53165-12-1

Upstream product

• 5226-51-7 2,2-dimethyl-1,4-dihydro-2H-3,1-benzoxazine 
• 108-98-5 thiophenol 
• 100-68-5 methyl-phenyl-thioether 
• 622-37-7 Phenyl azide 
• 91718-67-1 (2-nitrobenzyl)(phenyl)sulfane 
• 3958-60-9 2-nitrophenylmethyl bromide 
• 930-69-8 sodium thiophenolate 

Downstream Products

• 230-04-6 6H-dibenzothiopyran 
• 831-91-4 Benzyl phenyl sulfide 
• 882-33-7 diphenyldisulfane 

Relevant academic research and scientific papers

FLASH VACUUM PYROLYSIS OF 1-ALLYLBENZOTRIAZOLES AND DIHYDROBENZOXAZINES : FORMATION OF QUINOLINES

Pyrolysis of 1-allylbenzotriazoles gives quinolines whereas 2,2-dialkyl-dihydrobenzoxazines give azaxylylenes and not quinolines as previously reported.

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.

N-Phehylsulphimide Formation and Rearrangement in the Thermal Reaction of Phenylnitrene with Sulphides

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

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.