WO2009148191A1 - Process for producing fluorine-containing compound by rearrangement reaction - Google Patents

Process for producing fluorine-containing compound by rearrangement reaction Download PDF

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Publication number
WO2009148191A1
WO2009148191A1 PCT/JP2009/060651 JP2009060651W WO2009148191A1 WO 2009148191 A1 WO2009148191 A1 WO 2009148191A1 JP 2009060651 W JP2009060651 W JP 2009060651W WO 2009148191 A1 WO2009148191 A1 WO 2009148191A1
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reaction
compound represented
lewis acid
acid catalyst
general formula
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PCT/JP2009/060651
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French (fr)
Inventor
Daisuke Karube
Akinari Sugiyama
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Daikin Industries, Ltd.
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Publication of WO2009148191A1 publication Critical patent/WO2009148191A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation

Definitions

  • the present invention provides the following processe for producing a fluorine-containing compound.
  • Item 1 A process for producing a compound represented by the general formula:
  • X, Y and Z are same or different, and each represent H, F, Cl or an alkyl group, provided that the alkyl group and F are each not more than one; the process comprising contacting a fluorine-containing compound represented by the following general formula:
  • Item 3 The process according to item 1 or 2, wherein the Lewis acid catalyst contains at least one compound selected from the group consisting of aluminum compounds and zirconium compounds.
  • Item 5 The process according to any one of items 1 to 4 wherein the Lewis acid catalyst is fluorinated or fluoro- chlorinated by at least one compound selected from the group consisting of fluorocarbons, chlorofluorocarbons, and hydrogen fluoride .
  • Item 6 The process according to any one of items 1 to 5 wherein the compound represented by the general formula: wherein X, Y and Z are as defined above, is CF 2 ClCF 2 CCl 3 , CF 2 CICF 2 CHCl 2 , CF 2 ClCF 2 CH 2 Cl, or CF 2 ClCF 2 CH 3 .
  • the raw material used in the present invention is a fluorine-containing compound represented by the general formula:
  • X, Y and Z are the same or different, and each represent H, F, Cl or an alkyl group, provided that the alkyl group and F are each not more than one.
  • This fluorine-containing compound is a known compound, which is produced by, for example, a method comprising reacting tetrafluoroethylene and carbon tetrachloride, a method comprising hydrogenating CF 2 ClCF 2 CCl3 obtained by said method, or the like.
  • examples of an alkyl group include a Ci-C ⁇ straight-chain or branched-chain alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, and 3-methylpentyl .
  • the alkyl group may have one fluorine atom or two or more fluorine atoms, and also may have one chlorine atom or two or more chlorine atoms .
  • Examples of compounds represented by the above formula include CF 2 ClCF 2 CCl 3 (CFC-214cb) , CF 2 CICF 2 CHCl 2 (HCFC-224ca) , CF 2 ClCF 2 CH 2 Cl (HCFC-234cb) , and CF 2 ClCF 2 CH 3 (HCFC-244cc) .
  • reaction is performed by mixing a compound represented by the general formula:
  • X, Y and Z are as defined above, with a Lewis acid catalyst, and sufficiently contacting them with each other.
  • the reaction may be performed in a liquid phase or a gas phase.
  • reaction in the liquid phase is preferably performed at a temperature range from room temperature to 200 0 C.
  • the reaction in the gas phase is preferably performed at a temperature not less than the boiling point of the raw material and the boiling point of the rearranging compound, but not more than 500 0 C, in order to prevent condensation of the raw material or the rearranging compound in the reactor or on the catalyst surface.
  • the liquid-phase reaction is usually performed under normal pressure, it is also possible to perform the reaction under reduced pressure or increased pressure. By performing the reaction under increased pressure, the reaction can be performed at a temperature higher than the boiling point of the raw material in the liquid-phase reaction.
  • the liquid-phase reaction does not require a solvent, the reaction may be performed in a solvent inert to the reaction, such as methylene chloride, various fluorocarbons, etc.
  • the reaction without a solvent has a particular advantage in that it allows the solvent isolation process to be omitted.
  • the reaction time of the liquid-phase reaction is generally set to about 3 to 50 hours.
  • the gas-phase reaction can be performed, for example, by filling a reaction tube made of a metallic material with the Lewis acid catalyst, and passing the vaporized raw material through the reaction tube.
  • this reaction can usually be performed under normal pressure, it may also be performed under reduced or increased pressure.
  • the Lewis acid catalyst is not limited and any known Lewis acid catalyst can be used. Alternatively, the Lewis acid catalyst can be generated in the reaction system using an appropriate compound.
  • the Lewis acid catalyst may be used solely or in a combination of two or more kinds.
  • the Lewis acid catalyst may be supported on a carrier such as activated carbon, silica, etc.
  • these Lewis acid catalysts can be fluorinated or fluoro-chlorinated by various fluorocarbons, chlorofluorocarbons, or hydrogen fluoride to obtain fluorinated or fluoro-chlorinated Lewis acids that have improved catalytic activity.
  • the Lewis acid catalyst can be fluorinated or fluoro- chlorinated, for example, using the method disclosed in Japanese unexamined Patent No. 1978-121710, in which the catalyst is fluorinated or fluoro-chlorinated by filling a reaction tube with the catalyst and contacting the catalyst with the fluorocarbons, etc . , under heat .
  • the amount of the Lewis acid catalyst in the liquid- phase reaction is preferably about 0.0001 to 0.2 mol, per mol of fluorine-containing compound represented by the general formula:
  • the amount of the Lewis acid catalyst used in the gas- phase reaction can be expressed as the contact time of the fluorine-containing compound represented by the above general formula and the Lewis acid catalyst in the reaction tube.
  • the contact time is preferably 1 to 100 when expressed as a ratio W/Fo -wherein W(g) represents the amount of catalyst to be supplied to the tube, and Fo (g/ccsec) represents the gas volume flow rate per second at 0 0 C, 1 atm, of the fluorine-containing compound represented by the above general formula.
  • the above reaction is preferably performed in the absence of moisture. This prevents a decrease in the activity of the Lewis acid catalyst and allows the reaction to proceed more efficiently.
  • a reaction in the absence of moisture may be carried out, for example, by performing the reaction under a nitrogen stream.
  • CF 3 CFClCCl 3 (CFC-214bb) can be produced; when the raw material is CF 2 CICF 2 CHCl 2 (HCFC-224ca) , CF 3 CFCICHCI 2 (HCFC-224ba) can be produced; when the raw material is CF 2 ClCF 2 CH 2 Cl (HCFC- 234cb) , CF 3 CFCICH 2 Cl (HCFC-234bb) can be produced; and when the raw material is CF 2 ClCF 2 CH 3 (HCFC-244cc) , CF 3 CFClCH 3 (HCFC-244bb) can be produced.
  • the compound obtained by the above method can be recovered by distillation or the like.
  • the unreacted raw material can also be collected by distillation or the like, to be subjected to a chlorine rearrangement reaction again.
  • CF 3 CFCICCI 3 can be hydrogenated to produce
  • Example 1 Description of Embodiments The present invention is described more in detail below with reference to some examples .
  • Example 1 Description of Embodiments The present invention is described more in detail below with reference to some examples .
  • alumina pellets (Sumitomo Chemical Co., Ltd., JRC-ALO-I) represented by the composition formula Al 2 O 3 were supplied to a tubular Hastelloy reactor 10 mm in internal diameter and 1 m in length. Nitrogen gas was supplied to the reaction tube at 52 cc/min (a flow rate at O 0 C, 1 atm) , thereby drying at atmospheric pressure (1 atm) and at 45O 0 C. Maintaining the pressure, temperature, and nitrogen gas flow rate, CF 2 ClCF 2 CH 3 (HCFC-244cc) was supplied to the tube at 33 cc/min (a flow rate at 0 0 C, 1 atm) .
  • alumina pellets (Sumitomo Chemical Co., Ltd., JRC-ALO-I) were supplied to a Hastelloy reactor tube 10 mm in diameter. While supplying nitrogen gas at 100 cc/min (a flow rate at 0 0 C, 1 atm) , the reactor was heated to 400 0 C and was dried for 2 hours. Thereafter, the temperature of the reaction tube was lowered to 300 0 C, and HCFC-31 was supplied at 60 cc/min immediately after the nitrogen flow was stopped. Thirty minutes after beginning this supply, the discharged gas was analyzed by gas chromatography.
  • the gas contained 8 mol% of HCFC-31, 44 mol% of methyl chloride, and 46 mol% of dichloromethane. This proved that the fluorination of alumina was in progress.
  • Nitrogen gas was supplied at 52 cc/min (flow rate at 0 0 C, 1 atm) to a reaction tube filled with the fluorinated alumina pellet prepared in Reference Example 1, thereby drying at atmospheric pressure (1 atm) and at 450 0 C. Maintaining the pressure, temperature, and nitrogen gas flow rate, CF 2 CICF 2 CH 3 (HCFC-244cc) was supplied to the tube at 33 cc/min (a flow rate at 0 0 C, 1 atm) . One hour after the supply of HCFC-244cc, the outflow from the reaction tube was analyzed by gas chromatography.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a process for producing a compound represented by general formula (I): wherein X, Y and Z are same or different, and each represent H, F, Cl or an alkyl group, provided that the alkyl group and F are each not more than one; the process comprising contacting a fluorine-containing compound represented by general formula (II): wherein X, Y and Z are as defined above, with a Lewis acid catalyst to cause a chlorine rearrangement reaction. The present invention provides a novel reaction step, which can be used in the production process of a compound represented by the chemical formula CF3CF=CH2.

Description

Description
Title of Invention: PROCESS FOR PRODUCING FLUORINE-CONTAINING COMPOUND BY REARRANGEMENT REACTION
Technical Field
The present invention relates to a process for producing a fluorine-containing compound useful as an intermediate for producing a compound represented by the chemical formula CF3CF=CH2.
Background Art
The compound represented by the chemical formula
CFaCF=CH2 exhibits low toxicity and a low global warming potential. Therefore, the compound is drawing attention as a promising alternative solvent.
A known process for preparing the compound represented by the chemical formula CF3CF=CH2 is performed as follows. Tetrafluoroethylene is first reacted with carbon tetrachloride to form CF2ClCF2CCl3, which is then hydrogenated to form CF2ClCF2CH3, which is in turn fluorinated to form CF3CF2CH3 using the method disclosed, for example, in the following Patent Literature 1 (PTL 1) . Finally, the obtained CF3CF2CH3 is subjected to a dehydrofluorination reaction to produce CF3CF=CH2. However, along with the desired product, i.e., CF3CF=CH2, this method also produces a nearly equimolar amount of HF. Therefore, the process has a problem in that it is difficult to separate the HF from the mixture .
Citation List Patent Literature
PTL 1: Japanese Patent Publication No. 2717091
Summary of Invention Technical Problem A main object of the present invention is to provide a novel production process capable of producing the compound represented by the chemical formula CF3CF=CH2, without causing the aforementioned problem.
Solution to Problem
As a result of intensive study to find a novel process for producing the compound represented by the chemical formula CFaCF=CH2, the inventors of the present invention successfully found a novel reaction in which a product represented by the following general formula:
CF2CICF2C
\
obtained by reacting tetrafluoroethylene and carbon tetrachloride is used as a raw material, and the raw material, when contacted with a Lewis acid catalyst, undergoes a chlorine rearrangement reaction. The inventors further found that CF3CF=CH2 can be produced without incorporation of HF by conducting a process including this reaction step, and thereby completed the present invention.
Specifically, the present invention provides the following processe for producing a fluorine-containing compound. Item 1. A process for producing a compound represented by the general formula:
X
CF3CFCIC Y
Z wherein X, Y and Z are same or different, and each represent H, F, Cl or an alkyl group, provided that the alkyl group and F are each not more than one; the process comprising contacting a fluorine-containing compound represented by the following general formula:
Figure imgf000005_0001
wherein X, Y and Z are as defined above, with a Lewis acid catalyst to cause a chlorine rearrangement reaction. Item 2. The process according to item 1, wherein the chlorine rearrangement reaction of the fluorine-containing compound represented by the above general formula is performed in a gas phase.
Item 3. The process according to item 1 or 2, wherein the Lewis acid catalyst contains at least one compound selected from the group consisting of aluminum compounds and zirconium compounds.
Item 4. The process according to item 3, wherein the Lewis acid catalyst is at least one compound selected from the group consisting of aluminum chloride AlCl3; aluminum bromide AlBr3, aluminum fluorochloride AlFxCIy wherein 0<x<3, 0<y<3, and x+y=3; alumina Al2O3; fluoro-chlorinated alumina A10xFyClz wherein 0<x<1.5, 0≤y<3, 0≤z<3, and 2x+y+z=3; zirconia ZrO2; sulfated zirconia ZrOx ■ (S04)y wherein 0<x<2, 0<y<2, and x+y=2; and fluoro- chlorinated and sulfated zirconia ZrOxFyCl2 ■ (SO4) a wherein 0<x<2, 0≤y<4, 0<z<4, 0<a<2, and 2x+y+z+2a=4. Item 5. The process according to any one of items 1 to 4 wherein the Lewis acid catalyst is fluorinated or fluoro- chlorinated by at least one compound selected from the group consisting of fluorocarbons, chlorofluorocarbons, and hydrogen fluoride . Item 6. The process according to any one of items 1 to 5 wherein the compound represented by the general formula:
Figure imgf000006_0001
wherein X, Y and Z are as defined above, is CF2ClCF2CCl3, CF2CICF2CHCl2, CF2ClCF2CH2Cl, or CF2ClCF2CH3.
The raw material used in the present invention is a fluorine-containing compound represented by the general formula:
/
CF2CICF2C
\
wherein X, Y and Z are the same or different, and each represent H, F, Cl or an alkyl group, provided that the alkyl group and F are each not more than one.
This fluorine-containing compound is a known compound, which is produced by, for example, a method comprising reacting tetrafluoroethylene and carbon tetrachloride, a method comprising hydrogenating CF2ClCF2CCl3 obtained by said method, or the like.
In the above formula, examples of an alkyl group include a Ci-Cε straight-chain or branched-chain alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, and 3-methylpentyl . The alkyl group may have one fluorine atom or two or more fluorine atoms, and also may have one chlorine atom or two or more chlorine atoms .
Examples of compounds represented by the above formula include CF2ClCF2CCl3 (CFC-214cb) , CF2CICF2CHCl2 (HCFC-224ca) , CF2ClCF2CH2Cl (HCFC-234cb) , and CF2ClCF2CH3 (HCFC-244cc) .
According to the present invention, a fluorine- containing compound represented by the general formula:
Figure imgf000007_0001
wherein X, Y and Z are as defined above, is contacted with a Lewis acid catalyst, whereby a chlorine rearrangement reaction takes place, so as to produce a compound represented by the general formula: X
CF3CFCIC Y
Z wherein X, Y and Z are as defined above.
Specifically, the reaction is performed by mixing a compound represented by the general formula:
Figure imgf000007_0002
wherein X, Y and Z are as defined above, with a Lewis acid catalyst, and sufficiently contacting them with each other. The reaction may be performed in a liquid phase or a gas phase.
Although this reaction can proceed under room temperature, it is also possible to perform the reaction under heating at a temperature of up to about 5000C. By performing the reaction under heat, the reaction speed can be increased. However, an excessively high temperature is likely to cause a side reaction, and therefore is not desirable. The reaction in the liquid phase is preferably performed at a temperature range from room temperature to 2000C. The reaction in the gas phase is preferably performed at a temperature not less than the boiling point of the raw material and the boiling point of the rearranging compound, but not more than 5000C, in order to prevent condensation of the raw material or the rearranging compound in the reactor or on the catalyst surface.
Although the liquid-phase reaction is usually performed under normal pressure, it is also possible to perform the reaction under reduced pressure or increased pressure. By performing the reaction under increased pressure, the reaction can be performed at a temperature higher than the boiling point of the raw material in the liquid-phase reaction. Although the liquid-phase reaction does not require a solvent, the reaction may be performed in a solvent inert to the reaction, such as methylene chloride, various fluorocarbons, etc. The reaction without a solvent has a particular advantage in that it allows the solvent isolation process to be omitted. The reaction time of the liquid-phase reaction is generally set to about 3 to 50 hours.
The gas-phase reaction can be performed, for example, by filling a reaction tube made of a metallic material with the Lewis acid catalyst, and passing the vaporized raw material through the reaction tube. Although this reaction can usually be performed under normal pressure, it may also be performed under reduced or increased pressure.
The Lewis acid catalyst is not limited and any known Lewis acid catalyst can be used. Alternatively, the Lewis acid catalyst can be generated in the reaction system using an appropriate compound.
Examples of a Lewis acid catalyst include aluminum chloride AICI3; aluminum bromide AlBr3; aluminum fluorochloride AlFxCIy wherein 0<x<3, 0<y<3, and x+y=3; alumina Al2O3; fluoro- chlorinated alumina AlOxFyClz wherein 0<x<1.5, 0<y<3, 0<z<3, and 2x+y+z=3; zirconium chloride ZrCl4; zirconium fluorochloride ZrFxCIy wherein 0<x<4, 0<y<4, and x+y=4; zirconium oxychloride ZrOCl2; zirconia ZrO2; sulfated zirconia ZrOx- (SO4) y wherein 0<x<2, 0<y<2, and x+y=2; fluoro-chlorinated zirconia ZrOxFyCl2 wherein 0<x<2, 0<y<4, 0≤z<4, and 2x+y+z=4; fluoro-chlorinated and sulfated zirconia ZrOxFyClz • (SO4) a wherein 0<x<2, 0<y<4, 0<z<4, 0<a<2, and 2x+y+z+2a=4; zinc chloride ZnCl2; titanium tetrachloride TiCl4; titanium oxide TiO2; antimony pentachloride SbCl5; antimony pentafluoride SbF5; and antimony fluorochloride SbFxCIz wherein 0<x<5, 0<y<5, and x+y=5. Among them, aluminum chloride; aluminum bromide AlBr3; aluminum fluorochloride; alumina; fluoro-chlorinated alumina; zirconia; sulfated zirconia; fluoro-chlorinated and sulfated zirconia, etc., are preferred. The Lewis acid catalyst may be used solely or in a combination of two or more kinds. The Lewis acid catalyst may be supported on a carrier such as activated carbon, silica, etc.
Moreover, these Lewis acid catalysts can be fluorinated or fluoro-chlorinated by various fluorocarbons, chlorofluorocarbons, or hydrogen fluoride to obtain fluorinated or fluoro-chlorinated Lewis acids that have improved catalytic activity.
The Lewis acid catalyst can be fluorinated or fluoro- chlorinated, for example, using the method disclosed in Japanese unexamined Patent No. 1978-121710, in which the catalyst is fluorinated or fluoro-chlorinated by filling a reaction tube with the catalyst and contacting the catalyst with the fluorocarbons, etc . , under heat .
The amount of the Lewis acid catalyst in the liquid- phase reaction is preferably about 0.0001 to 0.2 mol, per mol of fluorine-containing compound represented by the general formula:
Figure imgf000009_0001
wherein X, Y, and Z are as defined above. If the amount of the Lewis acid catalyst is too large, side reactions tend to occur. If the amount of the Lewis acid catalyst is too small, the conversion will decrease, which is not desirable.
The amount of the Lewis acid catalyst used in the gas- phase reaction can be expressed as the contact time of the fluorine-containing compound represented by the above general formula and the Lewis acid catalyst in the reaction tube. The contact time is preferably 1 to 100 when expressed as a ratio W/Fo -wherein W(g) represents the amount of catalyst to be supplied to the tube, and Fo (g/ccsec) represents the gas volume flow rate per second at 00C, 1 atm, of the fluorine-containing compound represented by the above general formula.
The above reaction is preferably performed in the absence of moisture. This prevents a decrease in the activity of the Lewis acid catalyst and allows the reaction to proceed more efficiently. A reaction in the absence of moisture may be carried out, for example, by performing the reaction under a nitrogen stream.
The above method produces a compound represented by the general formula:
CF3CFCIC-
\ Z wherein X, Y, and Z are as defined above.
More specifically, when the raw material is CF2CICF2CCI3 (CFC-214cb) , CF3CFClCCl3 (CFC-214bb) can be produced; when the raw material is CF2CICF2CHCl2 (HCFC-224ca) , CF3CFCICHCI2 (HCFC-224ba) can be produced; when the raw material is CF2ClCF2CH2Cl (HCFC- 234cb) , CF3CFCICH2Cl (HCFC-234bb) can be produced; and when the raw material is CF2ClCF2CH3 (HCFC-244cc) , CF3CFClCH3 (HCFC-244bb) can be produced. The compound obtained by the above method can be recovered by distillation or the like. The obtained product is useful, for example, as an intermediate for producing the compound represented by the chemical formula CFaCF=CH2. The unreacted raw material can also be collected by distillation or the like, to be subjected to a chlorine rearrangement reaction again. For example, CF3CFCICCI3 can be hydrogenated to produce
CF3CFCICH3, which is then subjected to a dehydrochlorination reaction to produce CF3CF=CH2. CF3CFCICHCI2 can be hydrogenated to produce CF3CFClCH3, which is then subjected to a dehydrochlorination reaction to produce CF3CF=CH2. CF3CFClCH3 can be subjected to a dehydrochlorination reaction to produce CF3CF=CH2.
Each reaction product obtained by the above method is a mixture of CF3CF=CH2 and HCl. This mixture contains HCl, which are separated more easily than HF. By removing HCl, a high-purity CF3CF=CH2 can be obtained relatively easily.
Advantageous Effects of Invention
The present invention provides a novel reaction step, which can be used in the production process of a compound represented by the chemical formula CF3CF=CH2. According to the production process, CF3CF=CH2 can be produced without incorporation of HF.
Description of Embodiments The present invention is described more in detail below with reference to some examples . Example 1
10.0 g of alumina pellets (Sumitomo Chemical Co., Ltd., JRC-ALO-I) represented by the composition formula Al2O3 were supplied to a tubular Hastelloy reactor 10 mm in internal diameter and 1 m in length. Nitrogen gas was supplied to the reaction tube at 52 cc/min (a flow rate at O0C, 1 atm) , thereby drying at atmospheric pressure (1 atm) and at 45O0C. Maintaining the pressure, temperature, and nitrogen gas flow rate, CF2ClCF2CH3 (HCFC-244cc) was supplied to the tube at 33 cc/min (a flow rate at 00C, 1 atm) . One hour after the supply of HCFC-244cc, the outflow from the reaction tube was analyzed by gas chromatography. The result revealed that the outflow contained HCFC-244bb obtained by the rearrangement reaction and HFO-1234yf derived from the elimination of HCl from HCFC-244bb, in an amount of 2.1 mol% in total (total selectivity in the product = 17.6%). The following are the analysis results. Additionally, the existence of HCl was confirmed.
CF3CFClCH3 (244bb) : 0.2 moll CF3CF=CH2 (1234yf) : 1.9 mol%
CF3CCl=CH2 and CF2ClCF=CH2 (1233xf and 1233yf) : 5.9 mol% Other by-products : 3.9 mol% Raw material: CF2ClCF2CH3 (244cc) :88.1 mol%
Reference Example 1
Fluorination of Lewis acid catalyst
10.0 g of alumina pellets (Sumitomo Chemical Co., Ltd., JRC-ALO-I) were supplied to a Hastelloy reactor tube 10 mm in diameter. While supplying nitrogen gas at 100 cc/min (a flow rate at 00C, 1 atm) , the reactor was heated to 4000C and was dried for 2 hours. Thereafter, the temperature of the reaction tube was lowered to 3000C, and HCFC-31 was supplied at 60 cc/min immediately after the nitrogen flow was stopped. Thirty minutes after beginning this supply, the discharged gas was analyzed by gas chromatography. The gas contained 8 mol% of HCFC-31, 44 mol% of methyl chloride, and 46 mol% of dichloromethane. This proved that the fluorination of alumina was in progress. Five hours after beginning the HCFC-31 supply, the supply was stopped and a nitrogen flow was supplied instead. Keeping that state, the reactor tube was cooled to room temperature. Since the catalyst in the reaction tube was sensitive to the humidity in the atmosphere, the reaction tube was subjected to rearrangement reaction in this state. Example 2
Nitrogen gas was supplied at 52 cc/min (flow rate at 00C, 1 atm) to a reaction tube filled with the fluorinated alumina pellet prepared in Reference Example 1, thereby drying at atmospheric pressure (1 atm) and at 450 0C. Maintaining the pressure, temperature, and nitrogen gas flow rate, CF2CICF2CH3 (HCFC-244cc) was supplied to the tube at 33 cc/min (a flow rate at 0 0C, 1 atm) . One hour after the supply of HCFC-244cc, the outflow from the reaction tube was analyzed by gas chromatography. The result revealed that the outflow contained HCFC-244bb obtained by the rearrangement reaction and HFO-1234yf derived from the elimination of HCl from HCFC-244bb, in an amount of 3.6% in total (total selectivity in the product = 16.9%). The following are the analysis results. Additionally, the existence of HCl was confirmed.
CF3CFClCH3 (244bb) : 0.1mol% CF3CF=CH2 (1234yf) : 3.5mol%
CF3CCl=CH2 and CF2ClCF=CH2 (1233xf and 1233yf) : 13.6mol% Other by-products: 3.5mol%
Raw Material CF2ClCF2CH3 (244cc) : 79.3mol%
Example 3
2.8 g of commercially available sulfated zirconia pellets (Wako Pure Chemical Industries, Ltd. ) were supplied to a tubular Hastelloy reactor 10 mm in internal diameter and 1 m in length. Nitrogen gas was supplied to the reaction tube at 10.4 cc/min (a flow rate at 0°C, 1 atm) , thereby drying at atmospheric pressure (1 atm) and at 4500C. Maintaining the pressure, temperature, and nitrogen gas flow rate, CF2ClCF2CH3 (HCFC-244cc) was supplied to the tube at 6.4 cc/min (a flow rate at 00C, 1 atm) . One hour after the supply of HCFC-244cc, the outflow from the reaction tube was analyzed by gas chromatography. The result revealed that a conversion of 244cc was 1%; and the product contained HFO-1234yf at the selectivity of 3%, which was obtained by the elimination of HCl from HCFC-244bb derived from the rearrangement of 244cc. Most of the other products were CFaCH=CH2, CF2ClCF=CH2, or their isomers. Additionally, the existence of HCl was confirmed.
Example 4
1.1 g (8 mmol) of aluminum chloride and 100 g (394 mmol) of CF2ClCF2CCl3 (CFC-214cb) were placed in a 200ml flask under a nitrogen stream, and the mixture was heated while stirring at 115°C for 48 hours. After cooling to room temperature, the reaction liquid was sampled, and the sample was analyzed by gas chromatography. The results of the analysis are shown below. Additionally, the existence of HCl was confirmed.
CF3CFClCCl3 (214bb) : 6.5 mol%
CF2CICCI2CF2CI (214aa) : 5.2 moll
Perchloreothylene: 1.9 mol%
CCl4: 3.5mol%
Raw material CF2ClCF2CCl3 (214cb) : 82 . 9 mol%

Claims

Claims
[Claim 1] A process for producing a compound represented by the general formula:
Figure imgf000015_0001
wherein X, Y and Z are same or different, and each represent H, F, Cl or an alkyl group, provided that the alkyl group and F are each not more than one; the process comprising contacting a fluorine-containing compound represented by the following general formula:
Figure imgf000015_0002
wherein X, Y and Z are as defined above, with a Lewis acid catalyst to cause a chlorine rearrangement reaction.
[Claim 2] The process according to claim 1, wherein the chlorine rearrangement reaction of the fluorine-containing compound represented by the above general formula is performed in a gas phase.
[Claim 3] The process according to claim 1 or 2, wherein the Lewis acid catalyst contains at least one compound selected from the group consisting of aluminum compounds and zirconium compounds .
[Claim 4] The process according to claim 3, wherein the Lewis acid catalyst is at least one compound selected from the group consisting of aluminum chloride AICI3; aluminum bromide AlBr3; aluminum fluorochloride AlFxCIy wherein 0<x<3, 0<y<3, and x+y=3; alumina Al2O3; fluoro-chlorinated alumina AlOxFyCl2 wherein 0<x<1.5, 0≤y<3, 0≤z<3, and 2x+y+z=3; zirconia ZrO2; sulfated zirconia ZrOx ■ (S04)y wherein 0<x<2, 0<y<2, and x+y=2; and fluoro- chlorinated and sulfated zirconia ZrOxFyClz ■ (SO4) a wherein 0<x<2, 0<y<4, 0<z<4, 0<a<2, and 2x+y+z+2a=4.
[Claim 5] The process according to any one of claims 1 to 4 wherein the Lewis acid catalyst is fluorinated or fluoro- chlorinated by at least one compound selected from the group consisting of fluorocarbons, chlorofluorocarbons, and hydrogen fluorides .
[Claim 6] The process according to any one of claims 1 to 5 wherein the compound represented by the general formula:
Figure imgf000016_0001
wherein X, Y and Z are as defined above, is CF2ClCF2CCl3, CF2CICF2CHCl2, CF2ClCF2CH2Cl, or CF2ClCF2CH3.
PCT/JP2009/060651 2008-06-05 2009-06-04 Process for producing fluorine-containing compound by rearrangement reaction WO2009148191A1 (en)

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US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
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CN113292392A (en) * 2021-04-16 2021-08-24 台州益普高分子材料有限公司 Rearrangement reaction between saturated hydrochlorofluorocarbons and method for preparing fluoroalcohol by using rearrangement reaction

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