Method for producing halogenated olefin compound

Abstract

Provided is a method for producing a halogenated olefin compound represented by general formula (1): R1-CR2 = CR3-R4 (1), the method comprising a step in which a halogenated alkane compound represented by general formula (2): R1-CHR2-CXR3-R4 (2) is subjected to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound, the unsaturated compound is a compound represented by general formula (3): R5-CR6 = CR7-R8 (3) or general formula (4): R9-C = C-R10 (4), and the compound represented by general formula (1) and the unsaturated compound are different compounds, and a halogenated olefin compound can be efficiently obtained by the production method.

Description

Technical Field

[0001] The invention relates to a method for preparing a halogenated olefin compound. Background Art

[0002] As a method for producing a halogenated olefin compound, for example, Patent Document 1 discloses a method of subjecting a specific halogenated alkane compound to a dehydrohalogenation reaction (see, for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2020 / 171011 Summary of the invention

[0006] Problems to be solved by the invention

[0007] An object of the present invention is to provide a method for efficiently obtaining a halogenated olefin compound.

[0008] Technical solutions to solve problems

[0009] The present invention includes the following configurations.

[0010] Item 1. A method for producing a halogenated olefin compound represented by the following general formula (1), comprising a step of subjecting a halogenated alkane compound represented by the following general formula (2) to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound, wherein the unsaturated compound is a compound represented by the following general formula (3) or the following general formula (4), and the compound represented by the general formula (1) and the unsaturated compound are different compounds.

[0011] R 1 -CR 2 =CR 3 -R 4 (1)

[0012] [In formula (1), R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, a halogen atom or a halogenated alkyl group. 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom.]

[0013] R 1 -CHR 2 -CXR 3 -R 4 (2)

[0014] [In formula (2), R1 , R 2 , R 3 and R 4 The meanings are the same as above. X represents a halogen atom.]

[0015] R 5 -CR 6 =CR 7 -R 8 (3)

[0016] [In formula (3), R 5 , R 6 , R 7 and R 8 The same or different, represents a hydrogen atom or an organic group.]

[0017] R 9 -C≡C-R 10 (4)

[0018] [In formula (4), R 9 and R 10 The same or different, represents a hydrogen atom or an organic group.]

[0019] Item 2. The production method according to Item 1, wherein in the above general formulas (1) and (2), the above R 1 and R 4 is a fluorine atom or a perfluoroalkyl group.

[0020] Item 3. The production method according to Item 1 or 2, wherein the energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compound is higher than the highest occupied molecular orbital (HOMO) of the halogenated olefin compound represented by the general formula (1).

[0021] Item 4. The production method according to any one of Items 1 to 3, wherein the supply amount of the unsaturated compound is 0.001 to 0.40 mol per 1 mol of the halogenated alkane compound represented by the general formula (2).

[0022] Item 5. The production method according to any one of Items 1 to 4, wherein the dehydrohalogenation reaction is carried out in a gas phase.

[0023] Item 6. A composition comprising 50 to 80 mol% of a halogenated olefin compound represented by the following general formula (1) and 12 to 40 mol% of a halogenated olefin compound represented by the following general formula (5).

[0024] R 1 -CR 2 =CR 3 -R 4 (1)

[0025] [In formula (1), R 1, R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, a halogen atom or a halogenated alkyl group. 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom.]

[0026] R 1 -CH=CH-R 4 (5)

[0027] [In formula (5), R 1 and R 4 are the same or different and represent a hydrogen atom, a halogen atom or a halogenated alkyl group.]

[0028] Item 7. The composition according to Item 6, further comprising a halogenated alkane compound represented by the following general formula (6).

[0029] R 5 -CR 6 R 11 -CR 7 R 12 -R 8 (6)

[0030] [In formula (6), R 5 , R 6 , R 7 and R 8 The same or different, represents a hydrogen atom or an organic group. 11 and R 12 One of them is a hydrogen atom and the other is a halogen atom.]

[0031] Item 8. The composition according to Item 7, wherein the content of the halogenated alkane compound represented by the general formula (6) is 0.10 to 10.0 mol %.

[0032] Item 9. The composition according to any one of Items 6 to 8, which is used as a cleaning gas, an etching gas, a refrigerant, a heat transfer medium, or a building block for organic synthesis.

[0033] Effects of the Invention

[0034] By utilizing the present invention, halogenated olefin compounds can be efficiently synthesized. DETAILED DESCRIPTION

[0035] In the present specification, “comprising” is a concept that includes “including”, “consist essentially of” and “consist of”.

[0036] In addition, in this specification, when a numerical range is expressed by "A to B", it means not less than A and not more than B.

[0037] In the present invention, the "selectivity" refers to the ratio (mol %) of the total molar amount of the target compound contained in the outflow gas from the reactor outlet to the total molar amount of the compounds other than the raw material compounds in the outflow gas.

[0038] In the present invention, the "conversion rate" refers to the ratio (mol %) of the total molar amount of compounds other than the raw material compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0039] In the present invention, the "yield" refers to the ratio (mol %) of the total molar amount of the target compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0040] It is known that a halogenated butyne compound represented by hexafluoro-2-butyne can be synthesized by using a specific halogenated alkane compound as a starting material and subjecting it to a secondary dehydrohalogenation reaction.

[0041] Among them, when the dehydrohalogenation reaction is carried out from the halogenated alkane compound, the hydrogen halide is liberated. When the halogenated olefin compound as the product reacts with the free hydrogen halide, the halogenated alkane compound as the raw material is regenerated. Therefore, in order to obtain the halogenated butyne compound, the halogenated alkane compound is used as the starting material, and the dehydrohalogenation reaction is carried out twice instead of once, so that the yield is improved.

[0042] On the other hand, in the present invention, by subjecting the halogenated alkane compound to a dehydrohalogenation reaction in the presence of a specific unsaturated compound, the hydrogen halide generated by the dehydrohalogenation reaction can be captured by the specific unsaturated compound. Therefore, the halogenated alkane compound as a raw material reacts almost quantitatively, and a halogenated olefin compound can be obtained with high selectivity and high yield.

[0043] 1. Method for producing halogenated olefin compounds

[0044] The method for producing a halogenated olefin compound of the present invention is a method for producing a halogenated olefin compound represented by the following general formula (1), which comprises a step of subjecting a halogenated alkane compound represented by the following general formula (2) to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound, wherein the unsaturated compound is a compound represented by the following general formula (3) or the following general formula (4), and the compound represented by the general formula (1) and the unsaturated compound are different compounds.

[0045] R 1 -CR 2 =CR3 -R 4 (1)

[0046] [In formula (1), R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, a halogen atom or a halogenated alkyl group. 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom.]

[0047] R 1 -CHR 2 -CXR 3 -R 4 (2)

[0048] [In formula (2), R 1 , R 2 , R 3 and R 4 The meanings are the same as above. X represents a halogen atom.]

[0049] R 5 -CR 6 =CR 7 -R 8 (3)

[0050] [R 5 , R 6 , R 7 and R 8 The same or different, represents a hydrogen atom or an organic group.]

[0051] R 9 -C≡C-R 10 (4)

[0052] [In formula (4), R 9 and R 10 The same or different, represents a hydrogen atom or an organic group.]

[0053] According to the present invention, by carrying out the dehydrohalogenation reaction of the halogenated alkane compound represented by the general formula (2) in the presence of a specific unsaturated compound, the hydrogen halide generated by the dehydrohalogenation reaction can be captured by the specific unsaturated compound. Therefore, the halogenated alkane compound as a raw material reacts almost quantitatively, and the halogenated alkene compound represented by the general formula (1) in which 1 mole of hydrogen halide is removed relative to 1 mole of the halogenated alkane compound represented by the general formula (2) can be selectively obtained.

[0054] (1-1) Raw material compound (halogenated alkane compound)

[0055] The halogenated alkane compound that can be used as a substrate in the production method of the present invention is a halogenated alkane compound represented by the general formula (2) as described above.

[0056] R 1 -CHR 2 -CXR 3 -R 4 (2)

[0057] [In formula (2), R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, a halogen atom or a halogenated alkyl group. 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom. X represents a halogen atom.]

[0058] In the general formula (2), R 1 , R 2 , R 3 and R 4 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0059] In the general formula (2), R 1 , R 2 , R 3 and R 4 The haloalkyl group shown in the formula (1) refers to an alkyl group in which at least one hydrogen atom is replaced by a halogen atom. Among the haloalkyl groups, an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom is called a fluoroalkyl group, and an alkyl group in which all hydrogen atoms are replaced by fluorine atoms is called a perfluoroalkyl group. In addition, among the haloalkyl groups, an alkyl group in which at least one hydrogen atom is replaced by a chlorine atom is called a chloroalkyl group, and an alkyl group in which all hydrogen atoms are replaced by chlorine atoms is called a perchloroalkyl group. In addition, among the haloalkyl groups, an alkyl group in which at least one hydrogen atom is replaced by a bromine atom is called a bromoalkyl group, and an alkyl group in which all hydrogen atoms are replaced by bromine atoms is called a perbromoalkyl group. Among them, from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the haloolefin compound shown in the general formula (1), a fluoroalkyl group is preferred, and a perfluoroalkyl group is more preferred.

[0060] The halogenated alkyl group may be a linear, branched or cyclic one, but a linear halogenated alkyl group is preferred from the viewpoints of the reaction conversion rate, selectivity and yield of the halogenated olefin compound represented by the general formula (1).

[0061] The number of carbon atoms in the haloalkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3 from the viewpoint of reaction conversion, selectivity and yield of the haloolefin compound represented by the general formula (1).

[0062] As such fluoroalkyl groups, specifically trifluoromethyl, pentafluoroethyl, heptafluoropropyl, etc. can be cited. In addition, as chloroalkyl groups, specifically trichloromethyl, pentachloroethyl, heptachloropropyl, etc. can be cited. In addition, as bromoalkyl groups, specifically tribromomethyl, pentabromoethyl, heptabromopropyl, etc. can be cited.

[0063] The halogenated olefin compound represented by the general formula (1) can also function as an intermediate for subsequent dehydrohalogenation to obtain a halogenated alkyne compound, thus allowing the halogenated olefin compound represented by the general formula (1) to be dehydrohalogenated. Therefore, R in the general formula (2) 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom.

[0064] In the general formula (2), R 1 and R 4 From the viewpoint of the reaction conversion rate, the selectivity and yield of the halogenated olefin compound represented by the general formula (1), a fluorine atom or a fluoroalkyl group is preferred, a fluorine atom or a perfluoroalkyl group is more preferred, and a perfluoroalkyl group is further preferred.

[0065] In the general formula (2), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0066] Specific examples of halogenated alkane compounds that satisfy such conditions include CF2HCF2H, CFH2CF3, CCl2HCCl2H, CClH2CCl3, CBr2HCBr2H, CBrH2CBr3, CF3CFHCF2H, CF3CH2CF3, CCl3CClHCCl2H, CCl3CH2CCl3, CBr3CBrHCBr2H, CBr3CH2CBr3, CF3CFHCFHCF3, CF3CH2CF2CF3, CCl3CClHCClHC Cl3, CCl3CH2CCl2CCl3, CBr3CBrHCBrHCBr3, CBr3CH2CBr2CBr3, CH3CF3, CH3CCl3, CH3CBr3, CF3CF2CH3, CCl3CCl2CH3, C Br3CBr2CH3, CF3CH2CF2CH3, CF3CHFCF2CH3, CCl3CH2CCl2CH3, CCl3CHClCCl2CH3, CBr3CH2CBr2CH3, CBr3CHBrCBr2CH3, etc.

[0067] These halogenated alkane compounds may be used alone or in combination of two or more. As such halogenated alkane compounds, known compounds or commercially available products may be used.

[0068] (1-2) Dehydrofluorination reaction

[0069] In the step of subjecting the halogenated alkane compound to dehydrofluorination reaction of the present invention, the dehydrofluorination reaction can be carried out according to the following reaction formula.

[0070] R 1 -CHR 2 -CXR 3 -R 4 →R 1 -CR 2 =CR 3 -R 4 +HX

[0071] Among them, from the viewpoints of the reaction conversion rate, the selectivity and yield of the halogenated olefin compound represented by the general formula (1), R 1 and R 4 is trifluoromethyl, R 2 is a fluorine atom, R 3 is a hydrogen atom, and X is a fluorine atom. That is, the dehydrofluorination reaction is preferably carried out according to the following reaction formula.

[0072] CF3CFHCFHCF3→CF3CF=CHCF3+HF

[0073] (1-3) Catalyst

[0074] The step of subjecting the halogenated alkane compound to dehydrohalogenation reaction in the present invention is carried out in the presence of a catalyst.

[0075] Preferred catalysts used in the production method of the present invention include activated carbon catalysts, zeolite catalysts, chromium oxide catalysts, silica-alumina catalysts, etc. As these catalysts, both unfluorinated catalysts and fluorinated catalysts can be used.

[0076] The activated carbon catalyst is not particularly limited, and examples thereof include powdered activated carbon such as crushed carbon, molded carbon, granular carbon, and spherical carbon. The powdered activated carbon preferably has a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) according to the JIS test (JIS Z8801).

[0077] These activated carbons may be used alone or in combination of two or more. These activated carbons may be known activated carbons or commercially available products.

[0078] Activated carbon becomes more active by fluorination, so before using it in the reaction, it can also be fluorinated in advance and the resulting fluorinated activated carbon can be used as an activated carbon catalyst. In other words, both unfluorinated activated carbon and fluorinated activated carbon can be used as activated carbon catalysts.

[0079] As the fluorinating agent for fluorinating the activated carbon, for example, an inorganic fluorinating agent such as F2 and HF can be used, and an organic fluorinating agent such as hydrofluorocarbon (HFC) such as hexafluoropropylene, chlorofluorocarbon (CFC) such as chlorofluoromethane, and hydrochlorofluorocarbon (HCFC) can also be used.

[0080] Examples of a method for fluorinating activated carbon include a method of causing the fluorination to proceed by flowing the above-mentioned fluorinating agent under temperature conditions of about room temperature (25° C.) to about 400° C. and under atmospheric pressure.

[0081] As the zeolite catalyst, a wide range of known types of zeolites can be used. For example, crystalline hydrous aluminosilicates of alkali metals or alkaline earth metals are preferred. The crystal form of the zeolite is not particularly limited, and examples thereof include A-type, X-type, LSX-type, etc. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples thereof include potassium, sodium, calcium, lithium, etc.

[0082] The zeolite catalyst becomes more active when fluorinated, so the zeolite catalyst may be fluorinated before use in the reaction and then used as a fluorinated zeolite catalyst.

[0083] As the fluorinating agent for fluorinating the zeolite catalyst, for example, an inorganic fluorinating agent such as F2 and HF, or a fluorocarbon-based organic fluorinating agent such as hexafluoropropylene, etc. can be used.

[0084] Examples of a method for fluorinating the zeolite catalyst include a method of causing the fluorination to proceed by flowing the above-mentioned fluorinating agent under temperature conditions of about room temperature (25° C.) to about 400° C. and under atmospheric pressure.

[0085] There are no particular restrictions on the chromium oxide catalyst. m In the case of chromium oxide, preferably 1.5<m<3.0, more preferably 2.0<m<2.75, and still more preferably 2.0<m<2.3. m When nH2O represents chromium oxide, hydration may be performed so that the value of n becomes 3 or less, particularly 1.0 to 1.5.

[0086] The fluorinated chromium oxide catalyst can be prepared by fluorinating the above-mentioned chromium oxide catalyst. The fluorination can be performed using, for example, HF, fluorocarbon, etc. Such a fluorinated chromium oxide catalyst can be synthesized by the method described in, for example, Japanese Patent Application Laid-Open No. 05-146680.

[0087] Silica-alumina catalysts are composite oxide catalysts containing silica (SiO2) and alumina (Al2O3). When the total amount of silica and alumina is set to 100 mass %, for example, a catalyst with a silica content of 20 to 90 mass %, particularly 50 to 80 mass %, can be used.

[0088] The silica-alumina catalyst exhibits stronger activity through fluorination, so before being used in the reaction, the silica-alumina catalyst can be pre-fluorinated and then used as a fluorinated silica-alumina catalyst.

[0089] As the fluorinating agent for fluorinating the silica-alumina catalyst, for example, an inorganic fluorinating agent such as F2 and HF, or a fluorocarbon-based organic fluorinating agent such as hexafluoropropylene, etc. can be used.

[0090] Examples of a method for fluorinating a silica-alumina catalyst include a method of causing the fluorination to proceed by flowing the fluorinating agent under temperature conditions of about room temperature (25° C.) to about 400° C. and under atmospheric pressure.

[0091] The above catalysts may be used alone or in combination of two or more. In addition, the above catalysts may be known catalysts or commercially available products.

[0092] Among these, from the viewpoints of conversion rate, selectivity and yield, activated carbon catalysts (activated carbon or fluorinated activated carbon), chromium oxide catalysts (chromium oxide or fluorinated chromium oxide) and the like are preferred, and activated carbon catalysts (activated carbon or fluorinated activated carbon) are more preferred.

[0093] In addition, when the above-mentioned zeolite catalyst, chromium oxide catalyst, silicon aluminum catalyst, etc. are used as catalysts, they can also be supported by a carrier. Examples of such carriers include carbon, aluminum oxide (Al2O3), zirconium oxide (ZrO2), silicon dioxide (SiO2), titanium dioxide (TiO2), etc. As carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.

[0094] In the production method of the present invention, when a halogenated alkane compound is subjected to a dehydrohalogenation reaction in the presence of a catalyst in a gas phase, the catalyst is preferably brought into contact with the halogenated alkane compound in a solid state (solid phase). In this case, the catalyst may also be in a powdered form, and preferably in a granular form when used in a gas phase continuous flow reaction.

[0095] The specific surface area of ​​the catalyst measured by the BET method (hereinafter sometimes referred to as "BET specific surface area") is preferably generally 10 to 3000 m 2 / g, more preferably 15 to 2500 m 2 / g, more preferably 20 to 2000 m 2 / g, particularly preferably 30 to 1500 m 2 When the BET specific surface area of ​​the catalyst is within such a range, the density of the catalyst particles will not be too small, and the halogenated olefin compound can be obtained with a higher selectivity and yield. In addition, the conversion rate of the halogenated alkane compound can also be further improved.

[0096] (1-4) Unsaturated compounds

[0097] In the present invention, the step of subjecting the above-mentioned halogenated alkane compound to dehydrohalogenation is carried out in the presence of an unsaturated compound.

[0098] Here, the unsaturated compound refers to a compound having at least one unsaturated bond (double bond, triple bond, etc.).

[0099] The unsaturated compound can capture hydrogen halide generated by the dehydrohalogenation reaction of the halogenated alkane compound represented by the general formula (2). When the unsaturated compound captures hydrogen halide, the unsaturated compound undergoes a hydrogen halide addition reaction.

[0100] For example, when CF3CFHCFHCF3 is used as the halogenated alkane compound represented by the general formula (2), and CF3CF=CFCF3 is used as the unsaturated compound, the following reaction formula is used:

[0101] CF3CFHCFHCF3→CF3CF=CHCF3+HF

[0102] Generate hydrogen fluoride through the following reaction formula:

[0103] CF3CF=CFCF3+HF→CF3CF2CFHCF3

[0104] The generated hydrogen fluoride is captured.

[0105] This can inhibit the hydrogen halide produced by the dehydrohalogenation reaction of the halogenated alkane compound represented by the general formula (2) from reacting with the target halogenated alkene compound represented by the general formula (1) to produce the halogenated alkane compound represented by the general formula (2) as a raw material.

[0106] By capturing hydrogen halide with the unsaturated compound, the equilibrium of the dehydrohalogenation reaction is tilted toward the product side (the side of the halogenated olefin compound represented by the general formula (1)), and the halogenated alkane compound represented by the general formula (2) as the raw material reacts almost quantitatively, so that the halogenated olefin compound represented by the general formula (1) can be obtained with high selectivity and high yield.

[0107] Among them, the addition reaction of olefins, i.e. compounds having unsaturated bonds, and hydrogen halides is a reaction on the energy orbits of the highest occupied molecular orbital (HOMO) of the olefin and the lowest unoccupied molecular orbital (LUMO) of the hydrogen halide. Therefore, the smaller the difference in energy levels between the highest occupied molecular orbital (HOMO) of the olefin and the lowest unoccupied molecular orbital (LUMO) of the hydrogen halide, the higher the reactivity.

[0108] The added unsaturated compound and the halogenated olefin compound represented by the general formula (1) undergo addition reaction with the same hydrogen halide, and therefore the magnitude of the energy level difference between the highest occupied molecular orbital (HOMO) of the halogenated olefin compound and the lowest unoccupied molecular orbital (LUMO) of the hydrogen halide is caused by the energy level of the highest occupied molecular orbital (HOMO) of the halogenated olefin compound.

[0109] When the highest occupied molecular orbital (HOMO) of the unsaturated compound is higher than that of the halogenated olefin compound represented by the general formula (1), the reaction of capturing hydrogen fluoride by the unsaturated compound occurs preferentially over the reverse reaction of the halogenated olefin compound represented by the general formula (1) and hydrogen fluoride.

[0110] Similarly, when the unsaturated compound is a compound represented by the general formula (4) having a triple bond, if the highest occupied molecular orbital (HOMO) of the compound represented by the general formula (4) having a triple bond is at a higher energy level than the highest occupied molecular orbital (HOMO) of the halogenated olefin compound represented by the general formula (1), the reaction of capturing hydrogen fluoride using the compound represented by the general formula (4) having a triple bond also occurs preferentially over the reverse reaction of the halogenated olefin compound represented by the general formula (1) and hydrogen fluoride.

[0111] That is, as the unsaturated compound, it is preferred to select a compound having a highest occupied molecular orbital (HOMO) higher than the highest occupied molecular orbital (HOMO) of the halogenated olefin compound represented by the general formula (1).

[0112] Therefore, it is preferred that the unsaturated compound used in the present invention is specifically a compound represented by the following general formula (3) or the following general formula (4), and the highest occupied molecular orbital (HOMO) of the compounds represented by general formula (3) and (4) has a higher energy level than the highest occupied molecular orbital (HOMO) of the halogenated olefin compound represented by general formula (1).

[0113] R 5 -CR 6 =CR 7 -R 8 (3)

[0114] [In formula (3), R 5 , R 6 , R 7 and R 8 The same or different, represents a hydrogen atom or an organic group.]

[0115] R 9 -C≡C-R 10 (4)

[0116] [In formula (4), R 9 and R 10 The same or different, represents a hydrogen atom or an organic group.]

[0117] From such a viewpoint, the highest occupied molecular orbital (HOMO) of the unsaturated compound is preferably 0.1 eV or more higher, more preferably 0.2 to 30 eV higher, and even more preferably 0.5 to 15 eV higher than the highest occupied molecular orbital (HOMO) of the halogenated olefin compound represented by the general formula (1).

[0118] In the general formula (3) as an unsaturated compound, R 5 , R 6 , R 7 and R 8 The organic group shown and R in the general formula (4) 9 and R 10 The organic group shown in the formula (a) may include, for example, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted thiol group, an ester group (-COOR), a carbonyl group (-COR), a substituted or unsubstituted carboxyl group, a nitro group, a sulfone group, an amide group (-CONR2, -NRCOR), etc. Among them, R may be the same or different, and may include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, etc.

[0119] As R in the general formula (3) 5 , R 6 , R 7 and R 8 The organic group shown and R in the general formula (4) 9 and R 10 The halogen atom of the organic group shown here includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0120] As R in the general formula (3) 5 , R 6 , R 7 and R 8 The organic group shown and R in the general formula (4) 9 and R 10 The alkyl group of the organic group may be linear, branched or cyclic. Of these, linear alkyl groups are preferred from the viewpoints of reaction conversion rate, selectivity and yield of the halogenated olefin compound represented by the general formula (1).

[0121] The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3 from the viewpoint of reaction conversion, selectivity and yield of the halogenated olefin compound represented by the general formula (1).

[0122] Specific examples of such an alkyl group include a methyl group, an ethyl group, and an n-propyl group.

[0123] The alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a hydroxyl group, the above-mentioned halogen atom, a cyano group, an alkoxy group described below, an aryl group described below, an amino group described below, a thiol group described below, the above-mentioned ester group, the above-mentioned carbonyl group, a carboxyl group described below, and the above-mentioned amide group.

[0124] As R in the general formula (3) 5 , R 6 , R 7 and R 8 The organic group shown and R in the general formula (4) 9 and R 10 The alkoxy group of the organic group represented by the formula (1) may be linear, branched or cyclic. Of these, linear alkoxy groups are preferred from the viewpoints of reaction conversion rate, selectivity and yield of the halogenated olefin compound represented by the formula (1).

[0125] The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3 from the viewpoint of reaction conversion, selectivity and yield of the halogenated olefin compound represented by the general formula (1).

[0126] Specific examples of such an alkoxy group include a methoxy group, an ethoxy group, and an n-propoxy group.

[0127] The alkoxy group may have a substituent. Examples of the substituent that the alkoxy group may have include a hydroxyl group, the above-mentioned halogen atom, a cyano group, the above-mentioned alkoxy group, an aryl group described later, an amino group described later, a thiol group described later, and the above-mentioned amide group.

[0128] As R in the general formula (3) 5 , R 6 , R 7 and R 8 The organic group shown and R in the general formula (4) 9 and R 10 The aryl group of the organic group represented by the formula (1) is not particularly limited, but from the viewpoints of the reaction conversion rate, the selectivity and yield of the halogenated olefin compound represented by the general formula (1), an aryl group having 6 to 20 carbon atoms is preferred, an aryl group having 6 to 12 carbon atoms is more preferred, and an aryl group having 6 to 10 carbon atoms is further preferred. The aryl group may be monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic.

[0129] Specific examples of the aryl group include phenyl, naphthyl, biphenyl, pentalenyl, indenyl, anthracenyl, naphthacene, pentacene, pyrenyl, perylenyl, fluorenyl, and phenanthryl.

[0130] The aryl group may also have a substituent. Examples of the substituent that the aryl group may have include a hydroxyl group, the above-mentioned halogen atom, a cyano group, the above-mentioned alkyl group, the above-mentioned alkoxy group, the above-mentioned aryl group, the amino group described later, the thiol group described later, the above-mentioned ester group, the above-mentioned carbonyl group, the carboxyl group described later, the above-mentioned amide group, and the like.

[0131] The amino group may have a substituent. Examples of the substituent that the amino group may have include a hydroxyl group, the above-mentioned halogen atom, a cyano group, the above-mentioned alkyl group, the above-mentioned alkoxy group, the above-mentioned aryl group, the above-mentioned amino group, the thiol group described below, the above-mentioned ester group, the above-mentioned carbonyl group, the carboxyl group described below, the above-mentioned amide group, and the like.

[0132] The thiol group may have a substituent. Examples of the substituent that the thiol group may have include a hydroxyl group, the above-mentioned halogen atom, a cyano group, the above-mentioned alkyl group, the above-mentioned alkoxy group, the above-mentioned aryl group, the above-mentioned amino group, the above-mentioned thiol group, the above-mentioned ester group, the above-mentioned carbonyl group, the carboxyl group described later, the above-mentioned amide group, and the like.

[0133] The carboxyl group may have a substituent. Examples of the substituent that the carboxyl group may have include a hydroxyl group, the above-mentioned halogen atom, a cyano group, the above-mentioned alkyl group, the above-mentioned alkoxy group, the above-mentioned aryl group, the above-mentioned amino group, the above-mentioned thiol group, the above-mentioned ester group, the above-mentioned carbonyl group, the above-mentioned carboxyl group, the above-mentioned amide group, and the like.

[0134] Among them, the organic group is preferably a halogen atom, a halogenated alkyl group, etc., more preferably a fluorine atom, a fluoroalkyl group, etc., and further preferably a fluorine atom, a perfluoroalkyl group, etc., from the viewpoint of the reaction conversion rate, the selectivity and yield of the halogenated olefin compound represented by the general formula (1), etc.

[0135] However, the compound represented by the general formula (3) is a compound different from the target halogenated olefin compound represented by the general formula (1).

[0136] In the present invention, as described later, the reaction temperature is preferably 300 to 450° C. At this reaction temperature, hydrogen halide is easily captured and is not easily decomposed or ignited. From the viewpoint of easily improving the reaction conversion rate, the selectivity and yield of the halogenated olefin compound represented by the general formula (1), it is preferred that at least one of the decomposition temperature, the ignition point and the critical point of the unsaturated compound is higher than the reaction temperature, and it is more preferred that all of the decomposition temperature, the ignition point and the critical point are higher than the reaction temperature, regardless of whether there is a measured value.

[0137] As unsaturated compounds satisfying the above conditions, as compounds represented by general formula (3), CF3CF=CFCF3, CCl3CCl=CClCCl3, CBr3CBr=CBrCBr3, CF2=CH2, CHF=CHF, CHCl=CHCl, CHBr=CHBr, CF2=CFH, CBr2=CBrH, CCl2=CCl2, CBr2=CBr2, CHF=CHCF3, CHCl=CHCCl3, CF3CF=CHCl, CCl3CCl=CHCl, CF3CH=CHCl, CCl3CH=CHCl, CCl 3CCl=CH2, CH2=CClCN, CH2=CBrCN, CH2=CHCOOCH3, CH3OCH=CHCOOCH3, CH3CH2CH=CHCOOCH3, CH2=C(C2H5)COOCH3, (CH3)2C=CHCOOCH3, CH2=CHCH2OH, CH3CH2CH=CHOH, CH3CH=CHCH2OH, CH3CH=CHOCH3, CH2=CHCH2N(CH3)2, etc. As the compound represented by the general formula (4), CF3C≡CCF3, CH≡CCH2COOCH3, etc. can be listed.

[0138] The energy level of the highest occupied molecular orbital (HOMO) of these unsaturated compounds is preferably adjusted as follows. The unsaturated compounds are preferably selected so that the energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compounds is higher than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by the general formula (1) generated by dehydrohalogenation of the halogenated alkane compound represented by the general formula (2). Therefore, the energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compounds is preferably -15 eV to 40 eV, more preferably -14 eV to 35 eV, and further preferably -13 eV to 30 eV.

[0139] In addition, the energy level value of the highest occupied molecular orbital (HOMO) was calculated by optimizing the structure using MM2 calculation and then calculating the electronic structure using the extended Huckel method. The results are shown in Table 1.

[0140] [Table 1]

[0141]

[0142] These unsaturated compounds may be used alone or in combination of two or more. As such unsaturated compounds, known compounds or commercially available products may be used.

[0143] In the production method of the present invention, the amount of the unsaturated compound used is not particularly limited. From the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated olefin compound represented by the general formula (1), the amount is preferably 0.001 to 0.40 mol, more preferably 0.01 to 0.40 mol, and even more preferably 0.05 to 0.20 mol, relative to 1 mol of the halogenated alkane compound represented by the general formula (2) as the raw material compound.

[0144] (1-5) Examples of Dehydrohalogenation Reaction

[0145] In particular, from the viewpoint of productivity, the dehydrohalogenation reaction of the halogenated alkane compound of the present invention is preferably carried out in a gas phase. When the step of dehydrohalogenating the halogenated alkane compound of the present invention is carried out in a gas phase, there are advantages such as no need to use a solvent, no industrial waste is generated, and excellent productivity.

[0146] The dehydrohalogenation reaction of the halogenated alkane compound of the present invention can also be carried out by any of the following methods, i.e., a flow-through method or an intermittent method in which the halogenated alkane compound as the raw material compound is continuously added to the reactor and the halogenated olefin compound as the target compound is continuously taken out from the reactor. In the present invention, in order to further suppress the reverse reaction, it is preferably carried out in a gas phase continuous flow-through method.

[0147] When the dehydrohalogenation reaction of the halogenated alkane compound of the present invention is carried out in a gas phase continuous flow system, the apparatus, operation, etc. can be simplified, and it is economically advantageous.

[0148] Regarding the atmosphere when carrying out the dehydrohalogenation reaction of the halogenated alkane compound of the present invention, from the aspect of suppressing catalyst degradation, it is preferably under an inert gas atmosphere. The inert gas can include nitrogen, helium, argon, etc. Among these inert gases, nitrogen is preferred from the viewpoint of reducing costs.

[0149] (1-6) Reaction temperature

[0150] In the step of subjecting a halogenated alkane compound to dehydrohalogenation reaction of the present invention, the reaction temperature is preferably 300 to 450° C., more preferably 350 to 450° C., and even more preferably 350 to 400° C., from the viewpoint of being able to more efficiently carry out the dehydrohalogenation reaction and thereby further improving the conversion rate, and obtaining the halogenated olefin compound as the target compound with higher selectivity and higher yield.

[0151] (1-7) Reaction time

[0152] Regarding the reaction time of the dehydrohalogenation reaction of the halogenated alkane compound of the present invention, for example, in the case of adopting a gas phase flow method, from the viewpoint that the conversion rate of the reaction is particularly high and the halogenated alkane compound can be obtained with a higher yield and a high selectivity, the contact time (W / F) of the raw material compound with respect to the catalyst [W: weight of the catalyst (g), F: flow rate of the raw material compound (cc / sec)] is preferably 12 to 45 g·sec / cc, more preferably 15 to 40 g·sec / cc, and further preferably 20 to 30 g·sec / cc. The above contact time refers to the time for the raw material compound to contact the catalyst. The flow rate of the raw material compound does not include the above-mentioned unsaturated compound, and refers to the flow rate of the halogenated alkane compound represented by the general formula (2).

[0153] (1-8) Reaction pressure

[0154] From the viewpoint of more effectively carrying out the dehydrohalogenation reaction to further improve the conversion rate, and being able to obtain the halogenated olefin compound as the target compound with higher selectivity and higher yield, the reaction pressure of the halogenated alkane compound of the present invention for dehydrohalogenation is preferably 0 kPa or more, more preferably 10 kPa or more, further preferably 20 kPa or more, and particularly preferably 30 kPa or more. The upper limit of the reaction pressure is not particularly limited, and is usually about 2 MPa. Wherein, in the present invention, when there is no special statement about pressure, it is a gauge pressure.

[0155] In the dehydrohalogenation reaction of the halogenated alkane compound of the present invention, the reactor into which the halogenated alkane compound, the catalyst and the unsaturated compound are put to react is not particularly limited in shape and structure as long as it can withstand the above-mentioned temperature and pressure. As the reactor, for example, a vertical reactor, a horizontal reactor, a multi-tube reactor, etc. can be listed. As the material of the reactor, for example, glass, stainless steel, iron, nickel, iron-nickel alloy, etc. can be listed.

[0156] After the dehydrohalogenation reaction is completed, it can be purified according to a common method as needed to obtain a halogenated olefin compound represented by the general formula (1).

[0157] (1-9) Target compound (halogenated olefin compound)

[0158] The target compound of the present invention thus obtained is a halogenated olefin compound represented by the general formula (1).

[0159] R 1 -CR 2 =CR 3 -R 4 (1)

[0160] [In formula (1), R 1 , R2 , R 3 and R 4 are the same or different and represent a hydrogen atom, a halogen atom or a halogenated alkyl group. 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom.]

[0161] R in the general formula (1) 1 , R 2 , R 3 and R 4 R in the above general formula (2) 1 , R 2 , R 3 and R 4 Therefore, the halogenated olefin compound represented by the general formula (1) to be produced specifically includes, for example, CFH=CF2, CClH=CCl2, CBrH=CBr2, CF3CH=CF2, CF3CF=CFH, CCl3CH=CCl2, CCl3CCl=CClH, CBr3CH=CBr2, CBr3CBr=CBrH, CF3CF=CHCF3, CCl3CCl=CHCCl3, CBr3CBr=CHCBr3, CH2=CF2, CH2=CCl2, CH2=CBr2, CF3CF=CH2, CCl3CCl=CH2, CBr3 CBr=CH2、CF3CH2CF=CH2、CF3CH=CFCH3、CF3CHFCF=CH2、CF3CF2CH=CF2、CH3CF2CH=CF2、CCl3CH2CCl=CH2、CCl3CH=CClCH3、CCl3CHClCCl=CH2、CCl3CCl2CH=CCl2、CH3CCl2CH=CCl2、CBr3CH2CBr=CH2、CBr3CH=CBrCH3、CBr3CHBrCBr=CH2、CBr3CBr2CH=CBr2、CH3CBr2CH=CBr2、etc. These compounds include Z and E forms.

[0162] As described above, it is preferred to select an unsaturated compound so that the energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compound is higher than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by the general formula (1) produced by dehydrohalogenation of the halogenated alkane compound represented by the general formula (2). Therefore, the energy level of the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by the general formula (1) is preferably -25 eV to 10 eV, more preferably -20 eV to 5 eV, and further preferably -15 eV to -5 eV.

[0163] The energy level value of the highest occupied molecular orbital (HOMO) was calculated by optimizing the structure using MM2 calculation and then calculating the electronic structure using the extended Huckel method.

[0164] [Table 2]

[0165]

[0166] The halogenated olefin compound thus obtained can be effectively used in various applications such as cleaning gas, etching gas for forming the most advanced microstructures of semiconductors, liquid crystals, etc., deposition gas, refrigerant, heat transfer medium, and building blocks for organic synthesis. Deposition gas and building blocks for organic synthesis will be described later.

[0167] 2. Composition

[0168] As described above, a halogenated olefin compound can be obtained, and can also be obtained in the form of a composition containing the target compound.

[0169] The production method of the present invention can also be used to obtain, for example, a composition containing a halogenated olefin compound represented by the general formula (1) and a halogenated olefin compound as an impurity. In this case, the halogenated olefin compound as an impurity may be a halogenated olefin compound represented by the following general formula (5).

[0170] R 1 -CH=CH-R 4 (5)

[0171] [In formula (5), R 1 and R 4 are the same or different and represent a hydrogen atom, a halogen atom or a halogenated alkyl group.]

[0172] In the general formula (5), R 1 and R 4 The halogen atoms and halogenated alkyl groups shown may be those explained above.

[0173] That is, as the compound represented by the general formula (5), for example, CFH=CFH, CClH=CClH, CBrH=CBrH, CH2=CFH, CH2=CClH, CH2=CBrH, CF3CH=CFH, CCl3CH=CClH, CBr3CH=CBrH, CF3CH=CHCF3, CCl3CH=CHCCl3, CBr3CH=CHCBr3, CF3CH=CH2, CCl3CH=CH2, CBr3CH=CH2, CF3CH2CH=CH2, CF3CH=CHCH3, CF3CHFCH=CH2, CF3CF2CH=CHF, CH3CF2CH=CHF, CCl3CH2CH=CH2, CCl3CH=CHCH3, CCl3CHClCH=CH2, CCl3CCl2CH=CHCl, CH3CCl2CH=CHCl, CBr3CH2CH=CH2, CBr3CH=CHCH3, CBr3CHBrCH=CH2, CBr3CBr2CH=CHBr, CH3CBr2CH=CHBr, etc. These compounds include Z and E forms.

[0174] In addition, the composition may contain a halogenated alkane compound represented by the following general formula (6) obtained by an addition reaction between a hydrogen halide produced by a dehydrohalogenation reaction of a halogenated alkane represented by the general formula (1) and an unsaturated compound represented by the general formula (3) or (4).

[0175] R 5 -CR 6 R 11 -CR 7 R 12 -R 8 (6)

[0176] [In formula (6), R 5 , R 6 , R 7 and R 8 The same or different, represents a hydrogen atom or an organic group. 11 and R 12 One of them is a hydrogen atom and the other is a halogen atom.]

[0177] In the general formula (6), as R 5 , R 6 , R 7 and R 8 The organic group, R 11 and R 12 The halogen atoms shown may be the same as those described above.

[0178] The compound represented by the general formula (6) is one or two compounds obtained by adding hydrogen halide to the unsaturated compound added, that is, the compound represented by the general formula (3) or the general formula (4). That is, the compound represented by the general formula (6) is a compound obtained by adding hydrogen halide separated from the halogenated alkane (2) to the corresponding unsaturated compound, for example, [CF3CFHCF2CF3 (HF is added to the unsaturated compound CF3CF=CFCF3 added)], [CCl3CClHCCl2CCl3 (HCl is added to the unsaturated compound CCl3CCl=CClCCl3 added)], [CBr3CBrHCBr2CBr3 (HBr is added to the unsaturated compound CBr3CBr=CBrCBr3 added)], [CF3CH3, CHF2CH2F, CHF2CH2Cl, CF2ClCH 3. CHF2CH2Br or CF2BrCH3 (HF, HCl or HBr is added to the added unsaturated compound CF2=CH2)], [CHF2CH2F or CFClCFH2 (HF or HCl is added to the added unsaturated compound CFH=CFH)], [CHCl2CH2Cl or CHFClCH2Cl (HF or HCl is added to the added unsaturated compound CHCl=CHCl)], CHClBrCH2Br or CHBr2CH2Br (HCl or HBr is added to the added unsaturated compound CHBr=CHBr)], [CF3CH2F, CF2ClCH2F, CF2HC HF2 or CF2HCHFCl (HF or HCl is added to the added unsaturated compound CF2 = CHF)], [CHBr2CHBr2 (HBr is added to the added unsaturated compound CBr2 = CHBr)], [CFCl2CHCl2 or CCl3CHCl2 (HF or HCl is added to the added unsaturated compound CCl2 = CCl2)], [CBr3CHBr2 (HBr is added to the added unsaturated compound CBr2 = CBr2)], [CH2FCHFCF3, CHF2CH2CF3, CHFClCH2CF3 or CH2FCHClCF3 (the added unsaturated compound CHF =CHCF3 to which HF or HCl is added)], [CH2ClCHClCCl3, CHCl2CH2CCl3, CHFClCH2CCl3 or CH2ClCHFCCl3 (HF or HCl is added to the added unsaturated compound CHCl=CHCCl3)], [CF3CF2CH2Cl, CF3CHFCHFCl or CF3CFClCH2Cl (HF or HCl is added to the added unsaturated compound CF3CF=CHCl)], [CCl3CCl2CH2Cl or CCl3CHClCHCl2 (HCl is added to the added unsaturated compound CCl3CCl=CHCl)],[CCl3CHClCH2Cl, CCl3CCl2CH3 or CCl3CFClCH3 (HF or HCl is added to the added unsaturated compound CCl3CCl=CH2)], [CF3CH2CHFCl, CF3CHFCH2Cl, CF3CH2CHClBr, CF3CH2CHCl2, CF3CHClCH2Cl or CF3CHBrCH2Cl (HF, HCl or HBr is added to the added unsaturated compound CF3CH=CHCl)], [CCl3CH2CHCl2, CCl3CHClCH2Cl or CCl3CH2CHFCl (HF, HCl or HBr is added to the added unsaturated compound CCl3CH=CHCl HF or HCl is added)], [CH3CCl2CN or CH2ClCHClCN (HCl is added to the added unsaturated compound CH2=CClCN)], [CH2BrCHBrCN (HBr is added to the added unsaturated compound CH2=CBrCN)], [CH3CHFCOOCH3, CH3CHClCOOCH3, CH3CHBrCOOCH3, CH2ClCH2COOCH3 or CH2BrCH2COOCH3 (HF, HCl or HBr is added to the added unsaturated compound CH2=CHCOOCH3)], [CH3OCH2CHClCOOCH3 or CH3OCH2CHBrCOOCH 3 (HCl or HBr is added to the added unsaturated compound CH3OCH=CHCOOCH3)], [CH3CH2CH2CHClCOOCH3 or CH3CH2CH2CHBrCOOCH3 (HCl or HBr is added to the added unsaturated compound CH3CH2CH=CHCOOCH3)], [CH3CBr(CH2CH3)COOCH3 (HBr is added to the added unsaturated compound CH2=C(C2H5)COOCH3)], [(CH3)2CHCHClCOOCH3, (CH3)2CHCHBrCOOCH3 or (CH3)2CBrCH2COOCH3 (the added unsaturated compound (HCl or HBr is added to the unsaturated compound CH2=CHCH2OH added with HF, HCl or HBr)], [CH3CH2CHFCH2OH, CH3CH2CHClCH2OH, CH3CHBrCH2OH, CH2FCH2CH2OH, CH2ClCH2CH2OH or CH2BrCH2CH2OH (HF, HCl or HBr is added to the unsaturated compound CH2=CHCH2OH added with HF, HCl or HBr)], [CH3CH2CHFCH2OH, CH3CH2CHClCH2OH or CH3CH2CHBrCH2OH (HF, HCl or HBr is added to the unsaturated compound CH3CH2CH=CHOH added with HF)], [CH3CHFCH2CH2OH,CH3CHClCH2CH2OH, CH3CHBrCH2CH2OH, CH3CH2CFHCH2OH, CH3CH2CClHCH2OH or CH3CH2CBrHCH2OH (HF, HCl or HBr is added to the added unsaturated compound CH3CH=CHCH2OH)], [CH3CHClCH2OCH3 or CH3CHBrCH2OCH3 (HCl or HBr is added to the added unsaturated compound CH3CH=CHOCH3)], [CH2ClCH2CH2N(CH3)2 or CH2BrCH2CH2N(CH3)2 (HCl or HBr is added to the added unsaturated compound CH2=CHCH2N(CH3)2)], [CH3CCl2CH2COOCH3 or CHCl2CH2CH2COOCH3 (HCl is added to the added unsaturated compound CH≡CCH2COOCH3)], etc.

[0179] When the total amount of the composition of the present invention is set to 100 mol%, the content of the halogenated olefin compound represented by the general formula (1) is 50 to 80 mol%, and may also be 54 to 79 mol%, 58 to 78 mol%, 62 to 77 mol%, 65 to 76 mol%, etc.

[0180] When the total amount of the composition of the present invention is set to 100 mol%, the content of the halogenated olefin compound represented by the general formula (5) is 12 to 40 mol%, and may also be 13 to 37 mol%, 14 to 34 mol%, 15 to 30 mol%, 16 to 27 mol%, etc.

[0181] In addition, when the total amount of the composition of the present invention is set to 100 mol%, the content of the halogenated olefin compound represented by the general formula (6) is preferably 0.10 to 10.0 mol%, and may also be 0.15 to 9.5 mol%, 0.20 to 9.0 mol%, 0.25 to 8.5 mol%, 0.30 to 8.0 mol%, etc.

[0182] In addition, when the production method of the present invention is used, when the halogenated olefin compound is obtained in the form of a halogenated olefin composition, the halogenated olefin compound represented by the general formula (1) can be obtained with a high reaction conversion rate, high yield and high selectivity as described above, thereby reducing the components other than the halogenated olefin compound represented by the general formula (1) in the composition of the present invention, thereby reducing the labor required for purification to obtain the halogenated olefin compound represented by the general formula (1).

[0183] When the production method of the present invention is used, when a composition containing a halogenated olefin compound represented by the general formula (1) is obtained, the halogenated olefin compound represented by the general formula (1) can be obtained with a high conversion rate, high yield and high selectivity, so as a result, the components other than the halogenated olefin compound represented by the general formula (1) in the above composition can be reduced. The production method of the present invention can reduce the labor for refining the halogenated olefin compound represented by the general formula (1).

[0184] The composition containing the halogenated olefin compound of the present invention can be effectively used in various applications, such as cleaning gas, etching gas for forming cutting-edge microstructures of semiconductors, liquid crystals, etc., as well as deposition gas, refrigerant, heat transfer medium, building block for organic synthesis, etc., just like the case of the halogenated olefin compound alone.

[0185] The above-mentioned deposition gas is a gas that deposits the etching resistant polymer layer.

[0186] The organic synthesis building blocks are substances that are precursors of compounds that can form highly reactive skeletons. For example, when the composition of the present invention is reacted with a fluorinated organosilicon compound such as CF3Si(CH3)3, a fluorinated alkyl group such as a CF3 group can be introduced to form a substance that can form a cleaning agent or a fluorinated pharmaceutical intermediate.

[0187] Although the embodiment of the present invention has been described above, various changes may be made to the form and details without departing from the spirit and scope of the scope of the invention.

[0188] Example

[0189] Hereinafter, the features of the present invention will be clarified by describing examples, but the present invention is not limited to these examples.

[0190] In the methods for producing halogenated olefin compounds of Examples 1 to 3, as the raw material compounds, in the halogenated alkane compound represented by the general formula (2), R 1 and R 4 is trifluoromethyl, R 2 is a fluorine atom, R 3 is a hydrogen atom, X is a fluorine atom, according to the following reaction formula:

[0191] CF3CFHCFHCF3→CF3CF=CHCF3+HF

[0192] Through dehydrofluorination reaction, halogenated olefin compounds are obtained.

[0193] Examples 1 to 3 and Comparative Example 1

[0194] An activated carbon catalyst (manufactured by Osaka Gas Chemical Co., Ltd.; specific surface area: 1200 m 2 / g) 10g. After drying at 200°C for 2 hours under nitrogen atmosphere, the pressure was set to normal pressure, and CF3CFHCFHCF3 (raw material compound) was circulated in the reaction tube in such a manner that the contact time W / F [W: weight of catalyst (g), F: flow rate (cc / sec) of raw material compound CF3CFHCFHCF3] of CF3CFHCFHCF3 (raw material compound) and activated carbon catalyst was 23g·sec / cc or 47g·sec / cc. Then, in Examples 1 to 3, 0.01 to 0.20 mol (1 to 20 mol%) of CF3CF=CFCF3 (raw material compound) was circulated relative to 1 mol of CF3CFHCFHCF3 (raw material compound).

[0195] The reaction was carried out in a gas phase continuous flow system.

[0196] The reaction tube was heated at 350° C. to initiate a dehydrofluorination reaction.

[0197] One hour after the start of the dehydrofluorination reaction, the fraction passing through the detoxification tower was collected.

[0198] After that, a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014") was used to perform mass analysis using gas chromatography / mass spectrometry (GC / MS), and an NMR (manufactured by JEOL, trade name "400YH") was used to perform structural analysis using NMR spectra. Based on the results of mass analysis and structural analysis, it was confirmed that the target compound CF3CF=CHCF3 was generated. The results are shown in Table 3.

[0199] [Table 3]

[0200]

Claims

1. A method for producing a halogenated olefin compound represented by the following general formula (1), characterized in that: The method comprises the steps of subjecting a halogenated alkane compound represented by the following general formula (2) to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound. R 1 -CR 2 =CR 3 -R 4 (1) In formula (1), R 1 , R 2 , R 3 and R 4 are the same or different, representing a hydrogen atom, a halogen atom or a halogenated alkyl group, wherein R 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom, R 1 -CHR 2 -CXR 3 -R 4 (2) In formula (2), R 1 , R 2 , R 3 and R 4 The meanings are the same as above, X represents a halogen atom, The unsaturated compound is a compound represented by the following general formula (3) or the following general formula (4), and the compound represented by the general formula (1) and the unsaturated compound are different compounds, R 5 -CR 6 =CR 7 -R 8 (3) In formula (3), R 5 , R 6 , R 7 and R 8 The same or different, representing a hydrogen atom or an organic group, R 9 -C≡C-R 10 (4) In formula (4), R 9 and R 10 The same or different represent a hydrogen atom or an organic group.

2. The manufacturing method according to claim 1, characterized in that: In the general formulas (1) and (2), R 1 and R 4 is a fluorine atom or a perfluoroalkyl group.

3. The manufacturing method according to claim 1 or 2, characterized in that: The energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compound is higher than the energy level of the highest occupied molecular orbital (HOMO) of the halogenated olefin compound represented by the general formula (1).

4. The manufacturing method according to any one of claims 1 to 3, characterized in that: The supply amount of the unsaturated compound is 0.001 to 0.40 mol per 1 mol of the halogenated alkane compound represented by the general formula (2).

5. The manufacturing method according to any one of claims 1 to 4, characterized in that: The dehydrohalogenation reaction is carried out in the gas phase.

6. A composition, characterized in that: Contains 50 to 80 mol% of a halogenated olefin compound represented by the following general formula (1) and 12 to 40 mol% of a halogenated olefin compound represented by the following general formula (5): R 1 -CR 2 =CR 3 -R 4 (1) In formula (1), R 1 , R 2 , R 3 and R 4 are the same or different, representing a hydrogen atom, a halogen atom or a halogenated alkyl group, wherein R 2 and R 3 One of them is a hydrogen atom and the other is a halogen atom, R 1 -CH=CH-R 4 (5) In formula (5), R 1 and R 4 The same or different groups represent a hydrogen atom, a halogen atom or a halogenated alkyl group.

7. The composition according to claim 6, characterized in that: It also contains a halogenated alkane compound represented by the following general formula (6): R 5 -CR 6 R 11 -CR 7 R 12 -R 8 (6) In formula (6), R 5 , R 6 , R 7 and R 8 The same or different, representing a hydrogen atom or an organic group, R 11 and R 12 One of them is a hydrogen atom and the other is a halogen atom.

8. The composition according to claim 7, characterized in that: The content of the halogenated alkane compound represented by the general formula (6) is 0.10 to 10.0 mol %.

9. The composition according to any one of claims 6 to 8, characterized in that: It is used as a cleaning gas, etching gas, refrigerant, heat transfer medium or building block for organic synthesis.

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