- Formation of Sommelet-Hauser-Type Products, 2-Aminoarylmethyl Sulphides, and Nitrenium Ion Products, 2- and 4-Aminoaryl Sulphides, via an N-Arylazasulphonium Salt
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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.
- Takeuchi, Hiroshi,Itou, Kazuaki,Murai, Hirotaka,Koyama, Kikuhiko
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p. 3156 - 3188
(2007/10/02)
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- Synthesis of sulfilimines
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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.
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- Behavior of Benzyl Sulfoxides toward Acid Chlorides. Useful Departures from the Pummerer Reaction
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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.
- Chupp, John P.,Balthazor, Terry M.,Miller, Michael J.,Pozzo, Mark J.
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p. 4711 - 4716
(2007/10/02)
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