Proximity effects in diaryl derivatives. Part IV. Base-catalysed reactions of 2,2′-di(hydroxyamino)diaryl sulphones and of 2-(hydroxyamino)aryl phenyl sulphones
| Autor: | W. L. Matier, B. T. Johnston, M. F. Grundon |
|---|---|
| Rok vydání: | 1966 |
| Předmět: |
chemistry.chemical_classification
Aqueous solution Base (chemistry) Sodium Aryl Organic Chemistry Phenazine chemistry.chemical_element Disproportionation Medicinal chemistry chemistry.chemical_compound chemistry Sodium hydroxide Organic chemistry Smiles rearrangement Physical and Theoretical Chemistry |
| Zdroj: | J. Chem. Soc. B. :260-266 |
| ISSN: | 0045-6470 |
| DOI: | 10.1039/j29660000260 |
| Popis: | Reaction of 2,2′-di(hydroxyamino)diaryl sulphones with sodium hydroxide in aqueous dioxan at 20° yields dibenzo [b,f][1,4,5]thiadiazepine 5,11,11-trioxides (X), phenazine 5-oxides (XIV), and phenazine 5,10-dioxides (XV). The formation of the phenazine derivatives probably involves disproportionation of the aryl hydroxylamines, followed by Smiles rearrangement, and then loss of the sulphino-group. In the presence of zinc, the arylhydroxylamines are converted into phenazines (IV) and thiadiazepine 11,11-dioxides (VII). The mechanism of the alkaline reduction of 2,2′-dinitrodiaryl sulphones1 is discussed in the light of these results. Some of this work has been reported.2Treatment of 2-(hydroxyamino)aryl phenyl sulphones with sodium hydroxide at 20° results in loss of the phenylsulphonyl group. For example, 6-chloro-2-(hydroxyamino)diphenyl sulphone affords sodium benzenesulphinate and 3,3′-dichloroazoxybenzene. Cleavage of a C–S bond does not occur in 4-(hydroxyamino)diphenyl sulphone. Possible mechanisms for the reaction are discussed. |
| Databáze: | OpenAIRE |
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