Arylnitrenium-Ionen bei der Umlagerung vonO-(Arylsulfonyl)phenylhydroxylaminen
作者： Dieter Gutschke , Albert Heesing
关键词: Solvent 、 Chemistry 、 Polymer chemistry 、 Intimate ion pair 、 Sulfonyl 、 Heterolysis 、 Inorganic chemistry
摘要: Bei der Umlagerung von O-Arylsulfonyl-N-benzoylphenylhydroxylaminen zu O-Arylsulfonyl-o-benzamidophenolen treten bevorzugt, aber nicht ausschlieslich, die Sulfonyl-O-Atome in o-Stellung des Kerns. Temperatur-, Losungsmittel- und Substituenten-Effekte lassen sich durch eine Heterolyse N–O-Bindung einem inneren Ionenpaar aus Arylnitrenium- Tosylat-Ion deuten. Infolge sehr schnellen Rekombination zeigt letzteres nur beschrankte Beweglichkeit im Losungsmittelkafig. Nitrenium Ions during Rearrangement of O-(Arenesulfonyl)phenylhydroxylamines In the rearrangement O-(arenesulfonyl)phenylhydroxylamines to O-arenesulfonyl-o-benz-amidophenols sulfonyl oxygen preferentially attacks ortho-position. The effects temperature, solvents, and substituents can be explained by assuming that heterolysis N–O bond takes place give an intimate ion pair consisting aryl-nitrenium a tosylate ion. fast recombination limits mobility anion solvent cage.
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