- Mechanistic studies on fluorobenzene synthesis from 1,1-difluorocyclohexane via pd-catalyzed dehydrofluorodehydrogenation
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The chemical reactivity and reaction mechanism of fluorobenzene synthesis via dehydrofluorodehydrogenation of 1,1-difluorocyclohexane was investigated. 1,1-Difluorocyclohexane reacted with molecular oxygen to give fluorobenzene in good yields in the presence of both Pd and metal fluoride catalysts. The reaction proceeded with dehydrofluorination of 1,1-difluorocyclohexane to yield 1-fluorocyclohexene as the sole intermediate species, followed by oxidative dehydrogenation. The present system offers a selective synthesis of fluorobenzene.
- Tojo, Masahiro,Fukuoka, Shinsuke,Tsukube, Hiroshi
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p. 333 - 340
(2011/05/05)
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- Mechanistic studies on fluorocyclohexene conversion to fluorobenzene under Pd-catalyzed dehydrogenation
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The chemical reactivity and reaction mechanism of fluorobenzene formation by dehydrogenation of fluorocyclohexenes was investigated. 1-Fluorocyclohexene reacted with oxidants such as nitrobenzene and oxygen to give fluorobenzene in good yields under moderate conditions in the presence of a Pd catalyst. A detailed comparison of oxidative dehydrogenation with non-oxidative dehydrogenation proved that the oxidants effectively suppressed isomerization and disproportionation, and offered a selective synthesis of fluorobenzene.
- Tojo, Masahiro,Fukuoka, Shinsuke,Tsukube, Hiroshi
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experimental part
p. 89 - 94
(2011/04/21)
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- Reaction of chlorosulfonyl isocyanate with fluorosubstituted alkenes: Evidence of a concerted pathway
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Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a stepwise transition state more than the energy of the competing concerted pathw
- Shellhamer, Dale F.,Davenport, Kevyn J.,Hassler, Danielle M.,Hickle, Kelli R.,Thorpe, Jacob J.,Vandenbroek, David J.,Heasley, Victor L.,Boatz, Jerry A.,Reingold, Arnold L.,Moore, Curtis E.
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experimental part
p. 7913 - 7916
(2011/02/25)
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- Fluorination of boronic acids mediated by silver(I) Triflate
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A regiospecific Ag-mediated fluorination reaction of aryl- and alkenylboronic acids and esters Is reported. The fluorination reaction uses commercially available reagents, does not require the addition of exogenous ligands, and can be performed on a multigram scale. This report discloses the first practical reaction sequence from arylboronic acid to aryl fluorides.
- Furuya, Takeru,Ritter, Toblas
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supporting information; experimental part
p. 2860 - 2863
(2009/12/05)
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- METHOD OF FLUORINATION
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A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200°C where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.
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Page/Page column 15
(2008/06/13)
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- Process for producing alpha, alpha-difluorocycloalkane compound
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A method for producing an α,α-difluorocycloalkane at high purity with good efficiency, which comprises a step of treating a fluorocycloalkene with hydrogen fluoride wherein the fluorocycloalkene has one fluorine atom directly bonded to a carbon atom of carbon-carbon unsaturated double bond, more preferably, a step of directly adding the hydrogen fluoride to a reaction mixture obtained by treating the cycloalkanone with the de-oxygen fluorinating agent.
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- 2,2-Difluoro-1,3-dimethylimidazolidine (DFI). A new fluorinating agent
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2,2-Difluoro-1,3-dimethylimidazolidine (DFI) is a new deoxo-fluorinating agent that is useful for the conversion of alcohols to monofluorides, and aldehydes/ketones to gem-difluorides under mild conditions.
- Hayashi, Hidetoshi,Sonoda, Hiroshi,Fukumura, Kouki,Nagata, Teruyuki
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p. 1618 - 1619
(2007/10/03)
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- Transformation of Carbonyl Compounds into gem-Difluoro Compounds with Dibromodifluoromethane/Zinc Reagent
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Reaction of carbonyl compounds with dibromodifluoromethane/zinc gives the gem-difluoro compounds (12 examples).It seems to be that the reaction involves the generation of difluorocarbene by reaction of dibromodifluoromethane with zinc, followed by product
- Hu, Chang-Ming,Qing, Feng-Ling,Shen, Cun-Xi
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p. 335 - 338
(2007/10/02)
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- Mechanistic aspects of the fluorination of cyclohexane and cyclohexene with acetyl hypofluorite in acetic acid
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The reaction of acetyl hypofluorite in acetic acid with both cyclohexane and cyclohexene has been investigated.Analysis by GCMS and radio-HPLC, using (18)F as a tracer, revealed that apart from typical products expected from a radical reaction, several compounds originating from carbocationic intermediates were formed.On the basis of the observed products, a single-electrontransfer (SET) mechanism leading to an intermediate radical-cation is proposed.
- Visser, G. W. M.,Bakker, C. N. M.,Halteren, R. W. v.,Herscheld, J. D. M.,Brinkman, G. A.,Hoekstra, A.
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p. 214 - 219
(2007/10/02)
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- SYNTHESE D'ETHYLENIQUES MONOFLUORES
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Monofluorinated ethylenic compounds have been prepared by action of potassium tertiobutylate either on 2-fluorotosylates or 2-fluorochlorides.In the case of 2-fluorochlorides the action, at higher temperature, of basic salt such as KF in ethylene glycol, may be used to prepare monofluorinated ethylenics compounds.
- Baklouti, A.,Chaabouni, M. M.
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p. 181 - 190
(2007/10/02)
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- Reduction of 1-Substituted 7-Chloro-7-fluoronorcaranes with Tributyltin Hydride
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The stereospecificity of the reduction of 1-fluoro- (1), 1-methoxy- (2), 1-(methoxycarbonyl)- (3), 1-(trimethylsilyl)- (4), 1-methyl- (5), and 1-unsubstituted 7-chloro-7-fluoronorcarene (6) with neat tributyltin hydride has been measured and found to decr
- Ando, Teiichi,Ishihara, Takashi,Ohtani, Eiichi,Sawada, Hiroki
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p. 4446 - 4450
(2007/10/02)
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