Investigations on the Development of New Reactions and New Organic Reagents by Using High Reactivities of Heterocycles Bearing Sulfur Functional Groups
| Project/Area Number |
61470019
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | University of Tsukuba |
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Principal Investigator |
FURUKAWA Naomichi Department of Chemistry, University of Tsukuba, 化学系, 教授 (80015966)
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| Project Period (FY) |
1986 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥6,300,000 (Direct Cost: ¥6,300,000)
Fiscal Year 1988: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1987: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1986: ¥3,800,000 (Direct Cost: ¥3,800,000)
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| Keywords | Pyridyl Sulfoxides / Pyridyl Sulfones / Generation of Sulfenic Acids / Pyridyl Grignard Reagents / Optically Active Pyridyl Sulfoxides / Asymmetric Synthesis / Ligand Exchange and Ligand Coupling / σスルフラン / 複素環(ヘテロ環)スルホキシド / α-ピコリルスルホキシド / 光学活性スルホキシド / 不斉誘導 / 脱スルフィニル化 / スルホキシドのリチオ化 / キノリルスルホキシド / 複素環グリニヤール試薬 / ベンザイン / ピリザイン / グリニヤール交換反応 / イプリ置換反応 / リガンドカップリング / スルフィン酸 / スルフェン酸 |
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| Research Abstract |
1. Numerous organic sulfur compounds bearing pyridyl and related azaheterocycles were prepared and investigated their physical and chemical properties. Several new reactions of these compounds were found. alpha-Sulfinyl and sulfonyl-pyridines and N-oxides react readily with KOH in MeOH to afford various sulfenic and sulfinic acids. Especially, first preparation of stable sodium sulfenate was found.
2. beta- and gamma.-Pyridyl phenyl sulfoxides were found to react with alkyl Grignard reagents at the sulfinyl sulfur atom to give both beta- and gammapyridyl Grignard reagents which react further with electrophiles to provide various new pyridyl compounds. On the other hand, alpha-derivative reacts with alkyl grignard reagents to afford the corresponding alpha-phenylpyridine in good yield. These two reactions are considered to proeed via a common intermediate " -sulfurance".
3. When pyridyl sulfoxides were treated with pyridyl grignard reagents except in the reactions of gamma-pyridyl sulfoxide and gamma-PyMgBr, the corresponding both symmetric and unsymmetric bis-azaaryls were obtained in good yields. These compounds are useful for chelating agents of heavy metals and this procedures are convenient for preparation of these chelating agents.
4. alpha- beta- and gamma-pyridyl Grignard reagents were prepared from the reactions of iodobenzenes with ethyl Grignard reagent.
5. Pyridyl phenyl sulfoxides were found to react with LDA to give the corresponding alpha-lithiated sulfoxides specifically at the pyridyl ring. The lithiated sulfoxides react further with various electrophiles to be converted to the corresponding pyridyl derivatives in high yields.
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Report
(4 results)
Research Products
(28 results)
