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 language | English |
|---|---|
| Pages (from-to) | 6093-6096 |
| Number of pages | 4 |
| Journal | Journal of Organic Chemistry |
| Volume | 65 |
| Issue number | 19 |
| DOIs | |
| Publication status | Published - Sep 22 2000 |
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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 journal › Article
}
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.
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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 -