34774-87-3

Upstream product

• 75-18-3 dimethylsulfide 
• 2101-86-2 p-methylazidobenzene 
• 106-49-0 p-toluidine 
• 67-68-5 dimethyl sulfoxide 
• 27691-50-5 S,S-dimethyl-N-(4-tolyl)sulfimide 

Downstream Products

• 159014-85-4 1-(2-Methanesulfinylmethyl-4-methyl-phenyl)-1H-pyrrole 

Relevant academic research and scientific papers

Benzo[c]isothiazole 2-Oxides: Three-Dimensional Heterocycles with Cross-Coupling and Functionalization Potential

A robust method for the synthesis of benzo[c]isothiazole 2-oxides has been developed providing a range of functionalized derivatives starting from anilines and DMSO. The reaction sequence can be performed on a gram scale and leads to products that can easily be modified by standard cross-coupling reactions. (Figure presented.).

Formation of Sommelet-Hauser-Type Products, 2-Aminoarylmethyl Sulphides, and Nitrenium Ion Products, 2- and 4-Aminoaryl Sulphides, via an N-Arylazasulphonium Salt

Reactions of a salt (1) formed at -60 deg C from trifluoroacetic anhydride and dimethyl sulphoxide (DMSO) with primary and secondary arylamines gave 2-aminoarylmethyl sulphides (6), (6') and (12) by a Sommelet-Hauser rearrangement of an ylide (5) formed by loss of a methyl proton of an N-arylazasulphonium salt (3) in the absence of base.The use of ethyl methyl sulphoxide instead of DMSO afforded a similar product (19b) by loss of not the ethyl but the methyl proton.However, the use of diethyl sulphoxide merely caused loss of an ethyl group from the N-arylazasulphonium salt to yield ethanesulphenanilide (20).The reaction of (1) with N-phenyl-1-naphthylamine gave mainly aminoaryl sulphides (13) and (14) via an arylnitrenium ion from the N-arylazasulphonium salt.In fact, the reaction of dimethyl sulphide (DMS) with arylnitrenium ions formed in the acid decomposition of aryl azides gave no Sommelet-Hauser-type products but 2- and 4-aminoaryl sulphides (22), (22') and (23).We also discuss the possibility of the N-arylazasulphonium salt being formed by reaction of the arylnitrenium ion with DMS.

Thermal Reaction of Arylnitrenes with Dimethyl Sulphide, Thioanisole, and Tetrahydrothiophene

The thermal decomposition of the aryl azides (1) into dimethyl sulphide (2), thioanisole (3), and tetrahydrothiophene (4) generally affords the 2-substituted anilines (5)-(7) in practicable yields by Sommelet-Hauser rearrangement of the intermediate N-arylsulphimides (11a-c) which result from arylnitrene attack at the sulphur atom of (2)-(4).This constitutes a potential synthetic procedure.

Process for producing azasulfonium salts and rearrangement thereof to thio-ethers

Preparing ortho-substituted anilines by reacting an N-chloroaniline with a non-carbonylic di-hydrocarbon sulfide to form an azasulfonium chloride, reacting the azasulfonium chloride with a strong base to form an aniline substituted in the 2-position with a hydrocarbon-S-hydrocarbyl thio-ether group. The ortho-substituted thio-ether compounds can be reduced with a de-sulfurizing reducing agent such as Raney nickel or the like to form the ortho-alkylated aniline. The aniline may be an amino-pyridine. The azasulfonium salt and thio-ether intermediate products can be isolated and recovered. If desired, the thio-ether compounds can be reduced to form ortho-alkylated aniline products which are useful as intermediates for a wide variety of purposes, including their uses in making dyes, herbicides, and the like.

Process for preparing azasulfonium halide salts

Preparing azasulfonium halide salt derivatives of an aniline by reacting a halogen with a non-carbonylic dihydrocarbon sulfide, a beta-carbonylic hydrocarbon sulfide, or a β-thio ester or amide to form a halogen: sulfur compound complex and then reacting the complex with an aniline to form the azasulfonium halide salts. The azasulfonium halide salts are useful as intermediates in processes for making ortho-alkylated anilines, indoles, and 2-oxindoles which have a variety of known uses.