- Selective Direct Fluorination of Organolithium and Organomagnesium Compounds
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The first successful selective monofluorination of organolithium and organomagnesium compounds with elemental fluorine has been achieved in hydrocarbon ether solvents at low temperatures.
- DeYoung, James,Kawa, Hajima,Lagow, Richard J.
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- Conformational equilibrium and potential energy surface of 1-fluorobutane by microwave spectroscopy and Ab initio calculations
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The rotational spectra of four (GT, TT, TG, and GG) of the five possible conformers of 1-fluorobutane have been assigned by combining free jet and conventional microwave spectroscopy. The geometry optimization was performed at the MP2 (full) level of theory with the 6-31G (d) and 6-311G (d,p) basis sets and by using the B3LYP (3df, 3pd) density functional method. The relative stability of the five rotamers is calculated at the QCISD (T)/6-311G (d,p) level of theory. In spite of the fact that ab initio calculations indicated the unobserved GG' conformer to be more stable than at least one of the observed conformers it was not possible to detect its rotational spectrum. GT and TG are the most and the least stable species, respectively. The rotational spectra of several vibrational satellites of the four conformers have been studied by conventional microwave spectroscopy. The overall conformational equilibrium is governed by the two-dimensional potential energy surface of the skeletal torsions MeC-CC and FC-CC, which have been evaluated by a flexible model analysis, based on the experimental values of the relative conformational and vibrational energy spacings, and on the shifts of second moments of inertia upon conformational change and vibrational excitation. The relative energy of the fifth stable conformer (GG') was determined to be 333 cm-1 from flexible model calculations, and to be 271 cm-1 from the most accurate ab initio calculations.
- Favero, Laura B.,Maris, Assimo,Degli Esposti, Alessandra,Favero, Paolo G.,Caminati, Walther,Pawelke, Gottfried
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- METHOD FOR PRODUCING FLUORINATED ALKANE, METHOD FOR SEPARATING AND RECOVERING AMIDINE BASE, AND METHOD FOR USING RECOVERED AMIDINE BASE
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The present invention provides: a method for producing a fluorinated alkane represented by the formula (2): R2—F, wherein an alcohol having 3 to 5 carbon atoms is fluorinated by a fluorinating agent represented by the formula (1): R1SO2F in the absence of a solvent, and in the presence of a base selected from the group consisting of an amidine base and a phosphazene base; a method for separating and recovering an amidine base from an amidine base-sulfonate complex represented by the following formula (5); and a method for using a recovered amidine base. In the formula, R1 represents a methyl group, an ethyl group or an aromatic group, R2 represents an alkyl group having 3 to 5 carbon atoms, and n is 0 or 2.
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Paragraph 0199; 0200; 0201; 0202
(2018/05/17)
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- HIGH-PURITY 1-FLUOROBUTANE AND PLASMA ETCHING METHOD
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The present invention provides: 1-fluorobutane having a purity of 99.9% by volume or more and a total butene content of 1,000 ppm by volume or less; use of the 1-fluorobutane as a dry etching gas; and a plasma etching method using the 1-fluorobutane as an etching gas. According to the present invention, high-purity 1-fluorobutane which is suitable as a plasma reaction gas for semiconductors, the use of the high-purity 1-fluorobutane as a dry etching gas, and a plasma etching method using the high-purity 1-fluorobutane as an etching gas are provided.
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Paragraph 0078-0081
(2017/01/09)
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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 16
(2008/06/13)
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- Ionic liquids as media for nucleophilic flurination
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The use of Room Temperature Ionic Liquids (RTILs) for a variety of halogen exchange (Halex) fluorination processes using alkali metal fluorides is assessed. Whilst fluorination of a range of halogenated substrates is possible in good yield, the utility of RTILs as reusable, inert media for such reactions is limited by the gradual decomposition of the RTIL in the presence of highly basic fluoride ion.
- Murray, Christopher B.,Sandford, Graham,Korn, Stewart R.
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- A facile synthesis of organofluorine compounds using a semi-molten mixture of tetrabutylammonium bromide and an alkali metal fluoride
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A semi-molten mixture of tetrabutylammonium bromide and an alkali metal fluoride (KF or CsF) has been found to be an efficient reagent system for the preparation of organofluorine compounds, e.g., CH3(CH2)7F, CH2=CH-CH2F, FCH2CO2C2H5, C6H5COF, and related compounds through facile fluoride-ion exchange with organohalides.The system provides a simple and convenient alternative to 'anhydrous' tetrabutylammonium fluoride for the synthesis of organofluorine compounds. - Keywords: Semi-molten mixture; Tetrabutylammonium bromide; Alkali metal fluorides; Organofluorine compounds; NMR spectroscopy
- Bhadury, Pinaki S.,Pandey, Mamta,Jaiswal, Devendra K.
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p. 185 - 188
(2007/10/02)
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- REACTION OF ALKYL 2-CHLORO-1,1,2-TRIFLUOROETHYL ETHERS WITH LEWIS ACIDS
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Ethyl 2-chloro-1,1,2-trifluoroethyl ether heated with boron trifluoride etherate gave ethyl fluoride and chlorofluoroacetyl fluoride.When heated with aluminium chloride, it afforded a mixture of ethyl fluoride, ethyl chloride, chlorofluoroacetyl fluoride, and chlorofluoroacetyl chloride.Treatment of the acyl halides with ethanol yielded ethyl chlorofluoroacetate.Butyl and octyl 2-chloro-1,1,2-trifluoroethyl ethers gave directly butyl and octyl chlorofluoroacetates, respectively, under similar conditions.
- Hudlicky, Milos
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p. 349 - 354
(2007/10/02)
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- REDUCTION OF AROMATIC NITRO GROUPS WITH HEXAMETHYLDISILANE1): REACTIONS WITH HEXAMETHYLDISILANE AND FLUORIDE ION-II2).
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Reduction of aromatic nitro compounds with hexamethyldisilane and fluoride ion in THF at 24 deg C gives the corresponding azo- and azoxy-compounds in high yields.Hexamethyldisilane converts commercial tetrabutylammoniumfluoride-dihydrate into a highly reactive catalyst.
- Vorbrueggen, Helmut,Krolikiewicz, Konrad
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p. 1259 - 1262
(2007/10/02)
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- FLUORINATED 3-DIETHYLAMINOPROPENOATES AND THEIR REACTIONS
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The reaction of diethylamine with methyl trifluoropropenoate (I), methyl 2-chloro-3,3-difluoropropenoate (II), methyl 3,3-difluoropropenoate (III) and methyl 3-chloro-2,3-difluoropropenoate (IV) affords halogenated 3-diethylaminopropenoates V-VII via the vinylic substitution of fluorine or chlorine atoms.When hydrolyzed the latter give methyl N,N-diethylcarbamoylacetates X-XII.On addition of 1-butanol and 2,2,3,3-tetrafluoropropanol to aminopropenoates V-VII fluorinated 3-alkoxy-3-diethylaminopropenoates XIII-XVI were prepared which when hydrolyzed eliminate thediethylamino group under formation of alkyl methylpropanedioates XX to XXIII.Heating of aminoethers XIII-XVI at 150 deg C gives 1-fluorobutane or 1,1,2,2,3-pentafluoropropane, respectively.These fluoro derivatives are also formed on heating of the mentioned alcohols with 3-diethylaminopropenoates V-VII.During the thermal decomposition of methyl 2-chloro-3-diethylamino-3-fluoro-3-(2,2,3,3-tetrafluoropropoxy)propanoate (XV) 3-chloro-1,1,2,2-tetrafluoropropane was formed as a by-product.The substitution of the hydroxyl group with fluorine is discussed from the point of view of preparative application.
- Svoboda, Jiri,Paleta, Oldrich,Liska, Frantisek,Dedek, Vaclav
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p. 1389 - 1396
(2007/10/02)
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