1996 Fiscal Year Final Research Report Summary
Highly Effective and Selective Novel Fluoro-functionalization
| Project/Area Number |
06453125
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | HOKKAIDO UNIVERSITY |
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Principal Investigator |
YONEDA Norihiko Hokkaido Univ., Fac.of Eng., Pro., 工学部, 教授 (50001219)
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| Co-Investigator(Kenkyū-buntansha) |
FUKUHARA Tsuyoshi Hokkaido Univ., Fac.of Eng., Instructor, 工学部, 助手 (50238507)
HARA Shoji Hokkaido Univ., Fac.of Eng., Associate Pro., 工学部, 助教授 (20109490)
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| Project Period (FY) |
1994 – 1996
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| Keywords | hydrogen fluoride / HF-base solution / deaminative fluorination / ene reaction / iodoarene difluoride / electrochemical fluorination / fluorinative alkylation / triethylamine-pentakis (hydrofluoride) |
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| Research Abstract |
1) The fluorination of organic compounds using HF-base has been investigated. Triethylamine-Pentakis (hydrofluoride) Et_3N-5HF was found to be a useful fluorinating agent in the hydrofluorination, fluorinative cyclization and electrochemical partial fluorination of organic compounds.
2) One-pot deaminative fluorination of aminoarenes including heteroaromatics, namely, diazotization of aminoarenes followed by in situ fluoro-dediazoniation of the corresponding diazonium ions, was successfully accomplished to produce fluoroarenes in high yields by using HF-Base solutions. The fluoro-dediazoniation of ArN_2BF_4 using HF-pyridine solution has been also successfully carried out either thermally or photochemically to afford the corresponding ArF in good yields.
3) The reaction of CF_3CHO with dienes using ZnX_2 (X : Cl, OTf) in organic solvents give fairly good results in depressing unfavorable reactions and affording the preferential formation of the ene reaction products.
4) Heteroaromatic hal
… More
ides such as 2-chloropyrimidines and 2-choropyridines, and 2,4-dinitrochlorobenzene underwent halogen-exchange fluorination with the treatment of HF or HF-base solutions to afford the corresponding fluorides in good yields.
5) The selective displacement of formyl hydrogen to fluorine in aliphatic aldehydes was successfully carried out electrochemically to give acyl fluorides in base-nHF (base : pyridine or Et_3N,n=3-6) electrolyte solution with or without solvents such as acetonitrile and sulfolane. The electrochemical fluorinative of 2,2-disubstituted cyclic ketones were also successfully carried out using Et_3N5HF as the electrolyte. The selective cleavage of the carbon-carbon bond between the carbonyl. carbon and substituted alpha-carbon took place and fluorocarboxylic acid esters were obtained in good yields after the esterification of the resulting fluoroacyl fluorides.
6) The electrochemical oxidation of cyclic unsaturated esters was carried out using Et_3N-5HF as the electrolyte. The ring expansion and fluorination took place to give beta, beta-difluorocycloalkane-carboxylic esters selectively. Less
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