| Project/Area Number |
10650836
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
有機工業化学
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| Research Institution | Saga University |
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Principal Investigator |
HANAMOTO Takeshi Faculty of Science and Engineering, Saga University, Associate Professor, 理工学部, 助教授 (20228513)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1999: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1998: ¥2,300,000 (Direct Cost: ¥2,300,000)
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| Keywords | organofluorine compound / fluorine-containing building block / α-fluorovinylphosphonium salt / fluorinated olefin / 1,1-difluoroethylene / fluorinated heterocyclic compound / α-fluorovinylsilane / fluorinated allylic alcohol / 1,1-ジフルオロエチレン / マイケル付加反応 |
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| Research Abstract |
1) The α-fluorovinyltriphenylphosphonium triflate was prepared in two steps from 1,1-difluoroethylene in high yields. The reaction of lithium diphenylphosphide with 1,1-difluoroethylene was conducted over the temperature range of -60 to -40℃ in THF-toluene to give the corresponding α-fluorovinyldiphenylphosphine in 86% yield. The α-fluorovinyldiphenylphosphine was treated with diphenyliodonium triflate in the presence of a catalytic amount of CuCl at 140 ℃ for 30 min under an Ar atmosphere to afford the corresponding α-fluorovinyltriphenylphosphonium triflate in high yield. Theα-fluorovinyltriphenylphosphonium triflate then underwent Michael addition followed by wittig olefination to give the corresponding monofluoroethylene compounds in good yields. The reaction of α-fluorovinyltriphenylphosphonium triflate with the cesium salts of salicylaldehyde derivatives in DMF at 130 ℃ afforded the corresponding mono-fluorinated chromenes in a one-pot synthesis. The Rh-AlィイD22ィエD2OィイD23ィエD2 catalyzed hydrogenation of the 3-fluoro-2H-chromene gave the corresponding 3-fluorochroman in 73% yield without loss of the fluorine atom in the molecule. The hydrolysis of α-fluorovinyltriphenylphosphonium triflate containing sodium hydroxide gave triphenylphosphine oxide in quantitative yields.
2) α-Fluorovinyldiphenylmethylsilane was synthesized in one step from 1,1-difluoroethylene in the similar manner described above. The TBAF-initiated reaction of the silane with carbonyl compounds smoothly proceeded to give the corresponding α-fluoroallylic alcohols in good yields.
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