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Fluorination of Halogenated Alkanes with High-Valent Metal Fluorides

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Europaisches Patentamt 19 European Patent Office Office europeen des brevets © Publication number : 0 503 792 A1 EUROPEAN PATENT APPLICATION © Application number: 92301531.7 © int. ci.5: C07C 17/20, C07C 17/10, C07C 19/08 (22) Date of filing : 24.02.92 @ Priority: 12.03.91 GB 9105167 Inventor : Holloway, John Henry 43 Morlan Avenue Stoneygate Leicester LE2 2PF (EN) (43) Date of publication of application Inventor : Hope, Eric George 16.09.92 Bulletin 92/38 80 Norton Leys Hillside Rugby Warwickshire CV22 5RT (EN) @ Designated Contracting States : Inventor : Rieland Matthias BE DE ES FR GB IT NL Susseroderstrasse 4a W3000 Hannover 71 (DE) Inventor : Townson, Paul John @ Applicant : IMPERIAL CHEMICAL 5 Balmoral Road New Longton INDUSTRIES PLC Preston Lancashire PR4 4JJ (EN) Imperial Chemical House, Millbank Inventor : Powell, Richard Llewellyn London SW1P 3JF (GB) 9 Sadler's Wells Bunbury Tarporley Cheshire (EN) (72) Inventor : Dukat, Wolfgang Willi Seilerbahnweg 2a 74 Representative : Walmsley, David Arthur 6240 Konigstein (DE) Gregson et al ICI Group Patents Services Dept. PO Box 6 Shire Park Bessemer Road Welwyn Garden City, Herts, AL7 1HD (GB) © Fluorination of halogenated alkanes with high-valent metal fluorides. © A process for the preparation of an alkane containing fluorine by contacting a halogenated alkane containing at least one hydrogen atom and at least one halogen atom selected from chlorine, bromine and iodine with a transition metal fluoride selected from osmium hexafluoride, iridium hexafluoride, rhenium hexafluoride, ruthenium pentafluoride, chromium pentafluoride, vanadium pentafluoride, rhenium heptafluoride and uranium hexafluoride, whereby to replace at least one hydrogen atom or at least one chlorine, bromine or iodine atom in said halogenated alkane starting material by a fluorine atom. Use of certain of the defined transition metal fluorides, e.g. OsF6, lrF6 and ReF6 allows the selective replacement of halogen by fluorine, whilst others, e.g. UF6, VF5 and ReF7 allows selective replacement of hydrogen by fluorine. < CM o> CO o If) o Q_ UJ Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 503 792 A1 This invention relates to a process for the fluorination of aliphatic compounds, and more particularly to a process for the replacement by fluorine of at least one hydrogen atom and/or at least one halogen atom other than fluorine in aliphatic compounds. It is already known to manufacture aliphatic compounds containing fluorine by reacting aliphatic chlorocar- 5 bons or chlorohydrocarbons with fluorinating agents such as antimony pentafluoride. In many cases, however, known fluorinating agents do not give entirely satisfactory results, being somewhat deficient in activity and/or in product selectivity. It has now been found that certain transition metal fluorides are useful fluorinating agents capable of selec- tively replacing by fluorine one or more hydrogen atoms and/or one or more halogen atoms other than fluorine w in aliphatic compounds. According to the present invention there is provided a process for the preparation of an alkane containing fluorine which comprises contacting a halogenated alkane containing at least one hydrogen atom and at least one halogen atom selected from chlorine, bromine and iodine with a transition metal fluoride selected from osmium hexafluoride, iridium hexafluoride, rhenium hexafluoride, ruthenium pentafluoride, chromium pentaf- 15 luoride, vanadium pentafluoride, rhenium heptafluoride and uranium hexafluoride, and replacing at least one hydrogen atom or at least one one chlorine, bromine or iodine atom in said halogenated alkane by a fluorine atom. Halogenated alkanes which may be employed in the process of the invention may contain one or more carbon atoms, for example, typically up to 6 carbon atoms, and have at least one hydrogen atom and at least 20 one replaceable halogen atom selected from chlorine, bromine and iodine. Other atoms, for example fluorine, may also be present. Especially useful halogenated alkanes include hydrochlorocarbons and chlorofluorohydrocarbons. Specific examples of halogenated alkanes which may be used include dichloromethane, chlorof- luoromethane, dibromomethane, bromofluoromethane, and 2-chloro-1,1,1-trifluoroethane from which the pro- 25 ducts may be respectively difluoromethane, and 1 ,1 ,1 ,2-tetrafluoroethane. In operating the process of the invention, the halogenated alkane may be contacted with the transition metal fluoride at a temperature at which the halogenated alkane is in the liquid phase or the vapour phase but con- veniently the liquid phase. Accordingly the temperature may be from about -80 to about 25 °C depending upon the boiling point of the halogenated alkane, although the reaction proceeds, and may be conducted at, tem- 30 peratures higher than 25°C, for example up to 100°C, in which case the halogenated alkane may be in the vapour phase. The process of the invention is preferably operated under substantially anhydrous conditions, and is conveniently operated at atmospheric pressure, although superatmospheric or subatmospheric press- ures may be employed, if desired. The transition metal fluoride may, at the reaction temperature, be present in the reaction vessel in the solid 35 or vapour phase, and may be supported on a substrate, for example aluminium fluoride or carbon. The proportions of halogenated alkane and transition metal fluoride are not critical; either may be in excess over stochiometric, if desired. Thus, for example, the proportion of halogenated alkane to transition metal fluoride may be in the range from about 50:1 to about 1 :50, and preferably in the range from about 20:1 to about 1 :20 of the stoichiometrically required proportion, although these ranges are given merely by way of guidance 40 and are in no way limiting on the process of the present invention. Hydrogen fluoride may also be included in the reaction mixture as a fluorinating agent, the metal fluoride then optionally being employed in a catalytic amount. In operating the process of the invention, whether at least one hydrogen atom or at least one halogen atom other than fluorine, or both hydrogen and halogen in the halogenated alkane is/are replaced by fluorine may 45 depend to a large extent on the particular halogenated alkane and on the particular transition metal fluoride used. Where it is desired to replace at least one halogen atom in the halogenated alkane, the preferred transition metal fluorides are OsF6, lrF6and ReF6. The use of these particular fluorides allows the replacement of halogen atom other than fluorine in the halogenated alkane by fluorine with a selectivity which may be as high as 80% so and even as high as 95%, in particular where OsF6 is used. Where it is desired to replace a hydrogen atom in the halogenated alkane and the halogenated alkane is a chlorinated alkane, the preferred transition metal fluorides are UF6, VF5 and ReF7. The use of these particular fluorides allows the replacement of at least one hydrogen atom by fluorine with a selectivity which may be as high as 80% and even as high as 95%, in particular where UF6 is used. 55 Furthermore, certain of the transition metal fluorides, for example RuF5, may selectively replace at least one hydrogen atom in certain halogenated alkanes, for example CF3CH2CI, yet selectively replace at least one halogen atom other than fluorine in other halogenated alkanes, for example in dichloromethane. CrF5 may selectively replace at least one hydrogen atom although the selectivity may be better with certain halogenated 2 EP 0 503 792 A1 alkane starting materials than with others; for example high selectivity is obtained with CrF5forthe replacement of hydrogen in CF3CH2CI although selectivity may not be as high with CH2CI2. In addition, ReF7 may selectively replace at least one hydrogen atom where the halogenated alkane is a chlorinated alkane, but may selectively replace at least one halogen atom where the halogenated alkane is a brominated alkane. 5 The process of the invention is of particular value for the preparation of difluoromethane from dichloromethane orchlorofluoromethane and accordingly in a preferred aspect of the invention there is provided a process for the preparation of difluoromethane which process comprises contacting dichloromethane or chlorofluoromethane with a transition metal fluoride selected from OsF6, lrF6, ReF6 and RuF5 and maintaining the contact until at least a portion of the dichloromethane or chlorofluoromethane has been converted to dif- w luoromethane. The reaction mixture may, if desired, also contain hydrogen fluoride. The process of the invention is also of particular value for the preparation of 1,1,1, 2-tetrafluoroethane from 2-chloro-1 ,1 ,1-trifluoroethane and accordingly in a further aspect of the invention there is provided a process for the preparation of 1 ,1 ,1 ,2-tetrafluoroethame which comprises contacting 2-chloro-1 ,1 ,1-trifluoroethane with a transition metal fluoride selected from OsF6, lrF6, and ReF6 and maintaining the contact until at least a portion 15 of the 2-chloro-1,1,1-trifluoroethane has been converted to 1,1,1, 2-tetrafluoroethane. The reaction mixture may, if desired, also contain hydrogen fluoride. The process of the invention is also of particular value for the preparation of dichlorofluoromethane by con- tacting dichloromethane with ReF7, UF6 or VF5 and of 2-chloro-1, 1,1, 2-tetrafluoroethane by contacting 2-chlo- ro-1,1,1-trifluoroethane with RuF5, ReF7, CrF5, VF5 or UF6 and these processes represent further particular 20 embodiments of the invention. The invention is illustrated by the following examples in which the organic materials were handled in a vacuum line made from stainleas steel tubing with stainless steel valves and the metal fluorides were handled in satellite lines made from PTFE. Reactions were conducted in FEP tubes (copolymer of HFP and TFE) which could be sealed thermally in a small ring furnace after reaction had reached completion and could be inserted 25 into a standard precision 5mm n.m.r. glass tube with a thin film of the lock substance - d6 acetone placed be- tween the tubes.
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    CHEMISTRY OF RHENIUM A Thesis submitted by FATMA IBRAHIM MOHAMED TAHA, B.Sc. for the Degree of Doctor of Philosophy of the University of London. March, 1963. Royal College of Science, South Kensington, S.W.7. CONTENTS Chapter. page. 1. The Simple Chemistry of Rhenium 1 2. The Complex Chemistry of Rhenium 11 3. Carboxylic Acid Complexes 20 3a. Complexes derived from the reaction between rhenium trichloride and carboxylic acids in absence of air. 21 3b. Complexes derived from the reaction between rhenium trichloride and carboxylic acids in presence of air. 37 3c. Complex derived from the reaction between acetic acid and rhenium pentachloride 45 3d. The infra-red spectra of carboxylic acid complexes 47 Nitrogen ligands 58 Infra-red spectra of Nitrogen ligand complexes 63 4. Experimental 65 References 84 47 ABSTRACT Complex compounds of Re(III) of the type t'.e(RC00)2C11 2 (R = CH3, CH3CH2, CH3CH2CH2, (CH3)2CH and CH3(CH2)6) have been prepared. They are believed to have structures similar to copper and chromium acetates. The thiocyanate derivative te(CH3CH2CH2C00)2 SCN}2 is described as well as the sulphate [Re2(CH3CH2CH2C00)4. 213201SO4.. A five-co-ordinate Re(III) complex ReC13. (RC00H)2 (R = CH3, CH3CH2) is also described. A series of Re(IV) complex compounds [ReO(R000)CA 2 and Ite:01I(R000)012J 2 have been prepared. The Re(V) complexes Ne02(RC00)1 2 and ReC13. (CH3C00)2 have also been made. Compounds of rhenium with nitrogen ligands Re0(OH)PY2C129 ReO(OH) dipyC12, ...Re02py4101.2H20, [Re02py4lPh4.B are also described.