Selenium dioxide oxidations of dialkyl-3H-azepines: The first synthesis of 2-azatropone from oxidation of 2,5-di-tert-butyl-3H-azepine

Shizuka Takami, Akihide Oshida, Yuko Tawada, Setsuo Kashino, Kyosuke Satake, Masaru Kimura

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO2) were performed. The oxidation of 1 with SeO2 gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36% yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1,5-dihydro-pyrrol-2-one 4 in 13% yield, 2,6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12% yield, and 4,7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6% yield, respectively. Oxidation of 2 with SeO2 gave 2,2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55% yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5% yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative.

Original languageEnglish
Pages (from-to)6093-6096
Number of pages4
JournalJournal of Organic Chemistry
Volume65
Issue number19
DOIs
Publication statusPublished - Sep 22 2000

Fingerprint

Selenium Oxides
Azepines
Oxidation
1-Propanol
Derivatives

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Selenium dioxide oxidations of dialkyl-3H-azepines : The first synthesis of 2-azatropone from oxidation of 2,5-di-tert-butyl-3H-azepine. / Takami, Shizuka; Oshida, Akihide; Tawada, Yuko; Kashino, Setsuo; Satake, Kyosuke; Kimura, Masaru.

In: Journal of Organic Chemistry, Vol. 65, No. 19, 22.09.2000, p. 6093-6096.

Research output: Contribution to journalArticle

Takami, Shizuka ; Oshida, Akihide ; Tawada, Yuko ; Kashino, Setsuo ; Satake, Kyosuke ; Kimura, Masaru. / Selenium dioxide oxidations of dialkyl-3H-azepines : The first synthesis of 2-azatropone from oxidation of 2,5-di-tert-butyl-3H-azepine. In: Journal of Organic Chemistry. 2000 ; Vol. 65, No. 19. pp. 6093-6096.
@article{9ee05cf8ec9948018a0fd524b97f9f4e,
title = "Selenium dioxide oxidations of dialkyl-3H-azepines: The first synthesis of 2-azatropone from oxidation of 2,5-di-tert-butyl-3H-azepine",
abstract = "Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO2) were performed. The oxidation of 1 with SeO2 gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36{\%} yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1,5-dihydro-pyrrol-2-one 4 in 13{\%} yield, 2,6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12{\%} yield, and 4,7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6{\%} yield, respectively. Oxidation of 2 with SeO2 gave 2,2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55{\%} yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5{\%} yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative.",
author = "Shizuka Takami and Akihide Oshida and Yuko Tawada and Setsuo Kashino and Kyosuke Satake and Masaru Kimura",
year = "2000",
month = "9",
day = "22",
doi = "10.1021/jo000540e",
language = "English",
volume = "65",
pages = "6093--6096",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "19",

}

TY - JOUR

T1 - Selenium dioxide oxidations of dialkyl-3H-azepines

T2 - The first synthesis of 2-azatropone from oxidation of 2,5-di-tert-butyl-3H-azepine

AU - Takami, Shizuka

AU - Oshida, Akihide

AU - Tawada, Yuko

AU - Kashino, Setsuo

AU - Satake, Kyosuke

AU - Kimura, Masaru

PY - 2000/9/22

Y1 - 2000/9/22

N2 - Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO2) were performed. The oxidation of 1 with SeO2 gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36% yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1,5-dihydro-pyrrol-2-one 4 in 13% yield, 2,6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12% yield, and 4,7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6% yield, respectively. Oxidation of 2 with SeO2 gave 2,2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55% yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5% yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative.

AB - Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO2) were performed. The oxidation of 1 with SeO2 gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36% yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1,5-dihydro-pyrrol-2-one 4 in 13% yield, 2,6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12% yield, and 4,7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6% yield, respectively. Oxidation of 2 with SeO2 gave 2,2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55% yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5% yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative.

UR - http://www.scopus.com/inward/record.url?scp=0034703294&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034703294&partnerID=8YFLogxK

U2 - 10.1021/jo000540e

DO - 10.1021/jo000540e

M3 - Article

AN - SCOPUS:0034703294

VL - 65

SP - 6093

EP - 6096

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 19

ER -