

• 7669-54-7 2-nitrobenzenesulfenyl chloride 
• 13435-12-6 N-Trimethylsilylacetamide 
• 60-35-5 acetamide 
• 88047-02-3 4-chloro-N²-(4-chlorophenyl)-N¹,N²-bis(2-nitrophenylthio)-o-phenylenediamine 
• 85695-75-6 4-methoxy-N²-(4-methoxyphenyl)-N¹N²-bis(2-nitrophenylthio)-o-phenylenediamine 
• 7257-59-2 2-nitrobenzenesulfenamide 
• 75-36-5 acetyl chloride 

Downstream Products

• 73463-47-5 N,N'-bis(phenylsulfonyl)-o-nitrobenzenesulfinamidine 

Relevant academic research and scientific papers

Efficient synthesis of N-acylarenesulfenamides by acylation of arenesulfenamides

Acylation of arenesulfenamides proceeds efficiently by using either perfluorocarboxylic anhydrides or acid chlorides in the presence of pyridine as a base at low temperatures to give N-acylarenesulfenamides. Some N-alkylcarbonyl derivatives exist with imidic acid tautomers in an aprotic solvent.

Benzenesulphenanilidyl Radicals. Part 2. Substituent and Solvent Effects on the Reactivity of 4'-Substituted Benzenesulphenanilidyl Radicals Produced by Oxidation with Lead Dioxide of the Corresponding Benzenesulphenanilides

Oxidation of benzenesulphenanilide (1d) with lead dioxide in benzene affords the p-benzoquinone diimine (5d) together with minor amounts of N,N-bis(phenylthio)aniline (4d) and diphenyl disulphide (7a).The formation of the products is explained in terms of p-C-N coupling of the benzenesulphenanilidyl radicals (2d) and subsequent fragmentation of the resulting dimer.A similar trend is observed in the oxidation of 4'-chloro- and 4'-bromo-benzenesulphenanilides (1e) and (1f), whereas 4'-nitrobenzenesulphenanilide (1g) leads to the o-phenylenediamine (12g), arising from o-C-N coupling of the sulphenanilidyl radical (2g).The oxidation of the sulphenanilides (1e) and (1f) in acetonitrile produces the phenazines (3e) and (3f) and the disulphide (7a), whereas the anilide (1g) and 4'-cyanobenzenesulphenanilide (1h) give azobenzenes (11g) and (11h) and the disulphide (7a); these results are discussed in terms of a possible mechanism involving oxidation of the N-N dimers (14e-h) which are in rapid equilibrium with the corresponding sulphenanilidyl radicals (2e-h).Evidence is also presented that the oxidation of 2-nitrobenzenesulphenanilides leads to products ascribable to intermediate 2-nitrobenzenesulphenanilidyl radicals, in contrast with a previous claim.

Benzenesulphenanilidyl Radicals. Reactivity of 4'-Methoxy- and 4'-Methoxy-2-nitro-benzenesulphenanilidyl Radicals

Oxidation of 4'-methoxybenzenesulphenanilide (1a) with lead dioxide at 30 deg C afforded the NN-bis(phenylthio)-p-anisidine (7a) and 2,7-dimethoxypheazine (3a) together with minor amounts of diphenyl (4a), whereas at 10 deg C almost exclusive formation of compound (7a) and the o-benzoquinone di-imine (8a) was observed; compound (8a) was found to be thermally unstable and to give, quantitatively, compounds (4a) and (3a).The reaction products are rationalized by assuming that 4'-methoxybenzenesulphenanilidyl radicals (2a), produced by oxidation of compound (1a), undergo Cortho-N coupling to give the dimer (9a), which is responsible for the reaction products observed.A comparable trend was observed by producing the radical (2a) from reaction of compound (1a) with t-butoxy-radicals and by thermal decomposition of compound (7a).These findings rule out the nitrene mechanism previously suggested for the formation of compound (3) from oxidation of the reagent (1a).Evidence has been found that Cortho-N coupling is the main reaction path, exhibited also by 4'-methoxy-2-nitrobenzenesulphenanilidyl radicals (2c) generated from the corresponding anilide (1c) by reaction with t-butoxy-radicals or oxidation with lead dioxide, which thus rejects a previous claim that the radicals (2) (Ar = Ph and Ar = C6H4NO2-o) exhibit different chemical behaviour.

IMINATION OF SULFUR-CONTAINING COMPOUNDS. XII. ARYLSULFONYLIMINATION OF N-ACYLARENESULFENAMIDES

Arylsulfonylimination at the sulfur of N-acylarenesulfenamides was realized for the first time with the sodiochloroamides of sulfonic acids, where the acyl represents aroyl and alkanoyl groups.The imination of N-acyl-p-nitrobenzenesulfenamides occurs in an aqueous alkaline medium, and this is evidently due to an increase in the nucleophilicity of the sulfur in the corresponding anion on account of the displacement of electronic charge toward it from the nitrogen atom.During the imination of N-acyl-p- and N-acyl-o-nitrobenzenesulfenamides in pyridine cleavage of the sulfur-nitrogen bond occurs, and the NO2C6H4S residue is iminated to form N,N'-bis(arylsulfonyl)-p- and N,N'-bis(arylsulfonyl)-o-nitrobenzenesulfinamidines.