Reaction of 2-methoxy-3H-azepine with NBS: Efficient synthesis of 2-substituted 2H-azepines

Christopher E J Cordonier, Kyosuke Satake, Mikihiko Atarashi, Yousuke Kawamoto, Hideki Okamoto, Masaru Kimura

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

(Chemical Equation Presented) The reaction of 2-methoxy-3H-azepines, in the presence or absence of a nucleophile, with N-bromosuccinimide (NBS) gave a regioselective 1,4-adduct from which the corresponding 2H-azepine derivatives were formed via base-promoted hydrogen bromide elimination, generally in moderate to quantitative yield. Competitive formation of 4-bromo-2-methoxy-3H- azepine by electrophilic substitutuion or 3H-azepin-2-yl 2H-azepin-2-yl ether by transetherification was minimized at lower reaction temperatures. Quantitative substitution of 2-(2′,4′,6′-trichlorophenoxy)-2H-azepine derivatives, formed in moderate yield from the respective 3H-azepine and NBS in the presence of 2,4,6-trichlorophenol (TCP), by various nucleophiles gave the corresponding 2-substituted 2H-azepine. Among these nucleophiles were alkanethiol and alkylamine that are not tolerated in the reaction of 3H-azepine and NBS.

Original languageEnglish
Pages (from-to)3425-3436
Number of pages12
JournalJournal of Organic Chemistry
Volume70
Issue number9
DOIs
Publication statusPublished - Apr 29 2005

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Azepines
Bromosuccinimide
Nucleophiles
Hydrobromic Acid
Derivatives
Ether
Substitution reactions

ASJC Scopus subject areas

  • Organic Chemistry

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Reaction of 2-methoxy-3H-azepine with NBS : Efficient synthesis of 2-substituted 2H-azepines. / Cordonier, Christopher E J; Satake, Kyosuke; Atarashi, Mikihiko; Kawamoto, Yousuke; Okamoto, Hideki; Kimura, Masaru.

In: Journal of Organic Chemistry, Vol. 70, No. 9, 29.04.2005, p. 3425-3436.

Research output: Contribution to journalArticle

Cordonier, Christopher E J ; Satake, Kyosuke ; Atarashi, Mikihiko ; Kawamoto, Yousuke ; Okamoto, Hideki ; Kimura, Masaru. / Reaction of 2-methoxy-3H-azepine with NBS : Efficient synthesis of 2-substituted 2H-azepines. In: Journal of Organic Chemistry. 2005 ; Vol. 70, No. 9. pp. 3425-3436.
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