Nucleophilic reactions of 5-tert-butyl-2-methoxy-3H-azepine with alkoxides and alkyllithium reagents

Yasuhiro Kubota, Kyosuke Satake, Ryusuke Ikui, Hideki Okamoto, Masaru Kimura

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The reaction of 5-tert-butyl-2-methoxy-3H-azepine (2a) with sodium alkoxides gave 2-alkoxy-3H-azepine derivatives 3-6 by nucleophilic transetherification. The treatment of 2a with tert-butyllithium also yielded 2,5-di-tert-butyl-3H-azepine (7); however, the reaction of 2a and methyllithium gave the expected 5-tert-butyl-2-methyl-3H-azepine (8) along with unexpected 5-tert-butyl-2,2-dimethyl-2,3-dihydro-1H-azepine (9), but also 5,5′-di(tert-butyl)-2,2′-methylenedi(3H-azepine) (11), the structure of which was found to be tautomerized 5-tert-butyl-2-(5-tert-butyl-2,3-dihydro-1H-azepin-2-ylidene-methyl)- 3H-azepine (12). The energy profile for the observed tautomerization is discussed based on ab initio DFT calculations and kinetic measurements.

Original languageEnglish
Pages (from-to)805-811
Number of pages7
JournalBulletin of the Chemical Society of Japan
Volume76
Issue number4
Publication statusPublished - 2003

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Azepines
Discrete Fourier transforms
Sodium
Derivatives
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

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Nucleophilic reactions of 5-tert-butyl-2-methoxy-3H-azepine with alkoxides and alkyllithium reagents. / Kubota, Yasuhiro; Satake, Kyosuke; Ikui, Ryusuke; Okamoto, Hideki; Kimura, Masaru.

In: Bulletin of the Chemical Society of Japan, Vol. 76, No. 4, 2003, p. 805-811.

Research output: Contribution to journalArticle

Kubota, Yasuhiro ; Satake, Kyosuke ; Ikui, Ryusuke ; Okamoto, Hideki ; Kimura, Masaru. / Nucleophilic reactions of 5-tert-butyl-2-methoxy-3H-azepine with alkoxides and alkyllithium reagents. In: Bulletin of the Chemical Society of Japan. 2003 ; Vol. 76, No. 4. pp. 805-811.
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AU - Okamoto, Hideki

AU - Kimura, Masaru

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AB - The reaction of 5-tert-butyl-2-methoxy-3H-azepine (2a) with sodium alkoxides gave 2-alkoxy-3H-azepine derivatives 3-6 by nucleophilic transetherification. The treatment of 2a with tert-butyllithium also yielded 2,5-di-tert-butyl-3H-azepine (7); however, the reaction of 2a and methyllithium gave the expected 5-tert-butyl-2-methyl-3H-azepine (8) along with unexpected 5-tert-butyl-2,2-dimethyl-2,3-dihydro-1H-azepine (9), but also 5,5′-di(tert-butyl)-2,2′-methylenedi(3H-azepine) (11), the structure of which was found to be tautomerized 5-tert-butyl-2-(5-tert-butyl-2,3-dihydro-1H-azepin-2-ylidene-methyl)- 3H-azepine (12). The energy profile for the observed tautomerization is discussed based on ab initio DFT calculations and kinetic measurements.

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