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 language | English |
|---|---|
| Pages (from-to) | 3425-3436 |
| Number of pages | 12 |
| Journal | Journal of Organic Chemistry |
| Volume | 70 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - Apr 29 2005 |
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- Organic Chemistry
Cite this
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 journal › Article
}
TY - JOUR
T1 - Reaction of 2-methoxy-3H-azepine with NBS
T2 - Efficient synthesis of 2-substituted 2H-azepines
AU - Cordonier, Christopher E J
AU - Satake, Kyosuke
AU - Atarashi, Mikihiko
AU - Kawamoto, Yousuke
AU - Okamoto, Hideki
AU - Kimura, Masaru
PY - 2005/4/29
Y1 - 2005/4/29
N2 - (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.
AB - (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.
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UR - http://www.scopus.com/inward/citedby.url?scp=17744378990&partnerID=8YFLogxK
U2 - 10.1021/jo0500232
DO - 10.1021/jo0500232
M3 - Article
C2 - 15844975
AN - SCOPUS:17744378990
VL - 70
SP - 3425
EP - 3436
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 9
ER -