Production method of halogenated alkene compound and fluorinated alkyne compound

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 halogenated alkyne compound.

Background Art

[0002] As a method for producing a halogenated alkene compound, for example, in Patent Document 1, CF 3 CHClCHClCCl 3 , CF 3 CCl 2 CH 2 CCl 3 , CF 3 CClHCHFCCl 3 , CF 3 CClFCH 2 CCl 3 etc. are used as starting materials, reacted with hydrogen fluoride in the presence of an oxyfluorinated chromium catalyst, and dehydrofluorinated while being fluorinated to obtain CF CF=CHCF 3 CF=CHCF 3 is obtained.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a method capable of obtaining a halogenated alkene compound and a halogenated alkyne compound with high conversion rate and high selectivity.

Means for Solving the Problems

[0005] The present disclosure includes the following configurations. Item 1. General formula (2A): CX 1 X2 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 process for producing a halogenated butene compound represented by General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [wherein X 1 、X 2 、X 3 、X 4 、X 5 、X 6 and X 7 are the same as defined above.] The production method includes a step of subjecting a halogenated butane compound represented by Item 2. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [wherein X 1 、X 2 、X 3 、X 5 、X 6 and X 7 are the same or different and each represents a halogen atom.] A process for producing a halogenated butyne compound represented by General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX5 X 6 X 7 (2A) [wherein, X 1 、X 2 、X 3 、X 5 、X 6 and X 7 are the same as defined above. X 4 represents a halogen atom.] A step of subjecting a halogenated butene compound represented by to a dehydrohalogenation reaction Item 3. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [wherein, X 1 、X 2 、X 3 、X 5 、X 6 and X 7 are the same or different and each represents a halogen atom.] A method for producing a halogenated butyne compound represented by (IA) General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [wherein, X 1 、X 2 、X 3 、X 5 、X 6 and X 7 are the same as defined above. X 4 represents a halogen atom.] Subjecting a halogenated butane compound represented by to a defluorination reaction to obtain general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X7 (2A) [wherein, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same as described above.] 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) [wherein, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same as described above.] A step of subjecting the halogenated butene compound represented by to a dehydrohalogenation reaction to obtain the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [wherein, 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 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 dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a sealed reaction system. Item 7. The production method according to any one of Items 1 to 4, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in a gas phase. Item 8. The production method according to Item 7, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst, and a silica-alumina catalyst. Item 9. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and each represents a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] A production method of a halogenated alkene compound represented by General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 are the same as defined above. X 8 and X 9 are the same or different and each represents a halogen atom.] A production method comprising a step of subjecting a halogenated alkane compound represented by to a dehydrohalogenation reaction in a gas phase in the presence of a catalyst. Item 10. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and each represents a fluorine atom or a perfluoroalkyl group.] A method for producing an alkynyl fluoride compound represented by General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same as described above. X 8 represents a halogen atom.] A method for producing a halogenated alkene compound represented by, which includes a step of subjecting the halogenated alkene compound to a dehydrohalogenation reaction in the presence of a catalyst. Item 11. The production method according to item 10, wherein the step of subjecting the dehydrohalogenation reaction 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 are the same or different and represent a fluorine atom or a perfluoroalkyl group.] A method for producing an alkynyl 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 are the same as described above. X 8 and X 9 are the same or different and represent a halogen atom.] A halogenated alkane compound represented by is subjected to a gas-phase dehydrohalogenation reaction in the presence of a catalyst to obtain a halogenated alkene compound represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 are the same as described above.] A step of producing a halogenated alkene compound represented by (IIB) After the step (IB), a step of removing hydrogen halide, and (IIIB) After the step (IIB), the obtained general formula (2B): CX 8 A 1 =CHA 2 (2B) [wherein A 1 , A 2 and X 8 are the same as defined above.] The halogenated alkene compound represented by the formula is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst to obtain a general formula (3B): CA 1 ≡CA 2 (3B) [wherein A 1 and A 2 are the same as defined above.] A step of producing an alkyne fluoride compound represented by the formula A production method comprising the above steps Item 13. The production method according to any one of Items 1 to 12, wherein the dehydrofluorination reaction and / or the dehydrohalogenation reaction step is carried out in a gas-phase continuous flow system Item 14. The dehydrofluorination reaction and / or the dehydrohalogenation reaction step is carried out In the presence of a cyclic carbon halogen compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are substituted with halogen atoms. The production method according to any one of Items 1 to 13 Item 15. General formula (1A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (1A) [wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 independently represent a halogen atom.] A composition containing a halogenated butene compound represented by the formula A composition in which the content of the butene halide compound represented by the general formula (1A) is 80.00 to 99.99 mol% based on 100 mol% of the total amount of the composition. Item 16. The composition according to item 15, wherein the (E)-butene halide compound is contained in an amount of 85.00 to 99.98 mol% as the butene halide compound represented by the general formula (1A) based on 100 mol% of the total amount of the composition. Composition. Item 17. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and each represents a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] A composition containing an alkene halide compound represented by and at least one hydrofluorocarbon (HFC) compound (excluding the alkene halide compound represented by the general formula (2B)). Composition. Item 18. The composition according to item 17, wherein the content of the alkene halide compound represented by the general formula (2B) is 80 mol% or more and the content of the hydrofluorocarbon (HFC) compound is 20 mol% or less based on 100 mol% of the total amount of the composition. Item 19. The hydrofluorocarbon (HFC) compound is at least one selected from the group consisting of hexafluorobutene, hexafluorobutane, and octafluorobutane. The composition according to item 17 or 18. Item 20. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and each represents a fluorine atom or a perfluoroalkyl group.] A composition containing an alkyne fluoride compound represented by ​Comprising at least one hydrofluorocarbon (HFC) compound (excluding the alkyne fluoride compound represented by the general formula (3B)). Composition. Item 21. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [Wherein X 1 , X 2 , X 3 , X 5 , X 6 and X 7 independently represent a halogen atom.] A butyne halide compound represented by the formula, and Comprising at least one hydrofluorocarbon (HFC) compound (excluding the butyne halide compound represented by the general formula (3A)). Composition. Item 22. With the total amount of the composition being 100 mol%, the content of the alkyne fluoride compound represented by the general formula (3B) or the butyne halide compound represented by the general formula (3A) is 80 mol% or more and the content of the hydrofluorocarbon (HFC) compound is 20 mol% or less. The composition according to Item 20 or 21. Item 23. The hydrofluorocarbon (HFC) compound is at least one selected from the group consisting of trifluoromethane, difluoromethane, tetrafluoromethane and monofluoromethane. The composition according to any one of Items 20 to 22. Item 24. The composition according to any one of Items 15 to 23, which is used as a cleaning gas, an etching gas, a refrigerant, a heat transfer medium or a building block for organic synthesis.

Advantages of the Invention

[0006] ​

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0008] In this specification, "containing" is a concept encompassing any of "comprise", "consist essentially of", and "consist of". Also, in this specification, when a numerical range is indicated as "A to B", it means A or more and B or less.

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

[0010] In the present disclosure, the "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, CF 3 CHClCHClCCl 3 、CF 3 CCl 2 CH 2 CCl 3 、CF3 CClHCHFCCl 3 、CF 3 CClFCH 2 CCl 3 etc. are used as starting materials and reacted with hydrogen fluoride in the presence of a chromium oxyfluoride catalyst to cause dehydrogenation while fluorinating to obtain CF 3 CF=CHCF 3 However, the yield was only 14.8%.

[0012] From the above, according to the conventional method, the yield was only 14.8%. According to the production method of the present disclosure even compared with the conventional method, halogenated alkene compounds and halogenated alkyne compounds can be synthesized with high conversion rates and high selectivities.

[0013] 1. Process for producing halogenated butene compounds and halogenated butyne compounds [1-1] Production method from halogenated butane compounds to halogenated butene compounds The production method of the halogenated butene compound of the present disclosure is General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent halogen atoms.] It is a production method of a halogenated butene compound represented by General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [In the formula, X1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] It includes the step of dehydrogenating a butane halide compound represented by .

[0014] According to the present disclosure, by performing the dehydrogenation reaction of the butane halide compound represented by the above general formula (1A), a butene halide compound represented by the general formula (2A) in which 1 mole of hydrogen fluoride has been eliminated with respect to 1 mole of the butane halide compound represented by the general formula (1A) can be selectively obtained. Moreover, from the butene halide compound represented by the general formula (2A) continuously, the elimination reaction of hydrogen halide represented by HX 4 is unlikely to occur. Also, according to the present disclosure , as the butene halide compound represented by the general formula (2A), among the geometric isomers, the E-isomer can be selectively synthesized. This is because due to the electron-withdrawing effect of the trihalomethyl group such as the CF 3 group, the carbon at the α-position of the trihalomethyl group such as the CF group becomes electron-deficient, so it is difficult for a halogen anion such as a fluorine anion to be eliminated, resulting in the formation of a butene halide rather than a butyne halide. Also, the reason why the E-isomer can be selectively formed is that due to the steric hindrance of the trihalomethyl group such as the CF 3 group, the trans configuration is more energetically stable . 3 .

[0015] (1-1-1) Raw material compound (butane halide compound) The butane halide compound as a substrate that can be used in the production method of the present disclosure is, as described above, the 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 are the same or different and each represents a halogen atom.] It is a butane halide compound represented by .

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

[0017] As the butane halide compound that is the substrate, in terms of being able to produce a butene halide compound with particularly high conversion rate, yield, and selectivity, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are all preferably a fluorine atom and a chlorine atom, and more preferably a fluorine atom.

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

[0019] Specific examples of the butane halide compound as the substrate satisfying the above conditions include CF 3 CFHCFHCF 3 , CCl 3 CClHCFHCCl 3 , CBr 3 CBrHCFHCBr 3Examples include these halogens. The butane halide compounds can be used alone or in combination of two or more. Such butane halide compounds can employ known or commercially available products.

[0020] (1-1-2) Dehydrofluorination reaction In the step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction, for example, as the substrate, in the butane halide compound represented by the general formula (1A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are more preferably fluorine atoms.

[0021] That is, the following reaction formula: CF 3 CFHCFHCF 3 → CF 3 CF=CHCF 3 + HF According to this, a dehydrofluorination reaction is preferred.

[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 dehydrofluorination reaction of the butane halide compound in the present disclosure 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 dehydrofluorination reaction of the butane halide compound in the present disclosure 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-mentioned 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 rolactone, γ-valerolactone, lactones such as tetrahydrofuran and tetrahydropyran nes; 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 a hydrogen fluoride from a butane halide compound in the present disclosure is carried out in a liquid phase, as described above, it is preferably carried out in the presence of a base.

[0028] As the base, from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the butene halide compound, hydroxides or alkoxides of an alkali metal or an alkaline earth metal are preferable, and alkoxides of an alkali metal or an alkaline earth metal are more preferable. Specifically, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium tert-butoxide, etc. may be mentioned, and sodium methoxide, potassium tert-butoxide, etc. are preferable. In this step, it is preferable to use 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 preferable. Specifically, aqueous solutions of sodium methoxide, potassium methoxide, potassium ethoxide, potassium tert-but oxide, etc. are particularly preferable. By using such a base, the target compound can be obtained with a higher selectivity and a higher conversion rate.

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

[0030] Catalyst In this process, a catalyst can be used as needed. The catalyst used in this process is preferably a hydrocarbon-based alkoxide. Examples of the hydrocarbon-based alkoxide include tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium fluoride, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, benzyltributylammonium fluoride, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium iodide, methyltributylammonium fluoride, methyltributylammonium chloride, methyltributylammonium bromide, methyltributylammonium iodide, methyltrioctylammonium fluoride, methyltrioctylammonium chloride (trademark Aliquat336), methyltrioctylammonium bromide, methyltrioctylammonium iodide, etc. The catalyst can be used alone or in combination of two or more kinds. By using the catalyst, the target compound can be obtained with a higher selectivity and a higher conversion rate.

[0031] Cyclic carbon halide compound In the present disclosure, the step of subjecting the above-described butane halide compound to a dehydrofluorination reaction can also be carried out in the presence of a cyclic carbon halide compound. This cyclic carbon halide compound means a cyclic carbon halide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are substituted with halogen atoms. In other words, it means a cyclic carbon halide compound composed only of carbon atoms and halogen atoms and containing no hydrogen atoms.

[0032] By carrying out the step of subjecting the above-described butane halide compound to a dehydrofluorination reaction in the presence of such a cyclic carbon halide compound, it is possible to shift the equilibrium of the reaction to the product side, and the target butene halide compound can be obtained with a higher conversion rate and a higher yield.

[0033] As the halogen atoms contained in the cyclic carbon halide compound that can be used, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms can all be included. Among them, from the viewpoint of the efficiency of the reaction, it is preferable to contain the same kind of halogen atoms as the halogen atoms (X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、and X 7 ) contained in the butane halide compound as the raw material compound. When the butane halide compound has a plurality of types of halogen atoms (X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、and X 7 are not all the same), the cyclic carbon halide compound preferably contains one or more of the halogen atoms contained in the butane halide compound, and it is also preferable when the butane halide compound contains only one kind of halogen atom.

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

[0035] The cyclic carbon halogen compound that can be used may be a saturated cyclic carbon halogen compound having no unsaturated bond or an unsaturated cyclic carbon halogen compound having an unsaturated bond. Among them, from the viewpoints of the conversion rate, selectivity, and yield of the target butene halide compound, a saturated cyclic carbon halogen compound is preferred.

[0036] From the above, as the cyclic carbon halogen compound, a saturated cyclic carbon halogen compound is preferred. Such a saturated cyclic carbon halogen compound has the general formula (4):

[0037]

Chemical formula

[0038] [In the formula, A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 are the same or different and each represents a fluorine atom or a per fluoroalkyl group.] The saturated cyclic carbon halogen compound represented by is preferred.

[0039] In the 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 by fluorine atoms. The perfluoroalkyl group is, for example, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 ~6 carbon atoms, even more preferably 1 to 4 carbon atoms, and 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 (CF 3 -), and a pentafluoroethyl group (C 2 F 5 -) are preferred.

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

[0041]

Chemical formula

[0042] and the like.

[0043] In the production method of the present disclosure, when dehydrofluorinating a butane halide compound in the liquid phase in the presence of a cyclic carbon halogen compound, for example, the cyclic carbon halogen compound may be blown into a 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 dehydrofluorinating a butane halide compound in the presence of a cyclic carbon halogen compound, the amount of the cyclic carbon halogen compound used is not particularly limited. From the viewpoints of the conversion rate, selectivity, and yield of the target butene halide compound, it is preferably an excessive amount relative 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 even more preferable, per 1 mole of the butane halide compound as the raw material compound.

[0045] Sealed reaction system In the present disclosure, the halogenated butene compound represented by the general formula (2A) of the target compound has a low boiling point and exists as a gas at room temperature. Therefore, in the step of the dehydrofluorination reaction in the present disclosure, by making the reaction system a closed reaction system, the pressure in the closed reaction system naturally rises, and the reaction can be carried out under pressurized conditions. For this reason, the halogenated butene compound represented by the general formula (2A) which is the target compound can be obtained with a higher selectivity and a higher conversion rate.

[0046] Thus, due to the low boiling point of the target compound, the closed reaction system is pressurized, and it is possible to increase the concentration of the substrate (starting compound) in the reaction solution (base solution) and improve the reactivity. 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 a starting compound, a base solution (alkali aqueous solution), a 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. As the reaction atmosphere, it is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen, helium, or carbon dioxide gas.

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

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

[0049] Pressurized reaction system In the present disclosure, in the step of performing the dehydrofluorination reaction, the reaction can 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. Thereby, the halogenated butene compound represented by the general formula (2A), which is the target compound, can be obtained with a higher selectivity and a higher conversion rate. When the reaction system is pressurized in this way, it is possible to increase the concentration of the substrate (starting compound) in the reaction solution (base solution, aqueous alkali solution) and improve the reactivity. It is preferable to carry out the reaction in the pressurized reaction system 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 a starting compound, a base solution (aqueous alkali solution), a 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.

[0050] In the step of performing the elimination reaction in the present disclosure, it is preferable that the pressurization condition is to set the reaction pressure to 0 kPa or higher. The reaction pressure is the pressure inside the reaction vessel used in the pressurized reaction system. In the step of performing the dehydrofluorination reaction in the present disclosure, the reaction pressure is preferably 0 kPa or higher, more preferably 5 kPa or higher, still more preferably 10 kPa or higher, and particularly preferably 15 kPa or higher. The upper limit of the reaction pressure is not particularly limited and is usually about 2 MPa. In the present disclosure, when there is no particular notation regarding the pressure, it is a gauge pressure.

[0051] For pressurization, the pressure inside the reaction system can be increased by feeding an inert gas such as nitrogen, helium, or carbon dioxide gas into the reaction system.

[0052] In the step of performing the dehydrofluorination reaction in the present disclosure, from the viewpoints of more efficiently advancing the elimination reaction and obtaining the target compound with a higher selectivity and suppressing a decrease in the conversion rate, the reaction temperature in the pressurized reaction system is usually preferably 0°C or higher, more preferably 10°C or higher, and still more preferably 15°C or higher. above.

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

[0054] Combination of sealed reaction system and pressurized reaction system In the step of performing the dehydrofluorination reaction in the present disclosure, it can also be carried out in a continuous and pressurized reaction mode by a method such as connecting a back pressure valve to a continuous stirred tank reactor (CSTR) while withdrawing the liquid or while gasifying and withdrawing the product.

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

[0056] (1-1-2-2) Gas-phase reaction When the step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction is carried out in the gas phase, there is an advantage that it is not necessary to use a solvent, no industrial waste is generated, and the productivity is excellent.

[0057] The step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction is preferably carried out in the gas phase, particularly in a gas-phase continuous flow mode using a fixed bed reactor. When carried out in a gas-phase continuous flow mode, the apparatus, operation, etc. can be simplified and it is economically advantageous.

[0058] Catalyst 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.

[0059] As the catalyst used in the production method of the present disclosure, an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst, a silica-alumina catalyst, etc. are preferable. Any of these catalysts, either a non-fluorinated catalyst or a fluorinated catalyst, can be employed.

[0060] As the activated carbon catalyst, there is no particular limitation, and examples thereof include powdered activated carbon such as crushed carbon, formed carbon, granular carbon, and spherical carbon. As the 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 known or commercially available products can be adopted.

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

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

[0063] 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 about room temperature (25 °C) to 400 °C can be mentioned.

[0064] Regarding the chromium oxide catalyst, there is no particular limitation. However, 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 ·nH 2 O, it may be hydrated so that the value of n is 3 or less, particularly 1 to 1.5.

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

[0066] Hereinafter, an example of a method for synthesizing a chromium oxide catalyst and a fluorinated chromium oxide catalyst will be shown.

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

[0068] After filtering and washing this precipitate, it can be dried. Drying can be carried out, for example, in air at 70 to 200 °C for 1 to 100 hours. The catalyst at this stage may be referred to as being in the state of chromium hydroxide. Next, this catalyst can be crushed. From the viewpoints of pellet strength, catalyst activity, etc., it is preferable to adjust the precipitation reaction rate so that the bulk density of the crushed powder (for example, the particle size is 1000 μm or less, particularly 95% of the particle size product of 46 to 1000 μm) is 0.6 to 1.1 g / ml, preferably 0.6 to 1.0 g / ml. The specific surface area of the powder (specific surface area by the BET method) is preferably 100 m / g or more, more preferably 120 m 2 / g or more under the degassing conditions at 200 °C for 80 minutes. The upper limit of the specific surface area is, for example, about 220 m 2 / g. 2 / g.

[0069] If necessary, 3% by weight or less of graphite can be mixed with this chromium hydroxide powder, and pellets can be formed by a tableting machine. The size and strength of the pellets can be adjusted as appropriate.

[0070] The formed 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 - 460 °C is preferred. Further, the calcination time can be, for example, 1 - 5 hours.

[0071] From the viewpoint of the activity of the catalyst, the specific surface area of the calcined catalyst is, for example, preferably 170 m 2 / g or more and more preferably 180 m 2 / g or more, and even more preferably 200 m 2 / g or more. Note that the upper limit of the specific surface area is usually preferably about 240 m 2 / g, and more preferably about 220 m 2 / g.

[0072] Next, fluorinated chromium oxide can be obtained by fluorinating chromium oxide. The fluorination temperature may be in a temperature range where the generated water does not condense, and may be limited by the upper limit of the temperature at which the catalyst does not crystallize due to the heat of reaction. The fluorination temperature can be, for example, 100 - 460 °C. There is no limitation on the pressure during fluorination, but it is preferably carried out at the pressure when used in the catalytic reaction.

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

[0074] Since the zeolite catalyst shows stronger activity by fluorination, it can be fluorinated in advance before use in the reaction and used as a fluorinated zeolite catalyst.

[0075] As a fluorinating agent for fluorinating a zeolite catalyst, for example, F 2 , inorganic fluorinating agents such as HF, and organic fluorinating agents such as fluorocarbon-based hexafluoropropene can be used.

[0076] As a method for fluorinating a zeolite catalyst, for example, a method of fluorinating by flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of about room temperature (25 °C) to 400 °C can be mentioned.

[0077] A silica-alumina catalyst is a composite oxide catalyst containing silica (SiO 2 ) and alumina (Al 2 O 3 ). Taking the total amount of silica and alumina as 100% by mass, for example, a catalyst with a silica content of 20 to 90% by mass, particularly 50 to 80% by mass can be used.

[0078]

[0079] Since the silica-alumina catalyst exhibits stronger activity by fluorination, it can also be fluorinated in advance before use and used as a fluorinated silica-alumina catalyst.

[0080] 2 As a fluorinating agent for fluorinating a silica-alumina catalyst, for example, inorganic fluorinating agents such as F, HF, and organic fluorinating agents such as fluorocarbon-based hexafluoropropene can be used.

[0081] As a method for fluorinating a silica-alumina catalyst, for example, a method of fluorinating by flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of about room temperature (25 °C) to 400 °C can be mentioned.

[0081] The above-mentioned catalysts can be used alone or in combination of two or more. Among these, from the viewpoints of conversion rate, selectivity and yield, activated carbon catalysts (activated carbon or fluorinated activated carbon), chromium oxide catalysts (chromium oxide or fluorinated chromium oxide), etc. are preferable, and activated carbon catalysts (activated carbon or fluorinated activated carbon) are more preferable.

[0082] In addition, when using the above-mentioned chromium oxide catalyst, zeolite catalyst, silica-alumina catalyst, etc. as the catalyst, it is also possible to support it on a carrier. Examples of such carriers include carbon, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silica (SiO 2 ), titania (TiO 2 ) and the like. As the carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.

[0083] In the production method of the present disclosure, in the gas phase, when subjecting a butane halide compound to a dehydrofluorination reaction in the presence of a catalyst, for example, it is preferable to bring the catalyst into contact with the butane halide compound in a solid state (solid phase). In this case, the shape of the catalyst can be powder, but pellets are more preferable when employed in a gas-phase continuous flow reaction.

[0084] The specific surface area of the catalyst measured by the BET method (hereinafter, sometimes referred to as "BET specific surface area") is usually preferably 10 to 3000 m 2 / g, more preferably 10 to 2500 m 2 / g, still more preferably 20 to 2000 m 2 / g, and particularly preferably 30 to 1500 m 2 / g. When the BET specific surface area of the catalyst is in such a range , since the density of the catalyst particles is not too small, a butene halide compound can be obtained with a higher selectivity. Also, it is possible to further improve the conversion rate of the butane halide compound.

[0085] Cyclic carbon halide compound In the present disclosure, the step of subjecting the above-described butane halide compound to a dehydrofluorination reaction can also be carried out in the presence of a cyclic carbon halide compound. This cyclic carbon halide compound means a cyclic carbon halide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are substituted with halogen atoms. In other words, it means a cyclic carbon halide compound composed only of carbon atoms and halogen atoms and containing no hydrogen atoms.

[0086] By carrying out the step of subjecting the above-described butane halide compound to a dehydrofluorination reaction in the presence of such a cyclic carbon halide compound, it is possible to shift the equilibrium of the reaction to the product side, and the target butene halide compound can be obtained with a higher conversion rate and a higher yield.

[0087] Such a cyclic carbon halide compound can employ those described (1-1-2-1) Liquid-phase reaction above. Preferred specific examples and usage amounts are the same.

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

[0089] Reaction temperature In the step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction, from the viewpoint of more efficiently advancing the dehydrofluorination reaction to improve the conversion rate and obtaining the target butene halide compound with a higher selectivity, the reaction temperature is usually 230°C or higher, preferably 280°C or higher, and more preferably 320°C or higher. When activated carbon is used as a catalyst and when no cyclic carbon halide compound is used, the reaction temperature is preferably set higher in order to more efficiently advance the dehydrofluorination reaction, and 400 °C or higher is preferable, and 420°C or higher is more preferable. When activated carbon is used as a catalyst However, when a halogenated butane compound is subjected to dehydrofluorination in a gas phase in the presence of a cyclic halogenated hydrocarbon compound, the dehydrofluorination reaction can proceed more efficiently, and therefore the reaction temperature can be set to a slightly lower temperature, and is usually preferably 230°C or higher, more preferably 280°C or higher, and even more preferably 320°C or higher.

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

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

[0092] Reaction pressure The reaction pressure for subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction is preferably 0 kPa or more, more preferably 10 kPa or more, still more preferably 20 kPa or more, and particularly preferably 30 kPa or more from the viewpoint of allowing the dehydrofluorination reaction to proceed more efficiently to improve the conversion rate and obtaining the target butene halide compound with a higher selectivity. The reaction There is no particular limitation on the upper limit of the pressure, and it is usually about 2 MPa. In the present disclosure, when there is no particular notation regarding the pressure, it is taken as gauge pressure.

[0093] In the dehydrofluorination reaction of the butane halide compound in the present disclosure, as the reactor for charging the butane halide compound and preferably reacting it with a catalyst and a cyclic carbon halide compound, the shape and structure are not particularly limited as long as it can withstand the above temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multitubular reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloy.

[0094] Examples of dehydrofluorination reaction The dehydrofluorination reaction of the butane halide compound in the present disclosure can be carried out by either a flow type or a batch type in which the butane halide compound as the raw material compound is continuously charged into the reactor and the target butene halide compound is continuously withdrawn from the reactor. Since the elimination reaction may further proceed when the target butene halide compound remains in the reactor, it is preferably carried out by the flow type. In the step of subjecting the butane halide compound in the present disclosure to a dehydrofluorination reaction, it is preferably carried out in the gas phase, particularly preferably in a gas-phase continuous flow type using a fixed-bed reactor. When carried out in the gas-phase continuous flow type, the apparatus, operation, etc. can be simplified and it is economically advantageous. When the batch type is adopted, it is also possible to adopt the closed reaction system or the pressurized reaction system described in the above liquid-phase reaction.

[0095] Regarding the atmosphere during the dehydrofluorination reaction of the halogenated butane compound in the present disclosure, from the viewpoint of suppressing the deterioration of the catalyst, an inert gas atmosphere, a hydrogen fluoride gas atmosphere, etc. are preferable. Examples of the inert gas include nitrogen, helium, argon, etc. Among these inert gases, nitrogen is preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas components introduced into the reactor.

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

[0097] (1-1-3) Target compound (halogenated butene compound) The target compound of the present disclosure obtained in this way has the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 each independently represents a halogen atom.] is a halogenated butene compound represented by the formula.

[0098] X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 in the general formula (2A) are the same as X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7corresponds to. Therefore, the butene halide compound represented by the general formula (2A) to be produced is, for example, specifically, CF 3 CF=CHCF 3 、CCl 3 CCl=CHCCl 3 、CBr 3 CBr=CHCBr 3 and the like. These compounds contain both the Z-isomer and the E-isomer. Included.

[0099] The butene halide compound thus obtained can be effectively used in various applications such as etching gas, cleaning gas, deposit gas, refrigerant, heat transfer medium, and building blocks for organic synthesis for forming state-of-the-art fine structures such as semiconductors and liquid crystals. The deposit gas and the building blocks for organic synthesis will be described later.

[0100] [1-2] Method for producing butyne halide compound from butene halide compound The method for producing the butyne halide compound of the present disclosure is General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent halogen atoms.] It is a method for producing a butyne halide 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 , X3 and X 5 and X 6 and X 7 are the same as those above. X 4 represents a halogen atom.] includes a step of subjecting a halogenated butene compound represented by the formula to a dehydrohalogenation reaction.

[0101] According to the present disclosure, by performing the dehydrohalogenation reaction of the halogenated butene compound represented by the general formula (2A) above, per 1 mol of the halogenated butene compound represented by the general formula (2A) a halogenated butyne compound represented by the general formula (3A) in which 1 mol of hydrogen halide has been eliminated can be selectively obtained.

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

[0103] In the general formula (2A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 ​As the halogen atom represented by , those described above can be adopted. The same applies to preferred types.

[0104] Examples of the halogenated butene compound as a substrate satisfying the above conditions specifically include CF 3 CF=CHCF 3 , CCl 3 CCl=CHCCl 3 , CBr 3 CBr=CHCBr 3 and the like. These compounds include both the Z-isomer and the E-isomer. These halogenated butene compounds can be used alone or in combination of two or more. Such halogenated butene compounds can be known or commercially available products.

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

[0106] That is, the following reaction formula: CF 3 CF=CHCF 3 → CF 3 C≡CCF 3 + HF According to this, a dehydrofluorination reaction is preferred.

[0107] The step of subjecting the halogenated butene compound in the present disclosure to a dehydrohalogenation 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.

[0108] The step of performing dehydrohalogenation reaction on the halogenated butene compound in the present disclosure is preferably carried out in the presence of a catalyst and / or a base from the viewpoint that the target compound can be obtained with a higher selectivity and a higher conversion rate. More specifically, when a liquid-phase reaction is employed, it is preferably carried out in the presence of a base and, if necessary, a catalyst, and when a gas-phase reaction is employed, it is preferably carried out in the presence of a catalyst. In addition, regarding the details in the case of a liquid-phase reaction (solvent, base, catalyst, cyclic halogenated carbon compound, conditions of a closed reaction system and a pressurized reaction system, etc.) and the details in the case of a gas-phase reaction (catalyst, cyclic halogenated carbon compound, reaction temperature, reaction time, reaction pressure, etc.), except for reading the "reaction of obtaining a halogenated butene compound by dehydrofluorination reaction from a halogenated butane compound" as the "reaction of obtaining a halogenated butyne compound by dehydrohalogenation reaction from a halogenated butene compound", those described in the above-mentioned [1-1] production method of a halogenated butene compound from a halogenated butane compound can be adopted. The preferable types and contents are the same.

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

[0110] (1-2-3) Target compound (halogenated butyne compound) The target compound of the present disclosure thus obtained has 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 or different and each represents a halogen atom.] is a halogenated butyne compound represented by the formula.

[0111] X in the general formula (3A) 1, X 2 , X 3 , X 5 , X 6 and X 7 corresponds to X in the general formula (2A) described above 1 , X 2 , X 3 , X 5 , X 6 and X 7 Therefore, the butyne halide compound represented by the general formula (3A) to be produced is, for example, specifically, CF 3 C≡CCF 3 , CCl 3 C≡CCCl 3 , CBr 3 C≡CCBr 3 etc. can be mentioned.

[0112] The butyne halide compound thus obtained can be effectively used for various applications such as etching gas, cleaning gas, deposition gas, refrigerant, heat transfer medium, building block for organic synthesis, etc. for forming the most advanced fine structures such as semiconductors and liquid crystals. The deposition gas and the building block for organic synthesis will be described later.

[0113] [1-3] Production method of butyne halide compound from butane halide compound via butene halide compound The production method of the butyne halide compound of the present disclosure is General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent halogen atoms.] It is a production method of a butyne halide compound represented by (IA) General formula (1A): CX1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [Wherein, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same as described above. X 4 represents a halogen atom.] The butane halide compound represented by is subjected to a dehydrofluorination reaction 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 step of producing a butene halide 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) [Wherein, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same as described above.] The butene halide compound represented by is subjected to a dehydrohalogenation reaction to obtain the general formula (3A): CX1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [wherein X 1 、X 2 、X 3 、X 5 、X 6 and X 7 are the same as described above.] The step of producing a butyne halide compound represented by is included.

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

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

[0116] In the method for producing a butyne halide compound of the present disclosure, after step (IA), after separating and / or removing the hydrogen fluoride generated in the dehydrogenation reaction of step (IA), proceeding to the production of the butyne halide compound in the next step (IIIA) enables the production of the target butyne halide compound with a high conversion rate (yield) and a high selectivity by dehydrogenation.

[0117] To remove hydrogen fluoride from the mixture containing the halogenated butene 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 fluoride removing agent (removing column) such as alkali, secarid, alumina, silica, etc. (Figure 2) can preferably be adopted.

[0118] In the method for producing the halogenated butyne compound of 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 the halogenated butyne compound of the present disclosure, the unreacted halogenated butane compound separated by rectification can be returned to the reactor (reused) and used for dehydrofluorination.

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

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

[0121] Method for removing hydrogen fluoride using a hydrogen halide remover The hydrogen fluoride to be separated can be removed by a hydrogen fluoride removing agent. As the hydrogen fluoride removing agent, it is preferable to use a hydrogen fluoride removing agent such as alkali, alumina, silica, zeolite, secarid, etc. Secarid is an adsorbent (synthetic zeolite) mainly composed of an amorphous or low-crystallinity hydrated aluminum silicate called allophane, a non-crystalline clay-like mineral (alumina-silica gel) composed mainly of raw materials such as amorphous or low-crystallinity hydrated aluminum silicate.

[0122] In order to remove hydrogen fluoride from the mixture containing the halogenated butene compound and hydrogen fluoride obtained in step (IA), hydrogen fluoride can be removed using a hydrogen fluoride removing agent, and the halogenated butene compound can be recovered. In the production of the halogenated butyne compound in the next step (IIIA), the content of hydrogen fluoride can be reduced, and the target halogenated butyne compound can be produced at a high conversion rate (yield) and high selectivity.

[0123] Concentration of hydrogen fluoride In the method for producing a halogenated butyne compound of the present disclosure, after step (IA), after separating and / or removing the hydrogen fluoride generated by dehydrofluorination in step (IA), proceeding to the production of the halogenated butyne compound in the next step (IIIA), the target halogenated butyne compound can be produced at a high conversion rate (yield) and high selectivity by dehydrofluorination.

[0124] In the production of the halogenated butyne compound in the next step (IIIA), the halogenated butene compound represented by the above general formula (2A) is used as a raw material compound. At this time, in addition to the halogenated butene compound represented by the above general formula (2A), a mixture containing hydrogen fluoride generated by dehydrofluorination may be brought into the production of the halogenated butyne compound in the next step (IIIA).

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

[0126] (1-3-3) Step (IIIA) In the method for producing a butyne halide compound of the present disclosure, in step (IIIA), the description of the method for producing a butyne halide compound from the above-mentioned [1-2] butene halide compound can be directly adopted.

[0127] (1-3-4) Exemplification of dehydrofluorination In the step of dehydrofluorination in the present disclosure, the reaction can be carried out in either a continuous flow type or a batch type in which, in step (IA), the raw material compound (butane halide compound) is continuously charged into the reactor and the target compound (butene halide compound) is continuously withdrawn from the reactor. Thereafter, hydrogen fluoride is removed from the mixture containing the butene halide compound and hydrogen fluoride (step (IIA)), and in step (IIIA), the raw material compound (butene halide compound) is continuously charged into the reactor and the target compound (butyne halide compound) is continuously withdrawn from the reactor, and it can be carried out in either a continuous flow type or a batch type. Since the target compound (butene halide compound or butyne halide compound) does not remain in the reactor in each step and further dehydrofluorination can proceed, it is preferably carried out in a continuous flow type. In the step of dehydrofluorination in the present disclosure, the reaction is carried out in the gas phase, and it is particularly preferably carried out in a gas-phase continuous flow type using a fixed-bed reactor. When carried out in a gas-phase continuous flow type, the apparatus, operation, etc. can be simplified and it is economically advantageous.

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

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

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

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

[0132] According to the present disclosure, in the presence of a catalyst, by performing a dehydrohalogenation reaction of the alkane halide compound represented by the above general formula (1B) in the gas phase, 1 mol of hydrogen halide is eliminated per 1 mol of the alkane halide compound represented by the general formula (1B), and an alkene halide compound represented by the general formula (2B) can be selectively obtained. Moreover, from the alkene halide compound represented by the general formula (2B), further elimination of hydrogen halide represented by HX 8 The elimination reaction is unlikely to occur. Further, according to the present disclosure, as the alkene halide compound represented by the general formula (2B), the E-isomer can be selectively synthesized among geometric isomers. This effect is , A 1 and A 2 is more remarkable when A 3 and A are perfluoroalkyl groups. Due to the electron-withdrawing effect of the trihalomethyl group such as the CF 3 group, the carbon at the α-position of the trihalomethyl group such as the CF group becomes electron-deficient, so it is difficult for a halogen anion such as a fluoride anion to be eliminated, and an alkene halide rather than an alkyne halide is likely to be formed. Also, the E-isomer can be selectively formed because, A 1 and A 2 is more remarkable when A 3 and A are perfluoroalkyl groups. This is because due to the steric hindrance of the trihalomethyl group such as the CF

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

[0134] In the general formula (1B), A 1 and A 2 The perfluoroalkyl group represented by, X 8 and X 9 As the halogen atom represented by, those described above can be adopted. The same applies to preferred specific examples.

[0135] Examples of the halogenated alkane compound that is a raw material compound satisfying such conditions include, for example, CF 3 CHClCHClCF 3 (336mdd), CF 3 CHClCHFCl, CHFClCHFCl, CF 3 CHFCHFCF 3 (338mee), CF 3 CHFCHF 2 , CHF 2 CHF 2 , CF 3 CHClCHClC 2 F 5 , C 2 F 5 CHClCHClC 2 F 5 , C 2 F 5 CHClCHFCl, CF 3 CHFCHFC 2 F 5 , C 2 F 5 CHFCHFC 2 F 5 , C 2 F 5 CHFCHF 2 and so on. These halogenated alkane compounds can be used alone or in combination of two or more. Such halo genated alkane compounds can adopt known or commercially available products.

[0136] (2-1-2) Dehydrohalogenation reaction In the step of subjecting the alkane halide compound in the present disclosure to a dehydrohalogenation reaction, in terms of being able to produce an alkene halide compound from the alkane halide compound with a high conversion rate (yield) and a high selectivity. For example, as the substrate, in the alkane halide compound represented by the general formula (1B), A 1 and A 2 are both preferably trifluoromethyl groups (CF 3 -), and X 8 and X 9 are more preferably fluorine atoms or chlorine atoms.

[0137] That is, the following reaction formula: CF 3 CHClCHClCF 3 (336mdd) → CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) + HCl CF 3 CHFCHFCF 3 (338mee) → CF 3 CF=CHCF 3 ((Z) or (E)-1327myz) + HF Accordingly, it is preferably a dehydrofluorination reaction or a dehydrochlorination reaction.

[0138] Catalyst In the step of subjecting the alkane halide compound in the present disclosure to a dehydrohalogenation reaction to an alkene halide compound, it is carried out in the gas phase in the presence of a catalyst.

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

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

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

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

[0143] In this process, the catalyst may be in powder form, but pellets are more preferable for the gas-phase continuous flow reaction.

[0144] The specific surface area measured by the BET method of the catalyst (hereinafter also referred to as the BET specific surface area) is usually preferably 10 - 3000 m 2 / g, more preferably 100 - 2000 m 2 / g, still more preferably 500 - 1500 m 2 / g, particularly preferably 1000 - 1300 m 2 / g. When the BET specific surface area of the catalyst is in such a range, the density of the catalyst particles is not too small, so that the target compound can be obtained with a higher selectivity. It is also possible to further improve the conversion rate of the raw material compound.

[0145] When using activated carbon as a catalyst, it is preferable to use powdered activated carbon such as crushed carbon, formed carbon, granular carbon, spherical carbon, etc. As the powdered activated carbon, it is preferable to use powdered activated carbon having a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) in the JIS test.

[0146] When using activated carbon as a catalyst, the activated carbon (for example, specific surface area 1200 m 2 / g or so) is preferably used in either powder or granular form, and it is more preferable to use granular activated carbon.

[0147] When using a metal catalyst as a catalyst, it is preferably supported on a carrier. As the carrier, for example, carbon, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silica (SiO 2 ), titanium (Ti ania (TiO 2 ), etc. can be preferably used. As the carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be preferably used.

[0148] As an example of the catalyst in the present disclosure, chromium oxide and fluorinated chromium oxide will be described. Chromium oxide, for example, when represented as Cr 2 O 3 ·nH 2 O, it is preferable that the value of n is 3 or less, and more preferably 1 to 1.5. Further, the chromium oxide has a composition formula: CrO m wherein m is preferably in the range of usually 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 is described, for example, in Japanese Patent No. 3412165 It can be obtained according to the method described. 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 a 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 temperature higher than normal for a long time.

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

[0151] Cyclic carbon halide compound In the present disclosure, the step of subjecting the above-mentioned halogenated alkane compound to a dehydrohalogenation reaction can also be carried out in the presence of a cyclic carbon halogen compound. The cyclic carbon halogen compound means a cyclic carbon halogen compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are substituted with halogen atoms. In other words, it means a cyclic carbon halogen compound composed only of carbon atoms and halogen atoms and containing no hydrogen atoms.

[0152] By carrying out the step of subjecting the above-mentioned halogenated alkane compound to a dehydrohalogenation reaction in the presence of such a cyclic carbon halogen compound, the target halogenated alkene compound can be obtained with a higher conversion rate and higher yield.

[0153] Such a cyclic carbon halogen compound can be adopted as described above. Preferred specific examples, usage amounts, introduction methods in liquid-phase reactions and gas-phase reactions, etc. are the same.

[0154] Reaction temperature In the step of dehydrogenating hydrogen halide in the present disclosure, the lower limit value of the reaction temperature is usually 50°C, preferably 70°C, and more preferably 100°C, from the viewpoint of more efficiently promoting the dehydrogenating hydrogen halide reaction and obtaining the target compound (halogenated alkene compound) with a higher selectivity, and from the viewpoint of suppressing the decrease in the conversion rate from the raw material compound (halogenated alkane compound).

[0155] In the step of dehydrogenating hydrogen halide in the present disclosure, the upper limit value of the reaction temperature is usually 500°C, preferably 450°C, and more preferably 400°C, from the viewpoint of more efficiently promoting the dehydrogenating hydrogen halide reaction and obtaining the target compound (halogenated alkene compound) with a higher selectivity, and from the viewpoint of suppressing the decrease in the selectivity due to the decomposition or polymerization of the reaction product.

[0156] Reaction time In the step of dehydrogenating hydrogen halide in the present disclosure, the reaction time can increase the conversion rate of the raw material compound by increasing the contact time (W / F 0 ) of the raw material compound with respect to the catalyst [W: weight of the catalyst (g), F 0 : flow rate of the raw material compound (cc / sec)], but increasing the amount of the catalyst will increase the equipment size and is inefficient.

[0157] Therefore, in the step of dehydrogenating hydrogen halide in the present disclosure, the reaction time is preferably such that the contact time (W / F 0 ) of the raw material compound (halogenated alkane compound) with respect to the catalyst is 0.1 to 200 g·sec / cc, more preferably 0.2 to 150 g·sec / cc , even more preferably 0.4 to 100 g·sec / cc, and particularly preferably 0.5 to 50 g·sec / cc, from the viewpoint of improving the conversion rate of the raw material compound (halogenated alkane compound) and suppressing the equipment cost.

[0158] The contact time of the above raw material compound with respect to the catalyst means the time when the raw material compound and the catalyst are in contact.​

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

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

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

[0162] In the dehydrohalogenation reaction of the present disclosure, when using activated carbon as the catalyst, the reaction tem perature is preferably 50 to 600 °C, more preferably 100 to 400 °C. Also, the con tact time is preferably 0.2 to 100 g·sec / cc, more preferably 0.3 to 50 g·sec / cc, and even more preferably 0.5 to 43 g·sec / cc.

[0163] Reaction pressure In the step of performing the dehydrohalogenation reaction of the present disclosure, the reaction pressure is preferably -0.05 to 2 MPa, more preferably -0.01 to 1 MPa, and even more preferably normal pressure to 0.5 MPa from the viewpoint of more efficiently advancing the dehydrohalogenation reaction. In the present disclosure, when there is no notation for the pressure, it is the gauge pressure.

[0164] In the step of the dehydrohalogenation reaction in the present disclosure, as the reactor for bringing the raw material compound (alkane halide compound) into contact with the catalyst (activated carbon, metal catalyst, etc.) and reacting them, the shape and structure are not particularly limited as long as it can withstand the above temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, a multi-tube reactor, and the like. Examples of the material of the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy, and the like.

[0165] Examples of dehydrohalogenation reaction The step of the dehydrohalogenation reaction in the present disclosure can be carried out by either a flow-through method or a batch method in which the raw material compound (alkane halide compound) is continuously charged into the reactor and the target compound (alkene halide compound) is continuously withdrawn from the reactor. Since the target compound (alkene halide compound) does not remain in the reactor and the dehydrohalogenation reaction can further proceed, it is preferably carried out by the flow-through method.

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

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

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

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

[0170] A 1 , A 2 and X 8 in the general formula (2B) correspond to A 1 , A 2 and X 8 in the above general formula (1B). Therefore, the halogenated alkene compound represented by the general formula (2B) to be produced is, for example, specifically, CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz), CF 3 CCl=CHF, CFCl=CHF, CF 3 CF=CHCF 3 ((Z) or (E)-1327myz), CF 3 CF=CHF, CF 2 =CHF, CF 3 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHF, CF 3 CF=CHC 2 F 5, C 2 F 5 CF=CHC 2 F 5 , C 2 F 5 Examples include CF=CHF, etc. . These compounds include both the Z-form and the E-form.

[0171] The halogenated alkene compounds thus obtained can be effectively used in various applications such as etching gases, cleaning gases, deposition gases, refrigerants, heat transfer media, and building blocks for organic synthesis for forming state-of-the-art microstructures such as semiconductors and liquid crystals. The deposition gas and the building block for organic synthesis will be described later.

[0172] [2-2] Method for Producing Alkynyl Fluoride Compounds from Halogenated Alkene Compounds The method for producing an alkynyl fluoride compound of the present disclosure is represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and each represents a fluorine atom or a perfluoroalkyl group.] It is a method for producing an alkynyl fluoride compound represented by General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same as defined above. X 8 represents a halogen atom.] It includes a step of subjecting the halogenated alkene compound represented by to a dehydrohalogenation reaction in the presence of a catalyst.

[0173] (2-2-1) Starting Compound (Halogenated Alkene Compound) The halogenated alkene compound as a substrate that can be used in the production method of the present disclosure is, as described above, represented by the general formula (2B): CX 8 A1 =CHA 2 (2B) [Wherein, A 1 and A 2 are the same or different and each represents a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] is a halogenated alkene compound represented by the formula, and corresponds to the target compound in the method for producing a halogenated alkene compound from the above-described [2-1] halogenated alkane compound to a halogenated alkene compound.

[0174] In the general formula (2B), as the perfluoroalkyl group represented by A 1 and A 2 , and the halogen atom represented by X 8 , those described above can be adopted. The preferred types are the same.

[0175] Specific examples of the halogenated alkene compound as a substrate satisfying the above conditions include CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz), CF 3 CCl=CHF, CFCl=CHF, CF 3 CF=CHCF 3 ((Z) or (E)-1327myz), CF 3 CF=CHF, CF 2 =CHF, CF 3 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHF , CF 3 CF=CHC 2 F 5 , C 2 F 5 CF=CHC 2 F 5 , C 2 F 5Examples include CF=CHF and the like. These compounds include both the Z-isomer and the E-isomer. These halogenated alkene compounds can be used alone or in combination of two or more. Such halogenated alkene compounds can be known or commercially available products.

[0176] (2-2-2) Dehydrohalogenation reaction In the step of subjecting the halogenated alkene compound in the present disclosure to a dehydrohalogenation reaction, a fluorinated alkyne compound can be produced from the halogenated alkene compound with a high conversion rate (yield) and a high selectivity. For example, as the substrate, in the halogenated alkene compound represented by the general formula (2B), A 1 and A 2 are both preferably trifluoromethyl groups (CF 3 -), and X 8 is more preferably a fluorine atom or a chlorine atom.

[0177] That is, the following reaction formula: CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) → CF 3 C≡CCF 3 (PF2B) + HCl CF 3 CF=CHCF 3 ((Z) or (E)-1327myz) → CF 3 C≡CCF 3 (PF2B) + HF According to this, a dehydrofluorination reaction or a dehydrochlorination reaction is preferred.

[0178] The step of subjecting the halogenated butane 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.

[0179] The step of performing dehydrohalogenation reaction on the halogenated alkene compound in the present disclosure 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 a liquid-phase reaction is employed, it is preferably carried out in the presence of a base and, if necessary, a catalyst. When a gas-phase reaction is employed, it is preferably carried out in the presence of a catalyst. Regarding the details of the liquid-phase reaction (solvent, base, catalyst, cyclic carbon halogen compound, conditions of the closed reaction system and the pressurized reaction system, etc.), except for reading the "reaction of obtaining a halogenated butene compound by dehydrofluorination reaction from a halogenated butane compound" as the "reaction of obtaining an alkynyl fluoride compound by dehydrohalogenation reaction from a halogenated alkene compound", the same as those described in the above [1-1] production method from a halogenated butane compound to a halogenated butene compound can be adopted. Regarding the details of the gas-phase reaction (catalyst, cyclic carbon halogen compound, reaction temperature, reaction time, reaction pressure, etc.), except for reading the "reaction of obtaining a halogenated alkene compound by dehydrohalogenation reaction from a halogenated alkane compound" as the "reaction of obtaining an alkynyl fluoride compound by dehydrohalogenation reaction from a halogenated alkene compound", the same as those described in the above [2-1] production method from a halogenated alkane compound to a halogenated alkene compound can be adopted. The preferred types and contents are the same as well.

[0180] After completion of the dehydrohalogenation reaction, purification treatment is carried out according to a conventional method if necessary, and a butynyl fluoride compound represented by the general formula (3B) can be obtained.

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

[0182] A in general formula (3B) 1 and A 2 correspond to A in the above general formula (2B) 1 and A 2 Therefore, the butyne fluoride compound represented by the general formula (3B) to be produced is, for example, specifically, CF 3 C≡CCF 3 (PF2B), CF 3 C≡CF, CF≡CF, CF 3 C≡CC 2 F 5 , C 2 F 5 C≡CC 2 F 5 , C 2 F 5 C≡CF, etc. can be mentioned.

[0183] The butyne fluoride compound thus obtained can be effectively used in various applications such as etching gas, cleaning gas, deposit gas, refrigerant, heat transfer medium, building block for organic synthesis, etc. for forming state-of-the-art fine structures such as semiconductors and liquid crystals. The deposit gas and the building block for organic synthesis will be described later.

[0184] [2-3] Production method of alkyne fluoride compound from halogenated alkane compound via halogenated alkene compound The production method of the alkyne fluoride compound of the present disclosure is General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group.] It is a production method of an alkyne fluoride compound represented by (IB) General formula (1B): CHX 8 A 1 CHX9 A 2 (1B) [Wherein, A 1 and A 2 are the same as described above. X 8 and X 9 are the same or different and each represents a halogen atom.] The halogenated alkane compound represented by the formula is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst to obtain a general formula (2B): CX 8 A 1 =CHA 2 (2B) [Wherein, A 1 , A 2 and X 8 are the same as described above.] Step of producing a halogenated alkene compound represented by the formula, (IIB) After the step (IB), a step of removing hydrogen halide, and (IIIB) After the step (IIB), the obtained general formula (2B): CX 8 A 1 =CHA 2 (2B) [Wherein, A 1 , A 2 and X 8 are the same as described above.] The halogenated alkene compound represented by the formula is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst to obtain a general formula (3B): CA 1 ≡CA 2 (3B) [Wherein, A 1 and A 2 are the same as described above.] Step of producing an alkyne fluoride compound represented by the formula is included.

[0185] (2-3-1) Step (IB) In the method for producing a butyne fluoride compound of the present disclosure, in the step (IB), the description of the method for producing a halogenated alkene compound from the halogenated alkane compound described in the above [2-1] can be directly adopted.

[0186] (2-3-2) Process (IIB) In the method for producing an alkynyl fluoride compound of the present disclosure, the halogenated alkane compound represented by the general formula (1B) is subjected to a dehydrohalogenation reaction to produce a halogenated alkene compound represented by the general formula (2B) (Process (IB)), and then a step (IIB) of removing hydrogen halide from a mixture containing the halogenated alkene compound and hydrogen halide is included.

[0187] In the method for producing an alkynyl fluoride compound of the present disclosure, after Process (IB), after separating and / or removing the hydrogen halide generated in the dehydrohalogenation reaction of Process (IB), proceeding to the production of the alkynyl fluoride compound in the next Process (IIIB) enables the production of the target alkynyl fluoride compound with a high conversion rate (yield) and a high selectivity by the dehydrohalogenation reaction.

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

[0189] (2-3-3) Process (IIIB) In the method for producing an alkynyl fluoride compound of the present disclosure, in Process (IIIB), the description of the method for producing an alkynyl fluoride compound from the above-described [2-2] halogenated alkene compound can be adopted as it is.

[0190] (2-3-4) Exemplification of Dehydrohalogenation Reaction In the step of the dehydrohalogenation reaction in the present disclosure, the reaction is carried out in the reactor in Process (IB). The raw material compound (alkyl halide compound) can be continuously charged, and the target compound (alkenyl halide compound) can be continuously withdrawn from the reactor, and the process can be carried out by either a flow-through method or a batch method. Then, hydrogen halide is removed from the mixture containing the alkenyl halide compound and hydrogen halide (step (IIB)), and in step (IIIB), the reactor is continuously charged with the raw material compound (alkenyl halide compound), and the target compound (alkynyl fluoride compound) can be continuously withdrawn from the reactor, and the process can be carried out by either a flow-through method or a batch method. In each step, since the target compound (alkenyl halide compound or alkynyl fluoride compound) does not remain in the reactor and the dehydrohalogenation reaction can further proceed, it is preferably carried out by a flow-through method.

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

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

[0193] In the step of carrying out the dehydrohalogenation reaction in the present disclosure, after the reaction is completed, as described above, purification treatment is carried out according to a conventional method, and the target compound (alkenyl halide compound or alkynyl fluoride compound) can be obtained.

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

[0195] [3-1] Composition containing a halogenated butene compound or a halogenated alkene compound According to the production method of the present disclosure, for example, when the production method from the above-mentioned [1-1] halogenated butane compound to a halogenated butene compound is followed, for example, as the halogenated butene compound represented by the general formula (2A), it may be obtained as a composition containing both the E-isomer and the Z-isomer. Further, this composition has 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 defined above.] a halogenated butyne compound represented by General formula (4): CX 1 X 2 =CX 4 CF=CX 5 X 6 (4) [In the formula, X 1 , X 2 , X 4 , X 5 and X 6 are the same as defined above.] may also contain a halogenated butadiene compound represented by

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

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

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

[0199] According to the production method of the present disclosure, even when obtained as a halogenated butene composition, the halogenated butene compound represented by the general formula (2A) can be obtained with a high conversion rate of the reaction, and in a high yield and high selectivity. Therefore, it is possible to reduce the components other than the halogenated butene compound represented by the general formula (2A) in the halogenated butene composition, and thus reduce the purification labor for obtaining the halogenated butene compound represented by the general formula (2A).

[0200] On the other hand, when the production method from a halogenated alkane compound to a halogenated alkene compound is followed, for example, a composition containing a halogenated alkene compound represented by the general formula (2B) and at least one additional compound composed of at least one hydrofluorocarbon (HFC) compound (excluding the halogenated alkene compound represented by the general formula (2B)) can be produced.

[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 the halogenated alkane compound of the present disclosure, when obtaining 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (1326mxz) as the target product (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)) may be produced .

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

[0204] [3-2] Composition containing a halogenated butyne compound or a fluorinated alkyne compound According to the production method of the present disclosure, for example, when following the production method from the above-mentioned [2-2] halogenated alkene compound to a fluorinated alkyne compound, for example, the fluorinated alkyne compound represented by the general formula (3B) and at least one kind of additional compound composed of at least one hydrofluorocarbon (HFC) compound (excluding the fluorinated alkyne compound represented by the general formula (3B)) can form a composition. When following the production method from a [1-2] halogenated butene compound to a halogenated butyne compound, the resulting composition is the halogenated butyne compound represented by the general formula (3A) and at least one kind of additional compound composed of a hydrofluorocarbon (HFC) compound (excluding the halogenated butyne compound represented by the general formula (3A)) can form a composition.

[0205] It is preferable that the additional compound is at least one selected from the group consisting of trifluoromethane, difluoromethane, tetrafluoromethane, and monofluoromethane.

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

[0207] ​​​In the composition containing a butyne halide compound or an alkyne fluoride compound according to the present disclosure, with the total amount of the composition being 100 mol%, the content of the butyne halide compound or the alkyne fluoride compound is preferably 80 mol% or more, and the content of the additional compound is preferably 20 mol% or less. In the composition containing a butyne halide compound or an alkyne fluoride compound, with the total amount of the composition being 100 mol%, the content of the butyne halide compound or the alkyne fluoride compound is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. In the composition containing a butyne halide compound or an alkyne fluoride compound according to the present disclosure, with the total amount of the composition being 100 mol%, the content of the butyne halide compound or the 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 a composition containing a butene halide compound, a butyne halide compound, an alkene halide compound or an alkyne fluoride compound According to the production method of the present disclosure, even when a composition containing a butene halide compound, a butyne halide compound, an alkene halide compound or an alkyne fluoride compound is obtained, the butene halide compound, the butyne halide compound, the alkene halide compound or the alkyne fluoride compound can be obtained with a particularly high selectivity. As a result, it is possible to reduce the components other than the butene halide compound, the butyne halide compound, the alkene halide compound and the alkyne fluoride compound in the composition. According to the production method of the present disclosure, the labor for purification for obtaining a butene halide compound, a butyne halide compound, an alkene halide compound or an alkyne fluoride compound can be reduced.

[0209] A composition containing a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound, or a fluorinated alkyne compound of the present disclosure can be effectively used in various applications such as an etching gas for forming state-of-the-art microstructures such as semiconductors and liquid crystals, a cleaning gas, a deposit gas, a refrigerant, a heat transfer medium, and a building block for organic synthesis, in the same manner as each of the halogenated butene compound, the halogenated butyne compound, the halogenated alkene compound, or the fluorinated alkyne compound alone.

[0210] The deposit gas is a gas for depositing an etching-resistant polymer layer.

[0211] The building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, when the composition of the present disclosure is reacted with a fluorine-containing organosilicon compound such as CF 3 Si(CH 3 ) 3 etc., it is possible to introduce a fluoroalkyl group such as a CF group and convert it into a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate. 3 group and convert it into a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate. group and convert it into a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate.

[0212] As described above, the embodiments of the present disclosure have been described. However, various changes in form and details can be made without departing from the spirit and scope of the claims. As described above, the embodiments of the present disclosure have been described. However, various changes in form and details can be made without departing from the spirit and scope of the claims.

Examples

[0213] Examples are shown below to clarify the features of the present disclosure. The present disclosure is not limited to these examples.

[0214] In the production methods of the halogenated butene compounds of Examples 1 to 7, the raw material compound is a halogenated butane compound represented by the general formula (1A), where X 1 、X 2 、X 3 、X 4 、X 5 、X 6 and X 7 are fluorine atoms, and the following reaction formula: CF 3 CFHCFHCF 3 → CF 3 CF=CHCF 3 + HF According to this, a halogenated butene compound was obtained by a dehydrofluorination reaction.

[0215] In the method for producing a halogenated alkene compound and a butyne fluoride compound of Example 8, the raw material compound is a halogenated alkane compound represented by the general formula (1B), where X 8 and X 9 are chlorine atoms, and A 1 and A 2 are trifluoromethyl groups, and the following reaction: CF 3 CHClCHClCF 3 (336mdd) → CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) + HCl CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) → CF 3 C≡CCF 3 (PF2B) + HCl According to this, a halogenated alkene compound and a butyne fluoride compound were obtained by a dehydrochlorination reaction.

[0216] In the method for producing a halogenated alkene compound and a butyne fluoride compound of Examples 9 to 20, the raw material compound is a halogenated alkane compound represented by the general formula (1B), where X 8 and X 9 are fluorine atoms, and A 1 and A 2 are trifluoromethyl groups, and the following reaction: CF 3 CHFCHFCF 3 (338mee) → CF 3 CF=CHCF 3 ((Z) or (E)-1327myz) + HF CF 3CF=CHCF 3 ((Z) or (E)-1327myz) → CF 3 C≡CCF 3 (PF2B) + HF According to the above, a halogenated alkene compound and a butyne fluoride compound were obtained by a dehydrofluorination reaction.

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

[0218] By using an autoclave as the reaction system, this reaction system is in a mode where (1) in the presence of a base , it is a closed reaction system, or (2) the reaction temperature is 10 °C or higher, the reaction pressure is 0 kPa or higher, and it represents a pressurized reaction system carried out in the presence of a base. When pressurizing in this way, it is accompanied by sealing.

[0219] 7.0 g of a 50% by mass aqueous solution of KOH or potassium tert-butoxide (t-BuOK) was added to the autoclave as the reaction solution, and if necessary, 0.28 g of methyltrioctylammonium chloride (trademark Aliquat336) was added as a catalyst, and further 8.0 g of the raw material compound (CF 3 CFHCFHCF 3 ) was added. After covering the lid to make it a closed system, nitrogen was injected by pressure. The pressure at that time was 20 kPa. Then , it was stirred at room temperature (25 °C) to allow the reaction to proceed. After starting the dehydrofluorination reaction, sampling was carried out as appropriate, and the reaction was terminated when there was no change in the composition in the reaction system. The pressure at the end of the reaction was 80 kPa.

[0220] After stopping stirring, it was cooled to 0 °C, and gas chromatography / mass spectrometry (GC / MS) was performed using gas chromatography ((manufactured by Shimadzu Corporation, trade name "GC-2014")). Performed the operation and conducted structural analysis by NMR spectrum using NMR (manufactured by JEOL, product name "400YH"). From the results of mass spectrometry and structural analysis, CF 3 CF=CHCF 3 was confirmed to have been generated. The results are shown in Table 1.

[0221] Examples 4 to 6: Gas-phase reaction (activated carbon) To a SUS pipe (outer diameter: 1 / 2 inch) serving as a reaction tube, 10 g of an activated carbon catalyst (manufactured by Osaka Gas Chemical Co., Ltd.; specific surface area 1200 m 2 / g) was added. After drying at 200 °C for 2 hours under a nitrogen atmosphere , the pressure was set to normal pressure, and CF 3 CFHCFHCF 3 (raw material compound) was passed through the reaction tube so that the contact time (W / F) between the activated carbon catalyst and CF 3 CFHCFHCF 3 (raw material compound would be 15 g·sec / cc, 30 g·sec / cc, or 47 g·sec / cc.

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

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

[0224] One hour after the start of the dehydrofluorination reaction, the distillate passing through the scrubber tower was collected.

[0225] Thereafter, mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS) using gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014"), and structural analysis by NMR spectrum was carried out using NMR (manufactured by JEOL , product name "400YH"). From the results of mass spectrometry and structural analysis, CF CF=CHCF 3 CF=CHCF 3 was confirmed to have been generated. The results are shown in Table 1.

[0226] Example 7: Gas-phase reaction (chromium oxide catalyst) Using a chromium oxide catalyst (Cr 2 O 3 ) as the catalyst, the reaction temperature was 350 °C, and the reaction was allowed to proceed in the same manner as in Examples 4 to 6, except that the contact time (W / F) between CF 3 CFHCFHCF 3 (raw material compound) and the chromium oxide catalyst was set to 47 g·sec / cc. From the results of mass spectrometry and structural analysis, it was confirmed that CF 3 CF=CHCF 3 was produced. The results are shown in Table 1.

[0227]

Table 1

[0228] Example 8 (dehydrochlorination) 336mdd(CF 3 CHClCHClCF 3 ) → 1326mxz(CF 3 CCl=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) (1) 336mdd(CF 3 CHClCHClCF 3 ) → 1326mxz(CF 3 CCl=CHCF 3 ) Using a SUS pipe (outer diameter: 1 / 2 inch) as the reaction tube, 10 g of an activated carbon catalyst (specific surface area 1200 m 2 / g) was filled as the catalyst in the reaction tube. After drying at 200 °C for 2 hours under a nitrogen atmosphere, the pressure was set to atmospheric pressure , and CF 3 CHClCHClCF 3 (raw material compound) was fed into the reactor so that the contact time (W / F 0 ) between the activated carbon catalyst and CF3 CHClCHClCF 3 (The starting compound) was circulated.

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

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

[0231] (2) Removal of hydrogen chloride One hour after the initiation of dehydrochlorination, the distillate passing through the scrubber column was collected.

[0232] Thereafter, gas chromatography (manufactured by Shimadzu Corporation, trade name "GC-2014") was used for mass spectrometry by gas chromatography / mass spectrometry (GC / MS), and structural analysis by NMR spectrum was performed using an NMR (manufactured by JEOL Ltd., trade name "400YH").

[0233] From the results of mass spectrometry and structural analysis, the halogenated alkene compound (1326mxz: CF 3 CCl=CHCF 3 ) was confirmed to be produced as the target compound.

[0234] In addition, in the method for producing a halogenated alkene compound from the above halogenated alkane compound, in addition to 1326mxz (CF 3 CCl=CHCF 3 ), (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)) was also produced.

[0235]

Table 2

[0236] (3) 1326mxz(CF 3 CCl=CHCF 3 ) → PF2B(CF 3C≡CCF 3 ) An SUS pipe (outer diameter: 1 / 2 inch) was used as the reaction tube, and 10 g of activated carbon catalyst (specific surface area 1200 m 2 / g) was filled as the catalyst in the reaction tube.

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

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

[0239] After drying at 200 °C for 2 hours under a nitrogen atmosphere, the pressure was normal pressure, and CF 3 CCl=CHCF 3 (raw material compound) was passed through the reactor so that the contact time (W / F 0 ) with the activated carbon catalyst was 0.5 g·sec / cc, 20 g·sec / cc, or 43 g·sec / cc. 3 CCl=CHCF 3 (raw material compound) was flowed through.

[0240] The reaction was allowed to proceed in a gas-phase continuous flow mode.

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

[0242] One hour after the start of dehydrochlorination, the distillate passing through the scrubbing tower was collected.

[0243] After that, gas chromatography (manufactured by Shimadzu Corporation, trade name "GC-2014") was used Mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS), and structural analysis was carried out by NMR spectrum using NMR (manufactured by JEOL, product name "400YH"). The structural analysis by NMR spectrum was performed using NMR (manufactured by JEOL, product name "400YH").

[0244] From the results of mass spectrometry and structural analysis, it was confirmed that an alkyne fluoride compound (PF2B(CF 3 C≡CCF 3 )) was produced as the target compound.

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

[0246]

Table 3

[0247] Example 9 (dehydrofluorination) 338mee(CF 3 CHFCHFCF 3 ) → 1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) (1) 338mee(CF 3 CHFCHFCF 3 ) → 1327myz(CF 3 CF=CHCF 3 ) An SUS pipe (outer diameter: 1 / 2 inch) was used as the reaction tube, and 10 g of an activated carbon catalyst (specific surface area 1200 m 2 / g) was filled in the reaction tube.

[0248] After drying at 200 °C for 2 hours under a nitrogen atmosphere, the pressure was normal pressure, and CF 3 CHFCHFCF 3(Raw material compound) and activated carbon catalyst were contacted for a contact time (W / F 0 ) of 5 g·sec / cc or 25 g·sec / cc, and CF 3 CHFCHFCF 3 (Raw material compound) was circulated through the reactor.

[0249] The reaction was carried out in a gas-phase continuous flow system.

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

[0251] (2) Removal of hydrogen fluoride One hour after the start of dehydrofluorination, the distillate passing through the scrubbing tower was collected.

[0252] Thereafter, mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and structural analysis was performed by NMR spectrum using an NMR (manufactured by JEOL Ltd., trade name "400YH"). manufactured, trade name "400YH") for structural analysis by NMR spectrum. manufactured, trade name "400YH") for structural analysis by NMR spectrum.

[0253] From the results of mass spectrometry and structural analysis, it was confirmed that the halogenated alkene compound (1327myz: CF 3 CF=CHCF 3 ) was produced as the target compound.

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

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

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

[0257] After drying at 200 °C for 2 hours under a nitrogen atmosphere, the pressure was normal pressure, and CF 3 CCl=CHCF 3 (starting compound) was passed through the reactor so that the contact time (W / F 0 ) with the activated carbon catalyst became 0.5 g·sec / cc, 20 g·sec / cc, or 43 g·sec / cc. 3 CF=CHCF 3 (starting compound) was passed through the reactor so that the contact time (W / F

[0258] The reaction was allowed to proceed in a gas-phase continuous flow mode.

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

[0260] One hour after the start of dehydrofluorination, the distillate passing through the scrubber was collected.

[0261] After that, mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and structural analysis was performed by NMR spectrum using an NMR (manufactured by JEOL Ltd., trade name "400YH"). After that, mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and structural analysis was performed by NMR spectrum using an NMR (manufactured by JEOL Ltd., trade name "400YH"). Based on the results of mass spectrometry and structural analysis, the alkyne fluoride compound (PF2B(CF

[0262] As a target compound, the alkyne fluoride compound (PF2B(CF 3 C≡CCF3 )) was confirmed to have been generated.

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

[0264]

Table 4

[0265] Examples 10 to 16 (dehydrofluorination) 338mee(CF 3 CHFCHFCF 3 ) → 1327myz(CF 3 CF=CHCF 3 ) An SUS pipe (outer diameter: 1 / 2 inch) was used as the reaction tube, and 10 g of an activated carbon catalyst (specific surface area 1200 m 2 / g) was filled in the reaction tube. After drying at 200 °C for 2 hours under a nitrogen atmosphere, the pressure was returned to normal pressure , CF 3 CHFCHFCF 3 (raw material compound) was passed through the reactor so that the contact time (W / F 0 ) with the activated carbon catalyst was 2 to 47 g·sec / cc . Then, in Examples 10 to 13, 4 moles of octafluorocyclobutane (c-C 3 CHFCHFCF 3 (raw material compound) was passed through the reactor so that the contact time (W / F 3 CHFCHFCF 3 (raw material compound) was circulated. Then, in Examples 10 to 13, 4 moles of octafluorocyclobutane (c-C 4 F 8 ; C318) was circulated per 1 mole of the (raw material compound).

[0266] The reaction was allowed to proceed in a gas-phase continuous flow system.

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

[0268] One hour after starting the dehydrochlorination, the distillate passing through the decontamination column was collected.

[0269] Subsequently, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used for mass spectrometry by gas chromatography / mass spectrometry (GC / MS), and structural analysis was performed by NMR spectrum using NMR (manufactured by JEOL, product name "400YH").

[0270] From the results of mass spectrometry and structural analysis, it was confirmed that a halogenated alkene compound (1327myz: CF 3 CF=CHCF 3 ) was produced as the target compound.

[0271] In addition, in the method for producing a halogenated alkene compound from the above halogenated alkane compound, in addition to 1327myz (CF 3 CF=CHCF 3 ) as the target product, 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), 1,1,1,4,4,4-hexafluoro-2-butyne (PF2B), etc. were produced.

[0272]

Table 5

[0273] Examples 17 to 20 (dehydrofluorination) 1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) An SUS pipe (outer diameter: 1 / 2 inch) was used as the reaction tube, and 10 g of an activated carbon catalyst (specific surface area 1200 m 2 / g) was filled as the catalyst in the reaction tube. After drying at 200 °C for 2 hours under a nitrogen atmosphere, the pressure was normal pressure , CF3 CF=CHCF 3 (Raw material compound) and the activated carbon catalyst were contacted for a contact time (W / F 0 ) of 2 g·sec / cc, 2.8 g·sec / cc or 10 g·sec / cc, and CF 3 CF=CHCF 3 (Raw material compound) was passed through the reactor. Thereafter, in Examples 17 to 18, for 1 mol of CF 3 CF=CHCF 3 (Raw material compound), 4 mol of octa fluorocyclobutane (c-C 4 F 8 ; C318) was passed through.

[0274] The reaction was allowed to proceed in a gas-phase continuous flow mode.

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

[0276] One hour after the start of dehydrochlorination, the distillate passing through the scrubber column was collected.

[0277] Thereafter, gas chromatography (manufactured by Shimadzu Corporation, trade name "GC-2014") was used for mass spectrometry by gas chromatography / mass spectrometry (GC / MS), and structural analysis by NMR spectrum was performed using NMR (manufactured by JEOL Ltd. , trade name "400YH").

[0278] From the results of mass spectrometry and structural analysis, it was confirmed that the alkyne fluoride compound (PF2B: CF 3 C≡CCF 3 ) was produced as the target compound.

[0279] In addition, in the method for producing a halogenated alkene compound from the above halogenated alkane compound, in addition to PF2B (CF 3 C≡CCF 3 ) as the target product, trifluoromethane (HFC-23, R23) was produced .

[0280]

Table 6

Claims

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

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

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

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

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

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

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

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

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

10. General formula (3B): <h2 style=";text-align:left;direction:ltr">CA<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> ≡CA<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 is the same as above. X 8 represents a halogen atom. The production method includes a step of subjecting a halogenated alkene compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst.

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

12. General formula (3B): <h2 style=";text-align:left;direction:ltr">CA<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> ≡CA<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A method for producing a fluorinated alkyne compound represented by the following formula: (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. A halogenated alkane compound represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A step of producing a halogenated alkene compound represented by the formula: (IIB) a step of removing hydrogen halide after the step (IB); and (IIIB) After the step (IIB), the obtained compound of the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] In the presence of a catalyst, a halogenated alkene compound represented by the general formula (3B): <h2 style=";text-align:left;direction:ltr">CA<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> ≡CA<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> (3B) [In the formula, A 1 and A 2 is the same as above.] A process for producing a fluorinated alkyne compound represented by the following formula: A manufacturing method comprising:

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

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

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

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

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

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

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

20. General formula (3B): <h2 style=";text-align:left;direction:ltr">CA<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> ≡CA<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. A fluorinated alkyne compound represented by the formula: At least one hydrofluorocarbon (HFC) compound (represented by the general formula (3B) Fluorinated alkyne compounds are excluded), composition.

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

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

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

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

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