Nitro-sulfide rearrangements

The application of nitro-sulfide rearrangements in heterocycle synthesis has been more recently reported [75]. 

In contrast, reaction of allylic nitro compounds 4 with sodium benzenethiolate in HMPT leads to rearranged allylic sulfides 5.2... 

Orthanilic acid was first made by the reduction of nitro-benzenesulfonic acid by ammonium sulfide.2 This reduction has also been carried out electrolyticallv, and by the use of iron or zinc.3 The acid has also been made by the rearrangement of phenylsulfamic acid,4 by the action of sodium hypobromite upon potassium o-carbaminebenzenesulfonate,5 by the reduction of the mixed nitrobenzenesulfonic acids followed by separation of the isomers,6 by the action of methyl alcohol upon o-nitro-phenylsulfurchloride,7 by the action of acid upon diacetyl diphenylsulfamide,8 by the debromination of />-bromoaniline-e-sulfonic acid,9 by the reduction of 1,2,6-aminothiophenolsulfonic acid,10 and by the hydrolysis and reduction of e-nitrobenzene-sulfonyl chloride, which was obtained from di-o-nitrophenyl-disulfide.11... 

PFIA453, 93PFIA620, 92PFIA945). The intramolecular cyclization (via the Smiles rearrangement) of 2-nitro-2 -(/l-acetyl)-hydrazino-diphenyl sulfide yields 10-ace-tylaminophenothiazine (84PHA22). 

Attempts have been made to synthesize azaphenothiazines by a Smiles rearrangement of 2-formamidophenyl 3 -nitro-2-pyridyl sulfide and 2-formamidophenyl-3 -nitro-4 -pyridyl sulfide (88MI1, 58JOC1906). 

However, 1-azaphenothiazines have been prepared (58JA1651) by hydrolysis of 1-acetyl-1-azaphenothiazine, obtained by Smiles rearrangement of 2-acetamidophe-nyl 3 -nitro-2 -pyridyl sulfides (in acetone-ethanol and KOH). 

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