Method for producing halogenated alkene compounds and fluorinated alkyne compounds

Abstract

To obtain a halogenated alkene compound and a halogenated alkyne compound at a high conversion rate and selectivity.SOLUTION: Any of the following methods (1)-(4) is employed: (1) a halogenated butane compound represented by CX1X2X3CHX4CFHCX5X6X7 [where X1, X2, X3, X4, X5, X6 and X7 are identical to or different from each other, and are halogen atoms] is subjected to a dehydrofluorination reaction; (2) a halogenated butene compound represented by CX1X2X3CX4=CHCX5X6X7 [where X1, X2, X3, X4, X5, X6 and X7 are the same as above] is subjected to a dehydrohalogenation reaction; (3) a halogenated alkane compound represented by CHX8A1CHX9A2 [where A1 and A2 are fluorine atoms or perfluoroalkyl groups, and X8 and X9 are identical to or different from each other, and are halogen atoms] is subjected to a dehydrohalogenation reaction in a vapor phase in the presence of a catalyst; and (4) a halogenated alkene compound represented by CX8A1=CHA2 [where A1, A2, and X8 are the same as above] is subjected to a dehydrohalogenation reaction in the presence of a catalyst.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] As a method for producing a halogenated alkene compound, for example, in Patent Document 1, starting materials such as CF3CHClCHClCCl3, CF3CCl2CH2CCl3, CF3CClHCHFCCl3, CF3CClFCH2CCl3, etc. are reacted with hydrogen fluoride in the presence of an oxyfluorinated chromium catalyst, and dehydrofluorination is carried out while fluorination to obtain CF3CF=CHCF3.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure aims to provide a method capable of obtaining a halogenated alkene compound and a halogenated alkyne compound with a high conversion rate and a high selectivity.

Means for Solving the Problems

[0005] The present disclosure includes the following configurations. Item 1. General formula (2A): CX , 1 , ,

[0005] , 6 , , , 4 , , 2 ,

[0003] , 3 , , , , , 2 , , 7 , , 5 , , , 3 , ,

[0004] , 1 , , , 4 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 These represent halogen atoms, either identical or distinct. A method for producing a butene halogen compound represented by the following: 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 This is the same as above. A method for producing a butane halogenated compound represented by [formula], comprising the step of dehydrofluorinating the compound. 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 These represent halogen atoms, either identical or distinct. A method for producing a halogenated butyne compound represented by the following: 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 The same applies as above. X 4represents a halogen atom. A step of dehydrogenating a halogenated butene compound represented by A production method comprising Item 3. General formula (3A): CX 1 X 2 X​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​A step of producing a halogenated butene compound represented by (IIA) After the step (IA), a step of removing hydrogen fluoride, and (IIIA) After the step (IIA), the obtained 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 as described above.] The halogenated butene compound represented by is subjected to a dehydrohalogenation reaction to obtain 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 are the same as described above.] A step of producing a halogenated butyne compound represented by A production method comprising Item 4. The production method according to any one of Items 1 to 3, wherein the step of performing 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 step of performing the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a liquid phase. Item 6. The production method according to Item 5, wherein the step of performing the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a closed reaction system. <00007​ Item 8. The manufacturing method according to Item 7, wherein the step of performing the dehydrofluoride reaction and / or the dehydrohalogenate reaction is carried out in the presence of at least one catalyst selected from the group consisting of activated carbon catalysts, chromium oxide catalysts, zeolite catalysts and silica-alumina catalysts. Term 9. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 X represents a fluorine atom or a perfluoroalkyl group, and is either identical or different. 8 This indicates a halogen atom. A method for producing a halogenated alkene compound represented by the following: General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 The same applies as above. X 8 and X 9 These represent halogen atoms, either identical or distinct. A method for producing a halogenated alkane compound represented by [formula], comprising the step of dehydrohalogenating it in the 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 These are identical or distinct, representing a fluorine atom or a perfluoroalkyl group. A method for producing an alkyne fluoride compound represented by, General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 The same applies as above. X 8 This indicates a halogen atom. A method for producing a halogenated alkene compound represented by [formula], comprising the step of dehydrohalogenating it in the presence of a catalyst. Item 11. The manufacturing method according to Item 10, wherein the step of dehalogenating hydrogen is carried out in the gas phase. Item 12. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 These are identical or distinct, representing a fluorine atom or a perfluoroalkyl group. A method for producing an alkyne fluoride compound represented by, (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 The same applies as above. X 8 and X 9 These represent halogen atoms, either identical or distinct. A halogenated alkane compound represented by is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst, and the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 This is the same as above. A process for producing a halogenated alkene compound represented by the following: (IIB) After step (IB) above, a step to remove hydrogen halide, and (IIIB) After step (IIB), the general formula (2B) obtained: CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 This is the same as above. A halogenated alkene compound represented by is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst, and the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 This is the same as above. The process for producing alkyne fluoride compounds represented by A manufacturing method that includes this. Item 13. The manufacturing method according to any one of items 1 to 12, wherein the step of performing the dehydrofluoride reaction and / or the dehydrohalogenate reaction is carried out in a gas-phase continuous flow manner. Item 14. The steps of the dehydrofluoride reaction and / or the dehydrohalogenate reaction, A manufacturing method according to any one of items 1 to 13, carried out in the presence of a cyclic halogenated carbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are replaced 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 These represent halogen atoms, either identical or distinct. A composition containing a butene halogenated compound represented by, A composition in which, with the total amount of the composition being 100 mol%, the content of the butene halogen compound represented by the general formula (1A) is 80.00 to 99.99 mol%. Item 16. The combination described in Item 15, with the total amount of the composition being 100 mol%, comprising 85.00 to 99.98 mol% of (E)-butene halogenated compound as the butene halogenated compound represented by the general formula (1A). A finished product. Section 17. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 X represents a fluorine atom or a perfluoroalkyl group, and is either identical or different. 8 This indicates a halogen atom. A halogenated alkene compound represented by, It contains at least one hydrofluorocarbon (HFC) compound (excluding the halogenated alkene compound represented by the general formula (2B) above), composition. Item 18. The composition according to Item 17, wherein, with a total composition amount of 100 mol%, 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. Item 19. The hydrofluorocarbon (HFC) compound is hexafluorobutene, hex At least one selected from the group consisting of safluorobutane and octafluorobutane. The composition described in item 17 or 18. Section 20. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 These are identical or distinct, representing a fluorine atom or a perfluoroalkyl group. Alkyne fluoride compounds represented by and It contains at least one hydrofluorocarbon (HFC) compound (excluding alkyne fluoride compounds represented by the general formula (3B) above), 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 These represent halogen atoms, either identical or distinct. A halogenated butyn compound represented by, It contains at least one hydrofluorocarbon (HFC) compound (excluding the halogenated butyne compound represented by the general formula (3A) above), composition. Item 22. The total amount of the composition is 100 mol%, and the content of the alkyne fluoride compound represented by general formula (3B) or the butyne halogenate compound represented by general formula (3A) is 80 mol% or more. The composition according to 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, difluoro A composition according to any one of claims 20 to 22, which is at least one selected from the group consisting of romethane, tetrafluoromethane, and monofluoromethane. Item 24. A composition according to any one of items 15 to 23, used as a cleaning gas, etching gas, refrigerant, heat transfer medium, or building block for organic synthesis. [Effects of the Invention]

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

[0007] [Figure 1] This diagram schematically illustrates the methods for producing alkenes (halogenated butene compounds or halogenated alkene compounds) and alkynes (halogenated butyne compounds or fluorinated alkyne compounds) in this disclosure. In Figure 1, hydrogen fluoride generated can be separated in a rectification column. [Figure 2]Figure 2 schematically illustrates the methods for producing alkenes (halogenated butene compounds or halogenated alkene compounds) and alkynes (halogenated butyne compounds or fluorinated alkyne compounds) in this disclosure. In Figure 2, a hydrogen halide removal agent (removal column) can be used to remove the generated hydrogen halide. [Modes for carrying out the invention]

[0008] In this specification, "contains" is a concept that encompasses all of the following: "contains," "consist essentially of," and "consist of." Furthermore, in this specification, when a numerical range is indicated as "A~B," it means A or greater and B or less.

[0009] In this disclosure, "selectivity" means the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of compounds other than the raw material compound in the effluent gas.

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

[0011] Conventionally, in Patent Document 1, CF3CHClCHClCCl3, CF3CCl2CH2CCl3, CF3CClHCHFCCl3, CF3CClFCH2CCl3, etc., were used as starting materials and reacted with hydrogen fluoride in the presence of an oxyfluorinated chromium catalyst. By removing hydrogen fluoride while simultaneously fluorinating, CF3CF=CHCF3 was obtained, but the yield was only 14.8%.

[0012] From the above, the yield using the conventional method was only 14.8%. The manufacturing method disclosed herein Therefore, compared to conventional methods, halogenated alkene compounds and halogenated alkyne compounds can be synthesized with high conversion rates and high selectivity.

[0013] 1. Methods for producing butene halogenated compounds and butynic halogenated compounds [1-1] Method for producing butene halogenated compounds from butane halogenated compounds The method for producing the butene halogenated compound disclosed herein is: 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 These represent halogen atoms, either identical or distinct. A method for producing a butene halogen compound represented by the following: 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 This is the same as above. The process includes a step of dehydrofluorinating a butane halogenated compound represented by [formula].

[0014] According to this disclosure, by performing a dehydrofluorination reaction of the butane halogenated compound represented by the above-mentioned general formula (1A), it is possible to selectively obtain a butene halogenated compound represented by general formula (2A) in which 1 mole of hydrogen fluoride is removed for every 1 mole of the butane halogenated compound represented by general formula (1A), and furthermore, HX can be continuously obtained from the butene halogenated compound represented by general formula (2A). 4The elimination reaction of hydrogen halides represented by is unlikely to occur. Furthermore, according to this disclosure Furthermore, as a butene halide compound represented by general formula (2A), among the geometric isomers, the E isomer is particularly important. This allows for the selective synthesis of methyl trihalides such as CF3 groups. Due to the attraction effect, the carbon at the α position of the trihalide methyl group such as the CF3 group becomes electron-deficient, Because halogen anions such as the bisulfite anion are difficult to detach, butene halogenate is formed instead of butyne halogenate. Furthermore, the selective formation of the E isomer is due to the steric hindrance of trihalogenated methyl groups such as the CF3 group, which makes the trans configuration more energetically stable.

[0015] (1-1-1) Starting material compounds (halogenated butane compounds) The butane halogenated compound that can be used as a substrate in the manufacturing method of this disclosure is as described above, 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 These represent halogen atoms, either identical or distinct. It is a butane halogenated compound represented by [formula].

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

[0017] As for the substrate, the butane halogenated compound is particularly suitable for producing butane halogenated compounds with high conversion rates, yields, and selectivity. 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 In both cases, fluorine atoms and chlorine atoms are preferred, with fluorine atoms being more preferred.

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

[0019] Examples of butane halogenated compounds that satisfy the above conditions as substrates include CF3CFHCFHCF3, CCl3CClHCFHCCl3, CBr3CBrHCFHCBr3, and the like. Butane compounds can be used individually or in combination of two or more types. Such butane halogenated compounds can be known or commercially available.

[0020] (1-1-2) Dehydrofluoride reaction In the step of dehydrofluorinating a butane halogenated compound in this disclosure, for example, as a substrate, a butane halogenated compound represented by general formula (1A) is X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 It is more preferable that it be a fluorine atom.

[0021] In other words, the reaction equation is as follows: CF3CFHCFHCF3→ CF3CF=CHCF3+ HF According to the above, it is preferably a dehydrofluorination reaction.

[0022] The step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction can be carried out in the liquid phase or in the gas phase. Particularly from the viewpoint of productivity, it is preferably carried out in the gas phase.

[0023] The step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction is preferably carried out in the presence of a catalyst and / or a base from the viewpoint of obtaining the target compound with a higher selectivity and a higher conversion rate. More specifically, when adopting a liquid-phase reaction, it is preferably carried out in the presence of a base and, if necessary, a catalyst, and when adopting a gas-phase reaction, it is preferably carried out in the presence of a catalyst. Details of the catalyst and the base in each case will be described later.

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

[0025] When the step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction is carried out in the liquid phase, first, a solution of the butane halide compound represented by the above general formula (1A) is prepared, and then the reaction is preferably allowed to proceed in the presence of a base.

[0026] solvent As the solvent in the solution of the above-described butane halide compound, either water or a non-aqueous solvent can be adopted. As the non-aqueous solvent, carbonic acid esters 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-buty Lactones such as lactone, γ-valerolactone, tetrahydrofuran, and tetrahydropyran 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-dimethylformamide; sulfones such as dimethyl sulfoxide and sulfolane are preferred. The solvent can be used alone from the above-mentioned water and non-aqueous solvents, or two or more kinds can be used in combination. Among them However, it is preferably a solvent having a high boiling point and being difficult to decompose the base described later. Specifically, a non-aqueous solvent is preferred, an ether is more preferred, and dibutyl ether is particularly preferred.

[0027] base When the step of dehydrogenating hydrofluoride from the butane halide compound in the present disclosure is carried out in the liquid phase, as described above, it is preferably carried out in the presence of a base.

[0028] From the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated butene compound, hydroxides or alkoxides of alkali metals or alkaline earth metals are preferred as the base, and alkoxides of alkali metals or alkaline earth metals are more preferred. Specifically, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium tert-butoxide, etc. can be mentioned, and sodium methoxide, potassium tert-butoxide, etc. are preferred. In this step, it is preferably an aqueous solution of a hydroxide or alkoxide of an alkali metal or an alkaline earth metal, and an aqueous solution of an alkoxide of an alkali metal or an alkaline earth metal is more preferred. Specifically, aqueous solutions of sodium methoxide, potassium methoxide, potassium ethoxide, potassium tert-but oxide, etc. are particularly preferred. By using such a base, the target compound can be obtained with a higher selectivity and a higher conversion rate.

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

[0030] catalyst In this process, a catalyst may be used as needed. The catalyst used in this process is preferably a hydrocarbon-based alkoxide. Examples of hydrocarbon-based 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. Examples include 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 (trademark Aliquat336), methyltrioctylammonium bromide, and methyltrioctylammonium iodide. These can be used individually or in combination of two or more catalysts. It can also be used in this way. By using the catalyst, the target compound can be obtained with higher selectivity and higher conversion rate.

[0031] Cyclic halogen carbides In this disclosure, the step of dehydrofluorinating the above-described butane halogenated compound may also be carried out in the presence of a cyclic halogenated carbide compound. This cyclic halogenated carbide compound means a cyclic halogenated carbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are replaced by halogen atoms. In other words, it means a cyclic halogenated carbide compound composed only of carbon atoms and halogen atoms, and containing no hydrogen atoms.

[0032] By carrying out the dehydrofluorination reaction of the above-mentioned butane halogenated compound in the presence of such a cyclic halogenated carbide compound, it is possible to shift the reaction equilibrium toward the product side, thereby obtaining the target butene halogenated compound with an even higher conversion rate and higher yield.

[0033] The halogen atoms that can be used in cyclic halogenated carbide compounds include fluorine and chlorine atoms. It may contain any of the following atoms: X, bromine, and iodine atoms. In particular, from the viewpoint of reaction efficiency, halogen atoms (X) contained in the starting compound, the butane halide compound, are considered to be the most important. 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 It is preferable that the butane halogenated compound contains the same type of halogen atom as (X). 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 If not all of them are identical, the cyclic halogenated carbide compound preferably contains one or more halogen atoms of the butane halogenated compound, and it is also preferable that it contains only one halogen atom of the butane halogenated compound.

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

[0035] The cyclic halogenated carbide compounds that can be used may be saturated cyclic halogenated carbide compounds that do not have unsaturated bonds, or unsaturated cyclic halogenated carbide compounds that do have unsaturated bonds. Among these, saturated cyclic halogenated carbide compounds are preferred from the viewpoint of conversion rate, selectivity, and yield of the target butene halogenated compound.

[0036] From the above, saturated cyclic halogenated carbide compounds are preferred as cyclic halogenated carbide compounds. Examples of such saturated cyclic halogenated carbide compounds include those with 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 They are the same or different, fluorine atoms or par This indicates a fluoroalkyl group. A saturated cyclic halogenated carbide compound represented by [formula] is preferred.

[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 is an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. The perfluoroalkyl group has, for example, 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 ~6 carbon atoms, still more preferably 1 to 4 carbon atoms, particularly preferably 1 to 3 carbon atoms of perfluoroalkyl group. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. As the perfluoroalkyl group, a trifluoromethyl group (CF3-) and a pentafluoroethyl group (C2F5-) are preferable.

[0040] Specific examples of the cyclic carbon halogen compound satisfying the above conditions include

[0041]

Chemical formula

[0042] etc.

[0043] In the production method of the present disclosure, in the liquid phase, when the dehydrofluorination reaction of the butane halide compound is carried out in the presence of the cyclic carbon halogen compound, for example, the cyclic carbon halogen compound may be blown into the solution of the butane halide compound in a gaseous state, or a liquid phase (such as liquefied gas etc.) may be introduced.

[0044] In the production method of the present disclosure, when the dehydrofluorination reaction of the butane halide compound is carried out in the presence of the cyclic carbon halogen compound, the amount of the cyclic carbon halogen compound used is not particularly limited, and from the viewpoints of the conversion rate, selectivity and yield of the target butene halide compound, it is preferably an excessive amount with respect to the butane halide compound as the raw material compound. Specifically, 1 to 20 moles, preferably 2 to 10 moles are more preferable, and 3 to 5 moles are still more preferable, per 1 mole of the butane halide compound as the raw material compound.

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

[0046] Thus, because the target compound has a low boiling point, the sealed reaction system is pressurized, increasing the concentration of the substrate (starting compound) in the reaction solution (base solution) and improving reactivity. It is preferable to carry out the reaction in a sealed reaction system using a batch-type pressure-resistant reaction vessel. When carrying out the reaction in a batch manner, it is preferable to charge the starting compound, base solution (alkaline aqueous solution), catalyst, etc., into a pressure vessel such as an autoclave, raise the temperature to an appropriate reaction temperature with a heater, and react for a certain period of time under stirring. It is preferable to carry out the reaction in an inert gas atmosphere such as nitrogen, helium, or carbon dioxide.

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

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

[0049] Pressurized reaction system In this disclosure, the dehydrofluoride 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 makes it possible to obtain the target compound, a butene halogen compound represented by general formula (2A), with higher selectivity and a higher conversion rate. When the reaction system is pressurized in this way, the concentration of the substrate (starting compound) in the reaction solution (base solution, alkaline aqueous solution) increases, which improves the reactivity. In the pressurized reaction system, it is preferable to carry out the reaction by sealing the reaction system using a batch-type pressure-resistant reaction vessel. When carrying out the reaction in a batch type, for example, it is preferable to charge the starting compound, base solution (alkaline aqueous solution), catalyst, etc. in a pressure vessel such as an autoclave, raise the temperature to an appropriate reaction temperature with a heater, and react for a certain period of time under stirring.

[0050] In the desorption reaction step in this disclosure, the pressurized conditions are preferably such that the reaction pressure is 0 kPa or higher. The reaction pressure is the pressure inside the reaction vessel used in the pressurized reaction system. In the dehydrofluoride reaction step in this 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 around 2 MPa. In this disclosure, unless otherwise specified, pressure refers to gauge pressure.

[0051] Pressurization can be achieved by introducing inert gases such as nitrogen, helium, or carbon dioxide into the reaction system, thereby increasing the pressure within the system.

[0052] In the dehydrofluoride reaction step in this disclosure, the reaction temperature in the pressurized reaction system is usually preferably 0°C or higher, more preferably 10°C or higher, and 15°C or higher, from the viewpoint of more efficiently carrying out the elimination reaction, obtaining the target compound with higher selectivity, and suppressing a decrease in the conversion rate. The top one is even better.

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

[0054] Combination of closed reaction system and pressurized reaction system In the dehydrofluoride reaction step in this disclosure, the reaction can also be carried out in a continuous and pressurized manner, either by connecting a back pressure valve to a continuous-phase tank reactor (CSTR), while withdrawing the liquid or by gasifying and withdrawing the product.

[0055] After the dehydrofluoride reaction is complete, the product can be purified according to conventional methods as needed to obtain a halogenated cyclobutene compound represented by general formula (2A).

[0056] (1-1-2-2) Gas-phase reaction When the process of removing hydrogen fluoride from a butane halogenated compound in this disclosure is carried out in the gas phase, there is no need to use a solvent, no industrial waste is generated, and it has the advantage of being highly productive.

[0057] The step of removing hydrogen fluoride from a butane halogen compound in this disclosure is preferably carried out in the gas phase, particularly in a continuous gas flow system using a fixed-bed reactor. Carrying the reaction in a continuous gas flow system simplifies the equipment and operation, and is also economically advantageous.

[0058] catalyst The step of removing hydrogen fluoride from a butane halogen compound in this disclosure is preferably carried out in the presence of a catalyst.

[0059] Preferred catalysts used in the manufacturing method of this disclosure include activated carbon catalysts, chromium oxide catalysts, zeolite catalysts, and silica-alumina catalysts. These catalysts can 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. can also be used.

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

[0064] Regarding the chromium oxide catalyst, there are no particular restrictions, but when chromium oxide is expressed 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 expressed as CrO m ·nH2O, it may be hydrated so that the value of n is 3 or less, particularly 1 to 1.5.

[0065] Fluorinated chromium oxide catalysts can be prepared by fluorinating the chromium oxide catalyst described above. This fluorination can be carried out using, for example, HF, fluorocarbons, etc. Such fluorinated chromium oxide catalysts can be synthesized, for example, according to the method described in Japanese Patent Application Publication No. 05-146680.

[0066] The following is an example of a method for synthesizing chromium oxide catalysts and fluorinated chromium oxide catalysts.

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

[0068] This precipitate can be filtered and washed, and then dried. Drying can be done, for example, in air at 70-200°C. This process can be carried out for 1 to 100 hours. The catalyst at this stage is sometimes called the chromium hydroxide state. Next, this catalyst can be crushed. From the viewpoint of pellet strength, catalyst activity, etc., the crushed powder (for example, particle size of 1000 μm or less, especially 95% of which have a particle size of 46 to 1000 μm) 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 BET method) is, for example, 100 m² under degassing conditions of 200°C for 80 minutes. 2 Preferably 120m / g or more. 2 A value of 1 / g or more is more preferable. The upper limit of the specific surface area is, for example, 220 m². 2 It is approximately / g

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

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

[0071] The specific surface area of ​​the calcined catalyst is, from the viewpoint of catalytic activity, for example, 170 m². 2 Preferably 1 / g or more , 180m 2 More preferably 200m / g or more, 2 A value of 1 / g or more is even more preferable. The upper limit of the specific surface area is , typically 240m 2 Approximately 220m / g is preferred. 2 Approximately / g is preferable.

[0072] Next, fluorinated chromium oxide can be obtained by fluorinating the chromium oxide. The fluorination temperature should be within a range where the water produced does not condense, and the upper limit should be the temperature at which the catalyst does not crystallize due to the heat of the reaction. For example, the fluorination temperature can be 100 to 460°C. There is no limit to the pressure during fluorination, but it is preferable to carry it out at the pressure used in the catalytic reaction.

[0073] As the zeolite catalyst, a wide range of known types of zeolites can be used. For example, crystalline hydrated aluminosilicates of alkali metals or alkaline earth metals are preferred. The crystalline form of the zeolite is not particularly limited, and examples include type A, type X, LSX, etc. The alkaline metal or alkaline earth metal is not particularly limited and includes potassium, sodium, calcium, lithium, and the like.

[0074] Zeolite catalysts exhibit stronger activity when fluorinated; therefore, they can be fluorinated beforehand and used as fluorinated zeolite catalysts before being used in a reaction.

[0075] For fluorinating zeolite catalysts, examples of inorganic fluorinating agents such as F2 and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropene can be used.

[0076] One method for fluorinating zeolite catalysts is, for example, using a temperature range of approximately 25°C to 400°C. One method involves fluorinating the system by circulating the aforementioned fluorinating agent under atmospheric pressure and specific temperature conditions.

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

[0078] Since silica-alumina catalysts become more active when fluorinated, they can also be fluorinated beforehand and used as fluorinated silica-alumina catalysts before being used in a reaction.

[0079] For fluorinating silica-alumina catalysts, examples of fluorinating agents that can be used include inorganic fluorinating agents such as F2 and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropene.

[0080] Methods for fluorinating silica-alumina catalysts include, for example, temperatures ranging from room temperature (25°C) to approximately 400°C. One possible method is to fluorinate the material by circulating the aforementioned fluorinating agent under atmospheric pressure and under the specified temperature conditions.

[0081] The catalysts described above can be used individually or in combination of two or more types. Among these, activated carbon catalysts (activated carbon or fluorinated activated carbon) and chromium oxide catalysts (chromium oxide or fluorinated chromium oxide) are preferred from the viewpoint of conversion rate, selectivity, and yield, with activated carbon catalysts (activated carbon or fluorinated activated carbon) being more preferred.

[0082] Furthermore, when using the above-mentioned chromium oxide catalyst, zeolite catalyst, silica-alumina catalyst, etc., as a catalyst, it is also possible to support them on a carrier. Examples of such carriers include carbon, alumina (Al2O3), zirconia (ZrO2), silica (SiO2), and titania (TiO2). Examples include activated carbon, amorphous carbon, graphite, diamond, etc., can be used as carbon.

[0083] In the manufacturing method of this disclosure, when dehydrofluorinating a butane halogen compound in the gas phase in the presence of a catalyst, it is preferable, for example, to contact the butane halogen compound with the catalyst in a solid state (solid phase). In this case, the catalyst can be in powder form, but pellet form is preferable when used in a gas-phase continuous flow reaction.

[0084] The specific surface area of ​​a catalyst measured by the BET method (hereinafter sometimes referred to as "BET specific surface area") is typically 10 to 3000 m². 2 / g is preferred, and 10 to 2500m 2 / g is more preferable, 20-2000m 2 / g is even more preferable, 30-1500m 2 / g is particularly preferred when the BET specific surface area of ​​the catalyst is within this range. Because the density of catalyst particles is not too low, butene halogen compounds can be obtained with higher selectivity. Furthermore, it is possible to further improve the conversion rate of butene halogen compounds.

[0085] Cyclic halogen carbides In this disclosure, the step of dehydrofluorinating the above-described butane halogenated compound may also be carried out in the presence of a cyclic halogenated carbide compound. This cyclic halogenated carbide compound means a cyclic halogenated carbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are replaced by halogen atoms. In other words, it means a cyclic halogenated carbide compound composed only of carbon atoms and halogen atoms, and containing no hydrogen atoms.

[0086] By carrying out the dehydrofluorination reaction of the above-mentioned butane halogenated compound in the presence of such a cyclic halogenated carbide compound, it is possible to shift the reaction equilibrium toward the product side, thereby obtaining the target butene halogenated compound with an even higher conversion rate and higher yield.

[0087] Such cyclic halogenated carbides are as described above. (1-1-2-1) Liquid-phase reaction The methods described above can be adopted. The same applies to preferred specific examples and usage amounts.

[0088] In the manufacturing method of this disclosure, when dehydrofluorinating a butane halide compound in the presence of a cyclic halogenated carbide compound in the gas phase, it is preferable, for example, to contact the butane halide compound with the cyclic halogenated carbide compound in a gaseous state (gas phase).

[0089] Reaction temperature In the step of dehydrofluorinating the butane halogenated compound in this disclosure, the reaction temperature is typically 230°C or lower, from the viewpoint of more efficiently carrying out the dehydrofluorinating reaction, improving the conversion rate, and obtaining the target compound, the butane halogenated compound, with higher selectivity. The temperature above is preferred, 280°C or higher is more preferred, and 320°C or higher is even more preferred. When activated carbon is used as a catalyst, and when cyclic halogenated carbon compounds are not used, the reaction temperature is preferably higher to allow the dehydrofluoride reaction to proceed more efficiently, up to 400°C. Temperatures above ℃ are preferred, and above 420℃ are more preferred. When activated carbon is used as a catalyst. However, when a butane halogen compound is subjected to a dehydrofluorination reaction in the gas phase in the presence of a cyclic halogenated carbide compound, the dehydrofluorination reaction can proceed more efficiently, and therefore the reaction temperature can be set to a slightly lower temperature. Typically, 230°C or higher is preferred, 280°C or higher is more preferred, and 320°C or higher is even more preferred.

[0090] In this disclosure, the reaction temperature for the dehydrofluorination reaction of the butane halogenated compound is generally preferred to be 500°C or lower, from the viewpoint of more efficiently carrying out the dehydrofluorination reaction, improving the conversion rate, and obtaining the target compound, the butane halogenated compound, with higher selectivity. A temperature of 450°C or lower is more preferable.

[0091] Reaction time The reaction time for the dehydrofluoridation reaction of the butane halogenated compound in this disclosure is, for example, the contact time (W / F) of the starting compound with the catalyst when a gas-phase flow system is used. [W: catalyst] The weight (g), F: flow rate of the raw material compound (cc / sec) indicates that the reaction conversion rate is particularly high, and halogen From the viewpoint of obtaining butane halogen compounds in higher yield and selectivity, 5 to 100 g·sec. / cc is preferred, 10 to 90 g·sec. / cc is more preferred, and 15 to 80 g·sec. / cc is even more preferred. When the butane halogen compound is subjected to a dehydrofluorination reaction in the gas phase in the presence of a cyclic halogenated carbide compound, the dehydrofluorination reaction can be carried out more efficiently, so the lower limit of the contact time can be made smaller, with 1 to 100 g·sec. / cc being preferred, and 2 ~90 g·sec. / cc is more preferable, and 3~80 g·sec. / cc is even more preferable. "Interval" refers to the time during which the raw material compound and the catalyst are in contact.

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

[0093] In the dehydrofluoridation reaction of butane halogen compounds in this disclosure, the reactor used to react the butane halogen compound with a catalyst and a cyclic halogenated carbide compound is not particularly limited in shape and structure, as long as it can withstand the above-mentioned temperature and pressure. Examples of reactors include vertical reactors, horizontal reactors, and multi-tube reactors. Examples of reactor materials include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0094] Examples of dehydrofluoride reactions The dehydrofluorination reaction of butane halogen compounds in this disclosure can be carried out by either a continuous flow system or a batch system, in which the butane halogen compound, which is the starting compound, is continuously charged into a reactor and the butene halogen compound, which is the target compound, is continuously withdrawn from the reactor. Since the desorption reaction may proceed further if the butene halogen compound, which is the target compound, remains in the reactor, it is preferable to carry out the reaction by a continuous flow system. In the step of dehydrofluorinating the butane halogen compound in this disclosure, it is preferable to carry it out in the gas phase, and in particular to carry it out by a continuous gas-phase flow system using a fixed-bed reactor. When using a continuous gas-phase flow system, the equipment and operation can be simplified and it is economically advantageous. When using a batch system, it is also possible to use a closed reaction system or a pressurized reaction system as described in the liquid-phase reaction above.

[0095] The atmosphere used when carrying out the dehydrofluoridation reaction of butane halogen compounds in this disclosure is preferably an inert gas atmosphere or a hydrogen fluoride gas atmosphere, in order to suppress catalyst degradation. Examples of such inert gases include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred from the viewpoint of reducing costs. The concentration of the inert gas is preferably 0 to 50 mol% of the gaseous components introduced into the reactor.

[0096] After the dehydrofluoride reaction is complete, the product can be purified according to conventional methods as needed to obtain a butene halogen compound represented by general formula (2A).

[0097] (1-1-3) Target compound (butene halide compound) The target compound obtained in this manner has 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 These represent halogen atoms, either identical or distinct. It is a butene halogen compound represented by [formula].

[0098] X in general formula (2A) 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 This is X in the general formula (1A) described above. 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7This corresponds to the above. Therefore, examples of butene halogen compounds represented by general formula (2A) that are to be manufactured include CF3CF=CHCF3, CCl3CCl=CHCCl3, CBr3CBr=CHCBr3, etc. These compounds contain both the Z and E isomers. Includes.

[0099] The butene halide compounds obtained in this way can be effectively used in various applications such as etching gases, cleaning gases, deposit gases, refrigerants, heat transfer media, and building blocks for organic synthesis to form cutting-edge microstructures in semiconductors, liquid crystals, etc. Deposit gases and building blocks for organic synthesis will be discussed later.

[0100] [1-2] Method for producing butylenides from butene halogenated compounds The method for producing the halogenated butyne compound described herein is: 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 These represent halogen atoms, either identical or distinct. A method for producing a halogenated butyne compound represented by the following: 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 The same applies as above. X4 This indicates a halogen atom. The process includes a step of dehydrohalogenating a butene halogen compound represented by [formula].

[0101] According to this disclosure, by performing a dehalogenation reaction of the butene halogen compound represented by the general formula (2A) described above, 1 mole of the butene halogen compound represented by the general formula (2A) The butyn halogen compound represented by general formula (3A) is obtained by removing 1 mole of hydrogen halide. It is possible to selectively obtain them.

[0102] (1-2-1) Starting material compounds (butene halide compounds) The butene halogen compounds that can be used as substrates in the manufacturing method of this disclosure are as described above, with 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 These represent halogen atoms, either identical or distinct. This is a butene halogenated compound represented by [1-1], and corresponds to the target compound in the method for producing a butene halogenated compound from the [1-1]butane halogenated compound described above.

[0103] In general formula (2A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 The halogen atoms shown can be those listed above. The same applies to preferred types.

[0104] Examples of butene halogen compounds that satisfy the above conditions as substrates include CF3CF=CHCF3, CCl3CCl=CHCCl3, CBr3CBr=CHCBr3, etc. These compounds include both Z and E isomers. These butene halogen compounds can be used alone. It is also possible to use two or more types in combination. Such butene halogenated compounds Publicly known or commercially available products may be used.

[0105] (1-2-2) Dehalogenation reaction In the step of dehydrohalogenating a butene halogenated compound in this disclosure, for example, as a substrate, a butene halogenated compound represented by general formula (2A) is X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 It is more preferable that it be a fluorine atom.

[0106] In other words, the reaction equation is as follows: CF3CF=CHCF3→ CF3C≡CCF3+ HF Therefore, a dehydrofluoride reaction is preferable.

[0107] The step of dehydrohalogenating a butene halide compound in this disclosure can be carried out in the liquid phase or the gas phase. In particular, from the viewpoint of productivity, it is preferable to carry it out in the gas phase.

[0108] The step of dehydrohalogenating a butene halogenated compound in this disclosure 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 rate. More specifically, when employing a liquid-phase reaction, it is preferable to carry it out in the presence of a base and, if necessary, a catalyst, and when employing a gas-phase reaction, it is preferable to carry it out in the presence of a catalyst. Details for the liquid-phase reaction (solvent, base, catalyst, cyclic halogenated carbide compound, conditions of the closed reaction system and pressurized reaction system, etc.) and details for the gas-phase reaction (catalyst, cyclic halogenated carbide compound, reaction temperature, reaction time, reaction pressure, etc.) can be those described in the above-described [1-1] Method for producing a butene halogenated compound from a butane halogenated compound, except that "reaction to obtain a butene halogenated compound by dehydrofluorination from a butane halogenated compound" is read as "reaction to obtain a butyne halogenated compound by dehydrohalogenating from a butene halogenated compound." The same applies to preferred types and contents.

[0109] After the dehydrohalogenation reaction is complete, the compound can be purified according to conventional methods as needed to obtain the halogenated butyn compound represented by general formula (3A).

[0110] (1-2-3) Target compound (halogenated butyne compound) The compound of interest obtained in this manner has 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 These represent halogen atoms, either identical or distinct. It is a halogenated butyn compound represented by [formula].

[0111] X in general formula (3A) 1, X 2 , X 3 , X 5 , X 6 and X 7 This is X in the general formula (2A) described above. 1 , X 2 , X 3 , X 5 , X 6 and X 7 This corresponds to the above. For this reason, examples of butyn halogenated compounds represented by general formula (3A) that are to be manufactured include CF3C≡CCF3, CCl3C≡CCCl3, CBr3C≡CCBr3, etc.

[0112] The butyrine halide compounds obtained in this way can be effectively used in various applications such as etching gases, cleaning gases, deposit gases, refrigerants, heat transfer media, and building blocks for organic synthesis to form cutting-edge microstructures in semiconductors, liquid crystals, etc. The deposit gases and building blocks for organic synthesis will be described later.

[0113] [1-3] Method for producing butylenide compounds from halogenated butane compounds via halogenated butene compounds The method for producing the halogenated butyne compound described herein is: 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 These represent halogen atoms, either identical or distinct. A method for producing a halogenated butyne compound represented by the following: (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 The same applies as above. X 4 This indicates a halogen atom. The butane halogenated compound represented by is subjected to a dehydrofluoride reaction to obtain 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 This is the same as above. A process for producing a butene halogen compound represented by the following: (IIA) After step (IA) above, a step to remove hydrogen fluoride, and (IIIA) After step (IIA), the general formula (2A) obtained: 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 This is the same as above. The butene halogenated compound represented by the formula (3A) is subjected to a dehydrohalogenation reaction to obtain 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 This is the same as above. A process for producing a halogenated butyne compound represented by Includes.

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

[0115] (1-3-2) Process (IIA) The method for producing a halogenated butyne compound according to the present disclosure includes a step (IA) in which a halogenated butane compound represented by the above general formula (1A) is subjected to a dehydrofluoride reaction to produce a halogenated butene compound represented by the above general formula (2A), and a step (IIA) in which hydrogen fluoride is removed from a mixture containing the halogenated butene compound and hydrogen fluoride.

[0116] In the method for producing a halogenated butyne compound according to this disclosure, after step (IA), the hydrogen fluoride generated in the dehydrofluoride reaction of step (IA) is separated and / or removed, and then the process proceeds to the next step (IIIA) for the production of the halogenated butyne compound. By dehydrofluoride, the target compound, the halogenated butyne compound, can be produced with a high conversion rate (yield) and high selectivity.

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

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

[0119] Method for separating hydrogen fluoride using 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 butene halogen compound and hydrogen fluoride obtained in step (IA), rectification is performed based on the difference in boiling points of the two compounds, with the boiling points of the two compounds as the reference. The butene halogenated compound and hydrogen fluoride can be separated in a column, recovering the butene halogenated compound and separating the hydrogen fluoride. In the subsequent step (IIIA) of producing the butyrine halogenated compound, the hydrogen fluoride content can be reduced, and the target compound, the butyrine halogenated compound, can be produced with a high conversion rate (yield) and high selectivity.

[0121] A method for removing hydrogen fluoride using a hydrogen halogen remover. The separated hydrogen fluoride can be removed by a hydrogen fluoride removal agent. It is preferable to use a hydrogen fluoride removal agent such as alkali, alumina, silica, zeolite, or secard. Secard is also known as allophane. This is an adsorbent (synthetic zeolite) primarily made from amorphous or low-crystallinity hydrated aluminum silicate, such as non-crystalline clay quasi-minerals (alumina / silica gel).

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

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

[0124] In the subsequent step (IIIA) for the production of the halogenated butine compound, the halogenated butene compound represented by the above general formula (2A) is used as the raw material. At this time, in addition to the halogenated butene compound represented by the above general formula (2A), a mixture containing hydrogen fluoride produced by dehydrofluoridation may be introduced into the subsequent step (IIIA) for the production of the halogenated butine compound.

[0125] In the method for producing a halogenated butyne compound according to this disclosure, in the production of the halogenated butyne compound in the next step (IIIA), the target compound, the halogenated butyne compound, is produced with a high conversion rate (yield) and high selectivity by dehydrofluoridation. In the composition used as a raw material in the next step (IIIA), the hydrogen fluoride content (concentration) is 50 mol%, based on a mixture containing a halogenated butene compound represented by general formula (2A) and hydrogen fluoride (100 mol%). The following are preferred, more preferably 20 mol% or less, even more preferably 3 mol% or less, and 0.1 mol% or less. The lower form is particularly preferred. By having a low hydrogen fluoride content in the mixture containing the butene halogen compound represented by general formula (2A) and hydrogen fluoride, the target compound, the butyne halogen 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, step (IIIA) can be carried out as described above in the description of the method for producing a halogenated butyne compound from a [1-2] halogenated butene compound.

[0127] (1-3-4) Examples of hydrogen fluoride removal In the hydrogen fluoride removal process described herein, the reaction can be carried out by either a continuous flow or batch method in which, in step (IA), the starting compound (butane halogenated compound) is continuously charged into the reactor and the target compound (butene halogenated compound) is continuously withdrawn from the reactor. Subsequently, hydrogen fluoride is removed from the mixture containing the butene halogenated compound and hydrogen fluoride (step (IIA)), and in step (IIIA), the starting compound (halogenated compound) is charged into the reactor. The process can be carried out by either a continuous flow system or a batch system, in which a butene compound is continuously charged and the target compound (halogenated butyne compound) is continuously withdrawn from the reactor. The continuous flow system is preferable because it prevents the target compound (halogenated butene compound or halogenated butyne compound) from remaining in the reactor at each step, and allows for further dehydrofluoridation.

[0128] In the hydrogen fluoride removal process described herein, the reaction is carried out in the gas phase, and is particularly preferable to be carried out in a continuous gas flow system using a fixed-bed reactor. Carrying out the reaction in a continuous gas flow system simplifies the equipment and operation, and is also economically advantageous.

[0129] In the hydrogen fluoride removal process described herein, the atmosphere during the reaction is preferably one in the presence of an inert gas, in order to suppress the degradation of the catalyst (activated carbon, metal catalyst, etc.). In this disclosure, at least one selected from the group consisting of nitrogen, helium, argon, and carbon dioxide can preferably be used as the inert gas. However, nitrogen is more preferable in terms of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gaseous components introduced into the reactor.

[0130] In the hydrogen fluoride removal step in this disclosure, after the reaction is complete, the target compound (a butene halogenated compound or a butynic halogenated compound) can be obtained by purification treatment in accordance with conventional methods as described above.

[0131] 2. Methods for producing halogenated alkene compounds and fluorinated alkyne compounds [2-1] Method for producing halogenated alkene compounds from halogenated alkane compounds A method for producing a halogenated alkene compound in this disclosure is general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 X represents a fluorine atom or a perfluoroalkyl group, and is either identical or different. 8 This indicates a halogen atom. A method for producing a halogenated alkene compound represented by the following: General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 The same applies as above. X 8 and X 9 These represent halogen atoms, either identical or distinct. The process includes a step of dehydrohalogenating an alkane halide compound represented by the formula in the gas phase in the presence of a catalyst.

[0132] According to this disclosure, by carrying out the dehalogenation hydrogenation reaction of the halogenated alkane compound represented by the above general formula (1B) in the gas phase in the presence of a catalyst, a halogenated alkene compound represented by general formula (2B) can be selectively obtained in which 1 mole of hydrogen halide is removed for every 1 mole of the halogenated alkane compound represented by general formula (1B), and furthermore, HX can be continuously obtained from the halogenated alkene compound represented by general formula (2B). 8 Desorption reaction of hydrogen halide represented by The reaction is unlikely to occur. Furthermore, according to this disclosure, the E isomer can be selectively synthesized among the geometric isomers as a halogenated alkene compound represented by general formula (2B). This effect is , A 1 and A 2 This is more pronounced when the group is a perfluoroalkyl group, and trihedrons such as CF3 groups. Due to the electron-withdrawing effect of the methyl logenide group, the α-position carbon of trihalogenated methyl groups such as CF3 groups... Because of the electron deficiency, halogen anions such as fluorine anions are less likely to be eliminated, making it easier to form butene halogens instead of butyne halogens. Also, the E isomer is selectively formed. A 1 and A 2 This is more pronounced when the group is a perfluoroalkyl group, such as a CF3 group. This is because the trans configuration is more energetically stable due to the steric hindrance of the methyl dihalide group.

[0133] (2-1-1) Starting material compounds (halogenated alkane compounds) In this disclosure, the raw material compound for the method of producing a halogenated alkene compound from a halogenated alkane compound is general formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 X represents a fluorine atom or a perfluoroalkyl group, and is either identical or different.8 and X 9 These represent halogen atoms, either identical or distinct. It is a halogenated alkane compound represented by [formula].

[0134] In general formula (1B), A 1 and A 2 Perfluoroalkyl groups, X 8 and X 9 The halogen atoms shown can be those listed above. The same applies to preferred specific examples.

[0135] Examples of halogenated alkane compounds that satisfy these conditions include CF3CHClCHClCF3 (336mdd), CF3CHClCHFCl, CHFClCHFCl, CF3CHFCHFCF3 (338mee), CF3CHFCHF2, CHF2CHF2, CF3CHClCHClC2F5, C2F5CHClCHClC2F5, C2F5CHClCHFCl, CF3CHFCHFC2F5, C2F5CHFCHFC2F5, and C2F5CHFCHF2. These halogenated alkane compounds can be used individually or in combination of two or more. Alkane compounds can be known or commercially available.

[0136] (2-1-2) Dehalogenation reaction In the process of dehydrohalogenating a halide alkane compound in this disclosure, a halide alkene compound can be produced from the halide alkane compound with a high conversion rate (yield) and high selectivity. For example, if the substrate is a halide alkane compound represented by general formula (1B), A 1 and A 2 Both are preferably trifluoromethyl groups (CF3-), X 8 and X 9 It is more preferable that the atom is a fluorine atom or a chlorine atom.

[0137] In other words, the reaction equation is as follows: CF3CHClCHClCF3(336mdd) → CF3CCl=CHCF3((Z) or (E)-1326mxz) + HCl CF3CHFCHFCF3(338mee) → CF3CF=CHCF3((Z) or (E)-1327myz) + HF Accordingly, a dehydrofluoride reaction or a dehydrochlorination reaction is preferred.

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

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

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

[0141] In this process, the halogenated alkane compound of the raw material can be reacted with a high conversion rate (yield), and the halogenated alkene compound of the target compound can be produced with high selectivity. Among these catalysts, activated carbon, chromium oxide, chromium fluoride oxide, aluminum oxide, aluminum fluoride oxide, etc., are more preferred.

[0142] In this process, when contacting the raw material compound and 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 process, the catalyst may be in powder form, but pellet form is preferable for continuous gas-phase flow reactions.

[0144] The specific surface area of ​​the catalyst measured by the BET method (hereinafter also referred to as the BET specific surface area) is typically 10 to 3000 m². 2 / g is preferred, and 100-2000m 2 / g is more preferable, 500-1500m 2 / g is even more preferable, 1000~1300m 2 / g is particularly preferred. When the BET specific surface area of ​​the catalyst is within this range, Because the catalyst particle density is not too low, the target compound can be obtained with higher selectivity. Furthermore, it is possible to further improve the conversion rate of the starting compound.

[0145] When using activated carbon as a catalyst, it is preferable to use powdered activated carbon such as crushed carbon, molded carbon, granular carbon, or spherical carbon. For the powdered activated carbon, it is preferable to use powdered activated carbon with a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) according to JIS testing.

[0146] When using activated carbon as a catalyst, the activated carbon (for example, with a specific surface area of ​​1200 m²) 2 The activated carbon can be in powder or granular form (approximately per gram), and granular activated carbon is more preferable.

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

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

[0149] Fluorinated chromium oxide as a 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 temperature of fluorination is preferably, for example, 100°C to 460°C. The pressure of fluorination is preferably the pressure when subjected to the catalytic reaction. In the present disclosure, it is particularly preferable to use a highly fluorinated-chromium oxide catalyst with a high fluorine content. The highly fluorinated-chromium oxide catalyst can be obtained by fluorinating chromium oxide at a higher temperature and for a longer time than usual.

[0150] The highly fluorinated-chromium oxide catalyst preferably has a fluorine content of 30% by mass or more, and more preferably 30% to 45% by mass. The fluorine content can be measured by the mass change of the catalyst or by a general quantitative analysis method for chromium oxides.

[0151] Cyclic halogen carbides ​​​In this disclosure, the step of dehalogenating the above-described alkane halide compound may also be carried out in the presence of a cyclic halogenated carbide compound. A cyclic halogenated carbide compound means a cyclic halogenated carbide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are replaced by halogen atoms. In other words, it means a cyclic halogenated carbide compound that consists only of carbon atoms and halogen atoms and does not contain hydrogen atoms.

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

[0153] The cyclic halogenated carbide compounds described above can be used. Preferred specific examples, amounts used, and methods of introduction in liquid-phase and gas-phase reactions are also similar.

[0154] Reaction temperature In the dehalogenation reaction step in this 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 carrying out the dehalogenation reaction and obtaining the target compound (halogenated alkene compound) with higher selectivity, and from the viewpoint of suppressing a decrease in the conversion rate from the starting compound (halogenated alkane compound).

[0155] In the dehalogenation reaction step in this 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 carrying out the dehalogenation reaction and obtaining the target compound (halogenated alkene compound) with higher selectivity, and from the viewpoint of suppressing a decrease in selectivity due to the decomposition or polymerization of the reaction product.

[0156] Reaction time In the dehalogenation reaction process described herein, the conversion rate of the raw material compound can be increased by lengthening the contact time (W / F0) [W: weight of catalyst (g), F0: flow rate of raw material compound (cc / sec)] of the raw material compound. However, this requires a larger amount of catalyst, resulting in larger equipment and inefficiency.

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

[0158] The contact time of the raw material compound with the catalyst refers to the time during which the raw material compound and the catalyst are in contact.

[0159] In the dehalogenation reaction described herein, when carried out in the 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) in accordance with the catalyst.

[0160] In the dehalogenation reaction described herein, when chromium oxide is used as a catalyst, the reaction temperature is preferably 300°C or higher, and more preferably 350°C or higher. 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 dehalogenation reaction described herein, when alumina is used as a 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 dehalogenation reaction described herein, when activated carbon is used as a catalyst, the reaction temperature The temperature is preferably 50 to 600°C, and more preferably 100 to 400°C. The contact time is preferably 0.2 to 100 g·sec / cc, and preferably 0.3 to 50 g·sec / cc. Preferably, it is 0.5 to 43 g·sec / cc.

[0163] Reaction pressure In the dehalogenation reaction step in this 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, from the viewpoint of more efficiently carrying out the dehalogenation reaction. In this disclosure, unless otherwise specified, the pressure shall be gauge pressure.

[0164] In the dehalogenation reaction step described herein, the reactor used to contact and react the raw material compound (halogenated alkane compound) with the catalyst (activated carbon, metal catalyst, etc.) is not particularly limited in shape and structure, as long as it can withstand the above-mentioned temperature and pressure. Examples of reactors include vertical reactors, horizontal reactors, and multi-tube reactors. Examples of reactor materials include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0165] Examples of dehalogenation reactions The dehalogenation reaction step in this disclosure can be carried out by either a continuous flow method or a batch method, in which the starting material compound (halogenated alkane compound) is continuously charged into the reactor and the target compound (halogenated alkene compound) is continuously withdrawn from the reactor. It is preferable to carry out the reaction by the continuous flow method because the target compound (halogenated alkene compound) is not retained in the reactor and the dehalogenation reaction can proceed further.

[0166] The dehydrohalogenation reaction step in this disclosure is carried out in the gas phase, and is particularly preferably carried out in a continuous gas flow system using a fixed-bed reactor. Carrying the reaction in a continuous gas flow system simplifies the equipment and operation, and is also economically advantageous.

[0167] In the dehalogenation reaction step in this disclosure, the atmosphere during the reaction is preferably in the presence of an inert gas in order to suppress the degradation of the catalyst (activated carbon, metal catalyst, etc.). In this disclosure, at least one selected from the group consisting of nitrogen, helium, argon, and carbon dioxide can preferably be used as the inert gas. Among the gases, nitrogen is more preferable in terms of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gaseous components introduced into the reactor.

[0168] In the dehydrohalogenation reaction step described herein, after the reaction is complete, purification can be performed according to conventional methods as needed to obtain the target compound, which is a halogenated alkene compound represented by general formula (2B).

[0169] (2-1-3) Target compound (halogenated alkene compound) The target compound obtained in this manner has the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 X represents a fluorine atom or a perfluoroalkyl group, and is either identical or different. 8 This indicates a halogen atom. It is a halogenated alkene compound represented by [formula].

[0170] A in general formula (2B) 1 , A 2 and X 8 A in the general formula (1B) described above is 1 , A 2 and X 8This corresponds to the above. For this reason, examples of halogenated alkene compounds represented by general formula (2B) that are to be manufactured include, specifically, 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 the Z and E forms.

[0171] The alkene halide compounds obtained in this way can be effectively used in various applications such as etching gases, cleaning gases, deposit gases, refrigerants, heat transfer media, and building blocks for organic synthesis to form cutting-edge microstructures in semiconductors, liquid crystals, etc. Deposit gases and building blocks for organic synthesis will be discussed later.

[0172] [2-2] Method for producing alkyne fluoride compounds from halide alkene compounds A method for producing a halogenated alkyne compound in this disclosure is general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 These are identical or distinct, representing a fluorine atom or a perfluoroalkyl group. A method for producing an alkyne fluoride compound represented by, General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 The same applies as above. X 8 This indicates a halogen atom. The process includes a step of dehydrohalogenating an alkene halide compound represented by the formula in the presence of a catalyst.

[0173] (2-2-1) Starting material compounds (halogenated alkene compounds) The halogenated alkene compounds that can be used as substrates in the manufacturing method of this disclosure are as described above, with general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 X represents a fluorine atom or a perfluoroalkyl group, and is either identical or different. 8 This indicates a halogen atom. This is a halogenated alkene compound represented by [2-1], and corresponds to the target compound in the above-mentioned method for producing a halogenated alkene compound from a halogenated alkane compound.

[0174] In general formula (2B), A 1 and A 2 Perfluoroalkyl groups, X 8 The halogen atoms shown can be those listed above. The same applies to preferred types.

[0175] Examples of halogenated alkene compounds that satisfy the above conditions as substrates 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, and C2F5CCl=CHF Examples include CF3CF=CHC2F5, C2F5CF=CHC2F5, and C2F5CF=CHF. These compounds encompass both the Z and E isomers. These halogenated alkene compounds can also be used individually. It is possible to use two or more types in combination. Such halogenated alkene compounds Publicly known or commercially available products may be used.

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

[0177] In other words, the reaction equation is as follows: CF3CCl=CHCF3((Z) or (E)-1326mxz) → CF3C≡CCF3(PF2B) + HCl CF3CF = CHCF3((Z) or (E)-1327myz) → CF3C ≡ CCF3(PF2B) + HF Accordingly, a dehydrofluoride reaction or a dehydrochlorination reaction is preferred.

[0178] The step of removing hydrogen fluoride from a butane halogen compound in this disclosure can be carried out in the liquid phase or the gas phase. In particular, from the viewpoint of productivity, it is preferable to carry it out in the gas phase.

[0179] The step of dehalogenating an alkene halide compound in this disclosure 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 rate. More specifically, when employing a liquid-phase reaction, it is preferable to carry out the reaction in the presence of a base and, if necessary, a catalyst, and when employing a gas-phase reaction, it is preferable to carry out the reaction in the presence of a catalyst. Regarding the details of the liquid-phase reaction (solvent, base, catalyst, cyclic halogenated carbide compound, conditions of the closed reaction system and pressurized reaction system, etc.), the same as those described in the above-described method for producing a butene halide compound from a butane halide compound can be used, except that "the reaction to obtain a butene halide compound by dehalogenating an alkene halide compound" is read as "the reaction to obtain an alkyne fluoride compound by dehalogenating an alkene halide compound". Furthermore, for details in the case of gas-phase reactions (catalyst, cyclic halogenated carbide compound, reaction temperature, reaction time, reaction pressure, etc.), the same methods described in the above-mentioned [2-1] Method for producing halogenated alkene compounds from halogenated alkane compounds can be adopted, except that "reaction to obtain halogenated alkene compounds from halogenated alkane compounds by dehalogenation reaction" is read as "reaction to obtain fluorinated alkyne compounds from halogenated alkene compounds by dehalogenation reaction". The same applies to preferred types and content.

[0180] After the dehalogenation reaction is complete, the compound can be purified according to conventional methods as needed to obtain the butyne fluoride compound represented by general formula (3B).

[0181] (2-2-3) Target compound (fluorinated butyne compound) The compound of interest obtained in this manner has the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 These are identical or distinct, representing a fluorine atom or a perfluoroalkyl group. It is a butyne fluoride compound represented by [formula].

[0182] A in general formula (3B) 1 and A 2 A in the general formula (2B) described above is 1 and A 2 This corresponds to the following: Therefore, the butyrine fluoride compound represented by the general formula (3B) that we intend to manufacture is, for example, specifically CF3C≡CCF3(PF2B), CF3C≡CF, CF≡CF, CF3C≡CC2F5, C2F5C≡CC2F5 Examples include C2F5C≡CF.

[0183] The butynate compounds obtained in this way can be effectively used in various applications such as etching gases, cleaning gases, deposit gases, refrigerants, heat transfer media, and building blocks for organic synthesis to form cutting-edge microstructures in semiconductors, liquid crystals, etc. The deposit gases and building blocks for organic synthesis will be described later.

[0184] [2-3] Method for producing alkyne fluoride compounds from halogenated alkane compounds via halogenated alkene compounds The method for producing the alkyne fluoride compound described herein is: General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 These are identical or distinct, representing a fluorine atom or a perfluoroalkyl group. A method for producing an alkyne fluoride compound represented by, (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 The same applies as above. X 8 and X 9 These represent halogen atoms, either identical or distinct. A halogenated alkane compound represented by is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst, and the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 This is the same as above. A process for producing a halogenated alkene compound represented by the following: (IIB) After step (IB) above, a step to remove hydrogen halide, and (IIIB) After step (IIB), the general formula (2B) obtained: CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 This is the same as above. A halogenated alkene compound represented by is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst, and the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 This is the same as above. The process for producing alkyne fluoride compounds represented by Includes.

[0185] (2-3-1) Process (IB) In the method for producing the butyne fluoride compound of this disclosure, step (IB) can be carried out as described above in the explanation of the method for producing the halide alkene compound from the [2-1] halide alkane compound.

[0186] (2-3-2) Process (IIB) The method for producing the alkyne fluoride compound according to the present disclosure includes a step (IB) in which a halogenated alkane compound represented by the above general formula (1B) is subjected to a dehalogenation reaction to produce a halogenated alkene compound represented by the above general formula (2B), and a step (IIB) in which hydrogen halide is removed from a mixture containing the halogenated alkene compound and hydrogen halide.

[0187] In the method for producing alkyne fluoride compounds according to this disclosure, after step (IB), the hydrogen halide generated in the dehalogenation reaction of step (IB) is separated and / or removed, and then the process proceeds to the next step (IIIB) for the production of the alkyne fluoride compound. This allows the target compound, the alkyne fluoride compound, to be produced by the dehalogenation 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 description of step (IIA) of the above-mentioned method for producing a halogenated butane compound from a halogenated butane compound via a halogenated butene compound, instead of separating hydrogen fluoride, hydrogen halide is Aside from reinterpreting it to separate the parts, it can be adopted as is.

[0189] (2-3-3) Process (IIIB) In the method for producing alkyne fluoride compounds according to the present disclosure, step (IIIB) can be carried out as described above for the method for producing alkyne fluoride compounds from [2-2]halogenated alkene compounds.

[0190] (2-3-4) Examples of dehalogenation reactions In the dehydrohalogenation reaction process described herein, the reaction takes place in step (IB) in the reactor. The process can be carried out by either a continuous flow system or a batch system, in which the raw material compound (halogenated alkane compound) is continuously charged and the target compound (halogenated alkene compound) is continuously withdrawn from the reactor. Subsequently, hydrogen halide is removed from the mixture containing the haogenated alkene compound and hydrogen halide (step (IIB)), and in step (IIIB), the reactor The process can be carried out by either a continuous flow system or a batch system, in which the 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. It is preferable to carry out the process by a continuous flow system because the target compound (halogenated alkene compound or fluorinated alkyne compound) is not retained in the reactor at each step, and the dehalogenation reaction can proceed further.

[0191] In the dehydrohalogenation reaction step described herein, the reaction is carried out in the gas phase, and is particularly preferably carried out in a continuous gas flow system using a fixed-bed reactor. Carrying the reaction in a continuous gas flow system simplifies the equipment and operation, and is also economically advantageous.

[0192] In the dehalogenation reaction step in this disclosure, the atmosphere during the reaction is preferably in the presence of an inert gas in order to suppress the degradation of the catalyst (activated carbon, metal catalyst, etc.). In this disclosure, at least one selected from the group consisting of nitrogen, helium, argon, and carbon dioxide can preferably be used as the inert gas. Among the gases, nitrogen is more preferable in terms of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gaseous components introduced into the reactor.

[0193] In the dehydrohalogenation reaction step described herein, after the reaction is complete, the target compound (halogenated alkene compound or fluorinated alkyne compound) can be obtained by purification treatment in accordance with conventional methods as described above.

[0194] 3. Composition As described above, butene halogenated compounds, butyne halogenated compounds, alkene halogenated compounds, or alkyne fluoride compounds can be obtained, but they may also be obtained in the form of a composition containing the target compound.

[0195] [3-1] Composition comprising a halogenated butene compound or a halogenated alkene compound According to the manufacturing method of this disclosure, for example, when following the manufacturing method from the [1-1]halide butane compound to the halide butene compound described above, a composition may be obtained that includes both the E and Z isomers of the halide butene compound represented by general formula (2A). Furthermore, this composition may include 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 This is the same as above. Butylen halide compounds represented by, 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 This is the same as above. It may also contain a halogenated butadiene compound represented by [formula].

[0196] In general formulas (2A), (3A), and (4), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7As shown Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred, and fluorine atoms being more preferred.

[0197] With the total amount of the composition disclosed herein being 100 mol%, the content of the butene halogenated compound represented by general formula (2A) is preferably 80.00 to 99.99 mol%, preferably 90.00 to 99.98 mol%, and more preferably 92.00 to 99.97 mol%. Also, the butyne halogenated compound represented by general formula (3A) The content of is preferably 0.00 to 3.00 mol%, more preferably 0.01 to 2.00 mol%, but depending on the synthesis conditions, it can also be 1.00 to 10.00 mol% (particularly 2.00 to 8.00 mol%). In addition, the content of the halogenated butadiene compound represented by general formula (4) is preferably 0.00 to 0.50 mol%, more preferably 0.01 ~0.30 mol% is more preferable. If the butene halogen compound represented by general formula (2A) contains both the E and Z isomers, the above content is the total amount of both.

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

[0199] Furthermore, according to the manufacturing method of this disclosure, even when obtained as a halogenated butene composition, the halogenated butene compound represented by general formula (2A) can be obtained with a high conversion rate, high yield, and high selectivity as described above. Therefore, it is possible to reduce the amount of components other than the halogenated 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, when following the method for producing a halogenated alkene compound from a halogenated alkane compound, 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 general formula (2B)) is obtained. This 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 for producing a halogenated alkene compound from a halogenated alkane compound according to this disclosure, 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (1326mxz) is used as the target product. When obtained, (Z)-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz(Z)) is produced. It is possible.

[0203] A composition containing a halogenated alkene compound represented by general formula (2B) of this disclosure preferably has a content of 80 mol% or more of the halogenated alkene compound represented by general formula (2B) and a content of 20 mol% or less of the additional compound, with the total amount of the composition being 100 mol%. In a composition containing a halogenated alkene compound represented by general formula (2B) of this disclosure, with the total amount of the composition being 100 mol%, the content of the halogenated alkene compound represented by general formula (2B) preferably is 85 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. In a composition containing a kene compound, with the total amount of the composition being 100 mol%, 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%.

[0204] [3-2] Compositions comprising a halogenated butyne compound or an alkyne fluoride compound According to the manufacturing method of the present disclosure, for example, when following the method for producing an alkyne fluoride compound from a [2-2]halogenated alkene compound as described above, for example, an alkyne fluoride compound represented by the general formula (3B) and at least one hydrofluorocarbon (HFC) compound (excluding the alkyne fluoride compound represented by the general formula (3B)) A composition containing the additional compound may be produced. [1-2] If the method for producing a butylen halogenated compound from a butene halogenated compound is followed, the resulting composition will be of the general formula (3A) A halogenated butyn compound represented by the above, and a hydrofluorocarbon (HFC) compound (the above) At least one additional compound consisting of (excluding butyn halogenated compounds represented by general formula (3A)) A composition containing the 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 manufacturing methods for obtaining halogenated butyn compounds from halogenated butene compounds and for obtaining fluorinated alkyne compounds from halogenated alkene compounds according to the present disclosure, trifluoromethane (HFC-23, R23) may be produced when obtaining 1,1,1,4,4,4-hexafluoro-2-butyn (PF2B) as the target product.

[0207] In the composition containing a halogenated butine compound or an alkyne fluoride compound in this disclosure, it is preferable that the content of the halogenated butine compound or alkyne fluoride compound is 80 mol% or more, and the content of the additional compound is 20 mol% or less, with the total amount of the composition being 100 mol%. In the composition containing a halogenated butine compound or an alkyne fluoride compound, with the total amount of the composition being 100 mol%, it is preferable that the content of the halogenated butine compound or alkyne fluoride compound is 85 mol% or more, more preferably 90 mol% or more, and 95 mol% or less. It is even more preferable that the above is true. In a composition comprising a halogenated butyn compound or an alkyne fluoride compound of the present disclosure, with the total amount of the composition being 100 mol%, the content of the halogenated butyn compound or alkyne fluoride 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%.

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

[0209] The compositions comprising the butene halogenated compound, butyne halogenated compound, alkene halogenated compound, or alkyne fluoride compound of this disclosure can be effectively used in various applications, such as etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, etc., as well as cleaning gases, deposit gases, refrigerants, heat transfer media, and building blocks for organic synthesis, just as with the butene halogenated compound, butyne halogenated compound, alkene halogenated compound, or alkyne fluoride compound individually.

[0210] The aforementioned deposit gas is a gas used to deposit an etching-resistant polymer layer.

[0211] The aforementioned building blocks for organic synthesis refer to substances that can serve as precursors for compounds having a highly reactive skeleton. For example, the composition of this disclosure and fluorine-containing organic compounds such as CF3Si(CH3)3. When reacted with an ion compound, fluoroalkyl groups such as CF3 are introduced, forming a detergent or fluorine-containing compound. It is possible to convert it into a substance that can serve as a pharmaceutical intermediate.

[0212] The embodiments of this disclosure have been described above, but they do not deviate from the spirit and scope of the claims. In addition, a wide variety of changes to the form and details are possible. [Examples]

[0213] Examples are given below to clarify the features of this disclosure. This disclosure is not limited to these examples.

[0214] In the methods for producing butene halogenated compounds of Examples 1 to 7, the raw material compound is a butene halogenated compound represented by general formula (1A), where X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 Let be a fluorine atom, and the reaction equation is as follows: CF3CFHCFHCF3→ CF3CF=CHCF3+ HF Accordingly, a butene halogen compound was obtained by a dehydrofluoride reaction.

[0215] In the method for producing halogenated alkene compounds and butyne fluoride compounds of Example 8, the raw materials are The compound is a halogenated alkane compound represented by general formula (1B), where X 8 and X 9 Let A be a chlorine atom. 1 and A 2 Let be a trifluoromethyl group, and follow the reaction: CF3CHClCHClCF3(336mdd) → CF3CCl=CHCF3((Z) or (E)-1326mxz) + HCl CF3CCl=CHCF3((Z) or (E)-1326mxz) → CF3C≡CCF3(PF2B) + HCl According to the procedure, a halogenated alkene compound and a butyne fluoride compound were obtained by a dehydrochlorination reaction.

[0216] In the methods for producing halogenated alkene compounds and butyne fluoride compounds of Examples 9 to 20, The material compound is a halogenated alkane compound represented by general formula (1B), where X 8 and X 9 Let A be a fluorine atom. 1 and A 2 Let be a trifluoromethyl group, and follow the reaction: CF3CHFCHFCF3(338mee) → CF3CF=CHCF3((Z) or (E)-1327myz) + HF CF3CF = CHCF3((Z) or (E)-1327myz) → CF3C ≡ CCF3(PF2B) + HF Accordingly, a halogenated alkene compound and a fluorinated butyne compound were obtained by a dehydrofluorination reaction.

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

[0218] By using an autoclave as the reaction system, this reaction system can be carried out in the presence of (1) a base. (2) The reaction system is a closed system, and the reaction temperature is 10°C or higher and the reaction pressure is 0kPa or higher. This describes a configuration of a pressurized reaction system carried out in the presence of a base. This pressurization process involves sealing the system.

[0219] Add 7.0 g of a 50% by mass aqueous solution of KOH or potassium tert-butoxide (t-BuOK) to the autoclave as the reaction solution, and optionally add methyltrioctylammonium chloride as a catalyst. Add 0.28g of (trademark Aliquat336), then add 8.0g of the raw material compound (CF3CFHCFHCF3), and lid. After creating a sealed system, nitrogen was injected under pressure. The pressure at that time was 20 kPa. Afterward, the mixture was stirred at room temperature (25°C) to allow the reaction to proceed. Sampling was performed periodically after the start of the dehydrofluoride reaction, and the reaction was considered complete when there was no longer a change in the composition within the reaction system. The pressure at the end of the reaction was 80 kPa.

[0220] After stopping stirring, cool to 0°C and perform gas chromatography (Shimadzu Corporation, product name). Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS) with "GC-2014". The following steps were performed, and structural analysis was carried out using NMR spectroscopy (JEOL Corporation, product name "400YH"). Based on the results of mass spectrometry and structural analysis, the target compound CF3CF=CHCF3 was formed. This was confirmed. The results are shown in Table 1.

[0221] Examples 4-6: Gas-phase reaction (activated carbon) The reaction tube is a SUS pipe (outer diameter: 1 / 2 inch), and the catalyst is an activated carbon catalyst (manufactured by Osaka Gas Chemical Co., Ltd.; specific surface area 1200 m²). 2 10g of ( / g) was added. After drying at 200°C for 2 hours under a nitrogen atmosphere, The pressure is set to atmospheric pressure, and the contact time (W / F) between CF3CFHCFHCF3 (raw material compound) and the activated carbon catalyst is set to 15 g·sec / cc, 30 g·sec / cc, or 47 g·sec / cc. They circulated goods.

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

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

[0224] One hour after the start of the dehydrofluoride reaction, the distillate that passed through the decontamination tower was collected.

[0225] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used. Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Corporation) was used to analyze the results. Structural analysis was performed using NMR spectroscopy with the product name "400YH". Mass spectrometry and structural analysis confirmed the formation of the target compound, CF3CF=CHCF3. This is 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 4-6, 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 (starting 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 (Hydrogen Chloride Removal) 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 ) SUS piping (outer diameter: 1 / 2 inch) was used as the reaction tube, and activated carbon catalyst (specific surface area 1200 m²) was used as the catalyst in the reaction tube. 2 10g of ( / g) was packed in. After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to atmospheric pressure. The CF3CHClCHClCF3 (starting compound) was passed through the reactor so that the contact time (W / F0) between the CF3CHClCHClCF3 (starting compound) and the activated carbon catalyst was 5 g·sec / cc or 25 g·sec / cc.

[0229] The reaction was carried out using a continuous gas-phase flow system.

[0230] The reactor was heated to 300°C or 400°C to begin the dehydrochlorination process.

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

[0232] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used. Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Corporation) was used to analyze the results. Structural analysis was performed using NMR spectroscopy with the product name "400YH".

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

[0234] Furthermore, in the method for producing a halogenated alkene compound from the above-mentioned halogenated alkane compound, in addition to the target product 1326mxz(CF3CCl=CHCF3), (Z)-1,1,1,4,4,4-hexafluorobuta-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 ) SUS piping (outer diameter: 1 / 2 inch) was used as the reaction tube, and activated carbon catalyst (specific surface area 1200 m²) was used as the catalyst in the reaction tube. 2 10g of ( / g) was filled.

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

[0238] The hydrogen chloride concentration in the reaction gas containing the halogenated alkene compound at that time was 50 mol%. The reaction gas from the first reactor is subjected to rectification, alkali treatment, secard treatment, and alumina treatment. The hydrogen chloride concentration was adjusted to 20 mol%, 3 mol%, or 0.1 mol% by various methods.

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

[0240] The reaction was carried out using a continuous gas-phase flow system.

[0241] The reactor was heated to 400°C to begin the dehydrochlorination process.

[0242] One hour after the start of hydrogen chloride removal, the distillate that passed through the decontamination tower was collected.

[0243] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used. Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Corporation) was used to analyze the results. Structural analysis was performed using NMR spectroscopy with the product name "400YH".

[0244] Mass spectrometry and structural analysis confirmed that the target compound was an alkyne fluoride compound (PF2B(CF3C≡CCF3)).

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

[0246] [Table 3]

[0247] Example 9 (Hydrogen fluoride removal) 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 ) SUS piping (outer diameter: 1 / 2 inch) was used as the reaction tube, and activated carbon catalyst (specific surface area 1200 m²) was used as the catalyst in the reaction tube. 2 10g of ( / g) was filled.

[0248] After drying at 200°C for 2 hours under a nitrogen atmosphere, the CF3CHFCHFCF3 (raw material compound) was flowed through the reactor at atmospheric pressure, so that the contact time (W / F0) between the 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 using a continuous gas-phase flow system.

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

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

[0252] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used. Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Corporation) was used to analyze the results. Structural analysis was performed using NMR spectroscopy with the product name "400YH".

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

[0254] (3) 1327myz(CF 3 CF = CHCF 3 )→PF2B(CF 3 C≡CCF 3 ) SUS piping (outer diameter: 1 / 2 inch) was used as the reaction tube, and activated carbon catalyst (specific surface area 1200 m²) was used as the catalyst in the reaction tube. 2 10g of ( / g) was filled.

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

[0256] The hydrogen chloride concentration in the reaction gas containing the halogenated alkene compound at that time was 50 mol%. The reaction gas from the first reactor is subjected to rectification, alkali treatment, secard treatment, and alumina treatment. The hydrogen chloride concentration was adjusted to 20 mol%, 3 mol%, or 0.1 mol% by various methods.

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

[0258] The reaction was carried out using a continuous gas-phase flow system.

[0259] The reactor was heated to 400°C to begin the dehydrofluoridation process.

[0260] One hour after the start of the hydrogen fluoride removal process, the distillate that passed through the decontamination tower was collected.

[0261] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used. Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Corporation) was used to analyze the results. Structural analysis was performed using NMR spectroscopy with the product name "400YH".

[0262] Mass spectrometry and structural analysis confirmed that the target compound was an alkyne fluoride compound (PF2B(CF3C≡CCF3)).

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

[0264] [Table 4]

[0265] Examples 10-16 (Hydrogen fluoride removal) 338mee(CF 3 CHFCHFCF 3 )→1327myz(CF 3 CF = CHCF 3 ) SUS piping (outer diameter: 1 / 2 inch) was used as the reaction tube, and activated carbon catalyst (specific surface area 1200 m²) was used as the catalyst in the reaction tube. 2 10g of ( / g) was packed in. After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to atmospheric pressure. The contact time (W / F0) between CF3CHFCHFCF3 (raw material compound) and the activated carbon catalyst is 2-47 g·sec / cc. To achieve this, CF3CHFCHFCF3 (the starting compound) was passed through the reactor. Subsequently, in Examples 10 to 13, 4 moles of octafluorocyclobutane (c-C4F8; C318) were passed through the reactor per mole of CF3CHFCHFCF3 (the starting compound).

[0266] The reaction was carried out using a continuous gas-phase flow system.

[0267] The reactor was heated to 400°C to begin the dehydrochlorination process.

[0268] One hour after the start of hydrogen chloride removal, the distillate that passed through the decontamination tower was collected.

[0269] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used. Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Corporation) was used to analyze the results. Structural analysis was performed using NMR spectroscopy with the product name "400YH".

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

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

[0272] [Table 5]

[0273] Examples 17-20 (Hydrogen fluoride removal) 1327myz(CF 3 CF = CHCF 3 )→PF2B(CF 3 C≡CCF 3 ) SUS piping (outer diameter: 1 / 2 inch) was used as the reaction tube, and activated carbon catalyst (specific surface area 1200 m²) was used as the catalyst in the reaction tube. 2 10g of ( / g) was packed in. After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to atmospheric pressure. Then, CF3CF=CHCF3 (the raw material compound) was passed through the reactor so that the contact time (W / F0) between CF3CF=CHCF3 (the raw material compound) and the activated carbon catalyst was 2 g·sec / cc, 2.8 g·sec / cc, or 10 g·sec / cc. Subsequently, in Examples 17-18, 4 moles of octa per mole of CF3CF=CHCF3 (the raw material compound) were used. Fluorocyclobutane (c-C4F8; C318) was distributed.

[0274] The reaction was carried out using a continuous gas-phase flow system.

[0275] The reactor was heated to 400°C to begin the dehydrochlorination process.

[0276] One hour after the start of hydrogen chloride removal, the distillate that passed through the decontamination tower was collected.

[0277] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used. Mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Corporation) was used to analyze the results. Structural analysis was performed using NMR spectroscopy with the product name "400YH".

[0278] Mass spectrometry and structural analysis confirmed that the target compound was an alkyne fluoride compound (PF2B:CF3C≡CCF3).

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

[0280] [Table 6]

Claims

1. General form (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [wherein, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and each represents a halogen atom.], a method for producing a halogenated butene compound represented by: General formula (4): 【Chemistry 1】 [In the formula, A3, A4, A5, A6, A7, A8, A9, and A10 are the same or different and represent a fluorine atom or a trifluoromethyl group.] In the presence of a cyclic halogenated carbide compound represented by, 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 This is the same as above. A method for producing a butane halogenated compound represented by [formula], comprising the step of dehydrofluorinating the compound in the gas phase.

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 The halogenated butyn compounds represented by [ ] are the same or different and represent halogen atoms. General formula (4): 【Chemistry 2】 [In the formula, A3, A4, A5, A6, A7, A8, A9, and A10 are the same or different and represent a fluorine atom or a trifluoromethyl group.] In the presence of a cyclic halogenated carbide compound represented by, 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 The same applies as above. X 4 The symbol represents a halogen atom. This is a process of dehalogenating a butene halogenated compound represented by [ ] in the gas phase. A manufacturing method that includes this.

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 The halogenated butyn compounds represented by [ ] are the same or different and represent halogen atoms. (IA) General formula (4): 【Transformation 3】 [In the formula, A3, A4, A5, A6, A7, A8, A9, and A10 are the same or different and represent a fluorine atom or a trifluoromethyl group.] In the presence of a cyclic halogenated carbide compound represented by, 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 The same applies as above. X 4 represents a halogen atom. A butane halogenated compound represented by ] is subjected to a dehydrofluoride reaction in the gas phase to obtain the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [wherein, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same as described above.] A process for producing a butene halogen compound represented by the following: (IIA) A step of removing hydrogen fluoride after the above step (IA), and (IIIA) After step (IIA), General formula (4): 【Chemistry 4】 [In the formula, A3, A4, A5, A6, A7, A8, A9, and A10 are the same or different and represent a fluorine atom or a trifluoromethyl group.] In the presence of a cyclic halogenated carbide compound represented by, The resulting 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 This is the same as above. Butene halogen compounds represented by the general formula (3A): CX are subjected to a dehydrohalogenation reaction in the gas phase. 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 This is the same as above. A process for producing a halogenated butyne compound represented by A manufacturing method that includes this.

4. The manufacturing method according to any one of claims 1 to 3, wherein the step of performing the dehydrofluoride reaction and / or the dehydrohalogenate reaction is carried out in the presence of at least one catalyst selected from the group consisting of activated carbon catalyst, chromium oxide catalyst, zeolite catalyst and silica alumina catalyst.

5. The manufacturing method according to any one of claims 1 to 4, wherein the step of performing the dehydrofluoride reaction and / or the dehydrohalogenate reaction is carried out in a gas-phase continuous flow manner.

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