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Investigation of O ‐Sulfonylation‐promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes
Author(s) -
Hsieh TsungHan,
Liao PenYuan,
Liu YuTing,
Wang ChienHong,
Lin ChiaChi,
Chien TunCheng
Publication year - 2018
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201700104
Subject(s) - chemistry , beckmann rearrangement , oxime , heterolysis , medicinal chemistry , intramolecular force , adduct , electrophile , benzophenone , amide , rearrangement reaction , bond cleavage , organic chemistry , catalysis
Two different reaction pathways were observed in the sulfonylation of N ‐phenylbenzamidoximes. The reaction with o ‐ NsCl at a heating temperature gave N , N′ ‐diphenylureas via Tiemann rearrangement, while the reaction with Ts 2 O at a lower temperature formed 2‐phenylbenzimidazoles via intramolecular electrophilic aromatic substitution. When the amide nitrogen was replaced with carbon substituents, oxime derivatives of benzoins and benzils underwent Beckmann fragmentation reactions upon sulfonylation, whereas sulfonylation of 2‐phenylacetophenone oxime afforded exclusively the Beckmann rearrangement adduct.