| Project/Area Number |
60570996
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | Nagasaki University |
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Principal Investigator |
FURUKAWA Sunao Professor, Faculty of Pharmaceutical Sciences, Nagasaki Univ., 薬学部, 教授 (60039633)
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| Co-Investigator(Kenkyū-buntansha) |
KINOSHITA Toshio Ass. Prof., Faculty of Pharmaceutical Sciences, Nagasaki Univ., 薬学部, 助教授 (60039641)
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| Project Period (FY) |
1985 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1986: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1985: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | Stable Sulfur-Ylide / Chlorotrimethylsilane / Dienol-silylation / Disiloxydiene / 1,3-ジカルボニル化合物 |
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| Research Abstract |
This work was carried out as a part of the studies on the synthetic application of stable sulfur ylides. The reaction of dimethylsulfonium diacetylmethylide (1a) with acetyl chloride gave 3-methylthio-2,4-pentanedione (2) and 2-acetoxy-3-methylthio-2-penten-4-one (3). Compound 2 and 3 were treated with chlorotrimethylsilane-triethylamine-zinc chloride (Danishefsky method) afforded 2,4-bis(trimethylsiloxy)-3-methylthio-1,3-pentadiene (4) and 2-acetoxy-3-methylthio-4-trimethylsiloxy-1,3-pentadiene (5). However this methods consisted two steps from the ylide to the diene 4. We attempt to obtain the diene 4 from the ylide by direct dienol-silyletherification, the ylide was converted to the diene 4 in almost quantitatively by using a chlorotrimethylsilane-triethylamine-dichloromethane system.
On the other hand, dimethylsulfonium acetylmethoxycarbonylmethylide (1b) was converted to 2-methylthio-3-trimethylsiloxy-crotonate (6) by treatment with chlorotrimethylsilane-sodium iodide-acetonitrile system. However no disiloxy diene was obtained by the reaction of 6 with chlorotrimethylsilane in the presence of LDA (lithium diisopropylamine).
Diels-Alder cycloadditions to the diene 4 produced corresponding products. Similarly, the diene 4 proceeded Michael's type addition in the presence of Lewis acids catalyst.
This method is useful for the preparation of the dienes possessing alkylthio group, these diene are hard to get by other methods.
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