Studies on the N-Oxides of π-Deficient N-Heteroaromatics. XXXIV. A Novel Synthesis of Substituted Indoles by Photochemical Ring Contraction of 3, 1-Benzoxazepines

フォーマット:

論文

責任表示:

Kaneko, Chikara ; Fujii, Harue ; Kawai, Shinji ; Yamamoto, Atsushi ; Hashiba, Kazuhiko ; Kimata, Toshihiko ; Hayashi, Reiko ; Somei, Masanori

言語:

英語

出版情報:

Pharmaceutical Society of Japan = 日本薬学会, 1980-01-01

著者名:

Kaneko, Chikara

Fujii, Harue

Kawai, Shinji

Yamamoto, Atsushi

Hashiba, Kazuhiko

Kimata, Toshihiko

Hayashi, Reiko

Somei, Masanori

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掲載情報:

Chemical and Pharmaceutical Bulletin

ISSN:

0009-2363      

巻:

28

通号:

4

開始ページ:

1157

終了ページ:

1171

バージョン:

publisher

概要:

A novel photochemical ring-contraction reaction of 5-unsubstituted 3, 1-benzoxazepines and their 5-halogeno or carboxyl derivatives to yield 3-formylindoles in an aprotic solvent is reported. This ring contraction was successfully extended to oxazepines having an alkoxycarbonyl function at the 5-position to give the indoles having this function at the 3-position. Though most of the oxazepines underwent the ring-contraction reaction only on … irradiation at 254 nm, 5-carboxy derivatives or their esters afforded the ring-contraction products even at ≥ 300 nm. The intermediacy of 3H-indole species in these photochemical ring-contraction reactions was demonstrated by the isolation of methyl 3-acetyl-2-phenyl-3H-indole-3-carboxylate during the photolysis of methyl 4-methyl-2-phenyl-3, 1-benzoxazepine-5-carboxylate. It was found that this 3H-indole afforded methyl 6-and 4-acetyl-2-phenyl-indole-3-carboxylates upon further irradiation. The mechanism of this acetyl migration is discussed based on the result of the photochemical acetyl migration of methyl 1-acetyl-2-phenylindole-3-carboxylate. 続きを見る

URL:

http://hdl.handle.net/2297/43995