1994 Fiscal Year Final Research Report Summary
DEVELOPMENT OF SYNTHESIS IN ORGANO FLUORINE COMPOUNDS AND FLUORINATTON REAGENTS FOR FINE CHEMICALS
| Project/Area Number |
04555200
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Graduate School of Engineering, Hokkaido University |
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Principal Investigator |
YONEDA Norihiko Hokkaido University, Faculty of Engineering, Professor, 工学部, 教授 (50001219)
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| Co-Investigator(Kenkyū-buntansha) |
NISHIYAMA Tatsuo Tohchemproducts Co., Deputy Director, Research Fellow, 研究開発部次長
FUKUHARA Tsuyoshi Hokkaido University, Faculty of Engineering, Instructor, 工学部, 助手 (50238507)
HARA Shoji Hokkaido University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (20109490)
ITOH Hironori Hokkaido University, Faculty of Engineering, Professor, 工学部, 教授 (70001287)
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| Project Period (FY) |
1992 – 1994
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| Keywords | Fluorine-containing Strong Acids / Deaminative Fluorination / Photochemical Fluoro-dediazoniation / Heteroaromatic Fluorides / Ene Reaction / Cynanuric Fluoride / Electrochemical Fluorination / Hydrogen Fluoride |
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| Research Abstract |
1.Transformation of aminoarenes to fluorine-containing functionalized arenes has been successfully carried out using fluorine-continaing strog acids.
2.The studies of the diazotization of aminoarenes and fluoro-dediazonitaion of arene diazonium salts has been studied to elucidated primary factors for efficient formation of arenefluorides in the one-stage deaminative fluorination of aminoarenes using HF or HF-Base solutions. And, facile preparation of arenefluorides having polar substituents, such as hydroxy, alkoxy, halogens, nitro, mercapto, carboxy, trifluoromethyl and so on, has been successfully carried out by a photo-induced fluorinative decomposition of arenediazonium intermediates in HF and HF-base solutions.
3.Semi-comercial scale process has been achieved for an one-stage transformation of aminoarenes to fluoroarenes using HF-base.
4.Halogen-exchange fluorination of heteroaromatic halides took place effectively by using HF-base solutions to give the corresponding heteroaromatic fluorides in good yields.
5.The reaction of CF_3 CHO with dienes using Zn (OTf) _2 gave fairly good results in depressing unfavorable reactions and affording the preferential formation of the ene reaction products.
6.A facile preparation of azyril ethers was developped by the reaction of fluorinated pyridines or pyrimidines with alcohols and phenols.
7.Cyanuric fluoride was found to be an effective fluorination reagent for the hydroxyl groop in boronic esters, which are good for the 1,4-addition to alpha, beta-unsaturated carbonyl compounds affording gamma, delta-unsaturated ketones in good yields.
8.Electrochemical fluorination of aldehydes and ketones using Et_3N-5HF/CH_3CN afforded acylfluorides and/or alkylfluorides in good yields.
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