Method for producing halogenated alkene compound and fluorinated alkyne compound

Abstract

To obtain a halogenated alkene compound and a halogenated alkyne compound in high conversion and high selectivity.SOLUTION: Any one of the following methods (1) to (4) is employed: (1) CX1X2X3CHX4CFHCX5X6X7 wherein X1, X2, X3, X4, X5, X6, and X7 are identical or different and are halogen atoms. (2) CX1X2X3CX4 = CHCX5X6X7 [X1, X2, X3, X4, X5, X6, and X7 are as defined above]. (3) CHX8A1CHX9A2 wherein A1 and A2 are each independently a halogen atom or a perfluoroalkyl group. X8 and X9 are identical to or different from each other and each represent a halogen atom; (4) CX8A1 = CHA2 [wherein A1, A2 and X8 are as defined above] is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst. Is subjected to a dehydrohalogenation reaction in the presence of a catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to methods for producing halogenated alkene and fluorinated alkyne compounds. [Background technology]

[0002] As a method for producing a halogenated alkene compound, for example, Patent Document 1 discloses a method for producing a halogenated alkene compound by using CF3CHClCHClCCl3, CF3CCl2CH2CCl3, CF3CClHCHFCCl3, CF3CClFCH2CCl3, or the like as a starting material, followed by the reaction of oxyfluoride with alkene. CF3CF=CHCF3 is obtained by reacting it with hydrogen fluoride in the presence of a fluorinated chromium catalyst and dehydrofluorinating it at the same time. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2012 / 067864 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a method by which halogenated alkene compounds and halogenated alkyne compounds can be obtained with high conversion and high selectivity. [Means for solving the problem]

[0005] The present disclosure encompasses the following configurations. Term 1. General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4, X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butene compound represented by the following formula: General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The production method includes a step of dehydrofluorinating a halogenated butane compound represented by the following formula: Term 2. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the formula: General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4indicates a halogen atom.] a step of dehydrohalogenating a halogenated butene compound represented by the formula: A manufacturing method comprising: Term 3. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the formula: (IA) General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 indicates a halogen atom.] A halogenated butane compound represented by the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] a step of producing a halogenated butene compound represented by the formula: (IIA) a step of removing hydrogen fluoride after the step (IA); and (IIIA) After the step (IIA), the compound of the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The halogenated butene compound represented by the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above.] A process for producing a halogenated butyne compound represented by the formula: A manufacturing method comprising: Item 4. The production method according to any one of Items 1 to 3, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in the presence of a catalyst and / or a base. Item 5. The production method according to any one of Items 1 to 4, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction step is carried out in a liquid phase. Item 6. The production method according to Item 5, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a closed reaction system. Item 7. The production method according to any one of Items 1 to 4, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a gas phase. Item 8. The production method according to Item 7, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst, and a silica-alumina catalyst. Term 9. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. 8 indicates a halogen atom.] A method for producing a halogenated alkene compound represented by the formula: General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. A production method comprising a step of subjecting a halogenated alkane compound represented by the following formula (1) to a dehydrohalogenation reaction in a gas phase in the presence of a catalyst. Section 10. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 is the same as above. X 8 indicates a halogen atom.] A production method comprising a step of subjecting a halogenated alkene compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst. Item 11. The method according to Item 10, wherein the dehydrohalogenation reaction is carried out in a gas phase. Item 12. A compound represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. A halogenated alkane compound represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] a step of producing a halogenated alkene compound represented by the formula: (IIB) a step of removing hydrogen halide after the step (IB), and (IIIB) After the step (IIB), the compound of the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A halogenated alkene compound represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 is the same as above.] A process for producing a fluorinated alkyne compound represented by A manufacturing method comprising: Item 13. The production method according to any one of Items 1 to 12, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a gas-phase continuous flow system. Item 14. The dehydrofluorination reaction and / or the dehydrohalogenation reaction step is Item 14. The production method according to any one of Items 1 to 13, which is carried out in the presence of a cyclic hydrocarbon halide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are substituted with halogen atoms. Section 15. General formula (1A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A composition containing a halogenated butene compound represented by the formula: A composition in which the content of the halogenated butene compound represented by the general formula (1A) is 80.00 to 99.99 mol %, with the total amount of the composition being 100 mol %. Item 16. The composition according to Item 15, wherein the halogenated butene compound represented by the general formula (1A) is an (E)-halogenated butene compound in an amount of 85.00 to 99.98 mol %, based on 100 mol % of the total amount of the composition. Finished product. Section 17. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. 8 indicates a halogen atom.] a halogenated alkene compound represented by the formula: and at least one hydrofluorocarbon (HFC) compound (excluding the halogenated alkene compound represented by the general formula (2B)), composition. Item 18. The composition according to Item 17, wherein the content of the halogenated alkene compound represented by general formula (2B) is 80 mol% or more and the content of the hydrofluorocarbon (HFC) compound is 20 mol% or less, where the total amount of the composition is 100 mol%. Item 19. The hydrofluorocarbon (HFC) compound is hexafluorobutene, hexafluorobutene, At least one selected from the group consisting of trifluorobutane and octafluorobutane. Item 19. The composition according to item 17 or 18. Section 20. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. a fluorinated alkyne compound represented by the formula: and at least one hydrofluorocarbon (HFC) compound (excluding the fluorinated alkyne compound represented by the general formula (3B)), composition. Section 21. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. a halogenated butyne compound represented by the formula: and at least one hydrofluorocarbon (HFC) compound (excluding the halogenated butyne compound represented by the general formula (3A)), composition. Item 22. The content of the fluorinated alkyne compound represented by the general formula (3B) or the halogenated butyne compound represented by the general formula (3A) is 80 mol % or more, based on 100 mol % of the total amount of the composition. Item 20 or 21, wherein the content of the hydrofluorocarbon (HFC) compound is 20 mol% or less. Item 23. The hydrofluorocarbon (HFC) compound is trifluoromethane, difluoromethane, 23. The composition according to any one of items 20 to 22, wherein the fluoromethane is at least one selected from the group consisting of fluoromethane, tetrafluoromethane, and monofluoromethane. Item 24. The composition according to any one of Items 15 to 23, which is used as a cleaning gas, an etching gas, a refrigerant, a heat transfer medium, or a building block for organic synthesis. [Effects of the Invention]

[0006] According to the present disclosure, halogenated alkene compounds and halogenated alkyne compounds can be synthesized with high conversion and high selectivity. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a diagram schematically illustrating a method for producing an alkene (a halogenated butene compound or a halogenated alkene compound) and an alkyne (a halogenated butyne compound or a fluorinated alkyne compound) according to the present disclosure. In FIG. 1, the generated hydrogen fluoride can be separated in a rectification column. [Figure 2]2 is a diagram schematically illustrating a method for producing an alkene (a halogenated butene compound or a halogenated alkene compound) and an alkyne (a halogenated butyne compound or a fluorinated alkyne compound) according to the present disclosure. In FIG. 2, the generated hydrogen halide can be removed using a hydrogen halide remover (removal tower). DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, the term "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of." Furthermore, in this specification, when a numerical range is expressed as "A to B," it means A or more and B or less.

[0009] In the present disclosure, the term "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.

[0010] In the present disclosure, the term "conversion rate" means the ratio (mol %) of the total molar amount of compounds other than the raw material compounds contained in the gas effluent from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor.

[0011] Conventionally, Patent Document 1 discloses that CF3CHClCHClCCl3, CF3CCl2CH2CCl3, CF3CClHCHFCCl3, CF3CClFCH2CCl3, etc. are used as starting materials and reacted with hydrogen fluoride in the presence of a chromium oxyfluoride catalyst. CF3CF=CHCF3 was obtained by dehydrofluorination while fluorinating, but the yield was only 14.8%.

[0012] From the above, the yield of the conventional method was only 14.8%. By using this method, halogenated alkene compounds and halogenated alkyne compounds can be synthesized with a high conversion rate and high selectivity compared to conventional methods.

[0013] 1. Method for producing halogenated butene compounds and halogenated butyne compounds [1-1] Method for producing halogenated butane compounds into halogenated butene compounds The method for producing a halogenated butene compound of the present disclosure includes: General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butene compound represented by the following formula: General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The method includes a step of dehydrofluorinating a halogenated butane compound represented by the following formula:

[0014] According to the present disclosure, by carrying out the dehydrofluorination reaction of the halogenated butane compound represented by the general formula (1A), it is possible to selectively obtain a halogenated butene compound represented by the general formula (2A) in which 1 mole of hydrogen fluoride is eliminated per mole of the halogenated butane compound represented by the general formula (1A), and further, it is possible to continuously obtain a halogenated butene compound represented by the general formula (2A) by further dehydrofluorinating HX 4The hydrogen halide elimination reaction represented by the following formula is unlikely to occur. For example, among the geometric isomers of the halogenated butene compound represented by the general formula (2A), the E isomer is This is because the electron absorption of trihalogenated methyl groups such as CF3 groups can be selectively synthesized. Due to the attraction effect, the carbon at the α-position of the trihalogenated methyl group such as the CF3 group becomes electron deficient, Since halogenated anions such as fluorine anions are difficult to remove, halogenated butenes are produced instead of halogenated butynes. The reason why the E isomer is selectively produced is because the trans configuration is energetically more stable due to the steric hindrance of trihalogenated methyl groups such as the CF3 group.

[0015] (1-1-1) Raw material compound (halogenated butane compound) The halogenated butane compound that can be used as a substrate in the production method of the present disclosure is represented by the general formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. It is a halogenated butane compound represented by the formula:

[0016] In general formula (1A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0017] As the substrate halogenated butane compound, X is particularly preferred from the viewpoint of being able to produce halogenated butene compounds with high conversion, yield and selectivity. 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 In each of the groups, a fluorine atom and a chlorine atom are preferred, and a fluorine atom is more preferred.

[0018] The above X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 may be the same or different.

[0019] Specific examples of halogenated butane compounds that can be used as substrates and satisfy the above conditions include CF3CFHCFHCF3, CCl3CClHCFHCCl3, and CBr3CBrHCFHCBr3. The hydroxybutane compounds can be used alone or in combination of two or more. Such halogenated butane compounds may be known or commercially available products.

[0020] (1-1-2) Dehydrofluorination reaction In the step of dehydrofluorinating a halogenated butane compound according to the present disclosure, for example, in the case of a halogenated butane compound represented by general formula (1A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is more preferably a fluorine atom.

[0021] That is, the following reaction: CF3CFHCFHCF3→ CF3CF=CHCF3+ HF Therefore, the reaction is preferably a dehydrofluorination reaction.

[0022] The step of dehydrofluorinating a halogenated butane compound in the present disclosure can be carried out in a liquid phase or a gas phase, and is preferably carried out in a gas phase from the viewpoint of productivity.

[0023] In the present disclosure, the step of dehydrofluorinating a halogenated butane compound is preferably carried out in the presence of a catalyst and / or a base, from the viewpoint of obtaining the target compound with higher selectivity and higher conversion. More specifically, when a liquid phase reaction is employed, the reaction is preferably carried out in the presence of a base and, if necessary, a catalyst, and when a gas phase reaction is employed, the reaction is preferably carried out in the presence of a catalyst. Details of the catalyst and base in each case will be described later.

[0024] (1-1-2-1) Liquid Phase Reaction When the step of dehydrofluorinating a halogenated butane compound according to the present disclosure is carried out in a liquid phase, the yield of the target compound can be further improved by applying pressure, for example, by using a metal container, thereby increasing the boiling point of the raw material and increasing the liquid component.

[0025] When the step of dehydrofluorinating a halogenated butane compound according to the present disclosure is carried out in a liquid phase, it is preferable to first prepare a solution of the halogenated butane compound represented by the general formula (1A) described above, and then allow the reaction to proceed in the presence of a base.

[0026] solvent As the solvent for the solution of the halogenated butane compound, either water or a non-aqueous solvent can be used. Examples of the non-aqueous solvent include carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate; esters such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, and butyl propionate; ketones such as acetone, ethyl methyl ketone, and diethyl ketone; γ-butyl lactone, γ-valerolactone, tetrahydrofuran, tetrahydropyran, etc. Preferred solvents include ethers such as diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran; nitriles such as acetonitrile, propionitrile, and benzonitrile; amides such as N,N-dimethylform; and sulfones such as dimethyl sulfoxide and sulfolane. The solvent may be any of the above-mentioned water and non-aqueous solvents, or may be a combination of two or more of them. However, it is preferable to use a solvent that has a high boiling point and does not easily decompose the base described below. Specifically, a non-aqueous solvent is preferable, an ether is more preferable, and dibutyl ether is particularly preferable.

[0027] base When the step of dehydrofluorinating a halogenated butane compound according to the present disclosure is carried out in a liquid phase, it is preferably carried out in the presence of a base, as described above.

[0028] As the base, from the viewpoint of the conversion rate of the reaction and the selectivity and yield of the halogenated butene compound, hydroxides or alkoxides of alkali metals or alkaline earth metals are preferred, and alkoxides of alkali metals or alkaline earth metals are more preferred. Specific examples include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium tert-butoxide, etc. Thorium methoxide, potassium tert-butoxide, etc. are preferred. The aqueous solution of hydroxide or alkoxide of alkali metal or alkaline earth metal is preferred, and an aqueous solution of alkoxide of alkali metal or alkaline earth metal is more preferred. Specifically, sodium methoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, The use of such a base allows the target compound to be obtained with higher selectivity and higher conversion.

[0029] The content of the base in the reaction solution is not particularly limited, but is preferably 20 to 60 mass %, more preferably 40 to 55 mass %, based on 100 mass % of the entire reaction solution. By setting the content of the base in the reaction solution within the above range, the target compound can be obtained with higher selectivity and higher conversion.

[0030] catalyst In this step, a catalyst can be used as needed. The catalyst used in this step is preferably a hydrocarbon alkoxide. Examples of hydrocarbon alkoxides include tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, and benzyltriethylammonium fluoride. , benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, benzyltributylammonium fluoride, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium iodide, methyltributylammonium fluoride, methyltributylammonium chloride, methyltributylammonium bromide, methyltributylammonium iodide, methyltrioctylammonium fluoride, methyltrioctylammonium chloride (trade name Aliquat 336), methyltrioctylammonium bromide, methyltrioctylammonium iodide, etc. The catalyst may be used alone or in combination of two or more. By using the catalyst, the target compound can be obtained with higher selectivity and higher conversion.

[0031] Cyclic halocarbon compounds In the present disclosure, the dehydrofluorination reaction of the halogenated butane compound can also be carried out in the presence of a cyclic hydrocarbon halide compound. This cyclic hydrocarbon halide compound refers to a cyclic hydrocarbon halide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound have been substituted with halogen atoms. In other words, it refers to a cyclic hydrocarbon halide compound that is composed only of carbon atoms and halogen atoms and does not contain hydrogen atoms.

[0032] By carrying out the above-mentioned step of dehydrofluorinating a halogenated butane compound in the presence of such a cyclic hydrocarbon halide compound, it is possible to shift the reaction equilibrium toward the product side, and the target halogenated butene compound can be obtained at an even higher conversion and yield.

[0033] The halogen atoms contained in the usable cyclic hydrocarbon halogen compounds include fluorine atoms, chlorine atoms, and the like. Among them, from the viewpoint of reaction efficiency, halogen atoms (X) contained in the halogenated butane compound, which is the raw material compound, can be used. 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 It is preferable that the halogenated butane compound contains the same kind of halogen atoms as (X). 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are not all the same), the cyclic hydrocarbon halide compound preferably contains one or more of the halogen atoms contained in the halogenated butane compound, and it is also preferable that the cyclic hydrocarbon halide compound contains only one of the halogen atoms contained in the halogenated butane compound.

[0034] The number of carbon atoms in the cyclic hydrocarbon halide compound that can be used is not particularly limited. From the viewpoints of the conversion rate, selectivity, and yield of the target halogenated butene compound, the number of carbon atoms in the cyclic hydrocarbon halide compound is preferably 1 to 10, more preferably 2 to 7, and even more preferably 3 to 5.

[0035] The cyclic hydrocarbon halide compound that can be used may be a saturated cyclic hydrocarbon halide compound having no unsaturated bond or an unsaturated cyclic hydrocarbon halide compound having an unsaturated bond, among which saturated cyclic hydrocarbon halide compounds are preferred from the viewpoints of the conversion rate, selectivity, and yield of the target halogenated butene compound.

[0036] From the above, the cyclic hydrocarbon halide compound is preferably a saturated cyclic hydrocarbon halide compound. Such a saturated cyclic hydrocarbon halide compound is represented by the general formula (4):

[0037] [ka]

[0038] [In the formula, A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 are the same or different and are fluorine atoms or represents a fluoroalkyl group.] Preferred are saturated cyclic hydrocarbon halide compounds represented by the following formula:

[0039] In general formula (4), A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10The perfluoroalkyl group represented by the formula (I) is an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. The perfluoroalkyl group may, for example, have 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 Perfluoroalkyl having from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms, and particularly preferably from 1 to 3 carbon atoms. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. The perfluoroalkyl group is preferably a trifluoromethyl group (CF3-) or a pentafluoroethyl group (C2F5-).

[0040] Specific examples of cyclic halocarbon compounds that meet the above conditions include:

[0041] [ka]

[0042] etc.

[0043] In the production method of the present disclosure, when a halogenated butane compound is subjected to a dehydrofluorination reaction in a liquid phase in the presence of a cyclic hydrocarbon halide compound, for example, the cyclic hydrocarbon halide compound may be blown into a solution of the halogenated butane compound in a gaseous state, or a liquid phase (e.g., a liquefied gas) may be introduced.

[0044] In the production method of the present disclosure, when a halogenated butane compound is subjected to a dehydrofluorination reaction in the presence of a cyclic hydrocarbon halide compound, the amount of the cyclic hydrocarbon halide compound used is not particularly limited, and from the viewpoints of the conversion rate, selectivity and yield of the target halogenated butene compound, it is preferable to use an excess amount relative to the halogenated butane compound as a raw material compound. Specifically, the amount is preferably 1 to 20 moles, more preferably 2 to 10 moles, relative to 1 mole of the halogenated butane compound as a raw material compound. is more preferred, and 3 to 5 mol is even more preferred.

[0045] Closed reaction system In the present disclosure, the target compound, a halogenated butene compound represented by general formula (2A), has a low boiling point and exists as a gas at room temperature. Therefore, in the dehydrofluorination reaction step in the present disclosure, by using a sealed reaction system, the pressure in the sealed reaction system naturally increases, and the reaction can be carried out under pressurized conditions. As a result, the target compound, a halogenated butene compound represented by general formula (2A), can be obtained with higher selectivity and higher conversion.

[0046] In this way, due to the low boiling point of the target compound, the closed reaction system is pressurized, increasing the concentration of the substrate (raw material compound) in the reaction solution (base solution), and making it possible to improve reactivity. The closed reaction system is preferably carried out by sealing the reaction system using a batch-type pressure-resistant reaction vessel. When carrying out the reaction in a batch mode, it is preferable to charge the raw material compound, base solution (alkaline aqueous solution), catalyst, etc. into a pressure vessel such as an autoclave, heat the mixture to an appropriate reaction temperature using a heater, and carry out the reaction for a certain period of time while stirring. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen, helium, or carbon dioxide.

[0047] In the dehydrofluorination reaction step of the present disclosure, the reaction temperature in the closed pressure reaction system is generally preferably 0°C or higher, more preferably 10°C or higher, and more preferably 15°C or higher, from the viewpoint of more efficiently progressing the elimination reaction and obtaining the target compound with higher selectivity, and from the viewpoint of suppressing a decrease in conversion rate. The above is even more preferable.

[0048] In the dehydrofluorination reaction step according to the present disclosure, the reaction temperature in the closed reaction system is generally preferably 100°C or lower, and more preferably 80°C or lower, from the viewpoint of more efficiently progressing the dehydrofluorination reaction and obtaining the target compound with higher selectivity, and from the viewpoint of further suppressing a decrease in selectivity due to decomposition or polymerization of the reaction product.

[0049] Pressurized reaction system In the present disclosure, the dehydrofluorination reaction step can also be carried out in a pressurized reaction system by setting the reaction temperature to 10°C or higher and the reaction pressure to 0 kPa or higher. This allows the target compound, the halogenated butene compound represented by general formula (2A), to be obtained with higher selectivity and higher conversion. When the reaction system is pressurized in this manner, the concentration of the substrate (raw material compound) in the reaction solution (base solution, alkaline aqueous solution) increases, making it possible to improve reactivity. The pressurized reaction system is preferably carried out in a sealed batch-type pressure-resistant reaction vessel. When the reaction is carried out in a batch-type system, it is preferable to charge the raw material compound, base solution (alkaline aqueous solution), catalyst, etc. into a pressure vessel such as an autoclave, heat the mixture to an appropriate reaction temperature using a heater, and carry out the reaction for a certain period of time while stirring.

[0050] In the elimination reaction step of the present disclosure, the pressurization conditions preferably include a reaction pressure of 0 kPa or higher. The reaction pressure is the pressure inside a reaction vessel used in a pressurized reaction system. In the dehydrofluorination reaction step of the present disclosure, the reaction pressure is preferably 0 kPa or higher, more preferably 5 kPa or higher, even more preferably 10 kPa or higher, and particularly preferably 15 kPa or higher. There is no particular upper limit to the reaction pressure, and it is usually about 2 MPa. In the present disclosure, pressure refers to gauge pressure unless otherwise specified.

[0051] To increase the pressure, an inert gas such as nitrogen, helium, or carbon dioxide gas can be fed into the reaction system to increase the pressure in the reaction system.

[0052] In the dehydrofluorination reaction step of the present disclosure, the reaction temperature in the pressurized reaction system is generally preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher, from the viewpoint of more efficiently progressing the elimination reaction and obtaining the target compound with higher selectivity, and from the viewpoint of suppressing a decrease in conversion rate. Above is even more preferable.

[0053] In the dehydrofluorination reaction step according to the present disclosure, the reaction temperature in the closed reaction system is generally preferably 100°C or lower, and more preferably 80°C or lower, from the viewpoint of more efficiently progressing the dehydrofluorination reaction and obtaining the target compound with higher selectivity, and from the viewpoint of further suppressing a decrease in selectivity due to decomposition or polymerization of the reaction product.

[0054] Combination of closed and pressurized reaction systems The dehydrofluorination reaction step in the present disclosure can also be carried out in a continuous and pressurized reaction mode while withdrawing a liquid or while gasifying and withdrawing a product, for example, by connecting a back pressure valve to a continuous phase tank reactor (CSTR).

[0055] After the dehydrofluorination reaction is completed, purification treatment can be carried out according to a conventional method, if necessary, to obtain the halogenated cyclobutene compound represented by the general formula (2A).

[0056] (1-1-2-2) Gas-phase reaction When the step of dehydrofluorinating a halogenated butane compound according to the present disclosure is carried out in a gas phase, there is no need to use a solvent, no industrial waste is generated, and there are advantages in that productivity is excellent.

[0057] The step of dehydrofluorinating a halogenated butane compound in the present disclosure is preferably carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. When carried out in a gas phase continuous flow system, the equipment, operation, etc. can be simplified and it is economically advantageous.

[0058] catalyst The step of dehydrofluorinating a halogenated butane compound in the present disclosure is preferably carried out in the presence of a catalyst.

[0059] The catalyst used in the production method of the present disclosure is preferably an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst, a silica-alumina catalyst, etc. These catalysts may be either non-fluorinated or fluorinated.

[0060] As the activated carbon catalyst, there are no particular restrictions, and examples include powdered activated carbon such as crushed carbon, formed carbon, granular carbon, and spherical carbon. For powdered activated carbon, it is preferable to use powdered activated carbon having a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) in the JIS test (JIS Z8801). These activated carbons can employ known or commercially available products.

[0061] Since activated carbon exhibits stronger activity by fluorination, before use in the reaction, fluorinated activated carbon obtained by previously fluorinating activated carbon can also be used as the activated carbon catalyst. That is, as the activated carbon catalyst, either non-fluorinated activated carbon or fluorinated activated carbon can be used.

[0062] As the fluorinating agent for fluorinating activated carbon, for example, in addition to inorganic fluorinating agents such as HF, hydrofluorocarbons (HFCs) such as hexafluoropropene, chlorofluoromethanes such as chlorofluorocarbons (CFCs), and organic fluorinating agents such as hydrochlorofluorocarbons (HCFCs) can also be used.

[0063] Examples of the method for fluorinating activated carbon include a method of fluorinating by flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of about room temperature (25 °C) to 400 °C.

[0064] Regarding the chromium oxide catalyst, there are no particular restrictions. However, when chromium oxide is represented as CrOm, 1.5 < m < 3 is preferable, 2 < m < 2.75 is more preferable, and 2 < m < 2.3 is even more preferable. Also, when chromium oxide is represented as CrO m ·nH2O, it may be hydrated such that the value of n is 3 or less, particularly 1 to 1.5.

[0065] The fluorinated chromium oxide catalyst can be prepared by fluorinating the above-described chromium oxide catalyst. This fluorination can be carried out using, for example, HF, fluorocarbons, etc. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in JP-A-05-146680.

[0066] An example of a method for synthesizing a chromium oxide catalyst and a fluorinated chromium oxide catalyst will be described below.

[0067] First, chromium hydroxide precipitate can be obtained by mixing an aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, etc.) with aqueous ammonia. The physical properties of the chromium hydroxide can be controlled by the reaction rate of the precipitation reaction. A fast reaction rate is preferable. The reaction rate depends on the temperature of the reaction solution, the method of mixing the aqueous ammonia (mixing rate), the stirring condition, etc.

[0068] The precipitate can be filtered, washed, and then dried. Drying can be carried out in air at 70 to 200°C, for example. The catalyst can be pulverized for 1 to 100 hours. The catalyst at this stage is sometimes called a chromium hydroxide state. Next, the catalyst can be crushed. From the viewpoint of pellet strength, catalytic activity, etc., the crushed powder (for example, particle size is 1000 μm or less, and particularly, 95% of the particles have a particle size of 46 to 1000 μm) is It is preferable to adjust the precipitation reaction rate so that the powder density is 0.6 to 1.1 g / ml, preferably 0.6 to 1.0 g / ml. The specific surface area of ​​the powder (specific surface area by the BET method) is, for example, 100 m under degassing conditions at 200°C for 80 minutes. 2 / g or more is preferable, and 120m 2 The upper limit of the specific surface area is, for example, 220 m 2 / g.

[0069] This chromium hydroxide powder can be mixed with 3% by weight or less of graphite, if necessary, and formed into pellets using a tablet press. The size and strength of the pellets can be adjusted as needed.

[0070] The molded catalyst can be calcined in an inert atmosphere, for example, in a nitrogen stream, to form amorphous chromium oxide. The calcination temperature is preferably 360° C. or higher, and from the viewpoint of suppressing crystallization, a temperature of 380 to 460° C. The calcination time can be, for example, 1 to 5 hours.

[0071] The specific surface area of ​​the calcined catalyst is, for example, 170 m 2 / g or more is preferable , 180m 2 / g or more is more preferable, and 200m 2 / g or more is more preferable. , typically 240m 2 / g is preferable, and 220m 2 / g is more preferable.

[0072] The chromium oxide is then fluorinated to obtain fluorinated chromium oxide. The fluorination temperature may be set within a temperature range in which the generated water does not condense, and the upper limit of the temperature may be set to a temperature in which the catalyst does not crystallize due to the heat of reaction. The fluorination temperature may be, for example, 100 to 460°C. There is no limitation on the pressure during fluorination, but it is preferable to carry out the fluorination at the pressure used in the catalytic reaction.

[0073] As the zeolite catalyst, a wide variety of known types of zeolite 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 include A-type, X-type, and LSX-type. The crystalline form of the zeolite is preferably aluminosilicates of alkali metals or alkaline earth metals. The alkaline metal or alkaline earth metal is not particularly limited, and examples thereof include potassium, sodium, calcium, and lithium.

[0074] Zeolite catalysts exhibit stronger activity when fluorinated, and therefore, the zeolite catalyst can be fluorinated before use in the reaction to be used as a fluorinated zeolite catalyst.

[0075] As the fluorinating agent for fluorinating the zeolite catalyst, for example, inorganic fluorinating agents such as F2 and HF, and fluorocarbon organic fluorinating agents such as hexafluoropropene can be used.

[0076] As a method for fluorinating a zeolite catalyst, for example, a method for fluorinating a zeolite catalyst at a temperature of about room temperature (25°C) to about 400°C is used. For example, the fluorination can be carried out by passing the above-mentioned fluorinating agent through the reaction system under atmospheric pressure under high temperature conditions.

[0077] Silica-alumina catalyst is a composite oxide catalyst containing silica (SiO2) and alumina (Al2O3). With the total amount of silica and alumina being 100% by mass, a catalyst having a silica content of, for example, 20 to 90% by mass, particularly 50 to 80% by mass, can be used.

[0078] Since the silica-alumina catalyst exhibits stronger activity when fluorinated, it is also possible to fluorinate the silica-alumina catalyst before use in the reaction and use it as a fluorinated silica-alumina catalyst.

[0079] As the fluorinating agent for fluorinating the silica alumina catalyst, for example, inorganic fluorinating agents such as F2 and HF, and fluorocarbon organic fluorinating agents such as hexafluoropropene can be used.

[0080] The silica-alumina catalyst can be fluorinated, for example, at room temperature (25°C) to about 400°C. The fluorination can be carried out by flowing the above-mentioned fluorinating agent under the temperature condition of 100° C. under atmospheric pressure.

[0081] The above catalysts can be used alone or in combination of two or more. 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, with activated carbon catalysts (activated carbon or fluorinated activated carbon) being more preferred.

[0082] When the above-mentioned chromium oxide catalyst, zeolite catalyst, silica alumina catalyst, etc. are used as the catalyst, they can be supported on a carrier. Examples of such carriers include carbon, alumina (Al2O3), zirconia (ZrO2), silica (SiO2), titania (TiO2), etc. Examples of carbon that can be used include activated carbon, amorphous carbon, graphite, diamond, and the like.

[0083] In the production method of the present disclosure, when a halogenated butane compound is dehydrofluorinated in the gas phase in the presence of a catalyst, it is preferable to contact the catalyst in a solid state (solid phase) with the halogenated butane compound. In this case, the catalyst may be in the form of a powder, but a pellet form is preferred when the catalyst is used in a gas phase continuous flow reaction.

[0084] The specific surface area of ​​the catalyst measured by the BET method (hereinafter sometimes referred to as "BET specific surface area") is usually 10 to 3000 m 2 / g is preferred, and 10 to 2500m 2 / g is more preferable, and 20 to 2000m 2 / g is more preferable, and 30 to 1500m 2 When the BET specific surface area of ​​the catalyst is in this range, Since the density of the catalyst particles is not too small, the halogenated butene compounds can be obtained with higher selectivity, and the conversion rate of the halogenated butane compounds can be further improved.

[0085] Cyclic halocarbon compounds In the present disclosure, the dehydrofluorination reaction of the halogenated butane compound can also be carried out in the presence of a cyclic hydrocarbon halide compound. This cyclic hydrocarbon halide compound refers to a cyclic hydrocarbon halide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound have been substituted with halogen atoms. In other words, it refers to a cyclic hydrocarbon halide compound that is composed only of carbon atoms and halogen atoms and does not contain hydrogen atoms.

[0086] By carrying out the above-mentioned step of dehydrofluorinating a halogenated butane compound in the presence of such a cyclic hydrocarbon halide compound, it is possible to shift the reaction equilibrium toward the product side, and the target halogenated butene compound can be obtained at an even higher conversion and yield.

[0087] Such cyclic hydrocarbon halide compounds are (1-1-2-1) Liquid Phase Reaction The same applies to the preferred examples and amounts used.

[0088] In the production method of the present disclosure, when a halogenated butane compound is subjected to a dehydrofluorination reaction in the gas phase in the presence of a cyclic hydrocarbon halide compound, it is preferable, for example, to contact the cyclic hydrocarbon halide compound with the halogenated butane compound in a gaseous state (gas phase).

[0089] Reaction temperature In the step of dehydrofluorinating a halogenated butane compound in the present disclosure, the reaction temperature is generally set to 230°C or higher from the viewpoint of more efficiently progressing the dehydrofluorination reaction, further improving the conversion rate, and obtaining the target halogenated butene compound with a higher selectivity. Preferably, the reaction temperature is 280°C or higher, more preferably 280°C or higher, and even more preferably 320°C or higher. When activated carbon is used as a catalyst, and when a cyclic hydrocarbon halide compound is not used, the reaction temperature is preferably higher than 400°C in order to more efficiently proceed with the dehydrofluorination reaction. ℃ or higher, more preferably 420℃ or higher. However, when a halogenated butane compound is dehydrofluorinated in the gas phase in the presence of a cyclic hydrocarbon halide compound, the dehydrofluorination reaction can proceed more efficiently, and therefore the reaction temperature can be set to a slightly lower temperature, and is usually preferably 230°C or higher, more preferably 280°C or higher, and even more preferably 320°C or higher.

[0090] In the present disclosure, the reaction temperature for dehydrofluorinating a halogenated butane compound is generally preferably 500°C or lower, from the viewpoint of more efficiently proceeding the dehydrofluorination reaction, further improving the conversion rate, and obtaining the target halogenated butene compound with a higher selectivity. The temperature is preferably 450°C or lower.

[0091] Reaction time In the present disclosure, the reaction time for dehydrofluorinating a halogenated butane compound is, for example, when a gas-phase flow system is employed, the contact time of the raw material compound with the catalyst (W / F) [W: catalyst The reaction conversion rate is particularly high and the halogen From the viewpoint of obtaining halogenated butane compounds in higher yield and higher selectivity, the contact time is preferably 5 to 100 g sec. / cc, more preferably 10 to 90 g sec. / cc, and even more preferably 15 to 80 g sec. / cc. When dehydrofluorinating a halogenated butane compound in a gas phase in the presence of a cyclic hydrocarbon halide compound, the dehydrofluorination reaction can proceed more efficiently, and therefore the lower limit of the contact time can be made smaller, preferably 1 to 100 g sec. / cc, and even more preferably 2 The contact time is preferably 100 to 90 g·sec. / cc, and more preferably 3 to 80 g·sec. / cc. The term "during" refers to the time during which the raw material compound and the catalyst are in contact.

[0092] Reaction pressure The reaction pressure for dehydrofluorinating a halogenated butane compound in the present disclosure is preferably 0 kPa or more, more preferably 10 kPa or more, even more preferably 20 kPa or more, and particularly preferably 30 kPa or more, from the viewpoint of more efficiently proceeding the dehydrofluorination reaction, further improving the conversion rate, and obtaining the target halogenated butene compound with a higher selectivity. There is no particular upper limit to the pressure, and it is usually about 2 MPa. In this disclosure, the pressure is a gauge pressure unless otherwise specified.

[0093] In the dehydrofluorination reaction of a halogenated butane compound according to the present disclosure, the reactor into which the halogenated butane compound, preferably the catalyst and the cyclic hydrocarbon halide compound are introduced and reacted is not particularly limited in shape or structure as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tubular reactor. Examples of the reactor material include glass, stainless steel, iron, nickel, and an iron-nickel alloy.

[0094] Example of dehydrofluorination reaction The dehydrofluorination reaction of a halogenated butane compound in the present disclosure can be carried out by either a flow system or a batch system in which a halogenated butane compound as a raw material compound is continuously charged into a reactor and a halogenated butene compound as a target compound is continuously withdrawn from the reactor. If the halogenated butene compound as a target compound remains in the reactor, the elimination reaction may proceed further, so a flow system is preferred. The step of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in the gas phase, and in particular, preferably by a gas phase continuous flow system using a fixed bed reactor. When carried out by a gas phase continuous flow system, the equipment, operation, etc. can be simplified and it is economically advantageous. When a batch system is used, it is also possible to employ a closed reaction system or a pressurized reaction system as described above for the liquid phase reaction.

[0095] In the present disclosure, the atmosphere in which the dehydrofluorination reaction of the halogenated butane compound is carried out is preferably an inert gas atmosphere, a hydrogen fluoride gas atmosphere, or the like, from the viewpoint of suppressing catalyst deterioration. Examples of the inert gas include nitrogen, helium, and argon. Of these inert gases, nitrogen is preferred from the viewpoint of reducing costs. The concentration of the inert gas is preferably 0 to 50 mol % of the gas components introduced into the reactor.

[0096] After the dehydrofluorination reaction is completed, purification treatment can be carried out according to a conventional method, if necessary, to obtain the halogenated butene compound represented by the general formula (2A).

[0097] (1-1-3) Target compound (halogenated butene compound) The target compound of the present disclosure thus obtained is represented by the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. It is a halogenated butene compound represented by the formula:

[0098] X in general formula (2A) 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 represents X in the above general formula (1A). 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7Therefore, examples of the halogenated butene compound represented by general formula (2A) to be produced include CF3CF=CHCF3, CCl3CCl=CHCCl3, CBr3CBr=CHCBr3, etc. These compounds include both Z and E isomers. Includes.

[0099] The halogenated butene compounds thus obtained can be effectively used in a variety of applications, such as etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, etc., cleaning gases, deposit gases, refrigerants, heat transfer media, building blocks for organic synthesis, etc. Deposit gases and building blocks for organic synthesis will be described later.

[0100] [1-2] A method for producing halogenated butyne compounds from halogenated butene compounds The method for producing a halogenated butyne compound of the present disclosure includes the steps of: General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the formula: General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X4 indicates a halogen atom.] The process includes a step of dehydrohalogenating a halogenated butene compound represented by the following formula:

[0101] According to the present disclosure, by carrying out the dehydrohalogenation reaction of the halogenated butene compound represented by the general formula (2A), it is possible to obtain a compound having a hydrogen peroxide content of 1 mole of the halogenated butene compound represented by the general formula (2A). A halogenated butyne compound represented by general formula (3A) in which 1 mole of hydrogen halide is eliminated. can be selectively obtained.

[0102] (1-2-1) Raw material compound (halogenated butene compound) The halogenated butene compound that can be used as a substrate in the production method of the present disclosure is, as described above, a compound represented by the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. This corresponds to the target compound in the above-described method for producing a halogenated butene compound from a halogenated butane compound [1-1].

[0103] In general formula (2A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 The halogen atoms represented by the formula (I) can be those mentioned above. The preferred types are also the same.

[0104] Specific examples of halogenated butene compounds that can be used as substrates and satisfy the above conditions include CF3CF=CHCF3, CCl3CCl=CHCCl3, and CBr3CBr=CHCBr3. These compounds include both Z- and E-isomers. These halogenated butene compounds can be used alone. These halogenated butene compounds can be used in combination of two or more. Known or commercially available products can be used.

[0105] (1-2-2) Dehydrohalogenation reaction In the step of dehydrohalogenating a halogenated butene compound according to the present disclosure, for example, in the case of a halogenated butene compound represented by general formula (2A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is more preferably a fluorine atom.

[0106] That is, the following reaction: CF3CF=CHCF3→ CF3C≡CCF3+ HF Therefore, the reaction is preferably a dehydrofluorination reaction.

[0107] The step of dehydrohalogenating a halogenated butene compound in the present disclosure can be carried out in a liquid phase or a gas phase, and is preferably carried out in a gas phase from the viewpoint of productivity.

[0108] In the present disclosure, the step of dehydrohalogenating a halogenated butene compound is preferably carried out in the presence of a catalyst and / or a base, from the viewpoint of obtaining the target compound with higher selectivity and higher conversion. More specifically, when a liquid-phase reaction is employed, it is preferably carried out in the presence of a base and, if necessary, a catalyst. When a gas-phase reaction is employed, it is preferably carried out in the presence of a catalyst. Details of the liquid-phase reaction (e.g., solvent, base, catalyst, cyclic hydrocarbon halide compound, conditions for a closed reaction system and a pressurized reaction system) and details of the gas-phase reaction (e.g., catalyst, cyclic hydrocarbon halide compound, reaction temperature, reaction time, reaction pressure) can be those described in the above-mentioned [1-1] Production method from a halogenated butane compound to a halogenated butene compound, except that "a reaction for obtaining a halogenated butene compound by dehydrofluorination of a halogenated butane compound" is read as "a reaction for obtaining a halogenated butyne compound by dehydrohalogenation of a halogenated butene compound." The preferred types and contents are also the same.

[0109] After the dehydrohalogenation reaction is completed, purification treatment may be carried out according to a conventional method, if necessary, to obtain the halogenated butyne compound represented by the general formula (3A).

[0110] (1-2-3) Target compound (halogenated butyne compound) The target compound of the present disclosure thus obtained is represented by the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. It is a halogenated butyne compound represented by the formula:

[0111] X in general formula (3A) 1, X 2 , X 3 , X 5 , X 6 and X 7 represents X in the above general formula (2A). 1 , X 2 , X 3 , X 5 , X 6 and X 7 Therefore, specific examples of the halogenated butyne compound represented by general formula (3A) to be produced include CF3C≡CCF3, CCl3C≡CCCl3, CBr3C≡CCBr3, etc.

[0112] The halogenated butyne compounds thus obtained can be effectively used in a variety of applications, such as etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, etc., cleaning gases, deposit gases, refrigerants, heat transfer media, building blocks for organic synthesis, etc. Deposit gases and building blocks for organic synthesis will be described later.

[0113] [1-3] A method for producing halogenated butyne compounds from halogenated butane compounds via halogenated butene compounds The method for producing a halogenated butyne compound of the present disclosure includes the steps of: General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the formula: (IA) General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 indicates a halogen atom.] A halogenated butane compound represented by the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] a step of producing a halogenated butene compound represented by the formula: (IIA) a step of removing hydrogen fluoride after the step (IA); and (IIIA) After the step (IIA), the compound of the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The halogenated butene compound represented by the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above.] A process for producing a halogenated butyne compound represented by the formula: Includes:

[0114] (1-3-1) Process (IA) In the method for producing a halogenated butyne compound of the present disclosure, the above-described explanation for the method for producing a halogenated butene compound from a [1-1] halogenated butane compound can be adopted as is for step (IA).

[0115] (1-3-2) Process (IIA) The method for producing a halogenated butyne compound of the present disclosure includes a step (IIA) of removing hydrogen fluoride from a mixture containing the halogenated butane compound represented by the general formula (1A) above by dehydrofluorination to produce a halogenated butene compound represented by the general formula (2A) above (step (IA)).

[0116] In the method for producing a halogenated butyne compound according to the present disclosure, after step (IA), hydrogen fluoride produced in the dehydrofluorination reaction of step (IA) is separated and / or removed, and then the process proceeds to the production of a halogenated butyne compound in the next step (IIIA). This enables the production of a halogenated butyne compound, which is the target compound, with a high conversion rate (yield) and high selectivity by dehydrofluorination.

[0117] To remove hydrogen fluoride from the mixture containing the halogenated butene compound and hydrogen fluoride obtained in the step (IA), a method of separating hydrogen fluoride in a rectification column (FIG. 1) or a method of removing hydrogen fluoride using a hydrogen halide remover (removal column) such as an alkali, SEKADO, alumina, or silica (FIG. 2) can be preferably employed.

[0118] In the method for producing a halogenated butyne compound of the present disclosure, it is preferable to reuse the unreacted raw material (such as a halogenated butane compound) separated by rectification. In the method for producing a halogenated butyne compound of the present disclosure, the unreacted halogenated butane compound separated by rectification can be returned (reused) to the reactor and used for dehydrofluorination.

[0119] Method for separating hydrogen fluoride in a rectification column The boiling point of the separated hydrogen fluoride (HF) is 19.54°C.

[0120] To remove hydrogen fluoride from the mixture containing the halogenated butene compound and hydrogen fluoride obtained in step (IA), the mixture is subjected to rectification based on the difference in the boiling points of both compounds. The halogenated butene compound and hydrogen fluoride can be separated in the column, the halogenated butene compound can be recovered, and the hydrogen fluoride can be separated. In the next step (IIIA), in which a halogenated butyne compound is produced, the content of hydrogen fluoride can be reduced, and the target halogenated butyne compound can be produced with a high conversion rate (yield) and high selectivity.

[0121] Method for removing hydrogen fluoride using a hydrogen halide remover The separated hydrogen fluoride can be removed by a hydrogen fluoride remover. As the hydrogen fluoride remover, it is preferable to use an alkali, alumina, silica, zeolite, SEKADO, or the like. SEKADO is a type of hydrogen fluoride remover known as allophane. It is an adsorbent (synthetic zeolite) whose main raw material is a non-crystalline clay mineral (alumina / silica gel) composed of amorphous or hydrated aluminum silicate with low crystallinity.

[0122] To remove hydrogen fluoride from the mixture containing the halogenated butene compound and hydrogen fluoride obtained in step (IA), a hydrogen fluoride remover can be used to remove hydrogen fluoride and recover the halogenated butene compound. In the production of the halogenated butyne compound in the next step (IIIA), the content of hydrogen fluoride can be reduced, and the target halogenated butyne compound can be produced with a high conversion (yield) and high selectivity.

[0123] Hydrogen fluoride concentration In the method for producing a halogenated butyne compound according to the present disclosure, after step (IA), hydrogen fluoride produced by the dehydrofluorination in step (IA) is separated and / or removed, and then the process proceeds to the production of a halogenated butyne compound in the next step (IIIA). This enables the production of the target halogenated butyne compound with a high conversion rate (yield) and high selectivity by dehydrofluorination.

[0124] In the next step (IIIA), a halogenated butene compound represented by the general formula (2A) is used as a raw material. In this step, in addition to the halogenated butene compound represented by the general formula (2A), a mixture containing hydrogen fluoride produced by dehydrofluorination may be carried over to the next step (IIIA).

[0125] In the method for producing a halogenated butyne compound of the present disclosure, in the production of a halogenated butyne compound in the next step (IIIA), the target compound, a halogenated butyne compound, is produced with a high conversion (yield) and high selectivity by dehydrofluorination. In this respect, the content (concentration) of hydrogen fluoride in the composition used as a raw material in the next step (IIIA) is 50 mol% or less, based on the mixture containing the halogenated butene compound represented by general formula (2A) and hydrogen fluoride (100 mol%). Preferably, the content is 20 mol % or less, more preferably 3 mol % or less, and even more preferably 0.1 mol % or less. The following is particularly preferred: When the content of hydrogen fluoride is low in the mixture containing the halogenated butene compound represented by the general formula (2A) and hydrogen fluoride, the target compound, a halogenated butyne compound, can be produced with a high conversion rate (yield) and high selectivity.

[0126] (1-3-3) Process (IIIA) In the method for producing a halogenated butyne compound according to the present disclosure, the above-described explanation for the method for producing a halogenated butyne compound from a [1-2] halogenated butene compound can be adopted as is for step (IIIA).

[0127] (1-3-4) Example of dehydrofluorination In the dehydrofluorination step of the present disclosure, the reaction can be carried out by either a flow system or a batch system in which, in step (IA), a raw material compound (halogenated butane compound) is continuously charged into a reactor and the target compound (halogenated butene compound) is continuously withdrawn from the reactor. Thereafter, hydrogen fluoride is removed from a mixture containing the halogenated butene compound and hydrogen fluoride (step (IIA)). In step (IIIA), the raw material compound (halogenated butane compound) is continuously charged into the reactor. The process can be carried out by either a flow system or a batch system in which a target compound (halogenated butene compound) is continuously charged into the reactor and the target compound (halogenated butyne compound) is continuously withdrawn from the reactor. The flow system is preferred because the target compound (halogenated butene compound or halogenated butyne compound) is not allowed to remain in the reactor in each step, and dehydrofluorination can proceed further.

[0128] In the dehydrofluorination step of the present disclosure, the reaction is carried out in a gas phase, and in particular, it is preferably carried out in a gas phase continuous flow system using a fixed bed reactor. When carried out in a gas phase continuous flow system, the equipment, operation, etc. can be simplified and it is economically advantageous.

[0129] In the dehydrofluorination step of the present disclosure, the reaction is preferably carried out in an atmosphere in the presence of an inert gas in order to prevent deterioration of the catalyst (activated carbon, metal catalyst, etc.). In the present disclosure, at least one inert gas selected from the group consisting of nitrogen, helium, argon, and carbon dioxide can be preferably used. Among these inert gases, However, nitrogen is more preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol % of the gas components introduced into the reactor.

[0130] In the dehydrofluorination step of the present disclosure, after the reaction is completed, purification treatment can be carried out according to a conventional method as described above to obtain the target compound (a halogenated butene compound or a halogenated butyne compound).

[0131] 2. Method for producing halogenated alkene compounds and fluorinated alkyne compounds [2-1] Method for producing halogenated alkene compounds from halogenated alkane compounds The method for producing a halogenated alkene compound of the present disclosure comprises reacting a halogenated alkene compound with a compound represented by general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. 8 indicates a halogen atom.] A method for producing a halogenated alkene compound represented by the formula: General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. The method includes a step of subjecting a halogenated alkane compound represented by the following formula (1) to a dehydrohalogenation reaction in a gas phase in the presence of a catalyst.

[0132] According to the present disclosure, by carrying out a dehydrohalogenation reaction of the halogenated alkane compound represented by the general formula (1B) in the gas phase in the presence of a catalyst, it is possible to selectively obtain a halogenated alkene compound represented by the general formula (2B) in which 1 mole of hydrogen halide is eliminated per mole of the halogenated alkane compound represented by the general formula (1B), and further, it is possible to continuously obtain a halogenated alkene compound represented by the general formula (2B) by further dehydrohalogenating HX 8 The hydrogen halide elimination reaction represented by Furthermore, according to the present disclosure, it is possible to selectively synthesize the E-isomer among the geometric isomers as the halogenated alkene compound represented by general formula (2B). , A 1 and A 2 This is more pronounced when the group is a perfluoroalkyl group, and trihalides such as CF3 groups The electron-withdrawing effect of the halogenated methyl group allows the carbon atom at the α-position of the trihalogenated methyl group, such as the CF3 group, to Since the compound is electron deficient, halogenated anions such as fluorine anions are difficult to remove, making it easier to produce halogenated butenes rather than halogenated butynes. The one is A 1 and A 2 This is more pronounced when the group is a perfluoroalkyl group, and This is because the trans configuration is energetically more stable due to the steric hindrance of the rehalogenated methyl group.

[0133] (2-1-1) Raw material compound (halogenated alkane compound) In the present disclosure, the raw material compound for the method for producing a halogenated alkene compound from a halogenated alkane compound is a compound represented by the general formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group.8 and X 9 are the same or different and represent a halogen atom. It is a halogenated alkane compound represented by the formula:

[0134] In general formula (1B), A 1 and A 2 a perfluoroalkyl group represented by the formula: X 8 and X 9 The halogen atom represented by the formula (I) can be any of those mentioned above. Preferred examples are also the same.

[0135] Examples of halogenated alkane compounds, which are raw material compounds that satisfy these conditions, include CF3CHClCHClCF3(336mdd), CF3CHClCHFCl, CHFClCHFCl, CF3CHFCHFCF3(338mee), CF3CHFCHF2, CHF2CHF2, CF3CHClCHClC2F5, C2F5CHClCHClC2F5, C2F5CHClCHFCl, CF3CHFCHFC2F5, C2F5CHFCHFC2F5, C2F5CHFCHF2, etc. These halogenated alkane compounds can be used alone or in combination of two or more. The alkane nitrate compound may be a known or commercially available product.

[0136] (2-1-2) Dehydrohalogenation reaction In the step of dehydrohalogenating a halogenated alkane compound according to the present disclosure, a halogenated alkene compound can be produced from the halogenated alkane compound with a high conversion rate (yield) and high selectivity. For example, in the case of a halogenated alkane compound represented by general formula (1B) as a substrate, 1 and A 2 are preferably both trifluoromethyl groups (CF3-), and X 8 and X 9 is more preferably a fluorine atom or a chlorine atom.

[0137] That is, the following reaction: CF3CHClCHClCF3(336mdd) → CF3CCl=CHCF3((Z) or (E)-1326mxz) + HCl CF3CHFCHFCF3(338mee) → CF3CF=CHCF3((Z) or (E)-1327myz) + HF Therefore, the reaction is preferably a dehydrofluorination reaction or a dehydrochlorination reaction.

[0138] catalyst In the present disclosure, the dehydrohalogenation reaction from a halogenated alkane compound to a halogenated alkene compound is carried out in the gas phase in the presence of a catalyst.

[0139] The catalyst used in this step is preferably at least one selected from the group consisting of activated carbon and metal catalysts, from the viewpoints of conversion rate, selectivity, and yield.

[0140] When a metal catalyst is used as the catalyst in this step, it is preferably at least one selected from the group consisting of chromium oxide, chromium oxide fluoride, chromium fluoride, aluminum oxide, aluminum oxide fluoride, aluminum fluoride, iron oxide, iron oxide fluoride, iron fluoride, nickel oxide, nickel oxide fluoride, nickel fluoride, magnesium oxide, magnesium oxide fluoride, and magnesium fluoride.

[0141] Among these catalysts, activated carbon, chromium oxide, chromium oxide fluoride, aluminum oxide, aluminum oxide fluoride, and the like are more preferred in that they can react the halogenated alkane compound as the raw material compound in this step with a high conversion rate (yield) and can produce the halogenated alkene compound as the target compound with a high selectivity.

[0142] In this step, when the raw material compound is contacted with the catalyst in the gas phase, it is preferable to contact the catalyst with the raw material compound in a solid state (solid phase).

[0143] In this step, the catalyst may be in powder form, but pellet form is preferred for gas-phase continuous flow reactions.

[0144] The specific surface area of ​​the catalyst measured by the BET method (hereinafter also referred to as BET specific surface area) is usually 10 to 3000 m 2 / g is preferred, and 100 to 2000m 2 / g is more preferable, and 500 to 1500m 2 / g is more preferable, and 1000 to 1300m 2 When the BET specific surface area of ​​the catalyst is in this range, Since the density of the catalyst particles is not too small, the target compound can be obtained with higher selectivity, and the conversion rate of the raw material compound can also be improved.

[0145] When activated carbon is used as a catalyst, it is preferable to use powdered activated carbon such as crushed carbon, shaped carbon, granular carbon, spherical carbon, etc. It is preferable to use powdered activated carbon that has a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) in JIS testing.

[0146] When activated carbon is used as a catalyst, the activated carbon (for example, a specific surface area of ​​1200 m 2 The activated carbon is preferably in the form of either powder or granules (about 1 / g), and more preferably in the form of granules.

[0147] When a metal catalyst is used as the catalyst, it is preferable that the catalyst is supported on a carrier. Examples of the carrier include carbon, alumina (Al2O3), zirconia (ZrO2), silica (SiO2), and titanium. Preferably, titanium (TiO2) or the like can be used. As the carbon, preferably, activated carbon, amorphous carbon, graphite, diamond or the like can be used.

[0148] As an example of the catalyst in the present disclosure, chromium oxide and fluorinated chromium oxide will be described. For chromium oxide, for example, when chromium oxide is represented by Cr2O3·nH2O, the value of n is preferably 3 or less, and more preferably 1 to 1.5. Further, the chromium oxide has a composition formula: CrO m in which m is preferably in the range of 1.5 < m < 3. As the catalyst, fluorinated chromium oxide can be prepared by fluorinating chromium oxide. Examples of fluorination include fluorination with hydrogen fluoride (HF) and fluorination with fluorocarbons and the like.

[0149] Fluorinated chromium oxide as the catalyst can be obtained, for example, according to the method described in Japanese Patent No. 3412165. Fluorinated chromium oxide can be obtained by fluorinating chromium oxide with hydrogen fluoride (HF treatment). The fluorination temperature is preferably, for example, 100°C to 460°C. The fluorination pressure is preferably the pressure when used in the catalytic reaction. In the present disclosure, it is particularly preferable to use a highly fluorinated-chromium oxide catalyst having a high fluorine content. The highly fluorinated-chromium oxide catalyst can be obtained by fluorinating chromium oxide at a higher temperature than usual for a longer time. <​​​​​​​​​​In the present disclosure, the dehydrohalogenation reaction of the halogenated alkane compound can also be carried out in the presence of a cyclic hydrocarbon halide compound. The cyclic hydrocarbon halide compound refers to a cyclic hydrocarbon halide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound have been substituted with halogen atoms. In other words, it refers to a cyclic hydrocarbon halide compound that is composed only of carbon atoms and halogen atoms and does not contain hydrogen atoms.

[0152] By carrying out the above-mentioned step of dehydrohalogenating a halogenated alkane compound in the presence of such a cyclic hydrocarbon halide compound, the target halogenated alkene compound can be obtained with an even higher conversion and yield.

[0153] The cyclic hydrocarbon halide compounds can be those described above, and the preferred specific examples, amounts used, and methods of introduction in the liquid phase reaction and gas phase reaction are also the same.

[0154] Reaction temperature In the dehydrohalogenation reaction step according to the present disclosure, the lower limit of the reaction temperature is usually 50°C, preferably 70°C, and more preferably 100°C, from the viewpoint of more efficiently proceeding the dehydrohalogenation reaction, enabling the target compound (halogenated alkene compound) to be obtained with higher selectivity, and from the viewpoint of suppressing a decrease in the conversion rate from the raw material compound (halogenated alkane compound).

[0155] In the dehydrohalogenation reaction step according to the present disclosure, the upper limit of the reaction temperature is usually 500°C, preferably 450°C, and more preferably 400°C, from the viewpoint of more efficiently proceeding the dehydrohalogenation reaction, enabling the target compound (halogenated alkene compound) to be obtained with higher selectivity, and from the viewpoint of suppressing a decrease in selectivity due to decomposition or polymerization of the reaction product.

[0156] Reaction time In the dehydrohalogenation reaction step of the present disclosure, the conversion rate of the raw material compound can be increased by extending the reaction time (W / F0) of the raw material compound to the catalyst [W: weight of catalyst (g), F0: flow rate of the raw material compound (cc / sec)], but this increases the amount of catalyst, leading to larger equipment and inefficiency.

[0157] Therefore, in the dehydrohalogenation reaction step according to the present disclosure, the reaction time is preferably 0.1 to 200 g sec / cc, and more preferably 0.2 to 150 g sec / cc, in terms of improving the conversion rate of the raw material compound (halogenated alkane compound) and reducing equipment costs, in terms of the contact time (W / F0) of the raw material compound (halogenated alkane compound) with the catalyst. It is more preferable that the viscosity is 0.4 to 100 g·sec / cc, and particularly preferable that the viscosity is 0.5 to 50 g·sec / cc. Preferred.

[0158] The contact time of the raw material compound with the catalyst means the time during which the raw material compound and the catalyst are in contact with each other.

[0159] In the dehydrohalogenation reaction of the present disclosure, when the reaction is carried out in a gas phase in the presence of a catalyst, the target compound (halogenated alkene compound) can be obtained with higher selectivity by appropriately adjusting the reaction temperature and reaction time (contact time) particularly in accordance with the catalyst.

[0160] In the dehydrohalogenation reaction of the present disclosure, when chromium oxide is used as the catalyst, the reaction temperature is preferably 300°C or higher, more preferably 350°C or higher, and the contact time is preferably 10 g sec / cc or higher, more preferably 20 g sec / cc or higher, and even more preferably 40 g sec / cc or higher.

[0161] In the dehydrohalogenation reaction of the present disclosure, when alumina is used as the catalyst, the reaction temperature is preferably 300°C or higher, and the contact time is preferably 5 g·sec / cc or higher.

[0162] In the dehydrohalogenation reaction of the present disclosure, when activated carbon is used as a catalyst, the reaction temperature The temperature is preferably 50 to 600°C, more preferably 100 to 400°C. The contact time is preferably 0.2 to 100 g·sec / cc, more preferably 0.3 to 50 g·sec / cc. It is more preferable that the viscosity is 0.5 to 43 g·sec / cc, and even more preferable that the viscosity is 0.5 to 43 g·sec / cc.

[0163] Reaction pressure In the dehydrohalogenation reaction step according to the present disclosure, the reaction pressure is preferably -0.05 to 2 MPa, more preferably -0.01 to 1 MPa, and even more preferably atmospheric pressure to 0.5 MPa, in order to allow the dehydrohalogenation reaction to proceed more efficiently. In the present disclosure, the pressure is referred to as gauge pressure unless otherwise specified.

[0164] In the dehydrohalogenation reaction step of the present disclosure, the reactor in which the raw material compound (halogenated alkane compound) is brought into contact with the catalyst (activated carbon, metal catalyst, etc.) for reaction is not particularly limited in shape or structure as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tubular reactor. Examples of the reactor material include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0165] Example of dehydrohalogenation reaction The dehydrohalogenation reaction step in the present disclosure can be carried out by either a flow system or a batch system, in which a raw material compound (halogenated alkane compound) is continuously charged into a reactor and a target compound (halogenated alkene compound) is continuously withdrawn from the reactor. The flow system is preferred because the target compound (halogenated alkene compound) does not remain in the reactor and the dehydrohalogenation reaction can further proceed.

[0166] The dehydrohalogenation reaction step in the present disclosure is preferably carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. When carried out in a gas phase continuous flow system, the equipment, operation, etc. can be simplified and it is economically advantageous.

[0167] In the dehydrohalogenation reaction step of the present disclosure, the reaction is preferably carried out in an atmosphere in the presence of an inert gas in order to prevent deterioration of the catalyst (activated carbon, metal catalyst, etc.). In the present disclosure, at least one inert gas selected from the group consisting of nitrogen, helium, argon, and carbon dioxide can be preferably used. Among the gases, nitrogen is more preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol % of the gas components introduced into the reactor.

[0168] In the dehydrohalogenation reaction step of the present disclosure, after completion of the reaction, purification treatment can be carried out according to a conventional method as necessary to obtain the target compound, the halogenated alkene compound represented by general formula (2B).

[0169] (2-1-3) Target compound (halogenated alkene compound) The target compound of the present disclosure thus obtained is represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. 8 indicates a halogen atom.] It is a halogenated alkene compound represented by the formula:

[0170] A in general formula (2B) 1 , A 2 and X 8 represents A in the above general formula (1B). 1 , A 2 and X 8Therefore, specific examples of the halogenated alkene compound represented by general formula (2B) to be produced include CFCCl=CHCF((Z) or (E)-1326mxz), CFCCl=CHF, CFCl=CHF, CFCF=CHCF((Z) or (E)-1327myz), CFCF=CHF, CF=CHF, CFCCl=CHC2F5, C2F5CCl=CHC2F5, C2F5CCl=CHF, CF3CF=CHC2F5, C2F5CF=CHC2F5, C2F5CF=CHC2F5, C2F5CF=CHF, and the like. These compounds include both Z and E forms.

[0171] The halogenated alkene compounds thus obtained can be effectively used in a variety of applications, such as etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, etc., cleaning gases, deposit gases, refrigerants, heat transfer media, building blocks for organic synthesis, etc. Deposit gases and building blocks for organic synthesis will be described later.

[0172] [2-2] Method for producing fluorinated alkyne compounds from halogenated alkene compounds The method for producing a halogenated alkyne compound of the present disclosure comprises reacting a compound of general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 is the same as above. X 8 indicates a halogen atom.] The method includes a step of subjecting a halogenated alkene compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst.

[0173] (2-2-1) Raw material compound (halogenated alkene compound) The halogenated alkene compound that can be used as a substrate in the production method of the present disclosure is, as described above, a halogenated alkene compound represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. 8 indicates a halogen atom.] This corresponds to the target compound in the above-mentioned method for producing a halogenated alkene compound from a halogenated alkane compound [2-1].

[0174] In general formula (2B), A 1 and A 2 a perfluoroalkyl group represented by the formula: X 8 The halogen atoms represented by the formula (I) can be those mentioned above. The preferred types are also the same.

[0175] Specific examples of halogenated alkene compounds that can be used as substrates satisfying the above conditions include CF3CCl=CHCF3((Z) or (E)-1326mxz), CF3CCl=CHF, CFCl=CHF, CF3CF=CHCF3((Z) or (E)-1327myz), CF3CF=CHF, CF2=CHF, CF3CCl=CHC2F5, C2F5CCl=CHC2F5, C2F5CCl=CHF CF3CF=CHC2F5, C2F5CF=CHC2F5, C2F5CF=CHF, etc. These compounds include both Z- and E-isomers. These halogenated alkene compounds may be used alone or Such halogenated alkene compounds can be used in combination of two or more. Known or commercially available products can be used.

[0176] (2-2-2) Dehydrohalogenation reaction In the step of dehydrohalogenating a halogenated alkene compound according to the present disclosure, a fluorinated alkyne compound can be produced from the halogenated alkene compound with a high conversion rate (yield) and high selectivity. For example, in the case of a halogenated alkene compound represented by general formula (2B) as a substrate, 1 and A 2 are preferably both trifluoromethyl groups (CF3-), and X 8 is more preferably a fluorine atom or a chlorine atom.

[0177] That is, the following reaction: CF3CCl=CHCF3((Z) or (E)-1326mxz) → CF3C≡CCF3(PF2B) + HCl CF3CF=CHCF3((Z) or (E)-1327myz) → CF3C≡CCF3(PF2B) + HF Therefore, the reaction is preferably a dehydrofluorination reaction or a dehydrochlorination reaction.

[0178] The step of dehydrofluorinating a halogenated butane compound in the present disclosure can be carried out in a liquid phase or a gas phase, and is preferably carried out in a gas phase from the viewpoint of productivity.

[0179] In the present disclosure, the step of dehydrohalogenating a halogenated alkene compound is preferably carried out in the presence of a catalyst and / or a base, from the viewpoint of obtaining the target compound with higher selectivity and higher conversion. More specifically, when a liquid-phase reaction is employed, the reaction is preferably carried out in the presence of a base and, if necessary, a catalyst. When a gas-phase reaction is employed, the reaction is preferably carried out in the presence of a catalyst. Note that, with regard to details of the liquid-phase reaction (e.g., solvent, base, catalyst, cyclic hydrocarbon halide compound, conditions for a closed reaction system and a pressurized reaction system), those described above in the section [1-1] Production method from a halogenated butane compound to a halogenated butene compound can be adopted, except that "a reaction for obtaining a halogenated butene compound by dehydrofluorination of a halogenated butane compound" is read as "a reaction for obtaining a fluorinated alkyne compound by dehydrohalogenation of a halogenated alkene compound." In addition, details of the gas-phase reaction (catalyst, cyclic hydrocarbon halide compound, reaction temperature, reaction time, reaction pressure, etc.) can be the same as those explained in the above [2-1] Production method from a halogenated alkane compound to a halogenated alkene compound, except that "a reaction to obtain a halogenated alkene compound by a dehydrohalogenation reaction from a halogenated alkane compound" is read as "a reaction to obtain a fluorinated alkyne compound by a dehydrohalogenation reaction from a halogenated alkene compound." The preferred types and contents are also the same.

[0180] After the dehydrohalogenation reaction is completed, purification treatment can be carried out according to a conventional method, if necessary, to obtain the fluorobutyne compound represented by the general formula (3B).

[0181] (2-2-3) Target compound (fluorinated butyne compound) The target compound of the present disclosure thus obtained is represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. It is a fluorinated butyne compound represented by the formula:

[0182] A in general formula (3B) 1 and A 2 represents A in the above general formula (2B). 1 and A 2 Therefore, the fluorinated butyne compound represented by the general formula (3B) to be produced can be, for example, specifically, CF3C≡CCF3(PF2B), CF3C≡CF, CF≡CF, CF3C≡CC2F5, C2F5C≡CC2F5 , C2F5C≡CF, etc.

[0183] The fluorobutyne compounds thus obtained can be effectively used in a variety of applications, such as etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, etc., cleaning gases, deposit gases, refrigerants, heat transfer media, building blocks for organic synthesis, etc. Deposit gases and building blocks for organic synthesis will be described later.

[0184] [2-3] A method for producing a fluorinated alkyne compound from a halogenated alkane compound via a halogenated alkene compound The method for producing a fluorinated alkyne compound of the present disclosure includes the steps of: General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. A halogenated alkane compound represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] a step of producing a halogenated alkene compound represented by the formula: (IIB) a step of removing hydrogen halide after the step (IB), and (IIIB) After the step (IIB), the compound of the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A halogenated alkene compound represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 is the same as above.] A process for producing a fluorinated alkyne compound represented by Includes:

[0185] (2-3-1) Process (IB) In the method for producing a fluorinated butyne compound of the present disclosure, the above-mentioned explanation for the method for producing a halogenated alkene compound from a halogenated alkane compound [2-1] can be adopted as is for step (IB).

[0186] (2-3-2) Process (IIB) The method for producing a fluorinated alkyne compound of the present disclosure includes a step (IIB) of removing hydrogen halide from a mixture containing the halogenated alkane compound represented by the general formula (1B) to produce a halogenated alkene compound represented by the general formula (2B) (step (IB)).

[0187] In the method for producing a fluorinated alkyne compound according to the present disclosure, after step (IB), the hydrogen halide produced in the dehydrohalogenation reaction of step (IB) is separated and / or removed, and then the process proceeds to the production of a fluorinated alkyne compound in the next step (IIIB). As a result, the target compound, a fluorinated alkyne compound, can be produced by the dehydrohalogenation reaction with a high conversion rate (yield) and high selectivity.

[0188] Regarding the method for removing hydrogen halide from the mixture containing the halogenated alkene compound and hydrogen halide obtained in step (IB), in the explanation of step (IIA) of (1-3-2) in the above-mentioned method for producing a halogenated butane compound via a halogenated butene compound, instead of separating hydrogen fluoride, hydrogen halide is removed. It can be adopted as is, except that it is read so as to be separated.

[0189] (2-3-3) Process (IIIB) In the method for producing a fluorinated alkyne compound according to the present disclosure, the above-described method for producing a fluorinated alkyne compound from a [2-2] halogenated alkene compound can be directly adopted for step (IIIB).

[0190] (2-3-4) Example of dehydrohalogenation reaction In the dehydrohalogenation reaction step of the present disclosure, the reaction is carried out by adding, in step (IB), The reaction can be carried out by either a flow system or a batch system, in which a raw material compound (halogenated alkane compound) is continuously charged into the reactor and the target compound (halogenated alkene compound) is continuously withdrawn from the reactor. Thereafter, hydrogen halide is removed from the mixture containing the halogenated alkene compound and hydrogen halide (step (IIB)). In step (IIIB), the target compound is extracted from the reactor. The process can be carried out by either a flow system or a batch system, in which a raw material compound (halogenated alkene compound) is continuously charged into the reactor and the target compound (fluorinated alkyne compound) is continuously withdrawn from the reactor. The flow system is preferred because the target compound (halogenated alkene compound or fluorinated alkyne compound) is not allowed to remain in the reactor in each step, and the dehydrohalogenation reaction can proceed further.

[0191] In the dehydrohalogenation reaction step of the present disclosure, the reaction is carried out in a gas phase, and in particular, it is preferably carried out in a gas phase continuous flow system using a fixed bed reactor. When carried out in a gas phase continuous flow system, the equipment, operation, etc. can be simplified and it is economically advantageous.

[0192] In the dehydrohalogenation reaction step of the present disclosure, the reaction is preferably carried out in an atmosphere in the presence of an inert gas in order to prevent deterioration of the catalyst (activated carbon, metal catalyst, etc.). In the present disclosure, at least one inert gas selected from the group consisting of nitrogen, helium, argon, and carbon dioxide can be preferably used. Among the gases, nitrogen is more preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol % of the gas components introduced into the reactor.

[0193] In the dehydrohalogenation reaction step of the present disclosure, after completion of the reaction, purification treatment can be carried out according to a conventional method as described above to obtain the target compound (halogenated alkene compound or fluorinated alkyne compound).

[0194] 3. Composition In the manner described above, a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound or a fluorinated alkyne compound can be obtained, and the compound may also be obtained in the form of a composition containing the target compound.

[0195] [3-1] Composition containing a halogenated butene compound or a halogenated alkene compound According to the production method of the present disclosure, for example, when the above-mentioned [1-1] method for producing a halogenated butene compound from a halogenated butane compound is followed, for example, a halogenated butene compound represented by general formula (2A) may be obtained as a composition containing both E- and Z-isomers. In addition, this composition may be obtained as a composition containing a halogenated butene compound represented by general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above.] and halogenated butyne compounds represented by the formula: General formula (4): CX 1 X 2 =CX 4 CF=CX 5 X 6 (4) [where, X 1 , X 2 , X 4 , X 5 and X 6 is the same as above.] The halogenated butadiene compound may also be included.

[0196] In the general formulae (2A), (3A) and (4), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7is shown by Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom and a chlorine atom being preferred, and a fluorine atom being more preferred.

[0197] With the total amount of the composition of the present disclosure taken as 100 mol %, the content of the halogenated butene compound represented by general formula (2A) is preferably 80.00 to 99.99 mol %, more preferably 90.00 to 99.98 mol %, and more preferably 92.00 to 99.97 mol %. In addition, the content of the halogenated butyne compound represented by general formula (3A) is preferably 80.00 to 99.99 mol %, more preferably 90.00 to 99.98 mol %, and more preferably 92.00 to 99.97 mol %. The content of the halogenated butadiene compound represented by the general formula (4) is preferably 0.00 to 3.00 mol %, more preferably 0.01 to 2.00 mol %, but can be 1.00 to 10.00 mol % (particularly 2.00 to 8.00 mol %) depending on the synthesis conditions. The content of the halogenated butadiene compound represented by the general formula (4) is preferably 0.00 to 0.50 mol %, more preferably 0.01 to 2.00 mol %. It is more preferable that the content is from 0.30 mol % to 1.00 mol %. When the halogenated butene compound represented by the general formula (2A) contains both the E-isomer and the Z-isomer, the above content is the total amount thereof.

[0198] According to the production method of the present disclosure, the E-isomer of the halogenated butene compound represented by general formula (2A) can be selectively synthesized. The content of the (Z)-halogenated butene compound is preferably 85.00 to 99.98 mol % (particularly 86.00 to 99.00 mol %), and the content of the (Z)-halogenated butene compound is preferably 0.01 to 15.00 mol % (particularly 1.00 to 14.00 mol %).

[0199] According to the production method of the present disclosure, even when a halogenated butene composition is obtained, the halogenated butene compound represented by general formula (2A) can be obtained with a high reaction conversion rate, high yield, and high selectivity as described above. This makes it possible to reduce the amount of components other than the halogenated butene compound represented by general formula (2A) in the halogenated butene composition, thereby reducing the effort required for purification to obtain the halogenated butene compound represented by general formula (2A).

[0200] On the other hand, in the case of the method for producing a halogenated alkene compound from a halogenated alkane compound [2-1], for example, a composition containing a halogenated alkene compound represented by general formula (2B) and at least one additional compound consisting of at least one hydrofluorocarbon (HFC) compound (excluding the halogenated alkene compound represented by the general formula (2B)) can be generated.

[0201] The additional compound is preferably at least one selected from the group consisting of hexafluorobutene, hexafluorobutane, and octafluorobutane.

[0202] Specifically, in the method of producing a halogenated alkene compound from a halogenated alkane compound of the present disclosure, 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (1326mxz) is produced as the target product. When obtained, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)) is produced. It is possible.

[0203] In the composition containing the halogenated alkene compound represented by general formula (2B) of the present disclosure, the content of the halogenated alkene compound represented by general formula (2B) is preferably 80 mol% or more and the content of the additional compound is preferably 20 mol% or less, based on 100 mol% of the total amount of the composition. In the composition containing the halogenated alkene compound represented by general formula (2B) of the present disclosure, the content of the halogenated alkene compound represented by general formula (2B) is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more, based on 100 mol% of the total amount of the composition. In a composition containing an alkene compound, the content of the halogenated alkene compound represented by general formula (2B) is preferably 80 to 99.9 mol%, more preferably 85 to 99.9 mol%, even more preferably 90 to 99.9 mol%, and particularly preferably 95 to 99.9 mol%, relative to the total amount of the composition (100 mol%).

[0204] [3-2] Composition containing a halogenated butyne compound or a fluorinated alkyne compound According to the production method of the present disclosure, for example, when the above-described [2-2] method for producing a fluorinated alkyne compound from a halogenated alkene compound is followed, for example, a fluorinated alkyne compound represented by the general formula (3B) and at least one hydrofluorocarbon (HFC) compound (excluding the fluorinated alkyne compound represented by the general formula (3B)) can be produced. [1-2] When the method for producing a halogenated butyne compound from a halogenated butene compound is followed, the resulting composition contains a compound represented by the general formula (3A) and a hydrofluorocarbon (HFC) compound (the above At least one additional compound consisting of (excluding halogenated butyne compounds represented by general formula (3A) A composition containing the additive compound can be produced.

[0205] The additional compound is preferably at least one selected from the group consisting of trifluoromethane, difluoromethane, tetrafluoromethane, and monofluoromethane. stomach.

[0206] In the production method of the present disclosure for obtaining a halogenated butyne compound from a halogenated butene compound or for obtaining a fluorinated alkyne compound from a halogenated alkene compound, trifluoromethane (HFC-23, R23) may be produced when obtaining 1,1,1,4,4,4-hexafluoro-2-butyne (PF2B) as the target product.

[0207] In the composition according to the present disclosure containing a halogenated butyne compound or a fluorinated alkyne compound, the content of the halogenated butyne compound or the fluorinated alkyne compound is preferably 80 mol% or more and the content of the additional compound is preferably 20 mol% or less, based on 100 mol% of the total amount of the composition. In the composition according to the present disclosure containing a halogenated butyne compound or a fluorinated alkyne compound, the content of the halogenated butyne compound or the fluorinated alkyne compound is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more, based on 100 mol% of the total amount of the composition. In the composition containing a halogenated butyne compound or a fluorinated alkyne compound according to the present disclosure, the content of the halogenated butyne compound or the fluorinated alkyne compound is preferably 80 to 99.9 mol%, more preferably 85 to 99.9 mol%, even more preferably 90 to 99.9 mol%, and particularly preferably 95 to 99.9 mol%, where the total amount of the composition is 100 mol%.

[0208] [3-3] Use of a composition containing a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound, or a fluorinated alkyne compound According to the production method of the present disclosure, even when a composition containing a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound, or a fluorinated alkyne compound is obtained, the halogenated butene compound, the halogenated butyne compound, the halogenated alkene compound, or the fluorinated alkyne compound can be obtained with particularly high selectivity, and as a result, it is possible to reduce the amount of components other than the halogenated butene compound, the halogenated butyne compound, the halogenated alkene compound, and the fluorinated alkyne compound in the composition. According to the production method of the present disclosure, the purification effort required to obtain the halogenated butene compound, the halogenated butyne compound, the halogenated alkene compound, or the fluorinated alkyne compound can be reduced.

[0209] Compositions containing the halogenated butene compounds, halogenated butyne compounds, halogenated alkene compounds, or fluorinated alkyne compounds of the present disclosure can be effectively used in a variety of applications, such as etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, and the like, as well as cleaning gases, deposit gases, refrigerants, heat transfer media, and building blocks for organic synthesis, just like the halogenated butene compounds, halogenated butyne compounds, halogenated alkene compounds, or fluorinated alkyne compounds used alone.

[0210] The deposition gas is a gas that deposits an etch-resistant polymer layer.

[0211] The building block for organic synthesis refers to a substance that can be a precursor of a compound having a highly reactive skeleton. For example, the composition of the present disclosure and a fluorine-containing organic ketone such as CF3Si(CH3)3 can be used. When reacted with an isopropyl compound, fluoroalkyl groups such as CF3 groups are introduced, making it suitable for use in cleaning agents and fluorine-containing It is possible to convert them into substances that can be used as pharmaceutical intermediates.

[0212] Although the embodiments of the present disclosure have been described above, it is understood that the present disclosure will not deviate from the spirit and scope of the claims. Various modifications of form and details are possible without departing from the spirit and scope of the invention. [Example]

[0213] Examples will be given below to clarify the features of the present disclosure, but the present disclosure is not limited to these examples.

[0214] In the methods for producing a halogenated butene compound in Examples 1 to 7, the raw material compound is a halogenated butane compound represented by the general formula (1A), wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is a fluorine atom, and the reaction is as follows: CF3CFHCFHCF3→ CF3CF=CHCF3+ HF According to the procedure described above, a halogenated butene compound was obtained by dehydrofluorination reaction.

[0215] In the method for producing a halogenated alkene compound and a fluorobutyne compound in Example 8, The compound is a halogenated alkane compound represented by general formula (1B), wherein X 8 and X 9 is a chlorine atom, and A 1 and A 2 is a trifluoromethyl group, and the following reaction: CF3CHClCHClCF3(336mdd) → CF3CCl=CHCF3((Z) or (E)-1326mxz) + HCl CF3CCl=CHCF3((Z) or (E)-1326mxz) → CF3C≡CCF3(PF2B) + HCl According to the procedure described above, a halogenated alkene compound and a fluorinated butyne compound were obtained by dehydrochlorination reaction.

[0216] In the methods for producing halogenated alkene compounds and fluorobutyne compounds in Examples 9 to 20, raw materials The starting compound is a halogenated alkane compound represented by the general formula (1B), wherein X 8 and X 9 is a fluorine atom, and A 1 and A 2 is a trifluoromethyl group, and the following reaction: CF3CHFCHFCF3(338mee) → CF3CF=CHCF3((Z) or (E)-1327myz) + HF CF3CF=CHCF3((Z) or (E)-1327myz) → CF3C≡CCF3(PF2B) + HF According to the above, a halogenated alkene compound and a fluorinated butyne compound were obtained by dehydrofluorination reaction.

[0217] Examples 1 to 3: Liquid Phase Reaction An autoclave (200 cc) was used as the reaction system.

[0218] By using an autoclave as a reaction system, this reaction system can be carried out in the following manner: (1) in the presence of a base (2) a closed reaction system, (3) a reaction temperature of 10°C or higher, and a reaction pressure of 0 kPa or higher, This represents an embodiment in which the reaction system is pressurized in the presence of a base. When pressurizing in this manner, the system is sealed.

[0219] 7.0 g of a 50% by mass aqueous solution of KOH or potassium tert-butoxide (t-BuOK) was added to the autoclave as a reaction solution, and methyltrioctylammonium chloride was added as a catalyst as needed. Add 0.28 g of Aliquat 336 (trade name), then add 8.0 g of the raw material compound (CF3CFHCFHCF3), and cover. After making the system airtight, nitrogen was pumped in under pressure. The pressure at that time was 20 kPa. After this, the mixture was stirred at room temperature (25°C) to allow the reaction to proceed. After the dehydrofluorination reaction started, sampling was carried out as appropriate, and the reaction was deemed to have ended when there was no longer any change in the composition of the reaction system. The pressure at the end of the reaction was 80 kPa.

[0220] After stopping the stirring, the mixture was cooled to 0°C and analyzed by gas chromatography (Shimadzu Corporation, product name: Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS) using a GC-2014 Then, structural analysis was performed using NMR (JEOL, product name "400YH") Mass spectrometry and structural analysis revealed that the target compound was CF3CF=CHCF3. The results are shown in Table 1.

[0221] Examples 4 to 6: Gas Phase Reaction (Activated Carbon) The reaction tube was a stainless steel pipe (outer diameter: 1 / 2 inch) and an activated carbon catalyst (Osaka Gas Chemicals Co., Ltd.; specific surface area: 1200 m) was used as a catalyst. 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, The pressure was kept at atmospheric pressure, and the contact time (W / F) between CF3CFHCFHCF3 (raw material compound) and the activated carbon catalyst was set to 15 g·sec / cc, 30 g·sec / cc, or 47 g·sec / cc. goods) were circulated.

[0222] The reaction was carried out in a gas phase continuous flow system.

[0223] The reaction tube was heated to 450°C to initiate the dehydrofluorination reaction.

[0224] One hour after the start of the dehydrofluorination reaction, the distillate that had passed through the detoxification tower was collected.

[0225] Then, using a gas chromatograph (Shimadzu Corporation, product name "GC-2014") Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL) The structural analysis was carried out by NMR spectroscopy using a fluorine-containing ... Shown in Table 1.

[0226] Example 7: Gas Phase Reaction (Chromium Oxide Catalyst) The reaction was carried out in the same manner as in Examples 4 to 6, except that a chromium oxide catalyst (Cr2O3) was used as the catalyst, the reaction temperature was 350°C, and the contact time (W / F) between CF3CFHCFHCF3 (the raw material compound) and the chromium oxide catalyst was 47 g·sec / cc. Mass spectrometry and structural analysis confirmed that the target compound, CF3CF=CHCF3, was produced. The results are shown in Table 1.

[0227] [Table 1]

[0228] Example 8 (Dehydrochlorination) 336mdd(CF 3 CHClCHClCF 3 ) → 1326mxz(CF 3 CCl=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) (1)336mdd(CF 3 CHClCHClCF 3 ) → 1326mxz(CF 3 CCl=CHCF 3 ) The reaction tube was made of stainless steel pipe (outer diameter: 1 / 2 inch), and the reaction tube was filled with activated carbon catalyst (specific surface area: 1200 m 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to normal pressure. CF3CHClCHClCF3 (raw material compound) was passed through the reactor so that the contact time (W / F0) between CF3CHClCHClCF3 (raw material compound) and the activated carbon catalyst was 5 g·sec / cc or 25 g·sec / cc.

[0229] The reaction was carried out in a continuous gas flow mode.

[0230] The reactor was heated to 300°C or 400°C to initiate dehydrochlorination.

[0231] (2) Removal of hydrogen chloride One hour after the start of dehydrochlorination, the distillate that had passed through the detoxification tower was collected.

[0232] Then, using a gas chromatograph (Shimadzu Corporation, product name "GC-2014") Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL) Structural analysis was carried out by NMR spectroscopy using a compound of formula (II) manufactured by Epson Corporation, trade name "400YH".

[0233] Mass spectrometry and structural analysis confirmed that the target compound, a halogenated alkene compound (1326mxz:CF3CCl=CHCF3), was produced.

[0234] Furthermore, in the above-mentioned method for producing a halogenated alkene compound from a halogenated alkane compound, in addition to the target product 1326mxz (CF3CCl=CHCF3), (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)) was also produced.

[0235] [Table 2]

[0236] (3) 1326mxz(CF 3 CCl=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) The reaction tube was made of stainless steel pipe (outer diameter: 1 / 2 inch), and the reaction tube was filled with activated carbon catalyst (specific surface area: 1200 m 2 10 g of ...% ethanol (10 g / g) was filled.

[0237] In this operation, the reaction was carried out by returning the reaction gas containing the halogenated alkene compound produced by the above method to the reactor (first reactor) again, or by circulating the gas through the next reactor (second reactor) filled with an activated carbon catalyst.

[0238] The hydrogen chloride concentration of the reaction gas containing the halogenated alkene compound at that time was 50 mol%. The reaction gas coming out of the first reactor is subjected to rectification, alkali treatment, SEKADO treatment, alumina treatment, The hydrogen chloride concentration was adjusted to 20 mol %, 3 mol %, or 0.1 mol % by the following method.

[0239] After drying for 2 hours at 200°C under a nitrogen atmosphere, CF3CCl=CHCF3 (raw material compound) was passed through the reactor at atmospheric pressure so that the contact time (W / F0) between CF3CCl=CHCF3 (raw material compound) and the activated carbon catalyst was 0.5 g·sec / cc, 20 g·sec / cc, or 43 g·sec / cc.

[0240] The reaction was carried out in a continuous gas flow mode.

[0241] The reactor was heated to 400° C. to initiate dehydrochlorination.

[0242] One hour after the start of dehydrochlorination, the distillate that had passed through the detoxification tower was collected.

[0243] Then, using a gas chromatograph (Shimadzu Corporation, product name "GC-2014") Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL) Structural analysis was carried out by NMR spectroscopy using a compound of formula (II) manufactured by Epson Corporation, trade name "400YH".

[0244] Mass spectrometry and structural analysis confirmed that the target compound, a fluorinated alkyne compound (PF2B(CF3C≡CCF3)), was produced.

[0245] Furthermore, in the above-mentioned method for producing a fluorinated alkyne compound from a halogenated alkene compound, trifluoromethane (HFC-23, R23) was produced in addition to PF2B as the target product.

[0246] [Table 3]

[0247] Example 9 (Dehydrofluorination) 338mee(CF 3 CHFCHFCF 3 ) → 1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) (1)338mee(CF 3 CHFCHFCF 3 ) → 1327myz(CF 3 CF=CHCF 3 ) The reaction tube was made of stainless steel pipe (outer diameter: 1 / 2 inch), and the reaction tube was filled with activated carbon catalyst (specific surface area: 1200 m 2 10 g of ...% ethanol (10 g / g) was filled.

[0248] After drying for 2 hours at 200°C under a nitrogen atmosphere, CF3CHFCHFCF3 (raw material compound) was passed through the reactor at atmospheric pressure so that the contact time (W / F0) between CF3CHFCHFCF3 (raw material compound) and the activated carbon catalyst was 5 g·sec / cc or 25 g·sec / cc.

[0249] The reaction was carried out in a continuous gas flow mode.

[0250] The reactor was heated to 100°C, 200°C, 300°C, or 400°C to initiate dehydrofluorination.

[0251] (2) Removal of hydrogen fluoride One hour after the start of dehydrofluorination, the distillate that had passed through the detoxification tower was collected.

[0252] Then, using a gas chromatograph (Shimadzu Corporation, product name "GC-2014") Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL) Structural analysis was carried out by NMR spectroscopy using a compound of formula (II) manufactured by Epson Corporation, trade name "400YH".

[0253] Mass spectrometry and structural analysis confirmed that the target compound, a halogenated alkene compound (1327myz:CF3CF=CHCF3), was produced.

[0254] (3) 1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) The reaction tube was made of stainless steel pipe (outer diameter: 1 / 2 inch), and the reaction tube was filled with activated carbon catalyst (specific surface area: 1200 m 2 10 g of ...% ethanol (10 g / g) was filled.

[0255] In this operation, the reaction was carried out by returning the reaction gas containing the halogenated alkene compound produced by the above method to the reactor (first reactor) again, or by circulating the gas through the next reactor (second reactor) filled with an activated carbon catalyst.

[0256] The hydrogen chloride concentration of the reaction gas containing the halogenated alkene compound at that time was 50 mol%. The reaction gas coming out of the first reactor is subjected to rectification, alkali treatment, SEKADO treatment, alumina treatment, The hydrogen chloride concentration was adjusted to 20 mol %, 3 mol %, or 0.1 mol % by the following method.

[0257] After drying for 2 hours at 200°C under a nitrogen atmosphere, CF3CF=CHCF3 (raw material compound) was passed through the reactor at atmospheric pressure so that the contact time (W / F0) between CF3CCl=CHCF3 (raw material compound) and the activated carbon catalyst was 0.5 g·sec / cc, 20 g·sec / cc, or 43 g·sec / cc.

[0258] The reaction was carried out in a continuous gas flow mode.

[0259] The reactor was heated to 400° C. to initiate dehydrofluorination.

[0260] One hour after the start of dehydrofluorination, the distillate that had passed through the detoxification tower was collected.

[0261] Then, using a gas chromatograph (Shimadzu Corporation, product name "GC-2014") Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL) Structural analysis was carried out by NMR spectroscopy using a compound of formula (II) manufactured by Epson Corporation, trade name "400YH".

[0262] Mass spectrometry and structural analysis confirmed that the target compound, a fluorinated alkyne compound (PF2B(CF3C≡CCF3)), was produced.

[0263] Furthermore, in the above-mentioned method for producing a fluorinated alkyne compound from a halogenated alkene compound, trifluoromethane (HFC-23, R23) was produced in addition to PF2B as the target product.

[0264] [Table 4]

[0265] Examples 10 to 16 (Dehydrofluorination) 338mee(CF 3 CHFCHFCF 3 ) → 1327myz(CF 3 CF=CHCF 3 ) The reaction tube was made of stainless steel pipe (outer diameter: 1 / 2 inch), and the reaction tube was filled with activated carbon catalyst (specific surface area: 1200 m 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to normal pressure. The contact time (W / F0) between CF3CHFCHFCF3 (raw material compound) and activated carbon catalyst is 2 to 47 g·sec / cc. CF3CHFCHFCF3 (raw material compound) was passed through the reactor so that the reaction temperature became 100°C. Then, in Examples 10 to 13, 4 moles of octafluorocyclobutane (c-C4F8; C318) were passed through the reactor per mole of CF3CHFCHFCF3 (raw material compound).

[0266] The reaction was carried out in a continuous gas flow mode.

[0267] The reactor was heated to 400° C. to initiate dehydrochlorination.

[0268] One hour after the start of dehydrochlorination, the distillate that had passed through the detoxification tower was collected.

[0269] Then, using a gas chromatograph (Shimadzu Corporation, product name "GC-2014") Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL) Structural analysis was carried out by NMR spectroscopy using a compound of formula (II) manufactured by Epson Corporation, trade name "400YH".

[0270] Mass spectrometry and structural analysis confirmed that the target compound, a halogenated alkene compound (1327myz:CF3CF=CHCF3), was produced.

[0271] In addition, in the method for producing a halogenated alkene compound from a halogenated alkane compound, In addition to the target compound 1327myz (CF3CF=CHCF3), 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), 1,1,1,4,4,4-hexafluoro-2-butyne (PF2B), etc. were produced.

[0272] [Table 5]

[0273] Examples 17 to 20 (Dehydrofluorination) 1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) The reaction tube was made of stainless steel pipe (outer diameter: 1 / 2 inch), and the reaction tube was filled with activated carbon catalyst (specific surface area: 1200 m 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to normal pressure. In Examples 17 and 18, CF3CF=CHCF3 (raw material compound) was passed through the reactor so that the contact time (W / F0) between CF3CF=CHCF3 (raw material compound) and the activated carbon catalyst was 2 g sec / cc, 2.8 g sec / cc, or 10 g sec / cc. Thereafter, in Examples 17 and 18, 4 moles of octadecanoic acid were used per mole of CF3CF=CHCF3 (raw material compound). Fluorocyclobutane (c-C4F8; C318) was distributed.

[0274] The reaction was carried out in a continuous gas flow mode.

[0275] The reactor was heated to 400° C. to initiate dehydrochlorination.

[0276] One hour after the start of dehydrochlorination, the distillate that had passed through the detoxification tower was collected.

[0277] Then, using a gas chromatograph (Shimadzu Corporation, product name "GC-2014") Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL) Structural analysis was carried out by NMR spectroscopy using a compound of formula (II) manufactured by Epson Corporation, trade name "400YH".

[0278] Mass spectrometry and structural analysis confirmed that the target compound, a fluorinated alkyne compound (PF2B:CF3C≡CCF3), was produced.

[0279] In addition, in the above-mentioned method for producing a halogenated alkene compound from a halogenated alkane compound, trifluoromethane (HFC-23, R23) is produced in addition to the target product PF2B (CF3C≡CCF3). It was.

[0280] [Table 6]

Claims

1. General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butene compound represented by the following formula: General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The production method includes a step of dehydrofluorinating a halogenated butane compound represented by the following formula:

2. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the formula: General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 represents a halogen atom.] a step of dehydrohalogenating a halogenated butene compound represented by the formula: A manufacturing method comprising:

3. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the formula: (IA) General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 represents a halogen atom.] A halogenated butane compound represented by the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] a step of producing a halogenated butene compound represented by the formula: (IIA) a step of removing hydrogen fluoride after the step (IA); and (IIIA) After the step (IIA), the compound of formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The halogenated butene compound represented by the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above.] A process for producing a halogenated butyne compound represented by the formula: A manufacturing method comprising:

4. The method according to any one of claims 1 to 3, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in the presence of a catalyst and / or a base.

5. The method according to any one of claims 1 to 4, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a liquid phase.

6. The method according to claim 5 , wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a closed reaction system.

7. The production method according to any one of claims 1 to 4, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a gas phase.

8. 8. The production method according to claim 7, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst, and a silica-alumina catalyst.

9. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. 8 represents a halogen atom.] A method for producing a halogenated alkene compound represented by the formula: General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. A production method comprising a step of subjecting a halogenated alkane compound represented by the following formula (1) to a dehydrohalogenation reaction in a gas phase in the presence of a catalyst.

10. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 is the same as above. X 8 represents a halogen atom.] A production method comprising a step of subjecting a halogenated alkene compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst.

11. The method according to claim 10, wherein the dehydrohalogenation reaction is carried out in a gas phase.

12. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. A halogenated alkane compound represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] a step of producing a halogenated alkene compound represented by the formula: (IIB) a step of removing hydrogen halide after the step (IB); and (IIIB) After the step (IIB), the compound of the formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A halogenated alkene compound represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 is the same as above.] A process for producing a fluorinated alkyne compound represented by A manufacturing method comprising:

13. The method according to any one of claims 1 to 12, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a gas-phase continuous flow system.

14. The dehydrofluorination reaction and / or the dehydrohalogenation reaction step is The method according to any one of claims 1 to 13, wherein the method is carried out in the presence of a cyclic hydrocarbon halide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are substituted with halogen atoms.

15. General formula (1A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (1A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A composition containing a halogenated butene compound represented by the formula: A composition, wherein the content of the halogenated butene compound represented by the general formula (1A) is 80.00 to 99.99 mol %, with the total amount of the composition being 100 mol %.

16. The composition according to claim 15, wherein the halogenated butene compound represented by the general formula (1A) is an (E)-halogenated butene compound in an amount of 85.00 to 99.98 mol %, based on 100 mol % of the total amount of the composition. 。

17. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. 8 represents a halogen atom.] a halogenated alkene compound represented by the formula: and at least one hydrofluorocarbon (HFC) compound (excluding the halogenated alkene compound represented by the general formula (2B)), composition.

18. 18. The composition according to claim 17, wherein the content of the halogenated alkene compound represented by general formula (2B) is 80 mol% or more, and the content of the hydrofluorocarbon (HFC) compound is 20 mol% or less, where the total amount of the composition is 100 mol%.

19. The hydrofluorocarbon (HFC) compound is hexafluorobutene, hexafluorobutene, and at least one selected from the group consisting of octafluorobutane and octafluorobutane. Item 19. The composition according to item 17 or 18.

20. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. a fluorinated alkyne compound represented by the formula: At least one hydrofluorocarbon (HFC) compound (represented by the general formula (3B) Fluorinated alkyne compounds are excluded), composition.

21. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. a halogenated butyne compound represented by the formula: and at least one hydrofluorocarbon (HFC) compound (excluding the halogenated butyne compound represented by the general formula (3A)), composition.

22. the content of the fluorinated alkyne compound represented by the general formula (3B) or the halogenated butyne compound represented by the general formula (3A) is 80 mol % or more, with the total amount of the composition being 100 mol %, 22. The composition according to claim 20 or 21, wherein the content of the hydrofluorocarbon (HFC) compound is 20 mol% or less.

23. The hydrofluorocarbon (HFC) compound is trifluoromethane, difluoromethane at least one selected from the group consisting of tetrafluoromethane and monofluoromethane The composition according to any one of claims 20 to 22, wherein

24. The composition of any one of claims 15 to 23, used as a cleaning gas, etching gas, refrigerant, heat transfer medium or building block for organic synthesis.

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