CA2148752A1 - Process for preparing hexafluoro-c4 compounds - Google Patents
Process for preparing hexafluoro-c4 compoundsInfo
- Publication number
- CA2148752A1 CA2148752A1 CA 2148752 CA2148752A CA2148752A1 CA 2148752 A1 CA2148752 A1 CA 2148752A1 CA 2148752 CA2148752 CA 2148752 CA 2148752 A CA2148752 A CA 2148752A CA 2148752 A1 CA2148752 A1 CA 2148752A1
- Authority
- CA
- Canada
- Prior art keywords
- compound
- hydrogen
- carried out
- formula
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 11
- 239000007792 gaseous phase Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- -1 trifluoroethane compound Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical class CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 abstract description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 8
- XDIDQEGAKCWQQP-OWOJBTEDSA-N (e)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C(\Cl)=C(/Cl)C(F)(F)F XDIDQEGAKCWQQP-OWOJBTEDSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FBPCGFWEHOYDJO-UHFFFAOYSA-N 1-chloro-1,2,3,3,4,4-hexafluorobut-1-ene Chemical compound FC(F)C(F)(F)C(F)=C(F)Cl FBPCGFWEHOYDJO-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- BSRRYOGYBQJAFP-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluorobutane Chemical compound CC(F)C(F)(F)C(F)(F)F BSRRYOGYBQJAFP-UHFFFAOYSA-N 0.000 description 1
- RKOUFQLNMRAACI-UHFFFAOYSA-N 1,1,1-trifluoro-2-iodoethane Chemical compound FC(F)(F)CI RKOUFQLNMRAACI-UHFFFAOYSA-N 0.000 description 1
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical class FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- TZNJHEHAYZJBHR-UHFFFAOYSA-N 2-bromo-1,1,1-trifluoroethane Chemical compound FC(F)(F)CBr TZNJHEHAYZJBHR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- GWUSZQUVEVMBPI-UHFFFAOYSA-N nimetazepam Chemical compound N=1CC(=O)N(C)C2=CC=C([N+]([O-])=O)C=C2C=1C1=CC=CC=C1 GWUSZQUVEVMBPI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Hexafluoro-C4 compounds are prepared from trifluoroethane compounds in the liquid or gaseous phase by bringing these into contact with a metal and/or a metal compound.
Description
_ 2148752 BAYER AKTIENGESELLSCE~AFT 51368 Leverkusen Konzernzentrale RP
Patente Konzern Gai/klu/646-PE
Process for preparin~ hexafluoro-C1 compounds 5 The present invention relates to a process for preparing hexafluoro-C4 compounds by dehalogenative dimerization of trifluoroethane compounds in the liquid or gaseous phase.
Hexafluol~ul~les and hexafluorobutenes are of importance as CFC substitutes and as intermediates for preparing insecticides and acaricides (see, for example, ro DE-A 3 818 692 and EP-A 481 182).
It is known that hexafluorochlorobutene can be prepared by subjecting chlorin~ted butadienes to gas-phase fl~lorin~tion (see DE-A-42 12 084). This process requires the h~nrlling of hydrogen fluoride and chlorine in the gas phase, which is only possible with relatively large engineering expense.
Hexafluorochlorobutenes can also be prepared by pyrolysis of 1,1,1-trifluoro-2,2-dichoroethane (see DE-A-42 14 739). A disadvantage here is that this process has to be carried out at high temperatures. The hydrogen chloride formed requires particularly corrosion-resistant materials for the pyrolysis reactor. Considerable .
eng1neerlng expense lS thus necessary.
20 It is also possible to react compounds of the type CF3-CHal(Z)2, where Hal represents chlorine or bromine and Z, independently thereof, represents hydrogen, chlorine or bromine, with hydrogen in the gas phase over supported catalysts cont~inin~ palladium and/or nickel and thus obtain hexafluorobutane (see DE-A-42 12 876). A disadvantage here is that the operating life of the catalyst is influenced Le A 30 071-US - I -21~8752 both by its qualitative and qua~ a~ive composition and also by Z. It is thus difficult to verify reproducible conditions if the catalyst and/or the substrate is changed.
A process has now been found for preparing hexafluoro-C4 compounds of the formula (I) CF3-A-CF3 (I), in which A represents -CH2-CH2- or-CX=CX-and X in each case represents, independently of one another, hydrogen, chlorine, bromine or iodine, which is char~ct~ri7ed in that a trifluoroethane compound of the formula (II) CF3CXYZ (II) in which X is as defined above, and 5 Y and Z represent, independently of one another, hydrogen, fluorine, chlorine, bromine or iodine, but at least one of the substituents X, Y and Z is not hydrogen in liquid or gaseous phase is brought into contact with a metal and/or a metal compound.
Le A 30 071-US - 2 -`_ 2148752 Examples of compounds of the formula (II) which can be used are 1,1,1-trifluoro-2,2,2-trichloroethane,l ,1,1 -trifluoro-2-chloroethane,l ,1,1 -trifluoro-2,2-dichloroethane, 1,1,1 -trifluoro-2-bromo-2-chloroethane,1 , 1 ,1 -trifluoro-2-iodoethane, 1, 1,1 -trifluoro-2-bromoethane and mixtures of these compounds.
Preference is given to using 1,1,1-trifluoro-2,2,2-trichloroethane and 1,1,1-trifluoro-2,2-dichloroethane.
The process of the invention can be carried out in the liquid phase, for example at temperatures of from -70 to +200C, and in the gas phase, for example at from 100 to 1200C. Preference is given to working in the liquid phase at from 0 to 200C and in the gas phase at from 400 to 800C.
The pressure can be, for example, between 0.1 mbar and 300 bar, being selected in such a way that the desired phase is present. Preference is given to working in the liquid phase at pressures of from 100 mbar to 100 bar and in the gas phase at ples~ures of from 0.8 to 5 bar, in particular at atmospheric ples~ul~. Elevated 15 pressures can be realized, for example, in autoclaves by bringing the reaction mixture to an appropfiate temperature therein and/or ple,s.~ i7ing the autoclave with inert gases (e.g. nitrogen or noble gases).
In the gas phase, the reaction can optionally be carried out in the presence of diluents, in the liquid phase optionally in the presence of solvents. Suitable solvents 20 are, for example, nonaqueous polar solvents such as nitriles and ethers, in particular acetonitrile, diglyme and triglyme. It is possible to use, for example, from 0.5 to 20 ml of solvent per 1 g of compound of the formula (II) used.
A great variety of metals and metal compounds are suitable. Preference is given to metals and compounds of metals of the first transition group, the second main and 25 transition groups and iron, cobalt and nickel. The metals can be used, for example, individually, mixed with one another, mixed with other metals, as alloys with one another or as alloys with other metals. Suitable metal compounds are, for example, Le A 30 07 1-US - 3 -_ 21487S2 the halides, in particular the halides of the low oxidation states of the specified metals. The metal compounds can be used, for example, as such or mixed with one another, with other metal compounds and/or metals.
The amount of metals plus metal compounds can be, for example, from 0.1 to 10 g 5 atom equivalents, based on one halogen atom to be elimin~te~ This amount is preferably between 0.5 and 2 g atom equivalents.
It is advantageous to use the metal and/or the metal compound in pulverulent or otherwise finely divided form. The metal and/or the metal compound can be applied to a support material.
10 The process of the invention can optionally be carried out under the action of ultrasound, which is particularly advantageous when working in the liquid phase and at relatively low pressures.
The process of the invention can be carried out batchwise or continuously.
The workup of the reaction mixture formed in the reaction of the invention can be 15 carried out, for example, by fractional distillation. If the reaction of the invention has been carried out in the gas phase, it is advantageous to condense the gaseous reaction mixture.
The process of the invention has the advantages that it can be carried out without particular engineering expense, reproducible conditions can be verified relatively 20 simply even when catalysts and/or substrates change and, when the process is carried out in the gas phase, the workup can be carried out in a simple manner.
Le A 30 071-US - 4 -Examples E2~ample 1 In a 0.7 1 enamel autoclave, 188 g of CF3CCl3 are reacted at 180C with 127 g ofcopper powder for 15 hours, with the maximum pressure occurring being 41 bar. The 5 volatile reactlon products distilled out of the residue were analysed by means of mass spectroscopy coupled with gas chromatography. This gave a product mixture cont~ining 83% by weight of CF3-CCl=CCl-CF3 (hereinafter referred to as DCHFB), and also 6% by weight of unreacted starting material and 11% by weight of chlorofluoroalkanes.
10 Example 2 In a 0.7 l autoclave, 190 g of CF3CCl3 were reacted at 100C with 44 g of iron powder for 4 hours in 150 ml of aceloniLIile as solvent and in the further presence of 2 g of FeCl2. The maximum ples~ule oCcllrring was 7 bar. The volatile reaction products distilled out of the residue were analysed by means of mass spectroscopy 15 coupled to gas chromatography. The product mixture contained 9% by weight of DCHFB and 90% by weight of unreacted starting m~t~.ri~l.
Example 3 In a 3 l autoclave, 2345 g of CF3-CCl3 were pumped into 350 g of iron powder in 1000 ml of diglyme at 180C over a period of 10 hours. The DCHFB formed was 20 simultaneously distilled off by pressure distillation in the range from 10 to 12 bar.
This gave 287 g of DCHFB having a purity, determined by gas chromatography, of 92 %.
Le A 30 071-US - 5 -21~8752 Example 4 In a 0.3 1 autoclave, 24 g of CF3CH2Cl were reacted at 180C with 6 g of iron powder for 12 hours in 150 ml of diglyme as solvent and in the presence of 2 g of FeCl2. The maximum pressure occllrring was 7 bar. The volatile reaction productsdistilled out of the residue contained 38% by weight of CF3-CH2-CH2-CF3 .
Examples 5 to 8 A vertically arranged heatable quartz tube was filled with 200 ml of steel wool.CF3CCl3 was fed in via a metering pump. After flushing with nitrogen, CF3CCl3 was passed through the quartz tube in the amounts indicated at the le~e~;live indicated 10 telllpel~ re. The reaction mixture leaving the quartz tube was condensed at -78C
and admixed with water, whereupon an organic and an aqueous phase formed. The organic phase was separated off, dried over sodium sulphate and analysed by gas chromatography. Details are shown in Table 1.
Table 1 Example Temperature Weight hourly Conversion Selectivity of the No. (C) space velocity (%) formation of [g/l h] DCHFB (%) 600 510 12.3 94 6 550 120 17.3 91 7 600 105 24.7 92 8 650 250 39.4 59 Le A 30 071-US - 6 -Examples 9 to 12 In a glass flask, 79 g of CF3CCl3 in a stream of nitrogen were reacted with 20 g in each case of finely divided metal at from 38 to 42C in an ultrasonic bath. The duration of the reaction was 4 hours in each case. The solid constituents of the5 reaction mixture were subsequently filtered off and the liquid phase was analysed by gas chromatography. Details are shown in Table 2.
Table 2 Example No. Metal Mole ratio Selectivity of the formation of CF3CCl3: metal DCHFB (%) 9 Fe 1.17 97.1 Zn 1.37 96.6 11 Mg 0.51 97.3 12 Cu 1.33 84.1 I,e A 30 071-US - 7 -
Patente Konzern Gai/klu/646-PE
Process for preparin~ hexafluoro-C1 compounds 5 The present invention relates to a process for preparing hexafluoro-C4 compounds by dehalogenative dimerization of trifluoroethane compounds in the liquid or gaseous phase.
Hexafluol~ul~les and hexafluorobutenes are of importance as CFC substitutes and as intermediates for preparing insecticides and acaricides (see, for example, ro DE-A 3 818 692 and EP-A 481 182).
It is known that hexafluorochlorobutene can be prepared by subjecting chlorin~ted butadienes to gas-phase fl~lorin~tion (see DE-A-42 12 084). This process requires the h~nrlling of hydrogen fluoride and chlorine in the gas phase, which is only possible with relatively large engineering expense.
Hexafluorochlorobutenes can also be prepared by pyrolysis of 1,1,1-trifluoro-2,2-dichoroethane (see DE-A-42 14 739). A disadvantage here is that this process has to be carried out at high temperatures. The hydrogen chloride formed requires particularly corrosion-resistant materials for the pyrolysis reactor. Considerable .
eng1neerlng expense lS thus necessary.
20 It is also possible to react compounds of the type CF3-CHal(Z)2, where Hal represents chlorine or bromine and Z, independently thereof, represents hydrogen, chlorine or bromine, with hydrogen in the gas phase over supported catalysts cont~inin~ palladium and/or nickel and thus obtain hexafluorobutane (see DE-A-42 12 876). A disadvantage here is that the operating life of the catalyst is influenced Le A 30 071-US - I -21~8752 both by its qualitative and qua~ a~ive composition and also by Z. It is thus difficult to verify reproducible conditions if the catalyst and/or the substrate is changed.
A process has now been found for preparing hexafluoro-C4 compounds of the formula (I) CF3-A-CF3 (I), in which A represents -CH2-CH2- or-CX=CX-and X in each case represents, independently of one another, hydrogen, chlorine, bromine or iodine, which is char~ct~ri7ed in that a trifluoroethane compound of the formula (II) CF3CXYZ (II) in which X is as defined above, and 5 Y and Z represent, independently of one another, hydrogen, fluorine, chlorine, bromine or iodine, but at least one of the substituents X, Y and Z is not hydrogen in liquid or gaseous phase is brought into contact with a metal and/or a metal compound.
Le A 30 071-US - 2 -`_ 2148752 Examples of compounds of the formula (II) which can be used are 1,1,1-trifluoro-2,2,2-trichloroethane,l ,1,1 -trifluoro-2-chloroethane,l ,1,1 -trifluoro-2,2-dichloroethane, 1,1,1 -trifluoro-2-bromo-2-chloroethane,1 , 1 ,1 -trifluoro-2-iodoethane, 1, 1,1 -trifluoro-2-bromoethane and mixtures of these compounds.
Preference is given to using 1,1,1-trifluoro-2,2,2-trichloroethane and 1,1,1-trifluoro-2,2-dichloroethane.
The process of the invention can be carried out in the liquid phase, for example at temperatures of from -70 to +200C, and in the gas phase, for example at from 100 to 1200C. Preference is given to working in the liquid phase at from 0 to 200C and in the gas phase at from 400 to 800C.
The pressure can be, for example, between 0.1 mbar and 300 bar, being selected in such a way that the desired phase is present. Preference is given to working in the liquid phase at pressures of from 100 mbar to 100 bar and in the gas phase at ples~ures of from 0.8 to 5 bar, in particular at atmospheric ples~ul~. Elevated 15 pressures can be realized, for example, in autoclaves by bringing the reaction mixture to an appropfiate temperature therein and/or ple,s.~ i7ing the autoclave with inert gases (e.g. nitrogen or noble gases).
In the gas phase, the reaction can optionally be carried out in the presence of diluents, in the liquid phase optionally in the presence of solvents. Suitable solvents 20 are, for example, nonaqueous polar solvents such as nitriles and ethers, in particular acetonitrile, diglyme and triglyme. It is possible to use, for example, from 0.5 to 20 ml of solvent per 1 g of compound of the formula (II) used.
A great variety of metals and metal compounds are suitable. Preference is given to metals and compounds of metals of the first transition group, the second main and 25 transition groups and iron, cobalt and nickel. The metals can be used, for example, individually, mixed with one another, mixed with other metals, as alloys with one another or as alloys with other metals. Suitable metal compounds are, for example, Le A 30 07 1-US - 3 -_ 21487S2 the halides, in particular the halides of the low oxidation states of the specified metals. The metal compounds can be used, for example, as such or mixed with one another, with other metal compounds and/or metals.
The amount of metals plus metal compounds can be, for example, from 0.1 to 10 g 5 atom equivalents, based on one halogen atom to be elimin~te~ This amount is preferably between 0.5 and 2 g atom equivalents.
It is advantageous to use the metal and/or the metal compound in pulverulent or otherwise finely divided form. The metal and/or the metal compound can be applied to a support material.
10 The process of the invention can optionally be carried out under the action of ultrasound, which is particularly advantageous when working in the liquid phase and at relatively low pressures.
The process of the invention can be carried out batchwise or continuously.
The workup of the reaction mixture formed in the reaction of the invention can be 15 carried out, for example, by fractional distillation. If the reaction of the invention has been carried out in the gas phase, it is advantageous to condense the gaseous reaction mixture.
The process of the invention has the advantages that it can be carried out without particular engineering expense, reproducible conditions can be verified relatively 20 simply even when catalysts and/or substrates change and, when the process is carried out in the gas phase, the workup can be carried out in a simple manner.
Le A 30 071-US - 4 -Examples E2~ample 1 In a 0.7 1 enamel autoclave, 188 g of CF3CCl3 are reacted at 180C with 127 g ofcopper powder for 15 hours, with the maximum pressure occurring being 41 bar. The 5 volatile reactlon products distilled out of the residue were analysed by means of mass spectroscopy coupled with gas chromatography. This gave a product mixture cont~ining 83% by weight of CF3-CCl=CCl-CF3 (hereinafter referred to as DCHFB), and also 6% by weight of unreacted starting material and 11% by weight of chlorofluoroalkanes.
10 Example 2 In a 0.7 l autoclave, 190 g of CF3CCl3 were reacted at 100C with 44 g of iron powder for 4 hours in 150 ml of aceloniLIile as solvent and in the further presence of 2 g of FeCl2. The maximum ples~ule oCcllrring was 7 bar. The volatile reaction products distilled out of the residue were analysed by means of mass spectroscopy 15 coupled to gas chromatography. The product mixture contained 9% by weight of DCHFB and 90% by weight of unreacted starting m~t~.ri~l.
Example 3 In a 3 l autoclave, 2345 g of CF3-CCl3 were pumped into 350 g of iron powder in 1000 ml of diglyme at 180C over a period of 10 hours. The DCHFB formed was 20 simultaneously distilled off by pressure distillation in the range from 10 to 12 bar.
This gave 287 g of DCHFB having a purity, determined by gas chromatography, of 92 %.
Le A 30 071-US - 5 -21~8752 Example 4 In a 0.3 1 autoclave, 24 g of CF3CH2Cl were reacted at 180C with 6 g of iron powder for 12 hours in 150 ml of diglyme as solvent and in the presence of 2 g of FeCl2. The maximum pressure occllrring was 7 bar. The volatile reaction productsdistilled out of the residue contained 38% by weight of CF3-CH2-CH2-CF3 .
Examples 5 to 8 A vertically arranged heatable quartz tube was filled with 200 ml of steel wool.CF3CCl3 was fed in via a metering pump. After flushing with nitrogen, CF3CCl3 was passed through the quartz tube in the amounts indicated at the le~e~;live indicated 10 telllpel~ re. The reaction mixture leaving the quartz tube was condensed at -78C
and admixed with water, whereupon an organic and an aqueous phase formed. The organic phase was separated off, dried over sodium sulphate and analysed by gas chromatography. Details are shown in Table 1.
Table 1 Example Temperature Weight hourly Conversion Selectivity of the No. (C) space velocity (%) formation of [g/l h] DCHFB (%) 600 510 12.3 94 6 550 120 17.3 91 7 600 105 24.7 92 8 650 250 39.4 59 Le A 30 071-US - 6 -Examples 9 to 12 In a glass flask, 79 g of CF3CCl3 in a stream of nitrogen were reacted with 20 g in each case of finely divided metal at from 38 to 42C in an ultrasonic bath. The duration of the reaction was 4 hours in each case. The solid constituents of the5 reaction mixture were subsequently filtered off and the liquid phase was analysed by gas chromatography. Details are shown in Table 2.
Table 2 Example No. Metal Mole ratio Selectivity of the formation of CF3CCl3: metal DCHFB (%) 9 Fe 1.17 97.1 Zn 1.37 96.6 11 Mg 0.51 97.3 12 Cu 1.33 84.1 I,e A 30 071-US - 7 -
Claims (10)
1. A process for preparing a hexafluoro-C4 compound of the formula (I) CF3-A-CF3 (I) in which A represents -CH2-CH2- or -CX=CX-and X in each case represents, independently of one another, hydrogen, chlorine, bromine or iodine, in which a trifluoroethane compound of the formula(II) CF3CXYZ (II) in which X is as defined above, and Y and Z represent, independently of one another, hydrogen, fluorine, chlorine, bromine or iodine, but at least one of the substituents X, Y and Z is not hydrogen in liquid or gaseous phase is brought into contact with a metal.
2. A process for preparing a hexafluoro-C4 compound of the formula (I) CF3-A-CF3 (I) in which A represents -CH2-CH2- or -CX=CX-and X in each case represents, independently of one another, hydrogen, chlorine, bromine or iodine, in which a trifluoroethane compound of the formula (II) CF3CXYZ (II) in which X is as defined above, and Y and Z represent, independently of one another, hydrogen, fluorine, chlorine, bromine or iodine, but at least one of the substituents X, Y and Z is not hydrogen in liquid or gaseous phase is brought into contact with a metal compound.
3. The process of claim 1 or 2, which is carried out in the liquid phase at from -70 to +200°C.
4. The process of claim 1 or 2, which is carried out in the gas phase at from 100 to 1,200°C.
5. The process of claim 1 or 2, which is carried out in the liquid phase at from 100 mbar to 100 bar.
6. The process of claim 1 or 2, which is carried out in the gas phase at from 0.8 to 5 bar.
7. The process of claim 1 or 2, which is carried out in the liquid phase in the presence of solvents.
8. The process of claim 1, in which the compound of the formula (II) is brought into contact with a metal selected from the group comprising the first transition group, the second main and transition group and iron, cobalt and nickel.
9. The process of claim 2, in which the compound of the formula (II) is brought into contact with a compound of a metal selected from the group consisting of the first transition group, the second main and transition group and iron, cobalt and nickel.
10. The process of claim 1 or 2, in which from 0.1 to 10 g atom equivalents of metals and metal compounds are used, based on one halogen atom to be eliminated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4416326.6 | 1994-05-09 | ||
| DE19944416326 DE4416326A1 (en) | 1994-05-09 | 1994-05-09 | Prodn. of hexa:fluoro-butane or -butene cpds. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2148752A1 true CA2148752A1 (en) | 1995-11-10 |
Family
ID=6517675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2148752 Abandoned CA2148752A1 (en) | 1994-05-09 | 1995-05-05 | Process for preparing hexafluoro-c4 compounds |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0694512A3 (en) |
| JP (1) | JPH07316081A (en) |
| CA (1) | CA2148752A1 (en) |
| DE (1) | DE4416326A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668913A (en) * | 2019-09-16 | 2020-01-10 | 江苏三美化工有限公司 | Preparation method of trifluoroethyl compound |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2260015B1 (en) * | 2008-03-19 | 2012-10-31 | E. I. du Pont de Nemours and Company | Process for making 1,1,1,4,4,4-hexafluoro-2-butene |
| JP5266902B2 (en) * | 2008-06-20 | 2013-08-21 | 日本ゼオン株式会社 | Method for producing fluorine-containing olefin compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3008510B2 (en) * | 1991-02-16 | 2000-02-14 | ダイキン工業株式会社 | Method for producing dimer of fluorinated ethane |
| DE4214739A1 (en) * | 1992-05-04 | 1993-11-11 | Bayer Ag | Process for the preparation of hexafluorochlorobutenes |
| DE4215876A1 (en) * | 1992-05-14 | 1993-11-18 | Bayer Ag | Process for the preparation of hexafluorobutane |
-
1994
- 1994-05-09 DE DE19944416326 patent/DE4416326A1/en not_active Withdrawn
-
1995
- 1995-04-26 EP EP95106228A patent/EP0694512A3/en not_active Withdrawn
- 1995-05-02 JP JP13120895A patent/JPH07316081A/en active Pending
- 1995-05-05 CA CA 2148752 patent/CA2148752A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668913A (en) * | 2019-09-16 | 2020-01-10 | 江苏三美化工有限公司 | Preparation method of trifluoroethyl compound |
| CN110668913B (en) * | 2019-09-16 | 2022-09-20 | 江苏三美化工有限公司 | Preparation method of trifluoroethyl compound |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4416326A1 (en) | 1995-11-16 |
| EP0694512A2 (en) | 1996-01-31 |
| JPH07316081A (en) | 1995-12-05 |
| EP0694512A3 (en) | 1997-03-19 |
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