Method for producing alkene halide compounds

Abstract

To provide a method for efficiently producing a halogenated alkene compound.SOLUTION: The present invention provides a method for producing a halogenated alkene compound which is represented by general formula (1): R1-CR2=CR3-R4, the method comprising a step for subjecting a halogenated alkane compound which is represented by general formula (2): R1-CHR2-CXR3-R4 to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound. The unsaturated compound is represented by general formula (3): R5-CR6=CR7-R8 or general formula (4): R9-C≡C-R10, and the compound represented by general formula (1) and the unsaturated compound are different from each other.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for producing a halogenated alkene compound.

Background Art

[0002] As a method for producing a halogenated alkene compound, for example, in Patent Document 1, it is known to subject a specific halogenated alkane compound to a dehydrohalogenation reaction (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a method capable of efficiently obtaining a halogenated alkene compound.

Means for Solving the Problems

[0005] The present disclosure includes the following configurations.

[0006] Item 1. General formula (1): R 1 -CR 2 =CR 3 -R 4 (1) [In the formula, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group. However, one of R 2 and R 3 is a hydrogen atom and the other is a halogen atom.] A method for producing a halogenated alkene compound represented by General formula (2): R 1 -CHR 2 -CXR 3 -R 4 (2) [In the formula, R 1 , R 2 , R 3 and R 4 The same applies as above. X represents a halogen atom. The process involves a dehydrohalogenation reaction of a halogenated alkane compound represented by in the presence of a catalyst and an unsaturated compound. The aforementioned unsaturated compound is defined by general formula (3): R 5 -CR 6 =CR 7 -R 8 (3) [In the formula, R 5 , R 6 , R 7 and R 8 These are the same or different, representing a hydrogen atom or an organic group. ], or general formula (4): R 9 -C≡CR 10 (4) [In the formula, R 9 and R 10 These are identical or distinct, representing a hydrogen atom or an organic group. It is a compound represented by, and A method for producing a compound that is different from the compound represented by the general formula (1) and the unsaturated compound.

[0007] Section 2. In the above general formulas (1) and (2), the R 1 and R 4 The method for producing a food product according to item 1, wherein is a fluorine atom or a perfluoroalkyl group.

[0008] Item 3. The manufacturing method according to item 1 or 2, wherein the energy level of the highest occupied orbital (HOMO) of the unsaturated compound is higher than that of the highest occupied orbital (HOMO) of the halide alkene compound represented by general formula (1).

[0009] Item 4. The manufacturing method according to any one of items 1 to 3, wherein the amount of the unsaturated compound supplied is 0.001 to 0.40 moles per mole of the halogenated alkane compound represented by the general formula (2).

[0010] Item 5. The manufacturing method according to any one of items 1 to 4, wherein the dehalogenation reaction is carried out in the gas phase.

[0011] Section 6. General formula (1): R 1 -CR 2 =CR 3 -R 4 (1) [In the formula, R 1 , R 2 , R 3 and R 4 R represents a hydrogen atom, a halogen atom, or a haloalkyl group, either identical or distinct. 2 and R 3 One of them is a hydrogen atom, and the other is a halogen atom. A halogenated alkene compound represented by [formula] is used in a quantity of 50-80 mol%, General formula (5): R 1 -CH=CH-R 4 (5) [In the formula, R 1 and R 4 These are the same or different atoms, representing a hydrogen atom, a halogen atom, or a haloalkyl group. A halogenated alkene compound represented by the above is used in an amount of 12-40 mol% A composition containing the following:

[0012] Section 7. Furthermore, general formula (6): R 5 -CR 6 R 11 -CR 7 R 12 -R 8 (6) [In the formula, R 5 , R 6 , R 7 and R 8 R represents a hydrogen atom or an organic group, and may be identical or different. 11 and R12 One of them is a hydrogen atom, and the other is a halogen atom. The composition according to item 6, comprising a halogenated alkane compound represented by .

[0013] 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%.

[0014] Item 9. A composition according to any one of items 6 to 8, used as a cleaning gas, etching gas, refrigerant, heat transfer medium, or building block for organic synthesis. [Effects of the Invention]

[0015] According to this disclosure, alkene halide compounds can be synthesized efficiently. [Modes for carrying out the invention]

[0016] In this specification, "contains" is a concept that encompasses all of the following: "contains," "consist essentially of," and "consist of."

[0017] Furthermore, in this specification, when a numerical range is indicated as "A to B", it means A or greater and B or less.

[0018] In this disclosure, "selectivity" means the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of compounds other than the raw material compound in the effluent gas.

[0019] In this disclosure, "conversion rate" means the ratio (moles) of the total amount of compounds other than the raw material compounds contained in the effluent gas from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor. It means %).

[0020] In this disclosure, “yield” means the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0021] Halide butyne compounds, such as hexafluoro-2-butyne, are known to be synthesized by using specific halide alkane compounds as starting materials and undergoing two dehydrohalogenation reactions.

[0022] Here, when a dehalogenation reaction is carried out from a halogenated alkane compound, hydrogen halides are liberated. When the product, a halogenated alkene compound, reacts with the liberated hydrogen halides, the starting material, a halogenated alkane compound, is produced again. Therefore, to obtain a halogenated butyn compound, the yield can be improved by carrying out two dehalogenation reactions instead of one, using the halogenated alkane compound as the starting material.

[0023] On the other hand, in this disclosure, by carrying out a dehydrohalogenation reaction from a halogenated alkane compound in the presence of a specific unsaturated compound, the hydrogen halide produced by the dehydrohalogenation reaction can be trapped by the specific unsaturated compound. As a result, the starting material, the halogenated alkane compound, reacts almost quantitatively, and the halogenated alkene compound can be obtained with high selectivity and high yield.

[0024] 1. Method for producing halogenated alkene compounds The method for producing halogenated alkene compounds in this disclosure is: General formula (1): R 1 -CR 2 =CR 3 -R 4 (1) [In the formula, R 1 , R 2 , R 3 and R 4 R represents a hydrogen atom, a halogen atom, or a haloalkyl group, either identical or distinct. 2 and R 3One of them is a hydrogen atom, and the other is a halogen atom. A method for producing a halogenated alkene compound represented by the following: General formula (2): R 1 -CHR 2 -CXR 3 -R 4 (2) [In the formula, R 1 , R 2 , R 3 and R 4 The same applies as above. X represents a halogen atom. The process involves a dehydrohalogenation reaction of a halogenated alkane compound represented by in the presence of a catalyst and an unsaturated compound. The aforementioned unsaturated compound is defined by general formula (3): R 5 -CR 6 =CR 7 -R 8 (3) [R 5 , R 6 , R 7 and R 8 These are identical or distinct, representing a hydrogen atom or an organic group. , or general formula (4): R 9 -C≡CR 10 (4) [In the formula, R 9 and R 10 These are identical or distinct, representing a hydrogen atom or an organic group. It is a compound represented by, and The compound represented by the general formula (1) is a different compound from the unsaturated compound.

[0025] According to the present disclosure, by performing the dehydrohalogenation reaction of the halogenated alkane compound represented by the above general formula (2) in the presence of a specific unsaturated compound, the hydrogen halide generated by the dehydrohalogenation reaction can be trapped by the specific unsaturated compound. Therefore, the starting halogenated alkane compound reacts almost quantitatively, and a halogenated alkene compound represented by the general formula (1) in which 1 mol of hydrogen halide has been eliminated per 1 mol of the halogenated alkane compound represented by the general formula (2) can be selectively obtained.

[0026] (1-1) Starting compound (halogenated alkane compound) The halogenated alkane compound as a substrate that can be used in the production method of the present disclosure is, as described above, represented by the general formula (2): R 1 -CHR 2 -CXR 3 -R 4 (2) [In the formula, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group. However, one of R 2 and R 3 is a hydrogen atom and the other is a halogen atom. X represents a halogen atom.] is a halogenated alkane compound represented by.

[0027] In the general formula (2), examples of the halogen atom represented by R 1 , R 2 , R 3 and R 4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0028] In the general formula (2), R 1 , R 2 , R 3 and R 4The haloalkyl group shown in (1) refers to an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. Among haloalkyl groups, those in which at least one hydrogen atom is substituted with a fluorine atom are called fluoroalkyl groups, and those in which all hydrogen atoms are substituted with fluorine atoms are called perfluoroalkyl groups. Furthermore, among haloalkyl groups, those in which at least one hydrogen atom is substituted with a chlorine atom are called chloroalkyl groups, and those in which all hydrogen atoms are substituted with chlorine atoms are called perchloroalkyl groups. Furthermore, among haloalkyl groups, those in which at least one hydrogen atom is substituted with a bromine atom are called bromoalkyl groups, and those in which all hydrogen atoms are substituted with bromine atoms are called perbromoalkyl groups. In particular, from the viewpoint of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred.

[0029] Haloalkyl groups can be linear, branched, or cyclic. Among these, linear haloalkyl groups are preferred from the viewpoint of reaction conversion rate, selectivity and yield of the halogenated alkene compound represented by general formula (1).

[0030] The number of carbon atoms in the haloalkyl group is not particularly limited, but from the viewpoint of the reaction conversion rate, the selectivity and yield of the halogenated alkene compound represented by general formula (1), 1 to 5 is preferred, 1 to 4 is more preferred, and 1 to 3 is even more preferred.

[0031] Examples of such fluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and heptafluoropropyl groups. Examples of chloroalkyl groups include trichloromethyl, pentachloroethyl, and heptachloropropyl groups. Examples of bromoalkyl groups include tribromomethyl, pentabromoethyl, and heptabromopropyl groups.

[0032] Since the halide alkene compound represented by general formula (1) also functions as an intermediate for obtaining a halide alkyne compound by subsequent dehalogenation reactions, dehalogenation from the halide alkene compound represented by general formula (1) is permitted, and therefore, R in general formula (2) 2 and R 3 One of them is a hydrogen atom, and the other is a halogen atom.

[0033] In general formula (2), R 1 and R 4 From the viewpoint of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by 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 even more preferred.

[0034] In general formula (2), the halogen atoms represented by X include fluorine, chlorine, bromine, and iodine.

[0035] Examples of halogenated alkane compounds that satisfy these conditions as substrates include CF2HCF2H, CFH2CF3, CCl2HCCl2H, CClH2CCl3, CBr2HCBr2H, CBrH2CBr3, CF3CFHCF2H, CF3CH2CF3, CCl3CClHCCl2H, CCl3CH2CCl3, CBr3CBrHCBr2H, CBr3CH2CBr3, CF3CFHCFHCF3, CF3CH2CF2CF3, and CCl3CClHCC Examples include lHCl3, CCl3CH2CCl2CCl3, CBr3CBrHCBrHCBr3, CBr3CH2CBr2CBr3, CH3CF3, CH3CCl3, CH3CBr3, CF3CF2CH3, CCl3CCl2CH3, CBr3CBr2CH3, CF3CH2CF2CH3, CF3CHFCF2CH3, CCl3CH2CCl2CH3, CCl3CHClCCl2CH3, CBr3CH2CBr2CH3, CBr3CHBrCBr2CH3, etc.

[0036] These alkane halide compounds can be used individually or in combination of two or more. Such alkane halide compounds can be known or commercially available.

[0037] (1-2) Dehydrofluoride reaction In the step of removing hydrogen fluoride from a halogenated alkane compound in this disclosure, the following reaction formula is used: R 1 -CHR 2 -CXR 3 -R 4 → R 1 -CR 2 =CR 3 -R 4 + HX The dehalogenation reaction can be carried out accordingly.

[0038] In particular, from the viewpoint of reaction conversion rate, selectivity and yield of the halogenated alkene compound represented by general formula (1), R 1 and R 4 is a trifluoromethyl group, R 2 is a fluorine atom, R 3 It is preferable that X is a hydrogen atom and X is a fluorine atom. In other words, the reaction equation is as follows: CF3CFHCFHCF3→ CF3CF=CHCF3+ HF It is preferable to carry out the dehydrofluoride reaction according to the following.

[0039] (1-3) Catalyst The step of dehydrogenating a halide alkane compound in this disclosure is carried out in the presence of a catalyst.

[0040] Preferred catalysts used in the manufacturing method of this disclosure include activated carbon catalysts, zeolite catalysts, chromium oxide catalysts, and silica-alumina catalysts. These catalysts can be either non-fluorinated or fluorinated.

[0041] There are no particular restrictions on the activated carbon catalyst, and examples include powdered activated carbon such as crushed carbon, molded carbon, granular carbon, and spherical carbon. It is preferable to use powdered activated carbon that exhibits a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) according to the JIS test (JIS Z8801).

[0042] These activated carbons can be used individually or in combination of two or more types. These activated carbons can be known or commercially available products.

[0043] Activated carbon becomes more active when fluorinated, so fluorinated activated carbon, which is activated carbon that has been fluorinated beforehand, can also be used as an activated carbon catalyst. In other words, as an activated carbon catalyst, both unfluorinated activated carbon and fluorinated activated carbon can be used. The offset can also be used.

[0044] As fluorinating agents for fluorinating activated carbon, in addition to inorganic fluorinating agents such as F2 and HF, organic fluorinating agents such as hydrofluorocarbons (HFCs) such as hexafluoropropene, chlorofluorocarbons (CFCs) such as chlorofluoromethane, and hydrochlorofluorocarbons (HCFCs) can also be used.

[0045] One method for fluorinating activated carbon is to pass the aforementioned fluorinating agent through it under atmospheric pressure at a temperature of approximately 25°C to 400°C.

[0046] A wide range of known types of zeolites can be used as zeolite catalysts. For example, crystalline hydrated aluminosilicates of alkali metals or alkaline earth metals are preferred. The crystalline form of the zeolite is not particularly limited, and examples include type A, type X, and type LSX. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples include potassium, sodium, calcium, and lithium.

[0047] Since the zeolite catalyst exhibits stronger activity by fluorination, it can be pre-fluorinated before use in the reaction and used as a fluorinated zeolite catalyst.

[0048] As the fluorinating agent for fluorinating the zeolite catalyst, for example, inorganic fluorinating agents such as F2 and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropene can be used.

[0049] As a method for fluorinating the zeolite catalyst, for example, a method of flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of room temperature (25 °C) to about 400 °C for fluorination can be mentioned.

[0050] The chromium oxide catalyst is not particularly limited, but when chromium oxide is represented as CrO m when expressed, 1.5 < m < 3.0 is preferable, 2.0 < m < 2.75 is more preferable, and 2.0 < m < 2.3 is even more preferable. Also, when chromium oxide is expressed as CrO m ·nH2O, it may be hydrated so that the value of n is 3 or less, particularly 1.0 to 1.5.

[0051] The fluorinated chromium oxide catalyst can be prepared by fluorination of the above-mentioned chromium oxide catalyst. This fluorination can be carried out using, for example, HF, fluorocarbon, etc. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in JP-A-05-146680.

[0052] The silica-alumina catalyst is a composite oxide catalyst containing silica (SiO2) and alumina (Al2O3). Taking the total amount of silica and alumina as 100% by mass, for example, a catalyst with a silica content of 20 to 90% by mass, particularly 50 to 80% by mass can be used.

[0053] Since silica-alumina catalysts become more active when fluorinated, they can also be fluorinated beforehand and used as fluorinated silica-alumina catalysts before being used in a reaction.

[0054] For fluorinating silica-alumina catalysts, examples of fluorinating agents that can be used include inorganic fluorinating agents such as F2 and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropene.

[0055] One method for fluorinating silica-alumina catalysts is to pass the aforementioned fluorinating agent through the catalyst under atmospheric pressure at a temperature of approximately 25°C to 400°C.

[0056] The catalysts described above can be used individually or in combination of two or more. Furthermore, known or commercially available catalysts can be used.

[0057] Among these, activated carbon catalysts (activated carbon or fluorinated activated carbon) and chromium oxide catalysts (chromium oxide or fluorinated chromium oxide) are preferred from the viewpoint of conversion rate, selectivity, and yield, with activated carbon catalysts (activated carbon or fluorinated activated carbon) being more preferred.

[0058] Furthermore, when using the zeolite catalyst, chromium oxide catalyst, silica-alumina catalyst, etc., as described above, it is also possible to support them on a carrier. Examples of such carriers include carbon, alumina (Al2O3), zirconia (ZrO2), silica (SiO2), titania (TiO2), etc. As for carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.

[0059] In the manufacturing method of this disclosure, when dehydrohalogenating an alkane halide compound in the gas phase in the presence of a catalyst, it is preferable, for example, to contact the alkane halide compound with the catalyst in a solid state (solid phase). In this case, the catalyst can be in powder form, but pellet form is preferable when used in a gas-phase continuous flow reaction.

[0060] The specific surface area of ​​a catalyst measured by the BET method (hereinafter sometimes referred to as "BET specific surface area") is typically 10 to 3000 m². 2 / g is preferred, and 15-2500m 2 / g is more preferable, 20-2000m 2 / g is even more preferable, 30-1500m 2 A value of / g is particularly preferred. When the BET specific surface area of ​​the catalyst is within this range, the density of catalyst particles is not too low, allowing for the acquisition of alkene halide compounds with higher selectivity and yield. It is also possible to further improve the conversion rate of alkane halide compounds.

[0061] (1-4) Unsaturated compounds In this disclosure, the step of dehydrohalogenating the above-mentioned alkane halide compound is carried out in the presence of an unsaturated compound.

[0062] An unsaturated compound is defined as a compound that has at least one unsaturated bond (such as a double bond or triple bond).

[0063] This unsaturated compound can trap hydrogen halides produced by the dehydrohalogenation reaction of halide alkane compounds represented by general formula (2). When the unsaturated compound traps hydrogen halides, a hydrogen halide addition reaction occurs with the unsaturated compound.

[0064] For example, if CF3CFHCFHCF3 is used as the halogenated alkane compound represented by general formula (2) and CF3CF=CFCF3 is used as the unsaturated compound, the following reaction equation: CF3CFHCFHCF3→ CF3CF=CHCF3+ HF Hydrogen fluoride is generated by the following reaction: CF3CF=CFCF3+ HF → CF3CF2CFHCF3 The hydrogen fluoride generated by this process is trapped.

[0065] In this way, the hydrogen halide generated by the dehydrohalogenation reaction of the halogenated alkane compound represented by general formula (2) can be suppressed from reacting with the target halogenated alkene compound represented by general formula (1) to form the starting material, the halogenated alkane compound represented by general formula (2).

[0066] The unsaturated compound traps the hydrogen halide, shifting the equilibrium of the dehalogenation reaction towards the product side (the halogenated alkene compound represented by general formula (1)). This allows the starting material, the halogenated alkane compound represented by general formula (2), to react almost quantitatively, yielding the halogenated alkene compound represented by general formula (1) with high selectivity and high yield.

[0067] Here, the addition reaction between an olefin, i.e., a compound with an unsaturated bond, and a hydrogen halide occurs in the energy orbitals of the highest occupied orbital (HOMO) of the olefin and the lowest unoccupied orbital (LUMO) of the hydrogen halide. Therefore, the reactivity is higher the smaller the difference in energy levels between the highest occupied orbital (HOMO) of the olefin and the lowest unoccupied orbital (LUMO) of the hydrogen halide.

[0068] Since the added unsaturated compound and the halide alkene compound represented by general formula (1) undergo addition reactions with the same hydrogen halide, the magnitude of the energy level difference between the highest occupied orbital (HOMO) of the halide alkene compound and the lowest unoccupied orbital (LUMO) of the hydrogen halide is due to the high or low energy level of the highest occupied orbital (HOMO) of the halide alkene compound.

[0069] When the highest occupied orbital (HOMO) of the unsaturated compound is higher than that of the alkene halide compound represented by general formula (1), the reaction of the unsaturated compound trapping hydrogen fluoride will occur preferentially over the reverse reaction of the alkene halide compound represented by general formula (1) and hydrogen fluoride.

[0070] Similarly, if the unsaturated compound is a compound represented by general formula (4) having a triple bond, then if the highest occupied orbital (HOMO) of the compound represented by general formula (4) having a triple bond is at a higher energy level than the highest occupied orbital (HOMO) of the halide alkene compound represented by general formula (1), then the trapping reaction of hydrogen fluoride by the compound represented by general formula (4) having a triple bond will preferentially occur over the reverse reaction of the halide alkene compound represented by general formula (1) with hydrogen fluoride.

[0071] In other words, as an unsaturated compound, it is preferable to select a compound whose highest occupied orbital (HOMO) is higher than that of the alkene halide compound represented by general formula (1).

[0072] Therefore, the unsaturated compounds used in this disclosure are specifically those of general formula (3): R 5 -CR 6 =CR 7 -R 8 (3) [In the formula, R 5 , R 6 , R 7 and R 8 These are the same or different, representing a hydrogen atom or an organic group. ], or general formula (4): R 9 -C≡CR 10 (4) [In the formula, R 9 and R 10 [These are identical or different, representing a hydrogen atom or an organic group.] It is a compound represented by the following: The highest occupied orbital (HOMO) of the compounds represented by general formulas (3) and (4) is preferably at a higher energy level than the highest occupied orbital (HOMO) of the halide alkene compound represented by general formula (1).

[0073] From this perspective, the highest occupied 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 orbital (HOMO) of the halide alkene compound represented by general formula (1).

[0074] R in general formula (3) is an unsaturated compound. 5 , R 6 , R 7 and R 8 The organic group represented by, and R in general formula (4) 9 and R 10 Examples of organic groups represented by include halogen atoms, cyano groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted amino groups, substituted or unsubstituted thiol groups, ester groups (-COOR), carbonyl groups (-COR), substituted or unsubstituted carboxyl groups, nitro groups, sulfo groups, amide groups (-CONR2, -NRCOR), etc. Note that R may be the same or different, and examples include substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, etc.

[0075] In general formula (3), R 5 , R 6 , R 7 and R 8 The organic group represented by and general formula (4)R 9 and R 10 Examples of halogen atoms as organic groups shown include fluorine, chlorine, bromine, and iodine atoms.

[0076] In general formula (3), R 5 , R 6 , R 7 and R8 The organic group represented by, and in general formula (4), R 9 and R 10 The alkyl group represented by the formula can be linear, branched, or cyclic. Among these, linear alkyl groups are preferred from the viewpoint of reaction conversion rate, selectivity and yield of the halogenated alkene compound represented by general formula (1).

[0077] The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of the reaction conversion rate, the selectivity and yield of the halogenated alkene compound represented by general formula (1), 1 to 5 is preferred, 1 to 4 is more preferred, and 1 to 3 is even more preferred.

[0078] Examples of such alkyl groups include methyl groups, ethyl groups, and n-propyl groups.

[0079] Alkyl groups may have substituents. Examples of substituents that alkyl groups may have include hydroxyl groups, the halogen atoms mentioned above, cyano groups, alkoxy groups described below, aryl groups described below, amino groups described below, thiol groups described below, ester groups, carbonyl groups described below, carboxyl groups described below, and amide groups described above.

[0080] In general formula (3), R 5 , R 6 , R 7 and R 8 The organic group represented by and general formula (4)R 9 and R 10 The alkoxy group, as an organic group represented by , can be linear, branched, or cyclic. Among these, linear alkoxy groups are preferred from the viewpoint of reaction conversion rate, selectivity and yield of the halogenated alkene compound represented by general formula (1).

[0081] The number of carbon atoms in the alkoxy group is not particularly limited, but from the viewpoint of the reaction conversion rate, the selectivity and yield of the halogenated alkene compound represented by general formula (1), 1 to 5 is preferred, 1 to 4 is more preferred, and 1 to 3 is even more preferred.

[0082] Examples of such alkoxy groups include methoxy groups, ethoxy groups, and n-propoxy groups.

[0083] Alkoxy groups can also have substituents. Examples of substitution groups include hydroxyl groups, the halogen atoms mentioned above, cyano groups, alkoxy groups, aryl groups described later, amino groups described later, thiol groups described later, and amide groups.

[0084] In general formula (3), R 5 , R 6 , R 7 and R 8 The organic group represented by and general formula (4)R 9 and R 10 The aryl group as the organic group represented by is not particularly limited, but from the viewpoint of reaction conversion rate, selectivity and yield of the halogenated alkene compound represented by general formula (1), those with 6 to 20 carbon atoms are preferred, those with 6 to 12 carbon atoms are more preferred, and those with 6 to 10 carbon atoms are even more preferred. The aryl group can be monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic.

[0085] Examples of the aryl group include, for example, a phenyl group, a naphthyl group, a biphenyl group, a pentarenyl group, an indenyl group, anthranyl group, a tetracenyl group, a pentacenyl group, a pyrenyl group, a perilenyl group, a fluorenyl group, a phenanthryl group, and the like.

[0086] The aryl group may also have substituents. Examples of substituents that the aryl group may have include a hydroxyl group, the halogen atom mentioned above, a cyano group, the alkyl group mentioned above, the alkoxy group mentioned above, the aryl group mentioned below, the amino group mentioned below, the thiol group mentioned below, the ester group mentioned above, the carbonyl group mentioned above, the carboxyl group mentioned below, the amide group mentioned above, and so on.

[0087] The amino group may also have substituents. Examples of substituents that the amino group may have include a hydroxyl group, the halogen atom mentioned above, a cyano group, the alkyl group mentioned above, the alkoxy group mentioned above, the aryl group mentioned above, the amino group, the thiol group described below, the ester group mentioned above, the carbonyl group mentioned above, the carboxyl group described below, the amide group mentioned above, and so on.

[0088] The thiol group may also have substituents. Examples of substituents that the thiol group may have include a hydroxyl group, the halogen atom mentioned above, a cyano group, the alkyl group mentioned above, an alkoxy group mentioned above, an aryl group mentioned above, an amino group mentioned above, a thiol group mentioned above, an ester group mentioned above, a carbonyl group mentioned above, a carboxyl group as described later, an amide group mentioned above, and so on.

[0089] The carboxyl group may also have substituents. Examples of substituents that the carboxyl group may have include a hydroxyl group, the halogen atom, a cyano group, the alkyl group, the alkoxy group, the aryl group, the amino group, the thiol group, the ester group, the carbonyl group, the carboxyl group, and the amide group.

[0090] In particular, as organic groups, halogen atoms and alkyl halides are preferred from the viewpoint of reaction conversion rate, selectivity and yield of the halogenated alkene compound represented by general formula (1), fluorine atoms and fluoroalkyl groups are more preferred, and fluorine atoms and perfluoroalkyl groups are even more preferred.

[0091] However, the compound represented by general formula (3) is a different compound from the target product, the halide alkene compound represented by general formula (1).

[0092] In this disclosure, as described later, the reaction temperature is preferably 300 to 450°C. At this reaction temperature, it is preferable that the unsaturated compound has at least one of its decomposition temperature, ignition point, and critical point higher than the reaction temperature, regardless of whether or not measurements are available, and it is more preferable that all of the decomposition temperature, ignition point, and critical point are higher than the reaction temperature.

[0093] As an unsaturated compound that satisfies the above conditions, the compound represented by general formula (3) is CF3CF=CFCF3, CCl3CCl=CClCCl3, CBr3CBr=CBrCBr3, CF2=CH2, CHF=CHF, CHCl=CHCl, CHBr=CHBr, CF2=CFH, CBr2=CBrH, CCl2=CCl2, CBr2=CBr2, CHF=CHCF 3、 Examples include CHCl=CHCCl3, CF3CF=CHCl, CCl3CCl=CHCl, CF3CH=CHCl, CCl3CH=CHCl, CCl3CCl=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. Compounds represented by general formula (4) include CF3C≡CCF3, CH≡CCH2COOCH3, etc.

[0094] It is preferable to adjust the energy level of the highest occupied orbital (HOMO) of these unsaturated compounds as follows. It is preferable to select unsaturated compounds such that the energy level of the highest occupied orbital (HOMO) of the unsaturated compound is higher than that of the highest occupied orbital (HOMO) of the halide alkene compound represented by general formula (1) that is produced by dehydrohalogenation of the halide alkane compound represented by general formula (2). For this reason, the energy level of the highest occupied orbital (HOMO) of the unsaturated compound is preferably -15eV to 40eV, more preferably -14eV to 35eV, and even more preferably -13eV to 30eV.

[0095] The energy level of the highest occupied orbital (HOMO) is calculated by first optimizing the structure using MM2 calculations, and then calculating the electronic structure using the extended Hückel method. The results are shown in Table 1.

[0096] [Table 1] These unsaturated compounds can be used individually or in combination of two or more. Yes, it is possible. Such unsaturated compounds can be known or commercially available.

[0097] In the manufacturing method of this disclosure, there are no particular restrictions on the amount of unsaturated compound used, but from the viewpoint of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), it is preferable to use 0.001 to 0.40 moles, more preferably 0.01 to 0.40 moles, and even more preferably 0.05 to 0.20 moles per mole of the halogenated alkane compound represented by general formula (2), which is the starting compound.

[0098] (1-5) Examples of dehalogenation reactions The dehydrohalogenation reaction of the halide alkane compound in this disclosure is preferably carried out in the gas phase, particularly from the viewpoint of productivity. When the dehydrohalogenation reaction of the halide alkane compound in this disclosure is carried out in the gas phase, there is no need to use a solvent, no industrial waste is generated, and it has the advantage of being highly productive.

[0099] The dehalogenation reaction of the halogenated alkane compound in this disclosure can be carried out by either a continuous flow system or a batch system, in which the starting material, the halogenated alkane compound, is continuously charged into a reactor and the target compound, the halogenated alkene compound, is continuously withdrawn from the reactor. In this disclosure, it is preferable to carry out the reaction in a continuous gas-phase flow system in order to further suppress the reverse reaction.

[0100] When the dehalogenation reaction of the halide alkane compounds described in this disclosure is carried out using a continuous gas-phase flow system, the equipment and operation can be simplified, and it is also economically advantageous.

[0101] In carrying out the dehalogenation reaction of the halide alkane compounds in this disclosure, an inert gas atmosphere is preferred in order to suppress catalyst degradation. Examples of such inert gases include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred from the viewpoint of reducing costs.

[0102] (1-6) Reaction temperature In the step of dehydrohalogenating the halide alkane compound in this disclosure, 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 more efficiently carrying out the dehydrohalogenating reaction, further improving the conversion rate, and obtaining the target compound, the halide alkene compound, with higher selectivity and higher yield.

[0103] (1-7) Reaction time In this disclosure, the reaction time for the dehydrohalogenation reaction of the halide alkane compound is, for example, when a gas-phase flow system is adopted, the contact time (W / F) of the starting compound with the catalyst [W: weight of catalyst (g), F: flow rate of starting compound (cc / sec)] is preferably 12 to 45 g·sec / cc, more preferably 15 to 40 g·sec / cc, and even more preferably 20 to 30 g·sec / cc, from the viewpoint of obtaining a particularly high conversion rate of the reaction and obtaining the halide alkane compound in higher yield and with higher selectivity. The above contact time refers to the time during which the starting compound and the catalyst are in contact. Here, the flow rate of the starting compound refers to the flow rate of the halide alkane compound represented by general formula (2), which does not include the unsaturated compound mentioned above.

[0104] (1-8) Reaction pressure In this disclosure, the reaction pressure for the dehalogenation reaction of the halide alkane compound is preferably 0 kPa or higher, more preferably 10 kPa or higher, and more preferably 20 kPa or higher, from the viewpoint of more efficiently carrying out the dehalogenation reaction, improving the conversion rate, and obtaining the target compound, the halide alkene compound, with higher selectivity and higher yield. A pressure of 30 kPa or higher is preferred, and particularly preferred. There is no particular upper limit to the reaction pressure, but it is usually around 2 MPa. In this disclosure, unless otherwise specified, pressure refers to gauge pressure.

[0105] In the dehalogenation reaction of alkane halide compounds in this disclosure, the reactor used to react the alkane halide compound, catalyst, and unsaturated compound is not particularly limited in shape and structure, as long as it can withstand the above-mentioned temperature and pressure. Examples of reactors include vertical reactors, horizontal reactors, and multi-tube reactors. Examples of reactor materials include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0106] After the dehalogenation reaction is complete, the product can be purified according to conventional methods as needed to obtain the halogenated alkene compound represented by general formula (1).

[0107] (1-9) Target compound (halogenated alkene compound) The target compound obtained in this manner is given by general formula (1): R 1 -CR 2 =CR 3 -R 4 (1) [In the formula, R 1 , R 2 , R 3 and R 4 R represents a hydrogen atom, a halogen atom, or a haloalkyl group, either identical or distinct. 2 and R 3 One of them is a hydrogen atom, and the other is a halogen atom. It is a halogenated alkene compound represented by [formula].

[0108] R in general formula (1) 1 , R 2 , R 3 and R 4 This is R in the general formula (2) described above. 1 , R 2 , R 3 and R 4This corresponds to the following. Therefore, the halogenated alkene compounds represented by general formula (1) that are to be manufactured are, for example, specifically 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 Examples include CBr3CBr=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 encompass both the Z and MPE isomers.

[0109] As described above, it is preferable to select an unsaturated compound such that the highest occupied orbital (HOMO) of the unsaturated compound has a higher energy level than the highest occupied orbital (HOMO) of the halogenated alkene compound represented by general formula (1) that is produced by dehydrohalogenation of the halogenated alkane compound represented by general formula (2). Therefore, the energy level of the highest occupied orbital (HOMO) of the halogenated alkene compound represented by general formula (1) is preferably -25eV to 10eV, more preferably -20eV to 5eV, and even more preferably -15eV to -5eV.

[0110] The energy level of the highest occupied orbital (HOMO) is calculated by optimizing the structure using MM2 calculations, followed by calculating the electronic structure using the extended Hückel method. The results are shown in Table 2.

[0111] [Table 2] The resulting halogenated alkene compounds are used as cleaning gases; semiconductors; and liquids. It can be effectively used in various applications such as etching gas for forming cutting-edge microstructures like crystals, deposit gas, refrigerant, heat transfer medium, and building blocks for organic synthesis. Deposit gas and building blocks for organic synthesis will be discussed later.

[0112] 2. Composition As described above, a halogenated alkene compound can be obtained, but it may also be obtained in the form of a composition containing the target compound.

[0113] According to the manufacturing method of this disclosure, for example, a composition may be obtained containing a halogenated alkene compound represented by general formula (1) and an impurity halogenated alkene compound. In this case, the impurity halogenated alkene compound is general formula (5): R 1 -CH=CH-R 4 (5) [In the formula, R 1 and R 4 These are the same or different atoms, representing a hydrogen atom, a halogen atom, or a haloalkyl group. It can be a halogenated alkene compound represented by [formula].

[0114] In general formula (5), R 1 and R 4 The halogen atoms and haloalkyl groups shown can be those described above.

[0115] In other words, compounds represented by general formula (5) include, 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, CF Examples include 3CH=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 encompass both the Z and ME isomers.

[0116] Furthermore, this composition is formed by the addition reaction of hydrogen halide generated in the dehydrohalogenation reaction of a halogenated alkane represented by general formula (1) with an unsaturated compound represented by general formula (3) or general formula (4), resulting in general formula (6): R 5 -CR 6 R 11 -CR 7 R 12 -R 8 (6) [In the formula, R 5 , R 6 , R 7 and R 8 R represents a hydrogen atom or an organic group, and may be the same or different. 11 and R 12 One of them is a hydrogen atom, and the other is a halogen atom. It may also contain halogenated alkane compounds represented by .

[0117] In general formula (6), R 5 , R 6 , R 7 and R 8 Organic groups shown by, or R 11 and R12 The halogen atoms represented by can be those described above.

[0118] The compounds represented by general formula (6) are one or two compounds obtained by adding hydrogen halides to the added unsaturated compound, i.e., the compound represented by general formula (3) or general formula (4). In other words, the compounds represented by general formula (6) are compounds obtained by adding hydrogen halides eliminated from the halide alkane (2) to the corresponding unsaturated compound, for example, [CF3CFHCF2CF3 (addition of HF to the added unsaturated compound CF3CF=CFCF3)], [CCl3CClHCCl2CCl3 (addition of HCl to the added unsaturated compound CCl3CCl=CClCCl3)], [CBr3CBrHCBr2CBr3 (addition of HBr to the added unsaturated compound CBr3CBr=CBrCBr3)], [CF3CH3,CHF2CH2F,CH F2CH2Cl, CF2ClCH3, CHF2CH2Br or CF2BrCH3 (addition of HF, HCl, or HBr to the added unsaturated compound CF2=CH2), [CHF2CH2F, or CFClCFH2 (addition of HF or HCl to the added unsaturated compound CFH=CFH)], [CHCl2CH2Cl, or CHFClCH2Cl (addition of the added unsaturated compound CHCl=CHCl [Addition of HF or HCl to added unsaturated compound CHBr=CHBr], CHClBrCH2Br, or CHBr2CH2Br (addition of HCl or HBr to added unsaturated compound CHBr=CHBr)], [CF3CH2F, CF2ClCH2F, CF2HCHF2, or CF2HCHFCl (addition of HF or HCl to added unsaturated compound CF2=CHF)], [CHBr2CHBr2 (addition of HBr to added unsaturated compound CBr2=CHBr)], [CFCl2CHCl2, or CCl3CHCl2 (addition of HF or HCl to added unsaturated compound CCl2=CCl2)] [Addition of (1)], [CBr3CHBr2 (addition of HBr to the added unsaturated compound CBr2=CBr2)], [CH2FCHFCF3, CHF2CH2CF3, CHFClCH2CF3, or CH2FCHClCF3 (addition of HF or HCl to the added unsaturated compound CHF=CHCF3)], [CH2ClCHClCCl3, CHCl2CH2CCl3, CHFClCH2CCl3, or CH2ClCHFCCl3 (addition of HF or HCl to the added unsaturated compound CHCl=CHCCl3)], [CF3CF2CH2Cl, CF3CHFCHFCl, or CF3CFClCH2Cl (addition of unsaturated compound CHCl=CHCCl3)] [Addition of HF or HCl to the compound CF3CF=CHCl], [CCl3CCl2CH2Cl, or CCl3CHClCHCl2 (addition of HCl to the added unsaturated compound CCl3CCl=CHCl)], [CCl3CHClCH2Cl, CCl3CCl2CH3, or CCl3CFClCH3 (addition of HF or HCl to the added unsaturated compound CCl3CCl=CH2)], [CF3CH2CHFCl, CF3CHFCH2Cl, CF3CH2CHClBr, CF3CH2CHCl2, CF3CHClCH2Cl, or CF3CHBrCH2Cl (addition of the added unsaturated compound CF3C [H=CHCl with addition of HF, HCl, or HBr)], [CCl3CH2CHCl2, CCl3CHClCH2Cl, or CCl3CH2CHFCl (addition of HF or HCl to the added unsaturated compound CCl3CH=CHCl)], [CH3CCl2CN, or CH2ClCHClCN (addition of HCl to the added unsaturated compound CH2=CClCN)], [CH2BrCHBrCN (addition of HBr to the added unsaturated compound CH2=CBrCN)], [CH3CHFCOOCH3, CH3CHClCOOCH3, CH3CHBrCOOCH3, CH2ClCH2COOCH3, or C H2BrCH2COOCH3 (addition of HF, HCl, or HBr to the added unsaturated compound CH2=CHCOOCH3), [CH3OCH2CHClCOOCH3, or CH3OCH2CHBrCOOCH3 (addition of HCl or HBr to the added unsaturated compound CH3OCH=CHCOOCH3)], [CH3CH2CH2CHClCOOCH3, or CH3CH2CH2CHBrCOOCH3 (addition of HCl or HBr to the added unsaturated compound CH3CH2CH=CHCOOCH3)], [CH3CBr(CH2CH3)COOCH3 (addition of the added unsaturated compound CH2=C(C2H 5) Addition of HBr to COOCH3), [(CH3)2CHCHClCOOCH3, (CH3)2CHCHBrCOOCH3, or (CH3)2CBrCH2COOCH3 (addition of HCl or HBr to the added unsaturated compound (CH3)2C=CHCOOCH)], [CH3CHFCH2OH, CH3CHClCH2OH, CH3CHBrCH2OH, CH2FCH2CH2OH, CH2ClCH2CH2OH, or CH2BrCH2CH2OH (addition of HF, HCl or HBr to the added unsaturated compound CH2=CHCH2OH)], [CH3CH2CHFCH2OH,CH3CH2CHClCH2OH, or CH3CH2CHBrCH2OH (addition of HF, HCl, or HBr to the added unsaturated compound CH3CH2CH=CHOH), [CH3CHFCH2CH2OH, CH3CHClCH2CH2OH, CH3CHBrCH2CH2OH, CH3CH2CFHCH2OH, CH3CH2CClHCH2OH, or CH3CH2CBrHCH2OH (addition of HF, HCl, or HBr to the added unsaturated compound CH3CH=CHCH2OH)], [CH3CHClCH2OCH3, or CH3CHBrCH2OCH3 (addition of HCl or HBr to the added unsaturated compound CH3CH=CHOCH3)], [CH2ClCH2CH2N(CH3)2, or CH2BrCH2CH2N(CH3)2 (addition of HCl or HBr to the added unsaturated compound CH2=CHCH2N(CH3)2)], [CH3CCl2CH2COOC, H3, or CHCl2CH2CH2COOCH3 (addition of HCl to the added unsaturated compound CH≡CCH2COOCH3) These are some examples.

[0119] With the total amount of the composition disclosed herein being 100 mol%, the content of the halogenated alkene compound represented by general formula (1) is 50 to 80 mol%, and can also be 54 to 79 mol%, 58 to 78 mol%, 62 to 77 mol%, 65 to 76 mol%, etc.

[0120] Furthermore, with the total amount of the composition disclosed herein being 100 mol%, the content of the halogenated alkene compound represented by general formula (5) is 12 to 40 mol%, and can also be 13 to 37 mol%, 14 to 34 mol%, 15 to 30 mol%, 16 to 27 mol%, etc.

[0121] Furthermore, with the total amount of the composition disclosed herein being 100 mol%, the content of the halogenated alkene compound represented by general formula (6) is preferably 0.10 to 10.0 mol%, and can 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.

[0122] Furthermore, according to the manufacturing method of this disclosure, even when obtained as a halogenated alkene composition, the halogenated alkene compound represented by general formula (1) can be obtained with a high conversion rate, high yield, and high selectivity as described above. Therefore, it is possible to reduce the amount of components other than the halogenated alkene compound represented by general formula (1) in the composition of this disclosure, thereby reducing the effort required for purification to obtain the halogenated alkene compound represented by general formula (1).

[0123] According to the manufacturing method of this disclosure, even when obtained as a composition containing a halogenated alkene compound represented by general formula (1), the halogenated alkene compound represented by general formula (1) can be obtained with a high conversion rate, high yield, and high selectivity. As a result, it is possible to reduce the amount of components other than the halogenated alkene compound represented by general formula (1) in the composition. According to the manufacturing method of this disclosure, the effort required for purification to obtain the halogenated alkene compound represented by general formula (1) can be reduced.

[0124] Compositions containing the halogenated alkene compounds of this disclosure can be effectively used in various applications, such as cleaning gases, etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, etc., as well as deposit gases, refrigerants, heat transfer media, and building blocks for organic synthesis, just as with halogenated alkene compounds alone.

[0125] The aforementioned deposit gas is a gas used to deposit an etching-resistant polymer layer.

[0126] The aforementioned building blocks for organic synthesis refer to substances that can serve as precursors for compounds having a highly reactive skeleton. For example, by reacting the composition of this disclosure with a fluorine-containing organosilicon compound such as CF3Si(CH3)3, it is possible to introduce fluoroalkyl groups such as CF3 groups and convert the mixture into substances that can serve as detergents or fluorine-containing pharmaceutical intermediates.

[0127] While embodiments of this disclosure have been described above, various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0128] Examples are given below to clarify the features of this disclosure. This disclosure is not limited to these examples.

[0129] In the methods for producing halogenated alkene compounds of Examples 1 to 3, the starting compound is a halogenated alkane compound represented by general formula (2), where R 1 and R 4 R is a trifluoromethyl group, 2 Let R be a fluorine atom. 3 Let be a hydrogen atom and X be a fluorine atom, and the following reaction equation: CF3CFHCFHCF3→ CF3CF=CHCF3+ HF Accordingly, a halogenated alkene compound was obtained by a dehydrofluoride reaction.

[0130] Examples 1-3 and Comparative Example 1 The reaction tube is a SUS pipe (outer diameter: 1 / 2 inch), and the catalyst is an activated carbon catalyst (manufactured by Osaka Gas Chemical Co., Ltd.; specific surface area 1200 m²). 2 10 g of ( / g) was added. After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was set to atmospheric pressure, and CF3CFHCFHCF3 (the raw material compound) was flowed through the reaction tube so that the contact time between CF3CFHCFHCF3 (the raw material compound) and the activated carbon catalyst, W / F [W: weight of catalyst (g), F: flow rate of the raw material compound CF3CFHCFHCF3 (cc / sec)] was 23 g·sec / cc or 47 g·sec / cc. Subsequently, in Examples 1 to 3, 0.01 to 0.20 moles (1 to 20 mol%) of CF3CF=CFCF3 (the raw material compound) was flowed through the tube per mole of CF3CFHCFHCF3 (the raw material compound).

[0131] The reaction was carried out using a continuous gas-phase flow system.

[0132] The reaction tube was heated to 350°C to initiate the dehydrofluoride reaction.

[0133] One hour after the start of the dehydrofluoride reaction, the distillate that passed through the decontamination tower was collected.

[0134] Subsequently, mass spectrometry was performed using gas chromatography (GC / MS) with a gas chromatography apparatus (Shimadzu Corporation, product name "GC-2014"), and structural analysis was performed using NMR spectroscopy (JEOL Corporation, product name "400YH"). From the results of mass spectrometry and structural analysis, it was confirmed that the target compound CF3CF=CHCF3 was formed. The results are shown in Table 3.

[0135] [Table 3]

Claims

1. General formula (1): R １ -CR ２ =CR ３ -R ４ (1) [In the formula, R １ , R ２ , R ３ and R ４ are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a perfluoroalkyl group, or a perchloroalkyl group. However, one of R ２ and R ３ is a hydrogen atom and the other is a fluorine atom or a chlorine atom.] A halogenated alkene compound represented by the following is included in a quantity of 54 to 80 mol%, General formula (5): R １ -CH=CH-R ４ (5) [In the formula, R １ and R ４ These are the same or different atoms, representing a hydrogen atom, a fluorine atom, a chlorine atom, a perfluoroalkyl group, or a perchloroalkyl group. A halogenated alkene compound represented by the following is included in a quantity of 12 to 37 mol%, General formula (6): R ５ -CR ６ R １１ -CR ７ R １２ -R ８ (6) [In the formula, R ５ and R ６ These are identical or different, and represent organic groups. R ７ and R ８ These are identical or distinct, representing a fluorine atom or a perfluoroalkyl group. R １１ R is a halogen atom, １２ This is a hydrogen atom. A halogenated alkane compound represented by [formula] is used in a quantity of 0.10 to 10.0 mol%. It contains, The halogenated alkane compound represented by the general formula (6) is a compound produced by the addition of hydrogen halide to an unsaturated compound in which the energy level of the highest occupied orbital (HOMO) is higher than that of the highest occupied orbital (HOMO) of the halogenated alkene compound represented by the general formula (1). composition.

2. The composition according to claim 1, wherein the organic group is the same or different, 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, an ester group (-COOR), or a carbonyl group (-COR), and R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group.

3. The composition according to claim 1 or 2, which is used as a cleaning gas, etching gas, refrigerant, heat transfer medium, or building block for organic synthesis.

Images