Investigation of O-Sulfonylation-promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes

Tsung Han Hsieh; Pen Yuan Liao; Yu Ting Liu; Chien Hong Wang; Chia Chi Lin; Tun Cheng Chien

doi:10.1002/jccs.201700104

Investigation of O-Sulfonylation-promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes

Tsung Han Hsieh, Pen Yuan Liao, Yu Ting Liu, Chien Hong Wang, Chia Chi Lin, Tun Cheng Chien

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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 Ts₂O 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.

Original language	English
Pages (from-to)	325-330
Number of pages	6
Journal	Journal of the Chinese Chemical Society
Volume	65
Issue number	3
DOIs	https://doi.org/10.1002/jccs.201700104
Publication status	Published - 2018 Mar

Keywords

Beckmann fragmentation
Beckmann rearrangement
Electrophilic aromatic substitution
Tiemann rearrangement

ASJC Scopus subject areas

Chemistry(all)

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10.1002/jccs.201700104

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title = "Investigation of O-Sulfonylation-promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes",

abstract = "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 Ts2O 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.",

keywords = "Beckmann fragmentation, Beckmann rearrangement, Electrophilic aromatic substitution, Tiemann rearrangement",

author = "Hsieh, {Tsung Han} and Liao, {Pen Yuan} and Liu, {Yu Ting} and Wang, {Chien Hong} and Lin, {Chia Chi} and Chien, {Tun Cheng}",

year = "2018",

month = mar,

doi = "10.1002/jccs.201700104",

language = "English",

volume = "65",

pages = "325--330",

journal = "Journal of the Chinese Chemical Society",

issn = "0009-4536",

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T1 - Investigation of O-Sulfonylation-promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes

AU - Hsieh, Tsung Han

AU - Liao, Pen Yuan

AU - Liu, Yu Ting

AU - Wang, Chien Hong

AU - Lin, Chia Chi

AU - Chien, Tun Cheng

PY - 2018/3

Y1 - 2018/3

N2 - 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 Ts2O 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.

AB - 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 Ts2O 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.

KW - Beckmann fragmentation

KW - Beckmann rearrangement

KW - Electrophilic aromatic substitution

KW - Tiemann rearrangement

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