34774-86-2Relevant academic research and scientific papers
Formation of Sommelet-Hauser-Type Products, 2-Aminoarylmethyl Sulphides, and Nitrenium Ion Products, 2- and 4-Aminoaryl Sulphides, via an N-Arylazasulphonium Salt
Takeuchi, Hiroshi,Itou, Kazuaki,Murai, Hirotaka,Koyama, Kikuhiko
, p. 3156 - 3188 (2007/10/02)
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.
Synthesis of sulfilimines
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, (2008/06/13)
Processes are disclosed for preparation of N-aryl-S,S-dihydrocarbylsulfilimines by reaction of phenylisocyanate compounds with hydrocarbyl sulfoxides. The sulfilimines can be rearranged to ortho-thioalkylene anilines and the reactions can be employed in a route for converting nitrobenzene compounds to ortho-thioalkylene anilines, which are useful intermediates for preparation of herbicidal compounds.
Behavior of Benzyl Sulfoxides toward Acid Chlorides. Useful Departures from the Pummerer Reaction
Chupp, John P.,Balthazor, Terry M.,Miller, Michael J.,Pozzo, Mark J.
, p. 4711 - 4716 (2007/10/02)
The present study extends the reaction of certain electrophilic reagents with electron-rich sulfides and sulfoxides beyond previously known limits.Thus, treatment of methoxy- and, more particularly, aminobenzyl sulfoxides 2 with acyl or hydrogen chlorides gives rise in high yields to the corresponding benzyl chlorides, a departure from the normally expected Pummerer reaction.It is demonstrated that ideal substrates for this reaction are o-anilines 1 derived from the well-known rearrangment of aromatic sulfilimines.Further, certain of the o-ammoniobenzyl chloride salts 4 so produced provide a basis for a novel and superior desulfurization of 1 to the corresponding o-methylaniline without resorting to Raney nickel.
