50461-36-4Relevant articles and documents
Tetrahydrobenzo[c]thieno[2,1-e]isothiazole 4-Oxides: Three-Dimensional Heterocycles as Cross-Coupling Building Blocks
Lamers, Philip,Bolm, Carsten
supporting information, p. 116 - 118 (2018/01/17)
Unprecedented three-dimensional heterocycles are introduced, and their scaffold functionalization is described. A robust synthetic method utilizing cheap commercially available starting materials leads to a wide range of products on gram scale. The product portfolio can be expanded by applying newly devised building blocks with relevance for automated parallel synthesis in cross-coupling reactions.
Thermal Reaction of Arylnitrenes with Dimethyl Sulphide, Thioanisole, and Tetrahydrothiophene
Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
, p. 625 - 627 (2007/10/02)
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.
N-Phehylsulphimide Formation and Rearrangement in the Thermal Reaction of Phenylnitrene with Sulphides
Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
, p. 771 - 776 (2007/10/02)
Thermal reaction of phenyl azide (1) with thioanisole (2a), dimethyl sulphide (2b), and tetrahydrothiophen (2c) leads to the formation of 2-substituted anilines (3a-c) by Sommelet-Hauser rearrangement of the intermediate N-phenylsulphimides arising from phenylnitrene attack at the sulphur atom of (2a-c).Reaction with ethyl phenyl sulphide (2d) gives benzenesulphenanilide (8) and ethylene by cycloelimination of the resulting N-phenylsulphimide.Reaction with acyclic benzylic sulphides (2e-g) apparently leads only to the insertion products of phenylnitrene into benzylic C-H bond, presumably through Stevens rearrangement of the intermediate sulphimides, whereas Sommelet-Hauser rearrangement appears to compete favourably with Stevens rearrangement in the sulphimide resulting from reaction of phenylnitrene with the cyclic benzylic sulphide (2h).
Thermal Reaction of Phenylnitrene with Sulfides
Benati, Luisa,Grossi, Mario,Montevecchi, P. Carlo,Spagnolo, Piero
, p. 763 - 765 (2007/10/02)
Thermolysis of phenyl azide in the presence of sulfides bearing α-hydrogen atoms leads to the formation of significant amounts of 2-substituted anilines, presumably by Sommelet-Hauser type rearrangement of the intermediate N-phenylsulfimides.
Process for producing azasulfonium salts and rearrangement thereof to thio-ethers
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, (2008/06/13)
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.
