| Project/Area Number |
05640668
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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 |
物質変換
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| Research Institution | KYUSHU UNIVERSITY |
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Principal Investigator |
KITAMURA Tsugio KYUSHU UNIVERSITY,FACULTY OF ENGINEERING,ASSOCIATE PROFESSOR, 工学部, 助教授 (00153122)
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| Co-Investigator(Kenkyū-buntansha) |
TANIGUCHI Hiroshi KURUME NATIONAL COLLEGE OF TECHNOLOGY,PRESIDENT, 校長 (10037715)
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| Project Period (FY) |
1993 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1994: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1993: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | Hypervalent iodine compound / (p-Phnylene) bisiodonium salt / Pentene derivatives / Alkynylthiocyanate / Benzofuran derivatives / Alkynylcopper reagent / Liquid-crystalline diacetylene / l-Arylbenzothiophenium salt / 高反応性ヨウ素試薬 / アルキニルヨードニウム塩 / ビニリデンカルベン / アセチレン誘導体 / シクロペンテン誘導体 |
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| Research Abstract |
The aim of this research was devoted to develop new high efficient process for synthesis of organic compounds by utilizing hypervalent iodine compounds, especially (p-phenylene) bisiodonium salts.
1. Synthesis of (p-phenylene) bisiodonium salts
A new bisiodine (III) reagent was prepared from iodosylbenzene and trifluoromethanesulfonic acid and used to prepare the (p-phenylene) bisiodonium salts by reaction with aromatic substrates and acetylenic compounds.
Furthermore, new types of hypervalent iodine reagents were obtained from iodobenzene diacetate and o-iodosylbenzoic acid.
2. Reaction of (p-phenylene) bisiodonium salts with nucleophiles
Reaction of alkynyl (p-phenylene) bisiodonium salts with thiocyanate ion gave alkynylthiocyanates but the reaction with the enolate of phenylindanedione and phenoxide ion provided pentene and benzofuran derivatives, respectively. Although the (p-phenylene) bisiodonium salts showed a high reactivity to nucleophiles, the reaction proceeded via a Michael addition-rearrangement process. Reaction with alkynylcopper reagents gave diacetylene derivatives and was applied to synthesis of liquid-crystalline diacetylenes.
Aryl (p-phenylene) bisiodonium salts reacted with pyridine, triphenylphosphine, and diphenyl sulfide. l-Arylbenzothiophenium salts were prepared in a similar manner.
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