Process for producing fluorinated alkyne compounds

Abstract

This invention provides general formula (1): R 1 C≡CR 2 [R 1 and R 2 The same or different, indicating the method of manufacturing fluoroalkyne compounds represented by fluorine atoms or fluoroalkyl groups, includes making general formula (2): R in the presence of an ether solvent. 1 CHX 1 CFX 2 R 2 [R 1 and R 2 Same as above; X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 The process of dehydrofluorinating a fluoroalkane compound represented by a fluorine atom [ ] includes a step of performing a hydrogen defluorination reaction, and satisfies at least one of the following (I) or (II): (I) the fluoroalkyl group is a fluoroalkyl group having 1 to 4 carbon atoms; (II) the ether solvent is a chain ether compound; and the hydrogen defluorination reaction is carried out in the presence of a solvent containing the chain ether and a base containing an alkali metal and / or alkaline earth metal hydroxide and / or alkoxide. By this manufacturing method, fluoroalkane compounds can be efficiently synthesized from fluoroalkane compounds.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for producing a fluoroalkyne compound. BACKGROUND

[0002] A fluoroalkyne compound is expected to be used for a cleaning gas, an etching gas, a refrigerant, a heat transfer medium, a building block for organic synthesis, and the like.

[0003] As such a method for producing a fluoroalkyne compound, for example, in Non-Patent Literature 1, a fluoroalkyne compound is obtained from a fluoroalkane compound by a dehydrofluorination reaction using a base such as lithium diisopropylamide (LDA).

[0004] PRIOR ART DOCUMENTS

[0005] NON-PATENT LITERATURE

[0006] Non-Patent Literature 1: Tetrahedron, 1988, vol. 44, No. 10, p. 2865-2874 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] An object of the present application is to provide a method for efficiently synthesizing a fluoroalkyne compound from a fluoroalkane compound.

[0009] TECHNICAL SOLUTION TO THE PROBLEM

[0010] The present application includes the following solutions.

[0011] Item 1. A method for producing a fluoroalkyne compound represented by General Formula (1), comprising a step of subjecting a fluoroalkane compound represented by General Formula (2) to a dehydrofluorination reaction in the presence of a solvent containing an ether, and at least one of the following (I) or (II) is satisfied.

[0012] R 1 C≡CR 2 (1)

[0013] [In the formula, R 1 and R 2 are the same or different and represent a fluorine atom or a fluoroalkyl group.]

[0014] R 1 CHX 1 CFX 2 R 2 (2)

[0015] [In the formula, R 1 and R 2 are the same as above; X 1 and X 2 in X1 is a fluorine atom and X 2 is a hydrogen atom, or X 1 is a hydrogen atom and X 2 is a fluorine atom.

[0016] (I) The above-mentioned fluoroalkyl group is a fluoroalkyl group having 1 to 4 carbon atoms.

[0017] (II) The above-mentioned ether is a chain ether, and the above-mentioned dehydrofluorination reaction is performed in the presence of a solvent containing the above-mentioned chain ether, and an alkali containing a hydroxide and / or an alkoxide of an alkali metal and / or an alkaline earth metal.

[0018] Item 2. The production method according to item 1, wherein the moisture concentration of the above-mentioned solvent is 0.01 to 500 mass ppm, based on the total amount of the above-mentioned solvent being 100 mass %.

[0019] Item 3. The production method according to item 1 or 2, wherein the above-mentioned ether has 1 to 10 ether bonds.

[0020] Item 4. The production method according to any one of items 1 to 3, wherein the above-mentioned (I) is satisfied.

[0021] Item 5. The production method according to item 4, wherein the above-mentioned fluoroalkyl group is represented by general formula (3).

[0022] -CF2R 3 (3)

[0023] [In the formula, R 3 represents a fluorine atom or a fluoroalkyl group having 1 to 3 carbon atoms.]

[0024] Item 6. The production method according to item 4 or 5, wherein the above-mentioned dehydrofluorination reaction is performed in the presence of an alkali.

[0025] Item 7. The production method according to item 6, wherein the above-mentioned alkali is a hydroxide and / or an alkoxide of an alkali metal and / or an alkaline earth metal.

[0026] Item 8. The production method according to any one of items 1 to 3, wherein the above-mentioned (II) is satisfied.

[0027] Item 9. The production method according to item 8, wherein the above-mentioned fluoroalkyl group has 1 to 10 carbon atoms.

[0028] Item 10. The production method according to item 8 or 9, wherein the above-mentioned fluoroalkyl group is represented by general formula (3).

[0029] -CF2R 3 (3)

[0030] [In the formula, R 3fluoroalkyl group having 1 to 9 carbon atoms.

[0031] Item 11. The production method according to any one of items 1 to 10, wherein the reaction temperature of the above-mentioned dehydrofluorination reaction is 0 to 3000C.

[0032] Item 12. A composition containing a fluoroalkyne compound represented by the general formula (1) and a fluoroalkene compound represented by the general formula (4), wherein,

[0033] R 1 C≡CR 2 (1)

[0034] [In the formula, R 1 and R 2 are the same or different and represent a fluorine atom or a fluoroalkyl group.]

[0035] R 1 CF=CHR 2 (4)

[0036] [In the formula, R 1 and R 2 are the same as above.]

[0037] The total amount of the composition is set to 100 mole%, the content of the above-mentioned fluoroalkyne compound is 25.00 to 75.00 mole%, the content of the above-mentioned fluoroalkene compound is 25.00 to 75.00 mole%, and the total content of the above-mentioned fluoroalkyne compound and the above-mentioned fluoroalkene compound is 90.00 to 100.00 mole%.

[0038] Item 13. The composition according to item 12, which is used as a cleaning gas, an etching gas, a refrigerant, a heat transfer medium or a building block for organic synthesis.

[0039] Item 14. Use of the composition according to item 12 as a cleaning gas, an etching gas, a refrigerant, a heat transfer medium or a building block for organic synthesis.

[0040] Effects of the Invention

[0041] According to the present application, there is provided a method capable of efficiently synthesizing a fluoroalkyne compound from a fluoroalkane compound. DETAILED DESCRIPTION

[0042] In the present specification, "comprising" is a concept including "consisting essentially of", "consisting essentially of" and "consisting of" as any case. In addition, in the present specification, in the case of indicating a numerical range as "A to B", it means A or more and B or less.

[0043] In this invention, "selectivity" refers to the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of compounds other than the feedstock compound in the effluent gas.

[0044] In this invention, "conversion rate" refers to the ratio (mol%) of the total molar amount of compounds other than the feedstock compounds contained in the effluent gas from the reactor outlet to the molar amount of the feedstock compounds supplied to the reactor.

[0045] In this invention, "yield" refers to the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the molar amount of the feedstock compound supplied to the reactor.

[0046] As a method for manufacturing fluorinated alkynes, it is known to synthesize fluorinated alkenes such as CF3CF=CHCF3 by dehydrofluorination of fluorinated alkanes such as CF3CFHCFHCF3, and then further synthesize fluorinated alkenes by dehydrofluorination of these alkanes. This method requires two dehydrofluorination reactions, thus extending the manufacturing process.

[0047] Furthermore, a method is known, as in Non-Patent Document 1, that uses lithium diisopropylamide (LDA) as a base to obtain fluoroalkynes from fluoroalkanes via a single defluorination reaction in solvents such as hexane, diethyl ether, and monoethylene glycol dimethyl ether. In this method, KOC(CH3)3 is used as a base, and even in solvents such as tetrahydrofuran and dimethyl sulfoxide, fluoroalkynes can be obtained from fluoroalkanes via a single defluorination reaction. However, in this method, the use of lithium diisopropylamide (LDA) is not efficient due to its high cost, and the maximum yield is only 41% (compared to a maximum of 24% without the expensive LDA), making it a less than effective manufacturing method.

[0048] According to the manufacturing method of the present invention, compared with the prior art, a method is provided that can efficiently synthesize fluoroalkane compounds in high yield from fluoroalkane compounds.

[0049] 1. Process for producing a fluoroacetylene compound (first embodiment)

[0050] The method for manufacturing a fluoroalkyne compound according to the first embodiment of the present invention is a method for manufacturing a fluoroalkyne compound of general formula (1), which includes a step of causing a fluoroalkane compound of general formula (2) to undergo a dehydrofluorination reaction in the presence of a solvent containing an ether, and satisfies the following (I).

[0051] R 1 C≡CR2 (1)

[0052] [In the formula, R] 1 and R 2 "Identical" or "different" indicates a fluorine atom or a fluorinated alkyl group.

[0053] R 1 CHX 1 CFX 2 R 2 (2)

[0054] [In the formula, R] 1 and R 2 Same as above; X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 It consists of fluorine atoms.

[0055] (I) The above-mentioned fluoroalkyl groups are fluoroalkyl groups with 1 to 4 carbon atoms.

[0056] In other words, the method for manufacturing fluoroalkyne compounds according to the first embodiment of the present invention is a method for manufacturing fluoroalkyne compounds represented by general formula (1), which includes a step of causing fluoroalkanes represented by general formula (2) to undergo a dehydrofluorination reaction in the presence of an ether solvent.

[0057] R 1 C≡CR 2 (1)

[0058] [In the formula, R] 1 and R 2 "Same or different" indicates a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms.

[0059] R 1 CHX 1 CFX 2 R 2 (2)

[0060] [In the formula, R] 1 and R 2 Same as above. X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 It consists of fluorine atoms.

[0061] According to the present invention, by carrying out the dehydrofluorination reaction of the fluoroalkane compound represented by the above general formula (2), it is possible to obtain the fluoroalkyne compound represented by general formula (1) by dehydrofluorination of 2 moles of hydrogen fluoride for 1 mole of the fluoroalkane compound represented by general formula (2) in only one step.

[0062] (1-1) Raw material compounds (fluorinated alkanes)

[0063] As a matrix that can be used in the manufacturing method (first embodiment) of the present invention, the fluoroalkane compound is, as described above, a fluoroalkane compound represented by general formula (2).

[0064] R 1 CHX 1 CFX 2 R 2 (2)

[0065] [In the formula, R] 1 and R 2 Same or different, indicating fluorine atoms or fluoroalkyl groups with 1 to 4 carbon atoms. X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 It consists of fluorine atoms.

[0066] In other words, the fluoroalkane compounds represented by general formula (2) include any of the cases of general formulas (2A) and (2B).

[0067] R 1 CFHCFHR 2 (2A)

[0068] R 1 CH2CF2R 2 (2B)

[0069] [In the formula, R] 1 and R 2 "Same or different" indicates a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms.

[0070] In general formula (2), R 1 and R 2The fluoroalkyl group referred to is a group in which one or more hydrogen atoms of the alkyl group are replaced by fluorine atoms, and also includes perfluoroalkyl groups in which all hydrogen atoms of the alkyl group are replaced. Both straight-chain and branched fluoroalkyl groups can be used as such fluoroalkyl groups, and examples include monofluoromethyl, difluoromethyl, trifluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, heptafluoropropyl, monofluorobutyl, difluorobutyl, trifluorobutyl, tetrafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, and nonafluorobutyl, etc., which have 1 to 4 carbon atoms. From the viewpoint of being able to produce fluoroalkyne compounds with particularly high conversion, yield, and selectivity, fluoroalkyl groups with 1 to 3 carbon atoms are preferred. Furthermore, from the viewpoint of easily suppressing side reactions, these fluoroalkyl groups preferably have fewer hydrogen atoms, and perfluoroalkyl groups are particularly preferred.

[0071] Regarding fluoroalkane compounds as substrates, from the viewpoint that fluoroalkane compounds can be produced with particularly high conversion, yield, and selectivity, R 1 and R 2 All are preferably fluoroalkyl, more preferably perfluoroalkyl, and even more preferably trifluoromethyl.

[0072] The above R 1 and R 2 They can be the same or different.

[0073] Examples of fluoroalkane compounds that meet the above conditions as a matrix include CF2HCF2H, CF3CFHCF2H, CF3CFHCFHCF3, CF3CF2CFHCFHCF3, CF3CF2CFHCFHCF2CF3, CFH2CF3, CF3CH2CF3, CF3CH2CF2CF3, CF3CF2CH2CF2CF3, and CF3CF2CH2CF2CF2CF3. These fluoroalkane compounds can be used alone or in combination of two or more. Such fluoroalkane compounds can be either known or commercially available products.

[0074] (1-2) Defluorination reaction

[0075] In the step of the present invention, in which a fluoroalkane compound undergoes a dehydrofluorination reaction, for example, R is more preferably a fluoroalkane compound represented by general formula (2) as a matrix. 1 and R 2 It is trifluoromethyl.

[0076] In other words, the preferred reaction formula is as follows:

[0077] CF3CFHCFHCF3→CF3C≡CCF3+2HF

[0078] CF3CH2CF2CF3→CF3C≡CCF3+2HF,

[0079] The defluorination reaction of 1 mole of CF3CFHCFHCF3 or CF3CH2CF2CF3 away from 2 moles of hydrogen fluoride.

[0080] Regarding the dehydrofluorination reaction of fluoroalkanes in this invention, from the viewpoints of conversion, selectivity, and yield, the reaction is carried out in the presence of a solvent containing an ether, that is, in a liquid phase using a solvent containing an ether. When the reaction is carried out in a gas phase without a solvent, or in a liquid phase reaction using a solvent other than a solvent containing an ether, the dehydrofluorination reaction starting from the fluoroalkene will not occur, making it impossible to efficiently obtain fluoroalkynes from fluoroalkanes in a single step.

[0081] In this invention, for example by using a metal container, pressure is applied to increase the boiling point of the raw material, thereby increasing the amount of liquid phase, which can further improve the yield of the target compound.

[0082] In addition, in this invention, it is preferable to first prepare a solution of the fluoroalkane compound represented by the above general formula (2), and then carry out the reaction in the presence of a base.

[0083] (1-3) Solvents containing ethers

[0084] In this invention, in order to obtain fluoroalkynes from fluoroalkanes in one step via a defluorination reaction, the reaction is preferably carried out in the presence of a solvent containing an ether.

[0085] However, for easy defluorination of fluoroalkanes to fluoroalkynes via hydrogen defluorination, a low water content is preferred. From this perspective, the total amount of the ether-containing solvent is set to 100% by mass, and the water concentration of the ether-containing solvent is preferably 500 ppm by mass or less, more preferably 400 ppm by mass or less, and even more preferably 300 ppm by mass or less. Furthermore, there is no particular limitation on the lower limit of the water concentration of the ether-containing solvent, but from the viewpoint of ease of technical implementation, 0.01 ppm by mass or more is preferred.

[0086] Furthermore, in order to readily obtain fluoroalkynes from fluoroalkanes via a defluorination reaction, it is preferable that the ether has as few ether bonds as possible. From this viewpoint, the number of ether bonds in the ether is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0087] From the viewpoints of conversion, selectivity, and yield, chain ethers are preferred among ether-containing solvents that meet the above conditions. Chain ethers include not only ether compounds that are completely non-cyclic, but also ether compounds that contain cyclic structures without ether bonds. That is, the concept of chain ethers does not include ether compounds with cyclic structures formed by ether bonds, such as tetrahydrofuran, but includes ether compounds with cyclic structures without ether bonds, such as diphenyl ether. When using ether compounds that are completely non-cyclic, the yield of the target fluoroalkyne compound can be particularly improved; when using ether compounds with cyclic structures without ether bonds, the yield of impurities (hydrofluorocarbons other than fluoroalkanes, fluoroalkenes, and fluoroalkynes) can be particularly reduced. Specifically preferred ethers are diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and diethylene glycol dimethyl ether. Ether solvents can be used alone or in combination of two or more. From the perspectives of conversion rate, selectivity and yield, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc. are preferred, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, etc. are more preferred, and diisopropyl ether, di-n-butyl ether, diphenyl ether, etc. are even more preferred.

[0088] In this invention, as long as ether is used, it can also be used in combination with other solvents such as: carbonate solvents such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, and butyl propionate; ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone; lactone solvents such as γ-butyrolactone, γ-valerolactone, tetrahydrofuran, and tetrahydropyran; cyclic ether solvents such as tetrahydrofuran; nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; amide solvents such as N,N-dimethylformamide; and sulfone solvents such as dimethyl sulfoxide and sulfolane. However, from the viewpoint of reaction conversion, selectivity, and yield, the total amount of solvent used in the reaction is set to 100% by volume, and the amount of the above-mentioned ether is preferably 80 to 100% by volume (especially 90 to 100% by volume), and the amount of these other solvents is preferably 0 to 20% by volume (especially 0 to 10% by volume).

[0089] (1-4) base

[0090] Regarding the process of obtaining fluoroalkynes from fluoroalkanes by dehydrofluorination in this invention, from the viewpoints of conversion, selectivity and yield, it is preferable to carry out the process in the presence of a base.

[0091] From the viewpoint of reaction conversion, selectivity of haloalkyne compounds, and yield, at least one of alkali metal and alkaline earth metal hydroxides and alkoxides is preferred (i.e., at least one selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, and alkaline earth metal alkoxides). More preferably, at least one of alkali metal and alkaline earth metal hydroxides and alkali metal alkoxides is preferred (i.e., at least one selected from alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal alkoxides). Even more preferred are alkali metal hydroxides and / or alkali metal alkoxides (i.e., alkali metal hydroxides and / or alkali metal alkoxides). Particularly preferred are alkali metal hydroxides. Examples of such bases include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium methoxide, potassium tert-butoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, magnesium methoxide, magnesium ethoxide, magnesium tert-butoxide, calcium methoxide, calcium ethoxide, and calcium tert-butoxide. From the perspective of reaction conversion rate, selectivity and yield of haloalkyne compounds, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, etc. are preferred, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, etc. are more preferred, and sodium hydroxide, potassium hydroxide, etc. are even more preferred.

[0092] There is no particular limitation on the amount of alkali used, but it is preferably 1.0 to 10.0 moles, more preferably 1.5 to 5.0 moles, and even more preferably 2.0 to 3.0 moles, relative to 1 mole of the fluoroalkane compound shown in general formula (2).

[0093] (1-5) Reaction conditions

[0094] Closed reaction system

[0095] In this invention, the fluoroalkyne compound represented by general formula (1) as the target compound has a low boiling point and exists as a gas at room temperature. Therefore, in the dehydrofluorination reaction step of this invention, by making the reaction system a closed reaction system, the pressure inside the closed reaction system naturally increases, and the reaction can be carried out under pressure. Therefore, the fluoroalkyne compound represented by general formula (1) as the target compound can be obtained with higher selectivity and higher conversion.

[0096] As described above, due to the low boiling point of the target compound, pressurizing the closed reaction system increases the concentration of the matrix (starting compound) in the ether solvent, thereby enhancing reactivity. To form a closed reaction system, a batch-type pressure-resistant reaction vessel is preferred, allowing the reaction to proceed in a sealed environment. In the case of a batch reaction, for example, the starting compound, ether solvent, and, if necessary, a base are preferably added to a pressure vessel such as an autoclave, heated to a suitable reaction temperature using a heater, and reacted for a certain time with stirring. As the reaction atmosphere, an inert gas atmosphere such as nitrogen, helium, or carbon dioxide is preferred.

[0097] In the process of the defluorination reaction in this invention, the reaction temperature in the closed-pressure reaction system is generally preferred from the viewpoint of the conversion rate of the reaction and the selectivity and yield of the haloalkyne compound, preferably 0 to 400°C, more preferably 25 to 300°C, and even more preferably 50 to 200°C.

[0098] Furthermore, when no base is used, or when alkali metal and / or alkaline earth metal hydroxides are used as the base, the reaction temperature in the closed-pressure reaction system is generally preferred from the viewpoint of reaction conversion, selectivity of haloalkyne compounds, and yield, to be 25 to 400°C, more preferably 50 to 300°C, and even more preferably 100 to 200°C.

[0099] On the other hand, when alkali metal and / or alkaline earth metal alkoxides are used as the base, an addition reaction of the alkoxide onto the double bond occurs at excessively high reaction temperatures, so a slightly lower reaction temperature is preferred. Therefore, regarding the reaction temperature in a closed-pressure reaction system, from the viewpoint of reaction conversion, selectivity of haloalkynes, and yield, 0–200 °C is generally preferred, more preferably 25–150 °C, and even more preferably 50–100 °C.

[0100] In addition, there is no particular limitation on the reaction time, as long as it is sufficient for the reaction to proceed fully. Specifically, it is sufficient for the reaction to continue until the composition of the reaction system no longer changes.

[0101] Pressurized reaction system

[0102] In this invention, regarding the step of the defluorination reaction, the reaction temperature can be set to above 0°C and the reaction pressure to be greater than 0 kPa, and the reaction can be carried out in a pressurized reaction system. This allows for the acquisition of the fluoroalkyne compound of general formula (1) as the target compound with higher selectivity and higher conversion. When the reaction system is pressurized as described above, the concentration of the matrix (starting compound) in the ether solvent can be increased, thus improving reactivity. Preferably, the pressurized reaction system is carried out in a batch-type pressure-resistant reaction vessel, with the reaction system sealed. In the case of batch reaction, for example, it is preferable to add the starting compound, ether solvent, and, as needed, a base to a pressure vessel such as an autoclave, heat the mixture to an appropriate reaction temperature using a heater, and react for a certain time under stirring.

[0103] In the defluorination reaction step of this invention, the reaction pressure is preferably set to be greater than 0 kPa. In the defluorination reaction step of this invention, the reaction pressure is preferably greater than 0 kPa, more preferably 5 kPa or more, further preferably 10 kPa or more, and particularly preferably 15 kPa or more. There is no particular upper limit to the reaction pressure, which is usually around 2 MPa. In this invention, unless otherwise specified, pressure refers to gauge pressure. Furthermore, the reaction pressure described herein is for a pressurized reaction system, but the reaction can also be carried out under reduced pressure or atmospheric pressure without using a pressurized reaction system.

[0104] When pressurized, the pressure inside the reaction system can be increased by introducing inert gases such as nitrogen, helium, and carbon dioxide.

[0105] In the process of the defluorination reaction in this invention, regarding the reaction temperature in the pressurized reaction system, from the viewpoints of more efficiently carrying out the elimination reaction, obtaining the target compound with a higher selectivity, and suppressing the decrease in conversion rate, it is generally preferred to be 0 to 400°C, more preferably 25 to 300°C, and even more preferably 100 to 200°C.

[0106] Furthermore, when no alkali is used, or when alkali metal and / or alkaline earth metal hydroxides are used as the alkali, the reaction temperature in the pressurized reaction system is generally preferred from the viewpoint of reaction conversion, selectivity of haloalkyne compounds, and yield, to be 25 to 400°C, more preferably 50 to 300°C, and even more preferably 100 to 200°C.

[0107] On the other hand, when alkali metal and / or alkaline earth metal alkoxides are used as the base, an addition reaction of the alkoxide onto the double bond occurs at excessively high reaction temperatures, so a slightly lower reaction temperature is preferred. Therefore, regarding the reaction temperature in the pressurized reaction system, from the viewpoint of reaction conversion, selectivity of haloalkyne compounds, and yield, 0–200 °C is generally preferred, more preferably 25–150 °C, and even more preferably 50–100 °C.

[0108] Combination of closed reaction system and pressurized reaction system

[0109] In the process of the defluorination reaction in this invention, a method such as connecting a back pressure valve to a continuous phase tank reactor (CSTR) can be used to extract the liquid or extract the product after vaporization, while carrying out the reaction in a continuous and pressurized manner.

[0110] After the defluorination reaction is completed, the fluorinated alkyne compound can be purified according to conventional methods as needed to obtain the fluorinated alkyne compound shown in general formula (1).

[0111] (1-6) Target compounds (haloalkynes)

[0112] The target compound of the present invention obtained by the above method is a fluoroalkyne compound represented by general formula (1).

[0113] R 1 C≡CR 2 (1)

[0114] [In the formula, R] 1 and R 2 "Identical" or "different" indicates a fluorine atom or a fluorinated alkyl group.

[0115] R in general formula (1) 1 and R 2 R corresponds to the above general formula (2) 1 and R 2 Therefore, specific examples of the fluoroalkyne compounds represented by the general formula (1) to be manufactured include CF≡CF, CF3C≡CF, CF3C≡CCF3, CF3CF2C≡CCF3, CF3CF2C≡CCF2CF3, etc.

[0116] Furthermore, using the manufacturing method of the present invention, the fluoroalkyne compound represented by general formula (1) is sometimes not obtained alone, but in the form of a composition containing the fluoroalkyne compound represented by general formula (1). In this case, the majority of the compound contained other than the fluoroalkyne compound represented by general formula (1) is a fluoroalkene compound represented by general formula (4) which is a fluoroalkane compound represented by general formula (2) that has only been defluorinated by 1 mole of hydrogen fluoride. Therefore, by repeating the above-described process of undergoing the defluorination reaction, the selectivity and yield of the fluoroalkyne compound represented by general formula (1) can be further improved.

[0117] R 1 CF=CHR 2 (4)

[0118] [In the formula, R] 1 and R 2 Same as above.

[0119] For example, in Example 1 described later, when CF3CFHCFHCF3 was used as the starting compound, CF3C≡CCF3 was obtained in a yield of 49.9 mol% (conversion 97.9% × selectivity 51.00%), and CF3CF=CHCF3 was obtained in a yield of 41.7 mol% (conversion 97.9% × selectivity 42.62%).

[0120] In this invention, when the dehydrofluorination reaction is repeated, i.e., the number of steps is increased, CF3CF=CHCF3, obtained as an impurity, is used as a raw material and undergoes the same dehydrofluorination reaction. Therefore, assuming that the yield of CF3CF=CHCF3→CF3C≡CCF3 in the second step is also 49.9 mol%, the two steps combined can yield 70.7 mol% of CF3C≡CCF3 from the raw material CF3CFHCFHCF3.

[0121] On the other hand, in the existing method, the first step is CF3CFHCFHCF3→CF3CF=CHCF3 and the second step is CF3CF=CHCF3→CF3C≡CCF3. Even if the yield of the first step is 100 mol%, since the yield of the second step is 49.9 mol% as mentioned above, 49.9 mol% of CF3C≡CCF3 of the raw material CF3CFHCFHCF3 can be obtained through two steps.

[0122] As described above, according to the present invention, using a specified fluoroalkane compound as a starting material, a specified fluoroalkane compound can be obtained in only one step. Furthermore, by repeating the dehydrofluorination reaction multiple times, the yield of the fluoroalkane compound can be increased compared to existing methods. In any case, it will be understood that the manufacturing method of the present invention is useful.

[0123] The resulting fluorinated alkynes can be effectively utilized in a variety of applications, including etching gases, cleaning gases, deposition gases, refrigerants, heat transfer media, and building blocks for organic synthesis, for forming state-of-the-art fine structures such as semiconductors and liquid crystals. Deposition gases and building blocks for organic synthesis will be discussed in detail later.

[0124] 2. Process for producing a fluoroacetylene compound (second embodiment)

[0125] The method for manufacturing a fluoroalkyne compound according to the second embodiment of the present invention is a method for manufacturing a fluoroalkyne compound of general formula (1), which includes a step of causing a fluoroalkane compound of general formula (2) to undergo a dehydrofluorination reaction in the presence of a solvent containing an ether, and satisfies the following (II).

[0126] R 1 C≡CR 2 (1)

[0127] [In the formula, R] 1 and R 2 "Identical" or "different" indicates a fluorine atom or a fluorinated alkyl group.

[0128] R 1 CHX 1 CFX 2 R 2 (2)

[0129] [In the formula, R] 1 and R 2 Same as above. X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 It consists of fluorine atoms.

[0130] (II) The above ether is a chain ether, and the above defluorination reaction is carried out in the presence of a solvent containing the above chain ether and a base containing alkali metal and / or alkaline earth metal hydroxides and / or alkoxides.

[0131] In other words, the method for manufacturing fluoroalkyne compounds according to the second embodiment of the present invention is a method for manufacturing fluoroalkyne compounds represented by general formula (1), which includes a step of causing fluoroalkanes represented by general formula (2) to undergo a dehydrofluorination reaction in the presence of a solvent containing a chain ether and a base containing an alkali metal and / or an alkaline earth metal hydroxide and / or an alkoxide.

[0132] R 1 C≡CR 2 (1)

[0133] [In the formula, R] 1 and R 2 "Identical" or "different" indicates a fluorine atom or a fluorinated alkyl group.

[0134] R 1 CHX 1 CFX 2 R 2 (2)

[0135] [In the formula, R] 1 and R 2 Same as above. X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 It consists of fluorine atoms.

[0136] According to the present invention, by carrying out the dehydrofluorination reaction of the fluoroalkane compound represented by the above general formula (2), it is possible to obtain the fluoroalkyne compound represented by general formula (1) by dehydrofluorination of 2 moles of hydrogen fluoride for 1 mole of the fluoroalkane compound represented by general formula (2) in only one step.

[0137] (2-1) Raw material compounds (fluorinated alkanes)

[0138] As a matrix that can be used in the manufacturing method (second embodiment) of the present invention, the fluoroalkane compound is, as described above, a fluoroalkane compound represented by general formula (2).

[0139] R 1 CHX 1 CFX 2 R 2 (2)

[0140] [In the formula, R] 1 and R 2 Same or different indicates fluorine atom or fluoroalkyl group. X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 It consists of fluorine atoms.

[0141] In other words, the fluoroalkane compounds represented by general formula (2) include any of the cases of general formulas (2A) and (2B).

[0142] R 1 CFHCFHR 2 (2A)

[0143] R 1CH2CF2R 2 (2B)

[0144] [In the formula, R] 1 and R 2 "Identical" or "different" indicates a fluorine atom or a fluorinated alkyl group.

[0145] In general formula (2), R 1 and R 2 The fluoroalkyl group referred to is a group in which one or more hydrogen atoms of the alkyl group are replaced by fluorine atoms, and also includes perfluoroalkyl groups in which all hydrogen atoms of the alkyl group are replaced. As such fluoroalkyl groups, both straight-chain fluoroalkyl groups and branched fluoroalkyl groups can be used, and examples include fluoroalkyl groups with 1 to 10 carbon atoms such as monofluoromethyl, difluoromethyl, trifluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, and heptafluoropropyl. From the viewpoint of being able to produce fluoroalkyne compounds with particularly high conversion, yield and selectivity, fluoroalkyl groups with 1 to 4 carbon atoms are preferred, and fluoroalkyl groups with 1 to 3 carbon atoms are more preferred.

[0146] Regarding fluoroalkane compounds as substrates, from the viewpoint that fluoroalkane compounds can be produced with particularly high conversion, yield, and selectivity, R 1 and R 2 All are preferably fluoroalkyl, more preferably perfluoroalkyl, and even more preferably trifluoromethyl.

[0147] The above R 1 and R 2 They can be the same or different.

[0148] Examples of fluoroalkane compounds that meet the above conditions as a matrix include CF2HCF2H, CF3CFHCF2H, CF3CFHCFHCF3, CF3CF2CFHCFHCF3, CF3CF2CFHCFHCF2CF3, CFH2CF3, CF3CH2CF3, CF3CH2CF2CF3, CF3CF2CH2CF2CF3, and CF3CF2CH2CF2CF2CF3. These fluoroalkane compounds can be used alone or in combination of two or more. Such fluoroalkane compounds can be known or commercially available products.

[0149] (2-2) Defluorination reaction

[0150] The "defluorination reaction" can be carried out in the same way as the "(1-2) defluorination reaction" described above. All conditions can also be the same as above.

[0151] (2-3) Solvents containing chain ethers

[0152] In this invention, in order to obtain fluoroalkynes from fluoroalkanes in one step via a defluorination reaction, the reaction is preferably carried out in the presence of a solvent containing a chain ether.

[0153] However, for easy defluorination of fluoroalkanes to fluoroalkynes via hydrogen defluorination, a low water content is preferred. From this perspective, the total amount of solvent containing the chain ether is set to 100% by mass, and the water concentration of the solvent containing the chain ether is preferably 500 ppm by mass or less, more preferably 400 ppm by mass or less, and even more preferably 300 ppm by mass or less. Furthermore, there is no particular limitation on the lower limit of the water concentration of the solvent containing the chain ether, but from the viewpoint of ease of technical implementation, 0.01 ppm by mass or more is preferred.

[0154] Furthermore, in order to readily obtain fluoroalkynes from fluoroalkanes via a defluorination reaction, it is preferable that the chain ether has as few ether bonds as possible. From this perspective, the chain ether preferably has 1 to 10 ether bonds, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0155] The chain ethers in solvents containing chain ethers that meet the above conditions include not only ether compounds that do not have a cyclic structure at all, but also ether compounds that contain a cyclic structure without ether bonds. That is, the concept of chain ethers does not include ether compounds with cyclic structures formed by ether bonds, such as tetrahydrofuran, but includes ether compounds with cyclic structures without ether bonds, such as diphenyl ether. When using ether compounds that do not have a cyclic structure at all, the yield of the target fluoroalkyne compound can be particularly improved; when using ether compounds with cyclic structures without ether bonds, the yield of impurities (hydrofluorocarbons other than fluoroalkanes, fluoroalkenes, and fluoroalkynes) can be particularly reduced. Specifically preferred chain ethers are diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and diethylene glycol dimethyl ether. Chain ether solvents can be used alone or in combination of two or more. From the perspectives of conversion rate, selectivity and yield, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc. are preferred, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, etc. are more preferred, and diisopropyl ether, di-n-butyl ether, diphenyl ether, etc. are even more preferred.

[0156] In this invention, as long as a chain ether is used, it can also be used in combination with other solvents such as: carbonate solvents such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, and butyl propionate; ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone; lactone solvents such as γ-butyrolactone, γ-valerolactone, tetrahydrofuran, and tetrahydropyran; cyclic ether solvents such as tetrahydrofuran; nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; amide solvents such as N,N-dimethylformamide; and sulfone solvents such as dimethyl sulfoxide and sulfolane. However, from the viewpoint of reaction conversion, selectivity, yield, etc., it is preferable to use less of these other solvents. Specifically, the total amount of solvent used in the reaction is set to 100% by volume, the amount of the above-mentioned chain ether used is preferably 80 to 100% by volume (especially 90 to 100% by volume), and the amount of these other solvents used is preferably 0 to 20% by volume (especially 0 to 10% by volume).

[0157] (2-4) base

[0158] Regarding the process of obtaining fluoroalkynes from fluoroalkanes by dehydrofluorination in this invention, from the viewpoints of conversion, selectivity and yield, it is preferable to carry out the process in the presence of a base containing hydroxides and / or alkoxides of alkali metals and / or alkaline earth metals.

[0159] From the viewpoint of reaction conversion, selectivity of haloalkyne compounds, and yield, the base is selected from at least one of alkali metal and alkaline earth metal hydroxides and alkoxides (i.e., selected from at least one of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, and alkaline earth metal alkoxides), preferably selected from at least one of alkali metal and alkaline earth metal hydroxides and alkali metal alkoxides (i.e., selected from at least one of alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal alkoxides), more preferably selected from alkali metal hydroxides and / or alkali metal alkoxides (i.e., alkali metal hydroxides and / or alkali metal alkoxides), and even more preferably alkali metal hydroxides. Examples of such bases include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium methoxide, potassium tert-butoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, magnesium methoxide, magnesium ethoxide, magnesium tert-butoxide, calcium methoxide, calcium ethoxide, and calcium tert-butoxide. From the perspective of reaction conversion rate, selectivity and yield of haloalkyne compounds, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, etc. are preferred, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, etc. are more preferred, and sodium hydroxide, potassium hydroxide, etc. are even more preferred.

[0160] There is no particular limitation on the amount of base used, but it is preferably about 1 mole relative to 1 mole of the fluoroalkane compound shown in general formula (2). Specifically, the amount of base used is preferably 1.0 to 10.0 moles relative to 1 mole of the fluoroalkane compound shown in general formula (2), more preferably 1.5 to 5.0 moles, and even more preferably 2.0 to 3.0 moles.

[0161] (2-5) Reaction conditions and target compound

[0162] Regarding the "reaction conditions," they can be the same as those in "(1-5) Reaction Conditions" above. Additionally, regarding the "target compound," they can be the same as those in "(1-6) Target Compound" above. All other conditions can also be the same as above.

[0163] 3. Composition

[0164] As described above, fluoroalkane compounds can preferably be obtained from fluoroalkane compounds in one step, but they can also be obtained in the form of compositions containing fluoroalkane compounds. In particular, using the manufacturing method of the present invention, for example, it is possible to generate compositions containing fluoroalkane compounds of the above general formula (1) and fluoroalkene compounds of general formula (4) which are derived from fluoroalkane compounds of general formula (2) by removing only 1 mole of hydrogen fluoride.

[0165] R 1 CF=CHR 2 (4)

[0166] [In the formula, R] 1 and R 2 Same as above.

[0167] R in general formula (4) 1 and R 2 R corresponds to the above general formula (2) 1 and R 2 Therefore, specific examples of fluoroolefin compounds represented by general formula (4) include CF2=CFH, CF3CF=CFH, CF3CH=CFH, CF3CF=CHCF3, CF3CF2CF=CHCF3, CF3CF2CH=CFCF3, CF3CF2CF=CHCF2CF3, etc. These fluoroolefin compounds can be a single compound or a combination of two or more compounds.

[0168] Using the manufacturing method of the present invention, there is a tendency to easily produce compositions containing, to the same extent, the fluoroalkynyl compound represented by general formula (1) and the fluoroolefin compound represented by general formula (4), while the contents of other components are low. Therefore, in the composition containing fluoroalkynyl compounds of the present invention, the total amount of the composition is set to 100 mol%, and the content of the fluoroalkynyl compound represented by general formula (1) is preferably 25.00 mol% or more, more preferably 30.00 mol% or more, and even more preferably 35.00 mol% or more. Similarly, in the composition containing fluoroalkynyl compounds of the present invention, the total amount of the composition is set to 100 mol%, and the content of the fluoroalkynyl compound represented by general formula (1) can be, for example, 75.00 mol% or less, 70.00 mol% or less, or 65.00 mol% or less. Furthermore, in the composition containing fluorinated alkynes of the present invention, when the total amount of the composition is set to 100 mol%, the content of the fluorinated olefin compound represented by general formula (4) can be 25.00 mol% or more, 30.00 mol% or more, or 35.00 mol% or more. Similarly, in the composition containing fluorinated alkynes of the present invention, when the total amount of the composition is set to 100 mol%, the content of the fluorinated olefin compound represented by general formula (4) is preferably 75.00 mol% or less, more preferably 70.00 mol% or less, and even more preferably 65.00 mol% or less. Moreover, in the composition containing fluorinated alkynes of the present invention, when the total amount of the composition is set to 100 mol%, the total content of the fluorinated alkynes of general formula (1) and the fluorinated olefin compound represented by general formula (4) is preferably 90.00 mol% or more, more preferably 91.00 mol% or more, and even more preferably 92.00 mol% or more. Similarly, in the composition containing fluorinated alkyne compounds of the present invention, the total amount of the composition is set to 100 mol%, and the total content of the fluorinated alkyne compound represented by general formula (1) and the fluorinated olefin compound represented by general formula (4) can be less than 100.00 mol%, less than 99.99 mol%, or less than 99.98 mol%.

[0169] As described above, using the manufacturing method of the present invention, in addition to the fluoroalkynyl compounds represented by general formula (1) and the fluoroolefin compounds represented by general formula (4) contained in the obtained composition, hydrofluorocarbon compounds such as trifluoromethane (R23), difluoromethane (R32), tetrafluoromethane (R14), monofluoromethane (R41), 1,2-difluoroethylene (R1132), and 1,1,2-trifluoroethylene (R1123) may also be contained. In this case, when the total amount of the composition containing the fluoroalkynyl compounds of the present invention is set to 100 mol%, the content of these other hydrofluorocarbon compounds may be 0.00 mol% or more, 0.01 mol% or more, or 0.02 mol% or more. Similarly, when the total amount of the composition containing the fluoroalkynyl compounds of the present invention is set to 100 mol%, the content of these other hydrofluorocarbon compounds is preferably 10.00 mol% or less, more preferably 7.50 mol% or less, and even more preferably 5.00 mol% or less.

[0170] The manufacturing method of the present invention can produce fluoroalkane compounds with particularly high selectivity and yield compared with existing methods for obtaining fluoroalkane compounds from fluoroalkane compounds. As a result, the purification process for obtaining fluoroalkane compounds can be carried out more efficiently.

[0171] The compositions containing fluorinated alkynes of the present invention are similar to those containing fluorinated alkynes alone, and can be effectively used not only as etching gases for forming state-of-the-art fine structures such as semiconductors and liquid crystals, but also as cleaning gases, deposition gases, refrigerants, heat transfer media, building blocks for organic synthesis, and various other applications.

[0172] The aforementioned deposition gas is the gas that causes the etch-resistant polymer layer to deposit.

[0173] The aforementioned building blocks for organic synthesis refer to substances capable of forming precursors of compounds with highly reactive frameworks. For example, when the compositions of the present invention are reacted with fluorinated organosilicon compounds such as CF3Si(CH3)3, fluorinated alkyl groups such as CF3 groups can be introduced to convert them into substances that can become cleaning agents or fluorinated pharmaceutical intermediates.

[0174] The embodiments of the present invention have been described above, but various changes can be made to the methods and details as long as they do not depart from the spirit and scope of the present invention.

[0175] Example

[0176] The following embodiments are shown to make the features of the invention clearer. The invention is not limited to these embodiments.

[0177] In the methods for producing the fluoroalkynes in Examples 1-6 and Comparative Example 1, regarding the raw material compounds, R in the fluoroalkanes represented by general formula (2) 1 and R 3 The trifluoromethyl group is reacted with hydrogen fluoride to produce a fluoroalkyne compound according to the following reaction formula.

[0178] CF3CFHCFHCF3→CF3C≡CCF3+2HF

[0179] Examples 1 to 6 and Comparative Example 1

[0180] Sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium tert-butoxide (t-BuONa) or potassium tert-butoxide (t-BuOK) as bases are added to an autoclave, along with di-n-butyl ether (Bu2O), diphenyl ether (Ph2O), diethylene glycol dimethyl ether, or water as solvents. The starting compound (CF3CFHCFHCF3) is then added, and the autoclave is sealed to form a closed system. The concentration of the base in the added solvent is 2.5 mol / L. At this point, the amount of base used is adjusted to 2 mol relative to 1 mol of the starting compound. The pressure at this point is 0 kPa. The temperature is then raised to 100°C or 150°C and stirred to allow the reaction to proceed. After the defluorination reaction begins, appropriate samples are taken, and the reaction is considered complete when the composition of the reaction system no longer changes. The pressure at the end of the reaction is 500 kPa.

[0181] After stirring was stopped, the mixture was cooled to room temperature and subjected to mass analysis using gas chromatography / mass spectrometry (GC / MS) with a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis was performed using NMR spectroscopy (manufactured by Nippon Eiichiro Co., Ltd., trade name "400YH"). Based on the results of mass analysis and structural analysis, the target compound was confirmed to be CF3C≡CCF3. The results are shown in Table 1. In Table 1, R23 refers to trifluoromethane, R1132 refers to 1,2-difluoroethylene, PF2B refers to the target compound CF3C≡CCF3, and 1327myz refers to CF3CF=CHCF3.

[0182] [Table 1]

[0183]

[0184] Example 7 and Comparative Example 2

[0185] The discharge power of ICP (Inductively Coupled Plasma) was 800 W, the bias power was 100 W, the pressure was 3 mmTorr (0.399 Pa), and the electron density was 8 × 10⁻⁶. 10 ~2×1011 cm －3 Under etching conditions with an electronic temperature of 5–7 eV, the etching rate and resist selectivity (etching rate of SiO2 film / etching rate of resist) were measured using the composition obtained in Example 1 (containing 51.00 mol% CF3C≡CCF3 and 42.62 mol% CF3CF=CHCF3) when etching SiO2 film and resist film (Example 7). The same experiment was performed with the gas changed to only CF3C≡CCF3 (Comparative Example 2).

[0186] Use the results in Table 2.

[0187] [Table 2]

[0188]

Claims

1. A method for manufacturing a fluoroalkyne compound of general formula (1), characterized in that, The process includes a step of causing a fluoroalkane compound of general formula (2) to undergo a dehydrofluorination reaction in the presence of a solvent containing an ether and a base containing an alkali metal and / or alkaline earth metal hydroxide, and satisfies at least one of the following (I) or (II). R 1 C≡CR 2 (1) In equation (1), R 1 and R 2 The same or different indicates fluorine atoms or fluoroalkyl groups. R 1 CHX 1 CFX 2 R 2 (2) In equation (2), R 1 and R 2 Same as above; X 1 and X 2 In the middle, X 1 It is a fluorine atom and X 2 It is a hydrogen atom, or X 1 It is a hydrogen atom and X 2 It is a fluorine atom; (I) The fluoroalkyl group is a fluoroalkyl group having 1 to 4 carbon atoms. (II) The ether is a chain ether.

2. The manufacturing method as described in claim 1, characterized in that, The total amount of the ether-containing solvent is set to 100% by mass, and the water concentration of the ether-containing solvent is 0.01 to 500 ppm by mass.

3. The manufacturing method as described in claim 1 or 2, characterized in that, The ether has 1 to 10 ether bonds.

4. The manufacturing method as described in claim 1 or 2, characterized in that, Satisfy (I).

5. The manufacturing method as described in claim 4, characterized in that, The fluoroalkyl group is represented by general formula (3). -CF2R 3 (3) In equation (3), R 3 It refers to a fluoroalkyl group having 1 to 3 fluorine atoms or carbon atoms.

6. The manufacturing method as described in claim 1 or 2, characterized in that, Satisfy (II).

7. The manufacturing method as described in claim 6, characterized in that, The fluoroalkyl group has 1 to 10 carbon atoms.

8. The manufacturing method as described in claim 6, characterized in that, The fluoroalkyl group is represented by general formula (3). -CF2R 3 (3) In equation (3), R 3 It refers to fluoroalkyl groups having 1 to 9 fluorine atoms or carbon atoms.

9. The manufacturing method as described in claim 1 or 2, characterized in that, The reaction temperature for the defluorination reaction is 0–300 °C.

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