1992 Fiscal Year Final Research Report Summary
A Novel Synthesis of Biologically Active Perfluoroalkyl N-Heterocyclic Compounds Using Organosilicon Reagents
| Project/Area Number |
03640465
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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 |
有機化学一般
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| Research Institution | Science University of Tokyo |
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Principal Investigator |
KONAKAHARA Takeo Science University of Tokyo, Faculty of Science and Technology, Department of Industrial and Engineering Chemistry Associate Professor, 理工学部, 助教授 (80084333)
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| Project Period (FY) |
1991 – 1992
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| Keywords | Organosilicon reagent / Organofluorine compound / Pyridine / Quinolidine / Naphthyridine / Isoxazole / Cyclization / N-Silyl-l-aza-allyl anion |
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| Research Abstract |
N-Silyl-l-aza-allyl anions (1), generated from 3-methyl-5-(trimethylsilylmethyl)-isoxazole and aryl cyanides, reacted with perfluoro(2-methyl-2-pentane) (2) or 3-acethyl-4-methoxy-3-buten-2-one (3) to give the corresponding Rf or 4-Me pyridines (4) or (5) in high yields. The former product (4) was effectively converted into the corresponding 1,6-naphthyridine in good yield by hydrogenation of the isoxazole ring and the consecutive intramolecular cyclization in the presence of sodium hydoxide. On the other hand, 2-(Trimethylsilylmethyl)pyridine reacted with (2) in the presence of potassium fluoride to afford 2-pentafluoroethyl-3-trifluoromethyl-4H-quinolizin-4-one (6) in quantitative yield. The analogous reaction of the silyl derivatives of methylpyridines, methylquinolines, benzoxazole and benzothiazole gave the corresponding Rf-substituted compounds in good yields. The compound (6), furthermore, gave the methyl ester of the 3-carboxylic acid of (6) in high yield on treating with dimethyl sulfate whereas (6) quantitatively gave 2-pentafluoroethyl-4H-quinolizin-4-one (7) by decarboxylation after hydrolysis on treating with sulfuric acid. The mechanisms of these reactions were also discussed.
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