CA2062442A1 - Chemical process - Google Patents
Chemical processInfo
- Publication number
- CA2062442A1 CA2062442A1 CA002062442A CA2062442A CA2062442A1 CA 2062442 A1 CA2062442 A1 CA 2062442A1 CA 002062442 A CA002062442 A CA 002062442A CA 2062442 A CA2062442 A CA 2062442A CA 2062442 A1 CA2062442 A1 CA 2062442A1
- Authority
- CA
- Canada
- Prior art keywords
- halogenated alkane
- fluorine
- atom
- hexafluoride
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
Abstract
ABSTRACT
CHEMICAL PROCESS
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, IrF6 and ReF6 allows the selective replacement of halogen by fluorine, whilst others, e.g. UF6, VF5 and ReF7 allow selective replacement of hydrogen by fluorine.
CHEMICAL PROCESS
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, IrF6 and ReF6 allows the selective replacement of halogen by fluorine, whilst others, e.g. UF6, VF5 and ReF7 allow selective replacement of hydrogen by fluorine.
Description
CHE~ICAL PROCESS
Thi invention relate~ to a proces~ for the fluorination of aliphatic compoundc, end more particulerly 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 i8 elready kno~n to manufacture aliphatic compound containing fluorine by reacting aliphatic chlorocarbons or chlorohydrocarbons with fluorinating agents ~uch as ant~mony pentefluoride. In many cases, ho~ever, known fluorinating agents do not give entirely satisfactory reaults, being somewhat deficient in activity and/or in product selectivity.
lt has now been found that certain tran~ition metal fluorlde& are useful fluorinating agent~
capable of selectively replacing by fluorine one or more hydrogen atoms and/or one or more halogen atoms other than fluorine in aliphatic compound~.
~ ccording to the present invention there is provided a process for the preparation of an alkane cnntaining fluorine ~hich comprise~
contacting a halogenated alkane containing at Z~ least one hydrogen atom snd at least one halogen ~ atom selected from chlo~ine, bromine and iodine with a trensition metal fluoride selected from osmlum hexafluoride, iridium hexafluoride, rhenium hexafluoride, ruthenium pentafluoride, chromium pentafluoride, vanadium pentafluoride, rhenium heptafluoride and uranium hexafluoridet and replacing at least one hydrogen atom or at leect one one chlorine, bromine or iodine atom in said halogenated alkane by a fluorine atom.
Thi invention relate~ to a proces~ for the fluorination of aliphatic compoundc, end more particulerly 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 i8 elready kno~n to manufacture aliphatic compound containing fluorine by reacting aliphatic chlorocarbons or chlorohydrocarbons with fluorinating agents ~uch as ant~mony pentefluoride. In many cases, ho~ever, known fluorinating agents do not give entirely satisfactory reaults, being somewhat deficient in activity and/or in product selectivity.
lt has now been found that certain tran~ition metal fluorlde& are useful fluorinating agent~
capable of selectively replacing by fluorine one or more hydrogen atoms and/or one or more halogen atoms other than fluorine in aliphatic compound~.
~ ccording to the present invention there is provided a process for the preparation of an alkane cnntaining fluorine ~hich comprise~
contacting a halogenated alkane containing at Z~ least one hydrogen atom snd at least one halogen ~ atom selected from chlo~ine, bromine and iodine with a trensition metal fluoride selected from osmlum hexafluoride, iridium hexafluoride, rhenium hexafluoride, ruthenium pentafluoride, chromium pentafluoride, vanadium pentafluoride, rhenium heptafluoride and uranium hexafluoridet and replacing at least one hydrogen atom or at leect one one chlorine, bromine or iodine atom in said halogenated alkane by a fluorine atom.
2~2l~
Halogenated alkanes ~hich may be employed in the proce~ of t~e invention may contain one or more carbon atoms, for example, typically up to 6 carbon atom~, and ~ave ~t lea3t one hydrogen atom snd at least one replaceable halogen atom selected from chlorine, bromlne snd iodine. Other atom~, for example fluorlne, may also be present.
- Especlally useful halogenated alkanes lnclude hydrochlorocarbon6 and chlorofluorohydrocarbons.
Speciflc examples of halogenated alksneE
which may be u~ed include dichloromethane, chlorofluoromethane, dibromomethane, bromofluoromethane, and 2-chloro-l,l,l-trifluoroethane from ~hich the products may be re~pectively difluoromethsne, and l,ltl,2~tetrefluoroethane.
In operating the proces~ of the invention, tbe halogenated alkane may be contacted with the tran~ition metal fluoride at a tempereture at which the halogenated alkane is in the liquid phase or the vapour phase but conveniently the liquid phase. Accordin~ly the temperature may be from about -80 to about 25 C depending upon the boiling point of the halogenated alkane, although 2~ the reaction proceed~, and may be sonducted at, temperatures hlgher th~n 25C, for e~mple up to lOO C, in which case the halogenated alkane may be in t~e vapour phase. T~e proce~s of the invention 1s preferably operated under substantially anhydrou~ conditions, end i~ con~eniently operated -at atmospher1c pre~sure, although ~uper~tmo~pherlcor subatmo6pheric pres~ures may be employed, if desired.
~g2~2 The transition metal fluoride may, et the reaction temper~ture, be pre~ent in the reaction ve~sel in the solid or vapour p~ese, and may be supported on ~ ~ubstrate, for exemple aluminlum fluoride or carbon.
The proportion~ of halogen~ted alkane and transition metal fluoride are nDt critical; either - may be in exce~s over stochiometric, if desired.
Thu~, 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 range are given merely by way of guidance and are in no vay limiting on the proces of the preent invention. Hydrogen fluoride may al~o be included in the reaction mixture a~ a fluorinating agent, the metal fluoride then optionally being employed in a catalytic amount.
In opærating the process of the invention, whether at lea~t one hydrogen atom or at least one halogen atom other then fluorine, or both hydrogen and halogen in the halogenated alkane is/are replaced by fluorine may depend to a large e~tent 2 on the particular hslogenated alkane and on the particular transition metal fluoride used.
Where lt i8 desired to replace at least one halogen atom in the halogenated alkane, the preferred transition metal fluorides are OsF6, IrF6 and ReF6. The u~e of the~e particular fluorides allo~8 the replacement of halogen atom other than fluorine ln the halo~enated alkane by fluorine ~ith a selectivity ~hich may be a~ high 2 ~
a~ 80% and even aR high e~ 95X., in particular where O~F6 iE uaed.
Where it iQ deaired to replace a hydrogen atom in the halogenated alkane and the halogenated alkane i8 a chlorinated alkane, the preferred - tranRition metal fluorides are UF6, VF5 and ReF7.
The uRe of the~e p~rticular flucride~ allowa the - replace~ent of at least one hydrogen at~m by fluorine w1th a ~electivity ~hich may be ac high QC 80% and even a~ high a~ 95%, in partlcular where UF6 i~ uEed.
Furthermore, certain of the trsnsition metal fluoride~, for example RuF5, may ~electively replace at lea~t one hydrogen atom in certain halogenated alkanec, for example CF3CH2Cl, yet ~electively replace at least one halogen atom other than fluorine in other halogenated alkanes, for example in dichloromethane. CrF5 may ~electively replace at lea~t one hydrogen atom although the selectivity may be better with certain halogenated alkane ~tarting material~ than with other6; for example high selectivity i~
obtained with CrF5 for the replacement of hydrogen in CF3CH2Cl although ~electivity may not be a~
2~ high ~ith CH2C12. In addition, ReF7 may selectively replace at lea~t one hydrogen atom ~here the halogenated ~lkane iE a chlorinated alkane, but may ~electively replace at least one halogen atom ~here the halogenated alkane is a brominated alkane. -The proce~Q cf the invention i8 of partlcularvalue for the preparation of difluoromethane from dichlnromethane or chlorofluoromethane and 2 ~ 2 eccordingly ln a preferred a~pect of the invention there i~ provided a prnces6 for the preparation of d1fluoromethane ~hich proce~s c:ompr1~es contacting dichloromethane or chlorofluoromethane Yith a transition metal fluoride ~elected from OsF6, IrF6, ReF6 and RuF5 and maintainlng the contact until ~t lea~t a portion of the dichloromethane or - chlorofluorometh~ne ha6 been converted to difluoromethane. The re~ction mixture may, if de6ired, also contaln hydrogen fluoride.
The process of t~e ~nvention i~- al60 of particular value for t~e preparation of 1,1,1,2-tetrafluoroethane from 2-Ghloro-l,l,l-trifl~oroethane snd accordingly in a further a6pect of the invention there 1 provided a proce~s for the preparation of 1,1,1,2-tetrafluoroethane which compri6eF
contacting 2-chloro-1,1,1-trifluoroethane with a tran6ition metal fluoride 6elected from OsF6, IrF6, and ReF6 and maintaining the contact until at lea6t a portion of the 2-chloro-1,1,1-trifluoroethane ha~ been converted to 1,1,1,2-tetrafluoroethane. The rea~tlon mixture may, if de6ired, al60 contain hydrogen fluoride.
Z~ The proce6s of the invention i6 al~o of particular value for t~e preparatlon of dichlorofluoromethane by contacting dichloromethane with ReF7, UF6 or VF5 and of 2-chloro-1,1,1,~-tetra~luoroethane by contacting 2-chloro-1,1,1-trlfluoroethane ~ith RuF5, ReF7, CrF5, VF5 or UF6 and these processes represent further particular embodlments of the invent~on.
2~2'~
The invention i~ illu~trated by the following e~amples in which the organic m~terial~ vere ~andled in a vacuum line made from ~tainle~s ~teel tubing ~ith ~tainles~ steel valves and the metal fluorides ~ere bandled in ~atellite lines made from PTFE. React1ons Yere conducted in FEP tubes ~copolymer of HFP and TFE) ~ich could be sealed - thermally in a small ring furnace after reActiOn had reached completion and could be inserted into a ~tandard precision 5mm n.m.r. glas tube witb a thin film of the lock ubstance - d6 acetone placed between the tube~. To obtain a reliable integration of lH a~ainct 19F ~ignals, CF3CH20H
33% v~v) was added to the lock ~ubstance.
All equipment was ~easoned with fluorlne gas at a pre~ure of 700-800 mbar for about 16 hours.
The transition metal fluoridei ~ere prepared by conventional literature method~ and were stored in F2 paa~lvated Ni cylinders.
The products were analysed by n.m.r.
~pectroscopy on a Bruker FT spectrometer AM 300 ~lH at 300.0 nHz, 19F et 282,4 nHz) with a Smm bore selective probe.
2~ .
EXAMPLE 1. Fluorination of CH2C12 by 0sF6.
A 15cm long x 4mm diameter (out~ide diameter) x 0.5mm ~all thickness FEP tube was connected via a PTFE valve (6upplied by Production Technique~) to an all metal vacuum line, evacuated to < 10 5 Torr, pa~ivated with F2 gaB ( 400 Torr~ i'or 20 minutes, and re-evacuated. The valve vac clo~ed and the weiqht of the valve and tube mea~ured.
2 Q ~ 2 37.9 mg ~0.125 mmol) of OsF6 (prepared in accordance with J.Chem Soc., ~alton Tran~., 1988, 1341) wa~ conden6ed from the nickel storage cylinder into the pre-fluorinated FEP tube by vacuum tran~fer at -196C a~ follow6. The Ni ~torage contalner and FEP tube vere connected to the vacuum 11ne. The connections vere evacusted, pa~ivated with F2 gas and re-evacuated. The FEP
tube ~as cooled to -196C in liquid nitrogen and the valve~ to the FEP tube and Ni ~torege container were opened to allow the 06F6 to ~ublime into the FEP tube. The valve to the ~torage container wa~ closed and the apparatus vas re-evacuated, the valve to the FEP tube clo~ed and the FEP tube allowed to warm to room temperature.
The FEP tube and valve were taken off the vacuum line and re-weighed.
The FEP tube containing OsF6 and a glass ~torage vessel containing dried CH2C12 vere connected to the vacuum line via a PTFE T-piece.
The conneotors and T-piece were evacuated, passivated with F2 and re-evacuated.
236mg, 2.78 mmol of CH2C12 ~es 6ublimed into the FEP tube cooled to -196 C in liquid nitrogen.
2~ The PTFE valve va~ closed and the react~on mixture allowed to ~arm 810wly to -78C ln a dry-ice-acetone bath and then to room temperature (20C) vith frequent ~haking. After 1 hour the ~olution had turned from itc original yellow colour to black and there wa6 a black precipltate.
The FEP tube and PTFE valve vere taken off the vacuum line end re-~eighed.
- 8 - 2~ 2 The FEP re~ction tube and a second FEP tube were connected to the v~cuum line via a PTFE
T-piece, and the connector~ and T-piece were evacuated, pafisivated vith F2 and re-evacuated.
The aecond FEP tube wa~ cooled to -196C ln liquid nitroyen, the PTFE valve~ opened and the volatlle product from the reaction tube ~ao alloved to - eublime into the cecond FEP tube. The involatlle precipitate ln the reaction tube wa6 taken for elemental analy~i~, and wa6 determined to be O~C15.
The FEP tube containing the volatile product wa~ kept cold at -196 C and ~as placed in a emall ring furnace and heated gently to form a vacuum and presure tight 6eal. The n.m.r. ~pectra o~ the volatile product ~es run at 29BK.
The re~ult~ sre shown in Table 1. From the~e result6 it ~as calculated that the replacement of chlorine by fluorine was 87X. ~elective and that the overall yield of fluorinated product~ wa~ 8R%.
Example 2. Fluorlnation of CH2C12 by IrF6.
The procedure described in example 1 wa6 2~ folloYed except that 39.2mg, 0.12B mmol of IrF6 (prepsred aB de~cribed in J.Chem Phy~1cs., 1970, 53, 1411) and l90mg, 2.23 mmol of CH2C12 Yere ~ublimed into the reaction tube.
The reoult6 are shown ln Table 1. From theoe reculte it wac calculated that the replacement of chlorine by fluorine ~as 7B% eelective.
2 ~ 2 Example 3. Fluorination of CH2C12 by ReF6.
The procedure descrlbed in example 1 wa~
folloved except that 32.2mg, 0.107 mmol of ReF6 (prepared as de~crlbed ln J.Chem Soc. Dalton Trans., 1988, 1341) and 475mg, 5.6 mmol of CH2C12 were subllmed lnto the reactlon tube. The reactlon - wac allo~ed to run for S day~ before analysis by n.m.r. ~as carried out. Furthermore, after S days no precipitate had formed and the FEP reaction tube it~elf was sealed a~ de~cribed in example 1 without tran6ferring the volatile products to a ~econd FEP tube.
The result~ aræ shown ln Tsble 1. From these results it ~a calculated that the replacement of chlorine by ~luorine vas 88.5X ~elective snd that the overall yield of ~luorinated products wa6 95%.
Example 4. Fluorination of CH2C12 by RuF5.
The procedure descrlbed in example 1 was follo~ed except that 60.8mg, 0~310 mmol of solid RuF5 ~prepared as described in J.Chem Soc., 1963, 527) Yas loaded into the pre-~luorinated ~ei~hed 2~ FEP tube in a dry box ~Clppm H20, supplied by Vacuum Atmosphere~ LtdS and 647mg, 7.614 mmol of CH2C12 ~ere sublimed into the reaction tube. The reaction tube ~as allo~ed to warm up to 10 C.
The results are shown in Table 1. From these results it was calculated that the replacement of chlorlne by fluorine ~ac 96.5X selective.
2 ~ A 2 Example 5. Fluorlnation of CH2Cl2 by UF6.
The prDcedure de~crlbed in example 1 wa6 follo~ed except that 415.Omg, 1.179 mmol of UF6 ~prepared a6 de~cribed ln DOKL AKAD NAUK SSSR, 1962, 14~) and 1317mg, 15.5 mmol of CH2Cl2 were ~ublimed into the reactlon tube. The reaction was - allowed to proceed for 5 days before analysiG by n.m.r. wa6 carried out. The lnvolatile precipitate ~0 wa6 determined to be UF5.
The re~ult~ are fihown in Tsble 1. From these resultE it wa~ calculated that the replacement of hydrogen by fluorine vas 99.9X selective.
Example 6. Fluorination of CH2Cl2 by VF5.
The procedure described in example 1 was folloved except that l90.Smg, 1.305 mmol of VF5 (prepared a6 described in J.Chem Soc., 1949, 2979) and 942.5mg, 11.09 mmol of CH2Cl2 were ~ublimed into the reaction tube. The FEP tube Yas allowed to ~arm up to O C. The reaction was allowed to proceed for 2 hourE before carrying out analysiE
by n.m.r. The involatile product ~as determined to 2~ be VF4.
T~e results are shown in Table l. From these resultE it was cslculated that tbe replacement of hydrogen by fluorine waE 92.0X ~elective.
, 1 - 2 3 ti~ 2 Example 7. Fluorination of CH~,Cl2 by ReF7.
The pro~-edure descr1bed in example 1 was follo~ed except that 207.3mg, 0.649 mmol of ReF7 ~prepared a~ de~cribed in J.Inorg Nucl Chem., 1961, 20, lB9~ and 1061.3mg, 12.5 mmol of CH2Cl2 were ~ubllmed into the reactlon tube. The reactlon - wa8 allowed to run for 1 day before analy~i6 by n.m.r. ~as carried out. Furthermore, after 1 day l.û
no precipitate had formed and the FEP reaction tube it~elf WaB ~ealed ac described in example 1 without tran~ferring the volatile products to a ~econd FEP tube.
The re~ult6 are ~hown in Table 1. From the~e result~ it wa~ calculated that the repl~cement of hydrogen by fluorine ~as 96.0% 6elective.
Example 8. Fluorination of CH2Cl~ by CrF5.
2 This reactlon wa5 carried out in the presence of HF as solvent.
The procedure of example 1 was follo~ed except that 205.4mg, 1.397mmol of CrF5 (prepared as described in J. Inorg Chem, 1985, 24, 2286) was loaded into a large (lOcm x lOmm outside diameter x lmm wall thickne~s) FEP reactlon tube in a dry box. Dry HF was then sublimed into the reaction tube and the mixture of CrF5 and HF ~a~ stirred for 18 hours to allow dis~olution of CrF5 in the 3~ HF. 20a6 mg, 24.55 mmol of CH2Cl2 were then sublimed into the reaction ve~sel and the reaction mixture was stirred at room temperature for 2 hour~. After 2 hours, all the volatile products - 12 - 2~ 2 from the reaction tube Yere allowed to condense in a large FEP tube which was at -196 C. The volatile productfi ~ere ~armed up to -7~ C in a dry-ice acetone bath and the HF and organic layerc were separated by freezing the organlc layer at -196 C
and vacuum subliming the HF layer into a further FEP tube. The or~anlc pha~e ~as then ffarmed up to - room temperature and vacuum subllmed lnto a third FEP tube. The FEP tubes containing the organic phase and HF phase~ ~ere then heat sealed and taken for n.m.r. analy~is.
The results are ~hown in Table 1. The re~ults show that the fluorination of CH2C12 using CrF5 i8 not selective.
Example 9. Fluorination of CH2Br2 by ReF7.
The procedure descrlbed in example 1 was followed except that 49.Omg, 0.1535 mmol of ReF7 and 854.3mg, 4.91 mmol of CH2Br2 ~ere 6ublimed lnto the reaction tube. The reaction was allowed to run for 1 day before analysi6 by n.m.r. was carried out. Furthermore, after 1 day no precipitate hsd formed and the FEP reaction tube 2 itself ~as ~ealed a~ described in example 1 without transferring the volatile product~ to a second FEP tube.
The results are Qho~n in T~ble 2. From these results it was calculated that the replacement of 3Q bromine by fluorine was 98.0-/. 6elective.
- 13 - 2 ~6~ 2 Example 10. Fluorinatlon of CH~Br2 by UF6.
The procedure described in example 1 wa~
folloYed except that 217.5mg, 0.618 mmol of UF6 and 1142mg, ~.57 mmol of CH2Br2 were sublimed into the reaction tube. The reaction ~ac alloued to proceed for 14 days before analysi~ by n.m.r. ~a~
carried out.
The result~ are ~hown in Table 2. From these ~0 re~ult~ it waa calculated that the replacement of hydrogen by fluorine va~ 100.0% ~elective.
Example 11. Fluorination of CF3CH2Cl by VF5.
The procedure described in example 1 wa6 iolloYed except that 93.3mg, 0.639 mmol of VF5 and 464.Omg, 3.916 mmol of CF3CH2Cl were ~ublimed into the reaction tube, and the reaction was allowed to proceed for 4 day6.
The result6 are shown in Table 3. From these result~ it was calculated that the replacement of hydrogen by fluorine ~as 100% ~elective and that the yield of fluorinated products wa~ 70%.
2~
Example 12. Fluorination of CF3CH2Cl by ReF7.
The procedure de~cribed in example 1 wa6 followed except that lSl.Smg, 0.475 mmol of ReF7 and 443.7my, 3.74 mmol of CF3CH2Cl were ~ublimed into the reaction tube. The reaction wac allo~ed to run for 1 day before analyci~ by n.m.r. was carried out. Furthermore, after 1 day no precipitate had formed and the FEP reaction tube 4 '~ ~
itseli ~a~ ~ealed as decribed in example 1 without transferring the volatile productE to a ~econd FEP tube.
The result~ are shown in Table 3. From these results it ~a~ calculated that the replscement of hydrogen by fluorine ~a~ lOOX ~elective and that the yield of fluorinated product~ WaB 26%.
Example 13. Flunrination of CF3CH2Cl by RuF5.
The procedure de~cribed in example 1 was followe~ except that 200.Omg, 1.021 mmol of solld RuF5 vas losded into the pre-fluorlnated weighed FEP tube in a dry box ~<lppm H20, ~upplied by Vacuum Atmospheres Ltd) and 906.9mg, 7.653 mmol of CF3CH2Cl were ~ublimed into the reaction tube.
Reaction was allowed to proceed for 2 hour.
The results are ~hown in Table 3, From these reults it va calculated that the replacement of hydrogen by fluorine vas 43X selective. The large amount of CHF3 produced re6ulted from the fluorination by RuF5 of CHF2Cl which vas present as a reactive contaminant in the CF3CH2Cl used.
2~5 , .
2 ~ 2 _ _ TABLE 1.
PRODUCTS OF FLUORINATION OF CH2C12.
__ _ _ __ TM FLUORIDE. ReF7 ReF6 O~F6 IrF6 UF6 RuF5 YF5 CrF5 PRODUCTS.
~OLE %.
(Mole~.
_ _ CH2ClF. 1.2 85.1 22.1 42.0 37.4 2.0 27.8 (0.5) ~.17) ~.03) .
CH2F2 3.44 54.8 29.3 59.1 2.6 (0.01) ~.21) _ ~.~ ___ CHC12F. 43.2 4.1 11.1 99.9 1.68 91.9 8.17 ., ( ~) ~ ~
_ _ CHClF2. 0.6 3.2 1.3 10.2 1.2 6.2 27.5 (0.0~ ~.01) .0 _ : _ _ _ _ C~- 7.92) 7.4 0.~ _ 3.0 2~ CF2C12. 0.26 2.0 _ . ..... _ _ ~ .
CF3Cl. 1 67 2.4 CF4- ~ _ _ _ _ _ _ 4.4 _ _ _ _ ~.
HF. 54.7 4.1 12.5 (0.03~ ~0.1~ _ ~ _______ 2 ~ $ w ~
_ _ ~ .
TABLE 2.
PRODUCTS OF FLUORINATION OF CH2Br2.
PRODUCT/!lDle %. r~ r CHzF2 CHBr2F CHBrF2 ___~_ Tn FLUORIDE.
~0 ReF7. 40.1 58.2 0.33 1.21 UF6 85.5 14.5 L~ TABLE 3.
PRODUCTS OF FLUORINATION OF CF3CH~Cl.
TM FLUORIDE. VF5- ReF7. RuF5.
PRODUCT/Mole X.
(No.of nole~).
2~ CF3CHFCl. 100 100 43.0 ._ __ ~0.111) (0.0299) _ CF3CFC12. 4.
30 ~ 3CUC12. ~ ,
Halogenated alkanes ~hich may be employed in the proce~ of t~e invention may contain one or more carbon atoms, for example, typically up to 6 carbon atom~, and ~ave ~t lea3t one hydrogen atom snd at least one replaceable halogen atom selected from chlorine, bromlne snd iodine. Other atom~, for example fluorlne, may also be present.
- Especlally useful halogenated alkanes lnclude hydrochlorocarbon6 and chlorofluorohydrocarbons.
Speciflc examples of halogenated alksneE
which may be u~ed include dichloromethane, chlorofluoromethane, dibromomethane, bromofluoromethane, and 2-chloro-l,l,l-trifluoroethane from ~hich the products may be re~pectively difluoromethsne, and l,ltl,2~tetrefluoroethane.
In operating the proces~ of the invention, tbe halogenated alkane may be contacted with the tran~ition metal fluoride at a tempereture at which the halogenated alkane is in the liquid phase or the vapour phase but conveniently the liquid phase. Accordin~ly the temperature may be from about -80 to about 25 C depending upon the boiling point of the halogenated alkane, although 2~ the reaction proceed~, and may be sonducted at, temperatures hlgher th~n 25C, for e~mple up to lOO C, in which case the halogenated alkane may be in t~e vapour phase. T~e proce~s of the invention 1s preferably operated under substantially anhydrou~ conditions, end i~ con~eniently operated -at atmospher1c pre~sure, although ~uper~tmo~pherlcor subatmo6pheric pres~ures may be employed, if desired.
~g2~2 The transition metal fluoride may, et the reaction temper~ture, be pre~ent in the reaction ve~sel in the solid or vapour p~ese, and may be supported on ~ ~ubstrate, for exemple aluminlum fluoride or carbon.
The proportion~ of halogen~ted alkane and transition metal fluoride are nDt critical; either - may be in exce~s over stochiometric, if desired.
Thu~, 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 range are given merely by way of guidance and are in no vay limiting on the proces of the preent invention. Hydrogen fluoride may al~o be included in the reaction mixture a~ a fluorinating agent, the metal fluoride then optionally being employed in a catalytic amount.
In opærating the process of the invention, whether at lea~t one hydrogen atom or at least one halogen atom other then fluorine, or both hydrogen and halogen in the halogenated alkane is/are replaced by fluorine may depend to a large e~tent 2 on the particular hslogenated alkane and on the particular transition metal fluoride used.
Where lt i8 desired to replace at least one halogen atom in the halogenated alkane, the preferred transition metal fluorides are OsF6, IrF6 and ReF6. The u~e of the~e particular fluorides allo~8 the replacement of halogen atom other than fluorine ln the halo~enated alkane by fluorine ~ith a selectivity ~hich may be a~ high 2 ~
a~ 80% and even aR high e~ 95X., in particular where O~F6 iE uaed.
Where it iQ deaired to replace a hydrogen atom in the halogenated alkane and the halogenated alkane i8 a chlorinated alkane, the preferred - tranRition metal fluorides are UF6, VF5 and ReF7.
The uRe of the~e p~rticular flucride~ allowa the - replace~ent of at least one hydrogen at~m by fluorine w1th a ~electivity ~hich may be ac high QC 80% and even a~ high a~ 95%, in partlcular where UF6 i~ uEed.
Furthermore, certain of the trsnsition metal fluoride~, for example RuF5, may ~electively replace at lea~t one hydrogen atom in certain halogenated alkanec, for example CF3CH2Cl, yet ~electively replace at least one halogen atom other than fluorine in other halogenated alkanes, for example in dichloromethane. CrF5 may ~electively replace at lea~t one hydrogen atom although the selectivity may be better with certain halogenated alkane ~tarting material~ than with other6; for example high selectivity i~
obtained with CrF5 for the replacement of hydrogen in CF3CH2Cl although ~electivity may not be a~
2~ high ~ith CH2C12. In addition, ReF7 may selectively replace at lea~t one hydrogen atom ~here the halogenated ~lkane iE a chlorinated alkane, but may ~electively replace at least one halogen atom ~here the halogenated alkane is a brominated alkane. -The proce~Q cf the invention i8 of partlcularvalue for the preparation of difluoromethane from dichlnromethane or chlorofluoromethane and 2 ~ 2 eccordingly ln a preferred a~pect of the invention there i~ provided a prnces6 for the preparation of d1fluoromethane ~hich proce~s c:ompr1~es contacting dichloromethane or chlorofluoromethane Yith a transition metal fluoride ~elected from OsF6, IrF6, ReF6 and RuF5 and maintainlng the contact until ~t lea~t a portion of the dichloromethane or - chlorofluorometh~ne ha6 been converted to difluoromethane. The re~ction mixture may, if de6ired, also contaln hydrogen fluoride.
The process of t~e ~nvention i~- al60 of particular value for t~e preparation of 1,1,1,2-tetrafluoroethane from 2-Ghloro-l,l,l-trifl~oroethane snd accordingly in a further a6pect of the invention there 1 provided a proce~s for the preparation of 1,1,1,2-tetrafluoroethane which compri6eF
contacting 2-chloro-1,1,1-trifluoroethane with a tran6ition metal fluoride 6elected from OsF6, IrF6, and ReF6 and maintaining the contact until at lea6t a portion of the 2-chloro-1,1,1-trifluoroethane ha~ been converted to 1,1,1,2-tetrafluoroethane. The rea~tlon mixture may, if de6ired, al60 contain hydrogen fluoride.
Z~ The proce6s of the invention i6 al~o of particular value for t~e preparatlon of dichlorofluoromethane by contacting dichloromethane with ReF7, UF6 or VF5 and of 2-chloro-1,1,1,~-tetra~luoroethane by contacting 2-chloro-1,1,1-trlfluoroethane ~ith RuF5, ReF7, CrF5, VF5 or UF6 and these processes represent further particular embodlments of the invent~on.
2~2'~
The invention i~ illu~trated by the following e~amples in which the organic m~terial~ vere ~andled in a vacuum line made from ~tainle~s ~teel tubing ~ith ~tainles~ steel valves and the metal fluorides ~ere bandled in ~atellite lines made from PTFE. React1ons Yere conducted in FEP tubes ~copolymer of HFP and TFE) ~ich could be sealed - thermally in a small ring furnace after reActiOn had reached completion and could be inserted into a ~tandard precision 5mm n.m.r. glas tube witb a thin film of the lock ubstance - d6 acetone placed between the tube~. To obtain a reliable integration of lH a~ainct 19F ~ignals, CF3CH20H
33% v~v) was added to the lock ~ubstance.
All equipment was ~easoned with fluorlne gas at a pre~ure of 700-800 mbar for about 16 hours.
The transition metal fluoridei ~ere prepared by conventional literature method~ and were stored in F2 paa~lvated Ni cylinders.
The products were analysed by n.m.r.
~pectroscopy on a Bruker FT spectrometer AM 300 ~lH at 300.0 nHz, 19F et 282,4 nHz) with a Smm bore selective probe.
2~ .
EXAMPLE 1. Fluorination of CH2C12 by 0sF6.
A 15cm long x 4mm diameter (out~ide diameter) x 0.5mm ~all thickness FEP tube was connected via a PTFE valve (6upplied by Production Technique~) to an all metal vacuum line, evacuated to < 10 5 Torr, pa~ivated with F2 gaB ( 400 Torr~ i'or 20 minutes, and re-evacuated. The valve vac clo~ed and the weiqht of the valve and tube mea~ured.
2 Q ~ 2 37.9 mg ~0.125 mmol) of OsF6 (prepared in accordance with J.Chem Soc., ~alton Tran~., 1988, 1341) wa~ conden6ed from the nickel storage cylinder into the pre-fluorinated FEP tube by vacuum tran~fer at -196C a~ follow6. The Ni ~torage contalner and FEP tube vere connected to the vacuum 11ne. The connections vere evacusted, pa~ivated with F2 gas and re-evacuated. The FEP
tube ~as cooled to -196C in liquid nitrogen and the valve~ to the FEP tube and Ni ~torege container were opened to allow the 06F6 to ~ublime into the FEP tube. The valve to the ~torage container wa~ closed and the apparatus vas re-evacuated, the valve to the FEP tube clo~ed and the FEP tube allowed to warm to room temperature.
The FEP tube and valve were taken off the vacuum line and re-weighed.
The FEP tube containing OsF6 and a glass ~torage vessel containing dried CH2C12 vere connected to the vacuum line via a PTFE T-piece.
The conneotors and T-piece were evacuated, passivated with F2 and re-evacuated.
236mg, 2.78 mmol of CH2C12 ~es 6ublimed into the FEP tube cooled to -196 C in liquid nitrogen.
2~ The PTFE valve va~ closed and the react~on mixture allowed to ~arm 810wly to -78C ln a dry-ice-acetone bath and then to room temperature (20C) vith frequent ~haking. After 1 hour the ~olution had turned from itc original yellow colour to black and there wa6 a black precipltate.
The FEP tube and PTFE valve vere taken off the vacuum line end re-~eighed.
- 8 - 2~ 2 The FEP re~ction tube and a second FEP tube were connected to the v~cuum line via a PTFE
T-piece, and the connector~ and T-piece were evacuated, pafisivated vith F2 and re-evacuated.
The aecond FEP tube wa~ cooled to -196C ln liquid nitroyen, the PTFE valve~ opened and the volatlle product from the reaction tube ~ao alloved to - eublime into the cecond FEP tube. The involatlle precipitate ln the reaction tube wa6 taken for elemental analy~i~, and wa6 determined to be O~C15.
The FEP tube containing the volatile product wa~ kept cold at -196 C and ~as placed in a emall ring furnace and heated gently to form a vacuum and presure tight 6eal. The n.m.r. ~pectra o~ the volatile product ~es run at 29BK.
The re~ult~ sre shown in Table 1. From the~e result6 it ~as calculated that the replacement of chlorine by fluorine was 87X. ~elective and that the overall yield of fluorinated product~ wa~ 8R%.
Example 2. Fluorlnation of CH2C12 by IrF6.
The procedure described in example 1 wa6 2~ folloYed except that 39.2mg, 0.12B mmol of IrF6 (prepsred aB de~cribed in J.Chem Phy~1cs., 1970, 53, 1411) and l90mg, 2.23 mmol of CH2C12 Yere ~ublimed into the reaction tube.
The reoult6 are shown ln Table 1. From theoe reculte it wac calculated that the replacement of chlorine by fluorine ~as 7B% eelective.
2 ~ 2 Example 3. Fluorination of CH2C12 by ReF6.
The procedure descrlbed in example 1 wa~
folloved except that 32.2mg, 0.107 mmol of ReF6 (prepared as de~crlbed ln J.Chem Soc. Dalton Trans., 1988, 1341) and 475mg, 5.6 mmol of CH2C12 were subllmed lnto the reactlon tube. The reactlon - wac allo~ed to run for S day~ before analysis by n.m.r. ~as carried out. Furthermore, after S days no precipitate had formed and the FEP reaction tube it~elf was sealed a~ de~cribed in example 1 without tran6ferring the volatile products to a ~econd FEP tube.
The result~ aræ shown ln Tsble 1. From these results it ~a calculated that the replacement of chlorine by ~luorine vas 88.5X ~elective snd that the overall yield of ~luorinated products wa6 95%.
Example 4. Fluorination of CH2C12 by RuF5.
The procedure descrlbed in example 1 was follo~ed except that 60.8mg, 0~310 mmol of solid RuF5 ~prepared as described in J.Chem Soc., 1963, 527) Yas loaded into the pre-~luorinated ~ei~hed 2~ FEP tube in a dry box ~Clppm H20, supplied by Vacuum Atmosphere~ LtdS and 647mg, 7.614 mmol of CH2C12 ~ere sublimed into the reaction tube. The reaction tube ~as allo~ed to warm up to 10 C.
The results are shown in Table 1. From these results it was calculated that the replacement of chlorlne by fluorine ~ac 96.5X selective.
2 ~ A 2 Example 5. Fluorlnation of CH2Cl2 by UF6.
The prDcedure de~crlbed in example 1 wa6 follo~ed except that 415.Omg, 1.179 mmol of UF6 ~prepared a6 de~cribed ln DOKL AKAD NAUK SSSR, 1962, 14~) and 1317mg, 15.5 mmol of CH2Cl2 were ~ublimed into the reactlon tube. The reaction was - allowed to proceed for 5 days before analysiG by n.m.r. wa6 carried out. The lnvolatile precipitate ~0 wa6 determined to be UF5.
The re~ult~ are fihown in Tsble 1. From these resultE it wa~ calculated that the replacement of hydrogen by fluorine vas 99.9X selective.
Example 6. Fluorination of CH2Cl2 by VF5.
The procedure described in example 1 was folloved except that l90.Smg, 1.305 mmol of VF5 (prepared a6 described in J.Chem Soc., 1949, 2979) and 942.5mg, 11.09 mmol of CH2Cl2 were ~ublimed into the reaction tube. The FEP tube Yas allowed to ~arm up to O C. The reaction was allowed to proceed for 2 hourE before carrying out analysiE
by n.m.r. The involatile product ~as determined to 2~ be VF4.
T~e results are shown in Table l. From these resultE it was cslculated that tbe replacement of hydrogen by fluorine waE 92.0X ~elective.
, 1 - 2 3 ti~ 2 Example 7. Fluorination of CH~,Cl2 by ReF7.
The pro~-edure descr1bed in example 1 was follo~ed except that 207.3mg, 0.649 mmol of ReF7 ~prepared a~ de~cribed in J.Inorg Nucl Chem., 1961, 20, lB9~ and 1061.3mg, 12.5 mmol of CH2Cl2 were ~ubllmed into the reactlon tube. The reactlon - wa8 allowed to run for 1 day before analy~i6 by n.m.r. ~as carried out. Furthermore, after 1 day l.û
no precipitate had formed and the FEP reaction tube it~elf WaB ~ealed ac described in example 1 without tran~ferring the volatile products to a ~econd FEP tube.
The re~ult6 are ~hown in Table 1. From the~e result~ it wa~ calculated that the repl~cement of hydrogen by fluorine ~as 96.0% 6elective.
Example 8. Fluorination of CH2Cl~ by CrF5.
2 This reactlon wa5 carried out in the presence of HF as solvent.
The procedure of example 1 was follo~ed except that 205.4mg, 1.397mmol of CrF5 (prepared as described in J. Inorg Chem, 1985, 24, 2286) was loaded into a large (lOcm x lOmm outside diameter x lmm wall thickne~s) FEP reactlon tube in a dry box. Dry HF was then sublimed into the reaction tube and the mixture of CrF5 and HF ~a~ stirred for 18 hours to allow dis~olution of CrF5 in the 3~ HF. 20a6 mg, 24.55 mmol of CH2Cl2 were then sublimed into the reaction ve~sel and the reaction mixture was stirred at room temperature for 2 hour~. After 2 hours, all the volatile products - 12 - 2~ 2 from the reaction tube Yere allowed to condense in a large FEP tube which was at -196 C. The volatile productfi ~ere ~armed up to -7~ C in a dry-ice acetone bath and the HF and organic layerc were separated by freezing the organlc layer at -196 C
and vacuum subliming the HF layer into a further FEP tube. The or~anlc pha~e ~as then ffarmed up to - room temperature and vacuum subllmed lnto a third FEP tube. The FEP tubes containing the organic phase and HF phase~ ~ere then heat sealed and taken for n.m.r. analy~is.
The results are ~hown in Table 1. The re~ults show that the fluorination of CH2C12 using CrF5 i8 not selective.
Example 9. Fluorination of CH2Br2 by ReF7.
The procedure descrlbed in example 1 was followed except that 49.Omg, 0.1535 mmol of ReF7 and 854.3mg, 4.91 mmol of CH2Br2 ~ere 6ublimed lnto the reaction tube. The reaction was allowed to run for 1 day before analysi6 by n.m.r. was carried out. Furthermore, after 1 day no precipitate hsd formed and the FEP reaction tube 2 itself ~as ~ealed a~ described in example 1 without transferring the volatile product~ to a second FEP tube.
The results are Qho~n in T~ble 2. From these results it was calculated that the replacement of 3Q bromine by fluorine was 98.0-/. 6elective.
- 13 - 2 ~6~ 2 Example 10. Fluorinatlon of CH~Br2 by UF6.
The procedure described in example 1 wa~
folloYed except that 217.5mg, 0.618 mmol of UF6 and 1142mg, ~.57 mmol of CH2Br2 were sublimed into the reaction tube. The reaction ~ac alloued to proceed for 14 days before analysi~ by n.m.r. ~a~
carried out.
The result~ are ~hown in Table 2. From these ~0 re~ult~ it waa calculated that the replacement of hydrogen by fluorine va~ 100.0% ~elective.
Example 11. Fluorination of CF3CH2Cl by VF5.
The procedure described in example 1 wa6 iolloYed except that 93.3mg, 0.639 mmol of VF5 and 464.Omg, 3.916 mmol of CF3CH2Cl were ~ublimed into the reaction tube, and the reaction was allowed to proceed for 4 day6.
The result6 are shown in Table 3. From these result~ it was calculated that the replacement of hydrogen by fluorine ~as 100% ~elective and that the yield of fluorinated products wa~ 70%.
2~
Example 12. Fluorination of CF3CH2Cl by ReF7.
The procedure de~cribed in example 1 wa6 followed except that lSl.Smg, 0.475 mmol of ReF7 and 443.7my, 3.74 mmol of CF3CH2Cl were ~ublimed into the reaction tube. The reaction wac allo~ed to run for 1 day before analyci~ by n.m.r. was carried out. Furthermore, after 1 day no precipitate had formed and the FEP reaction tube 4 '~ ~
itseli ~a~ ~ealed as decribed in example 1 without transferring the volatile productE to a ~econd FEP tube.
The result~ are shown in Table 3. From these results it ~a~ calculated that the replscement of hydrogen by fluorine ~a~ lOOX ~elective and that the yield of fluorinated product~ WaB 26%.
Example 13. Flunrination of CF3CH2Cl by RuF5.
The procedure de~cribed in example 1 was followe~ except that 200.Omg, 1.021 mmol of solld RuF5 vas losded into the pre-fluorlnated weighed FEP tube in a dry box ~<lppm H20, ~upplied by Vacuum Atmospheres Ltd) and 906.9mg, 7.653 mmol of CF3CH2Cl were ~ublimed into the reaction tube.
Reaction was allowed to proceed for 2 hour.
The results are ~hown in Table 3, From these reults it va calculated that the replacement of hydrogen by fluorine vas 43X selective. The large amount of CHF3 produced re6ulted from the fluorination by RuF5 of CHF2Cl which vas present as a reactive contaminant in the CF3CH2Cl used.
2~5 , .
2 ~ 2 _ _ TABLE 1.
PRODUCTS OF FLUORINATION OF CH2C12.
__ _ _ __ TM FLUORIDE. ReF7 ReF6 O~F6 IrF6 UF6 RuF5 YF5 CrF5 PRODUCTS.
~OLE %.
(Mole~.
_ _ CH2ClF. 1.2 85.1 22.1 42.0 37.4 2.0 27.8 (0.5) ~.17) ~.03) .
CH2F2 3.44 54.8 29.3 59.1 2.6 (0.01) ~.21) _ ~.~ ___ CHC12F. 43.2 4.1 11.1 99.9 1.68 91.9 8.17 ., ( ~) ~ ~
_ _ CHClF2. 0.6 3.2 1.3 10.2 1.2 6.2 27.5 (0.0~ ~.01) .0 _ : _ _ _ _ C~- 7.92) 7.4 0.~ _ 3.0 2~ CF2C12. 0.26 2.0 _ . ..... _ _ ~ .
CF3Cl. 1 67 2.4 CF4- ~ _ _ _ _ _ _ 4.4 _ _ _ _ ~.
HF. 54.7 4.1 12.5 (0.03~ ~0.1~ _ ~ _______ 2 ~ $ w ~
_ _ ~ .
TABLE 2.
PRODUCTS OF FLUORINATION OF CH2Br2.
PRODUCT/!lDle %. r~ r CHzF2 CHBr2F CHBrF2 ___~_ Tn FLUORIDE.
~0 ReF7. 40.1 58.2 0.33 1.21 UF6 85.5 14.5 L~ TABLE 3.
PRODUCTS OF FLUORINATION OF CF3CH~Cl.
TM FLUORIDE. VF5- ReF7. RuF5.
PRODUCT/Mole X.
(No.of nole~).
2~ CF3CHFCl. 100 100 43.0 ._ __ ~0.111) (0.0299) _ CF3CFC12. 4.
30 ~ 3CUC12. ~ ,
Claims (8)
1. 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 end 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, and replacing at least one hydrogen atom or at least one chlorine, bromine or iodine atom in said halogenated alkane by a fluorine atom.
2. A process as claimed in claim 1 in which the halogenated alkane comprises a hydrochlorocarbon or chlorofluorohydrocarbon.
3. A process as claimed in claim 2 in which the halogenated alkane is selected from the group consisting of dichloromethane, chlorofluoromethane, dibromomethane, bromofluoromethane, and 2-chloro-1,1,1-trifluoroethane.
4. A process as claimed in claim 1 wherein the halogenated alkane is contacted with OsF6, IrF6 or ReF6 and at least one chlorine, bromine or iodine atom in said halogenated alkane is replaced by a fluorine atom.
5. A process as claimed in claim 1 in which the halogenated alkane is contacted with UF6, VF5 or ReF7 and at least one hydrogen atom in said halogenated alkane is replaced by a fluorine atom.
6. A process for the preparation of difluoromethane which process comprises contacting dichloromethane or chlorofluoromethane with 2 transition metal fluoride selected from OsF6, IrF6, ReF6 and RuF5 a] maintaining the contact until at least a portion of the dichloromethane or chlorofluoromethane has been converted to difluoromethane.
7. A process for the preparation of 1,1,1,2-tetrafluoroethane which comprises contacting 2-chloro-1,1,1-trifluoroethane with a transition metal fluoride selected from OsF6, IrF6, and ReF6 and maintaining the contact until at least a portion of the 2-chloro-1,1,1-trifluoroethane has been converted to l,1,1,2-tetrafluoroethane.
8. A process as claimed in any one of claims 1 to 7 which comprises contacting the transition metal fluoride with the halogenated alkane in the liquid or vapour phase at a temperature in the range from about -80°C to about 100°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9105167.2 | 1991-03-12 | ||
| GB919105167A GB9105167D0 (en) | 1991-03-12 | 1991-03-12 | Chemical process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2062442A1 true CA2062442A1 (en) | 1992-09-13 |
Family
ID=10691391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002062442A Abandoned CA2062442A1 (en) | 1991-03-12 | 1992-03-06 | Chemical process |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5254772A (en) |
| EP (1) | EP0503792A1 (en) |
| JP (1) | JPH05178769A (en) |
| CA (1) | CA2062442A1 (en) |
| GB (1) | GB9105167D0 (en) |
Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR960008639B1 (en) * | 1992-08-25 | 1996-06-28 | Kukje Chemical Technology Co L | Preparation of ethane compounds containing fluorine |
| ZA959080B (en) * | 1994-11-23 | 1996-08-02 | Allied Signal Inc | Conversion of oxygenated organic compounds to fluoro-carbons and anhydrous hydrogen fluoride using uranium hexafluoride |
| US5834519A (en) | 1996-10-11 | 1998-11-10 | Wayne State University | Stabilized gas-supersaturated emulsions and suspensions |
| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| WO2005021468A1 (en) | 2003-07-15 | 2005-03-10 | Grt, Inc. | Hydrocarbon synthesis |
| US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| UA95276C2 (en) | 2006-02-03 | 2011-07-25 | ДжиАрТи, ИНК. | Continuous process for converting hydrocarbon feedstock into one or more higher hydrocarbons |
| CN101395088B (en) | 2006-02-03 | 2012-04-04 | Grt公司 | Separation method of light gases from halogens |
| MX2009012581A (en) | 2007-05-24 | 2010-03-15 | Grt Inc | Zone reactor incorporating reversible hydrogen halide capture and release. |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| AU2009270801B2 (en) | 2008-07-18 | 2014-04-24 | Reaction 35, Llc | Continuous process for converting natural gas to liquid hydrocarbons |
| EP2172441A1 (en) * | 2008-10-02 | 2010-04-07 | Solvay Fluor GmbH | Process for the manufacture of hydrochlorofluorocarbons using trifluoromethane as fluorinating agent |
| CN102665890B (en) * | 2009-10-09 | 2016-02-24 | 蓝立方知识产权公司 | The adiabatic plug flow reactor of production chlorination and/or fluorinated acrylamide and higher alkene and method |
| KR20120084729A (en) * | 2009-10-09 | 2012-07-30 | 다우 글로벌 테크놀로지스 엘엘씨 | Process for the production of chlorinated and/or fluorinated propenes and higher alkenes |
| WO2011044447A2 (en) * | 2009-10-09 | 2011-04-14 | Dow Global Technologies, Inc | Process for the production of chlorinated and/or fluorinated propenes |
| EP2485832B1 (en) * | 2009-10-09 | 2016-11-23 | Blue Cube IP LLC | Process for producing a chlorinated and/or fluorinated propene in an isothermal multitube reactors and |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| WO2012166393A1 (en) | 2011-05-31 | 2012-12-06 | Dow Global Technologies, Llc | Process for the production of chlorinated propenes |
| EP2714631B1 (en) | 2011-05-31 | 2020-05-13 | Blue Cube IP LLC | Process for the production of chlorinated propenes |
| CN103596908A (en) | 2011-06-08 | 2014-02-19 | 陶氏益农公司 | Process for the production of chlorinated and/or fluorinated propenes |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| CN103717557A (en) | 2011-08-07 | 2014-04-09 | 陶氏环球技术有限责任公司 | Process for the production of chlorinated propenes |
| WO2013022676A1 (en) | 2011-08-07 | 2013-02-14 | Dow Global Technologies, Llc | Process for the production of chlorinated propenes |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| JP6050372B2 (en) | 2011-11-21 | 2016-12-21 | ブルー キューブ アイピー エルエルシー | Method for producing chloroalkane |
| JP6059246B2 (en) | 2011-12-02 | 2017-01-11 | ブルー キューブ アイピー エルエルシー | Method for producing chlorinated alkane |
| US9284239B2 (en) | 2011-12-02 | 2016-03-15 | Blue Cube Ip Llc | Process for the production of chlorinated alkanes |
| JP6170068B2 (en) | 2011-12-13 | 2017-07-26 | ブルー キューブ アイピー エルエルシー | Method for producing chlorinated propane and propene |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
| EP2794528B1 (en) | 2011-12-22 | 2020-02-26 | Blue Cube IP LLC | Process for the production of tetrachloromethane |
| US9512049B2 (en) | 2011-12-23 | 2016-12-06 | Dow Global Technologies Llc | Process for the production of alkenes and/or aromatic compounds |
| EP2897930A1 (en) | 2012-09-20 | 2015-07-29 | Dow Global Technologies LLC | Process for the production of chlorinated propenes |
| JP2015529247A (en) | 2012-09-20 | 2015-10-05 | ダウ グローバル テクノロジーズ エルエルシー | Process for the production of chlorinated propene |
| CA2885329A1 (en) | 2012-09-30 | 2014-03-04 | Dow Global Technologies Llc | Weir quench and processes incorporating the same |
| EP2911773B1 (en) | 2012-10-26 | 2017-10-04 | Blue Cube IP LLC | Mixer and reactor and process incorporating the same |
| JP6247311B2 (en) | 2012-12-18 | 2017-12-13 | ブルー キューブ アイピー エルエルシー | Method for producing chlorinated propene |
| EP2935166A1 (en) | 2012-12-19 | 2015-10-28 | Blue Cube IP LLC | Process for the production of chlorinated propenes |
| EP2961722A2 (en) | 2013-02-27 | 2016-01-06 | Blue Cube IP LLC | Process for the production of chlorinated propenes |
| WO2014164368A1 (en) | 2013-03-09 | 2014-10-09 | Dow Global Technologies Llc | Process for the production of chlorinated alkanes |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA705927A (en) * | 1965-03-16 | A. Davis Ralph | Method of fluorinating with antimony pentafluoride | |
| US2423045A (en) * | 1943-09-04 | 1947-06-24 | Kellogg M W Co | Liquid phase catalytic reactions of hydrocarbons |
| US2759026A (en) * | 1950-02-01 | 1956-08-14 | Texas Co | Process for fluorination of hydrocarbons |
| US3235608A (en) * | 1962-03-19 | 1966-02-15 | Du Pont | Fluorination with uranium hexafluoride |
| BE766395A (en) * | 1971-04-28 | 1971-10-28 | Solvay | PROCESS FOR MANUFACTURING 1,1-DIFLUORETHANE, |
| US3972953A (en) * | 1975-01-22 | 1976-08-03 | Sun Ventures, Inc. | Group VIII metal complex catalyzed halogen exchange reaction |
| AU563307B2 (en) * | 1981-09-01 | 1987-07-02 | G.A. Olah | Methyl halides and methyl alcohol from methane |
-
1991
- 1991-03-12 GB GB919105167A patent/GB9105167D0/en active Pending
-
1992
- 1992-02-24 EP EP92301531A patent/EP0503792A1/en not_active Withdrawn
- 1992-03-06 CA CA002062442A patent/CA2062442A1/en not_active Abandoned
- 1992-03-10 JP JP4051358A patent/JPH05178769A/en active Pending
- 1992-03-12 US US07/849,604 patent/US5254772A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5254772A (en) | 1993-10-19 |
| GB9105167D0 (en) | 1991-04-24 |
| EP0503792A1 (en) | 1992-09-16 |
| JPH05178769A (en) | 1993-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2062442A1 (en) | Chemical process | |
| I Troyanov et al. | Synthesis and structure of halogenated fullerenes | |
| EP0452363B1 (en) | Aluminum fluoride catalyst and use thereof in a chlorofluorination process for preparing 1,1-dichloro-1,2,2,2-tetrafluoroethane | |
| EP1104748A2 (en) | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon | |
| US3632834A (en) | Process for preparing trichlorotrifluoroethane and dichlorotetrafluoroethane | |
| US4967024A (en) | Catalyzed hydrofluorination process | |
| KR100363940B1 (en) | Hydrofluorination of Chloro (fluoro) butane | |
| O'Donnell et al. | Reactivity of transition metal fluorides. I. Higher fluorides of chromium, molybdenum, and tungsten | |
| EP0576600B1 (en) | Process for the manufacture of 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane | |
| Cassoux et al. | Synthesis and crystal and molecular structure of the 2: 1 molecular adduct between N, N'-(1, 2-phenylene) bis (salicylaldiminato) copper (II) and 7, 7, 8, 8-tetracyanoquinodimethane | |
| DesMarteau | Fluoroperoxytrifluoromethane, CF3OOF. Preparation from trifluoromethyl hydroperoxide and fluorine in the presence of cesium fluoride | |
| US5254775A (en) | Chemical process | |
| EP0420916B1 (en) | Catalyzed hydrofluorination process | |
| US4078007A (en) | Fluorine substitution in 1,1,1-trihalomethanes | |
| Clifford et al. | Preparation and properties of pentafluorosulfanyldichloramine, SF5NCl2 | |
| WO1989012617A1 (en) | Catalyzed hydrofluorination process | |
| US4138355A (en) | Fluorine substitution in 1,1,1-trihalomethanes | |
| US2654789A (en) | New chlorofluoro derivatives of cyclohexane and method of making same | |
| CA1247141A (en) | Fluorination process | |
| JPH0873385A (en) | Production of 1, 1, 1, 3, 3-pentafluoropropane | |
| EP0300724A1 (en) | Process for the preparation of 1,1,1,2-tetrafluoroethane | |
| US5055624A (en) | Synthesis of 1,1-dichloro-1,2,2,2-tetrafluoroethane | |
| EP0576591B1 (en) | Process for the manufacture of 1,1,1,2-tetrafluoroethane | |
| EP0404297A1 (en) | Process for preparing chlorofluorocarbons via an in situ generated activated aluminum trihalide catalyst | |
| Buschmann et al. | (Trifluoroethylidyne) sulfur trifluoride, F3CC. tplbond. SF3: two solid-state structures and reactivity as a carbene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |