Method for producing vinyl fluoride compounds

Abstract

To provide a method capable of obtaining a fluorinated vinyl compound at high yield and high selectivity.SOLUTION: Under the presence of alkali metal fluoride, a fluorinated vinyl compound is obtained which expressed by CHR1=CFR2 [In the formula, R1 denotes a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R2 denotes a halogen atom, an alkyl group or a fluoroalkyl group. Where, when R2 denotes a fluoroalkyl group, R1 denotes a halogen atom, an alkyl group or a fluoroalkyl group.] by reacting a halogenated vinyl compound which is expressed by CHR1=CXR3 [In the formula, R1 denotes a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. R3 denotes a halogen atom, an alkyl group, or a fluoroalkyl group. Where, when the R3 is a fluoroalkyl group, R1 is a halogen atom, an alkyl group, or a fluoroalkyl group. X denotes a halogen atom other than a fluorine atom.].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a vinyl fluoride compound. [Background technology]

[0002] When a halogen atom other than a fluorine atom bonded to an SP2 carbon atom in a halogenated vinyl compound is substituted with a fluorine atom, for example, a method of fluorinating a chlorine atom in tetrachloroethylene (PCE) with hydrogen fluoride and boron trifluoride (BF3) is also known (for example, see Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Journal of American Chemical Society, 1948, 70 (2), pp 758-760. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a method by which a vinyl fluoride compound can be obtained in high yield and with high selectivity. [Means for solving the problem]

[0005] The present disclosure encompasses the following configurations.

[0006] Term 1. General formula (1): CHR 1 =CFR 2 (1) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 2 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 2 When R is a fluoroalkyl group,1 is a halogen atom, an alkyl group or a fluoroalkyl group. A method for producing a vinyl fluoride compound represented by the following formula: In the presence of an alkali metal fluoride, General formula (2): CHR 1 =CXR 3 (2) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 3 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 3 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group. X is a halogen atom other than a fluorine atom. A reaction step of obtaining a vinyl fluoride compound represented by the general formula (1) by reacting a vinyl halide compound represented by the general formula (1) A manufacturing method comprising:

[0007] Item 2. The vinyl fluoride compound represented by the general formula (1) is represented by the general formula (1A):

[0008] [ka]

[0009] [In the formula, R 1 and R 2 is the same as above.] Item 2. The method according to item 1, wherein the vinyl fluoride compound is represented by the formula:

[0010] Item 3. The vinyl halide compound represented by the general formula (2) is represented by the general formula (2A):

[0011] [ka]

[0012] [In the formula, R 1 , R 3and X is the same as above.] Item 3. The method according to item 1 or 2, wherein the vinyl halide compound is represented by the formula:

[0013] Item 4. The specific surface area of ​​the alkali metal fluoride is 500 to 2000 m 2 / g.

[0014] Item 5. The method according to any one of Items 1 to 4, wherein the alkali metal fluoride is supported on a carrier.

[0015] Item 6. The production method according to Item 5, wherein the content of the alkali metal fluoride is 0.1 to 75 mass % relative to 100 mass % of the total amount of the support and the alkali metal fluoride.

[0016] Item 7. The method according to any one of Items 1 to 6, wherein the reaction step is carried out in the presence of a fluorine-containing gas.

[0017] Item 8. The method according to any one of Items 1 to 7, wherein in the reaction step, a contact time (W / F) of the vinyl halide compound with the catalyst containing the alkali metal fluoride is 5 to 200 g sec / cc.

[0018] Item 9. The method according to any one of Items 1 to 8, wherein the reaction temperature in the reaction step is 200 to 500° C.

[0019] Section 10. General formula (1A):

[0020] [ka]

[0021] [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 2 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 2 When R is a fluoroalkyl group,1 is a halogen atom, an alkyl group or a fluoroalkyl group. and a vinyl fluoride compound represented by general formula (3): R 1 -C≡CR 2 (3) [In the formula, R 1 and R 2 is the same as above.] and an alkyne compound represented by the formula:

[0022] Item 11. The composition according to item 10, wherein the content of the vinyl fluoride compound represented by the general formula (1) is 60 to 99.9 mol % and the content of the alkyne compound represented by the general formula (3) is 0.1 to 20 mol %, relative to 100 mol % of the total amount of the composition.

[0023] Item 12. The vinyl fluoride compound represented by the general formula (1A) is represented by the general formula (1A1):

[0024] [ka]

[0025] [In the formula, R 1 is the same as above.] and a difluorovinyl compound represented by the formula: General formula (1A2):

[0026] [ka]

[0027] [In the formula, R 1 is the same as above. X 1 represents a halogen atom other than a fluorine atom. Item 12. The composition according to item 10 or 11, comprising a vinyl fluoride compound represented by the formula:

[0028] Item 13. The composition according to item 12, wherein the content of the difluorovinyl compound represented by general formula (1A1) is 40 to 98 mol % and the content of the fluorinated vinyl compound represented by general formula (1A2) is 2 to 30 mol %, based on 100 mol % of the total amount of the composition.

[0029] Item 14. The composition according to any one of Items 10 to 13, which is used as a cleaning gas, an etching gas, a refrigerant, or a building block for organic synthesis. Effect of the Invention

[0030] According to the present disclosure, a vinyl fluoride compound can be obtained in high yield and high selectivity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of." In addition, in this specification, when a numerical range is shown as "A to B," it means A or more and B or less.

[0032] In the present disclosure, "selectivity" means the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of compounds other than the raw material compound in the effluent gas.

[0033] In the present disclosure, the term "conversion rate" means the ratio (mol %) of the total molar amount of compounds other than the raw material compounds contained in the effluent gas from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor.

[0034] In the present disclosure, the term "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 raw material compounds supplied to the reactor.

[0035] 1. Manufacturing method of vinyl fluoride compounds The method for producing a vinyl fluoride compound according to the present disclosure includes the steps of: General formula (1): CHR 1 =CFR 2 (1) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 2 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 2 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group. A method for producing a vinyl fluoride compound represented by the following formula: In the presence of an alkali metal fluoride, General formula (2): CHR 1 =CXR 3 (2) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 3 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 3 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group. X is a halogen atom other than a fluorine atom. A reaction step of obtaining a vinyl fluoride compound represented by the general formula (1) by reacting a vinyl halide compound represented by the general formula (1) Equipped with.

[0036] Conventionally, fluorine atoms have been introduced by first carrying out a hydrogen fluoride addition reaction and then carrying out a dehydrohalogenation reaction. This method requires two separate reaction steps, and in addition, when carrying out the dehydrohalogenation reaction, a dehydrofluorination reaction also occurs at the same time, and a large amount of by-products are generated, resulting in low selectivity for the target product. In addition, as shown in Non-Patent Document 1, a method is known in which chlorine atoms are fluorinated in tetrachloroethylene (PCE) using hydrogen fluoride and boron trifluoride (BF3), but the yield in this case was only about 20%.

[0037] According to the present disclosure, as described above, a vinyl fluoride compound can be obtained in a single step with high yield and high selectivity by reacting a vinyl halide compound having a halogen atom other than a fluorine atom as a substrate in the presence of an alkali metal fluoride.

[0038] (1-1) Vinyl halide compounds The vinyl halide compound usable as a substrate in the production method of the present disclosure is represented by the general formula (2): CHR 1 =CXR 3 (2) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 3 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 3 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group. X is a halogen atom other than a fluorine atom. It is a vinyl halide compound represented by the formula:

[0039] The vinyl halide compound may include both cis and trans isomers. From the viewpoint of producing a vinyl fluoride compound with particularly high conversion, yield and selectivity, the trans isomer is preferred, and the vinyl halide compound represented by the general formula (2A):

[0040] [ka]

[0041] [In the formula, R 1 , R 3 and X is the same as above.] Preferred are vinyl halide compounds represented by the following formula:

[0042] In the general formulas (2) and (2A), R 1 and R 3The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0043] In the general formulas (2) and (2A), R 1 and R 3 Examples of the alkyl group represented by the formula (I) include alkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. This alkyl group may also have 1 to 6, particularly 1 to 3, substituents such as the above-mentioned halogen atoms.

[0044] In the general formulas (2) and (2A), R 1 and R 3 Examples of the fluoroalkyl group represented by the formula (I) include fluoroalkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms (particularly perfluoroalkyl groups), such as a trifluoromethyl group and a pentafluoroethyl group.

[0045] However, R 1 is a hydrogen atom, and R 3 is a fluoroalkyl group, the vinyl fluoride compound represented by general formula (3): R 1 -C≡CR 2 (3) [In the formula, R 1 and R 2 is the same as above.] Therefore, alkyne compounds represented by R 3 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group.

[0046] In the general formulae (2) and (2A), examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom.

[0047] As the vinyl halide compound as the substrate, a vinyl fluoride compound is particularly preferred from the viewpoint of producing the vinyl fluoride compound with a high conversion rate, yield and selectivity. 1 and R 3 Each of the groups is preferably a fluoroalkyl group (particularly a perfluoroalkyl group), and X is preferably a chlorine atom.

[0048] In addition, R 3 When both X and X are halogen atoms other than fluorine atoms, the reaction of the halogenated vinyl compounds represented by the above general formulas (2) and (2A) results in the formation of a CHR in which only one halogen atom is replaced by a fluorine atom. 1 =CFX 1 , in particular of the general formula (1A2):

[0049] [ka]

[0050] [In the formula, R 1 is the same as above. X 1 represents a halogen atom other than the above-mentioned fluorine atom.] and a vinyl fluoride compound represented by the general formula (1A1): in which two halogen atoms are replaced by fluorine atoms:

[0051] [ka]

[0052] [In the formula, R 1 is the same as above.] Both the difluorovinyl compound represented by the general formula (1A1) and the vinyl fluoride compound represented by the general formula (1A2) are the target compounds.

[0053] The above R 1 , R 3 and X may be the same or different.

[0054] Specific examples of vinyl halide compounds that can serve as substrates that satisfy the above conditions include:

[0055] [ka]

[0056] These vinyl halide compounds may be used alone or in combination of two or more. Such vinyl halide compounds may be known or commercially available products.

[0057] (1-2) Substitution reaction In the reaction step of reacting a vinyl halide compound represented by the general formula (2) in the present disclosure, for example, the vinyl halide compound represented by the general formula (2) is used as a substrate. 1 and R 3 is preferably a trifluoromethyl group, X is preferably a chlorine atom, and is preferably a trans isomer. 1 is a hydrogen atom, R 3 It is also preferred that X is a chlorine atom.

[0058] That is, the reaction is as follows:

[0059] [ka]

[0060] It is preferable to obtain a vinyl fluoride compound in one step according to the following procedure.

[0061] (1-3) Alkali metal fluorides The reaction step of reacting the vinyl halide compound represented by the general formula (2) in the present disclosure is a step in which halogen atoms are replaced with fluorine atoms in one step in the presence of an alkali metal fluoride. The alkali metal fluoride functions as a catalyst, and the vinyl halide compound can be produced with particularly high conversion, yield and selectivity.

[0062] The alkali metal fluoride is not particularly limited, but from the viewpoint of producing a vinyl fluoride compound with a particularly high conversion rate, yield and selectivity, the fluorides of alkali metals of the 4th to 7th periods are preferred, and for example, potassium fluoride (KF), cesium fluoride (CsF) and the like are more preferred, and cesium fluoride (CsF) is even more preferred. These alkali metal fluorides can be used alone or in combination of two or more kinds.

[0063] The specific surface area of ​​the alkali metal fluoride is preferably 500 to 2000 m from the viewpoint of producing a vinyl fluoride compound with a particularly high conversion rate, yield, and selectivity. 2 / g is preferable, and 800 to 1500m 2 / g is more preferable. In the present disclosure, the specific surface area of ​​the alkali metal fluoride is measured by the BET method. When the specific surface area of ​​the alkali metal fluoride is in such a range, the density of the alkali metal fluoride 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 substrate. As described later, even when the alkali metal fluoride is supported on a carrier, there is no significant difference in the specific surface area, and the specific surface area when the alkali metal fluoride is supported on a carrier is also preferably in the above-mentioned range.

[0064] In the present disclosure, when the reaction is carried out in a gas phase, the above-mentioned substrate is contacted with a fluorine source. In this case, from the viewpoint of reactivity, it is preferable to contact the alkali metal fluoride with the substrate in a solid state (solid phase).

[0065] In the present disclosure, for example, when a gas-phase continuous flow reaction is performed, from the viewpoint of reactivity, the alkali metal fluoride may be in a powder form, but is preferably in a pellet form. The above-mentioned alkali metal fluoride may be used as it is, but may be supported on a carrier and used (hereinafter, the alkali metal fluoride supported on a carrier may be referred to as "support-supported alkali metal fluoride"). This increases the specific surface area of ​​the fluorine source to improve the reaction efficiency, and the vinyl fluoride compound can be produced with a particularly high conversion rate, yield, and selectivity. There is no particular restriction on the support, and examples of the support include carbon, alumina, zirconia, silica, titania, zeolite, silica alumina, and chromium oxide. Examples of carbon include activated carbon, amorphous carbon, graphite, and diamond. These supports may be used alone or in combination of two or more. Among them, carbon is preferred from the viewpoint of a large specific surface area and easy support of the alkali metal fluoride, and activated carbon is more preferred.

[0066] When the alkali metal fluoride is supported on a carrier, the amount of the supported alkali metal fluoride is not particularly limited, but from the viewpoint of being able to produce a vinyl fluoride compound with particularly high conversion rate, yield and selectivity, the amount of the alkali metal fluoride supported on a carrier is preferably 0.1 to 75 mass%, and more preferably 1 to 60 mass%, of 100 mass% of the total amount of the alkali metal fluoride supported on a carrier.

[0067] The bulk density of the alkali metal fluoride supported on a carrier is preferably 0.01 to 10 g / mL, more preferably 0.1 to 5 g / mL, from the viewpoint of producing a vinyl fluoride compound with particularly high conversion, yield and selectivity. In the present disclosure, the bulk density of the alkali metal fluoride supported on a carrier is measured by a bulk density measuring device. When the bulk density of the alkali metal fluoride supported on a carrier is within such a range, the density of the particles of the alkali metal fluoride supported on a carrier is not too small, so that the target compound can be obtained with a higher selectivity. In addition, it is also possible to further improve the conversion rate of the substrate.

[0068] The pore volume of the alkali metal fluoride supported on the carrier is preferably 0.1 to 1.5 mL / g, more preferably 0.25 to 1.0 mL / g, from the viewpoint of producing a vinyl fluoride compound with particularly high conversion, yield and selectivity. In the present disclosure, the pore volume of the alkali metal fluoride supported on the carrier is measured by the BET method. When the pore volume of the alkali metal fluoride supported on the carrier is within such a range, the density of the particles of the alkali metal fluoride supported on the carrier is not too small, so that the target compound can be obtained with a higher selectivity. In addition, it is also possible to further improve the conversion rate of the substrate.

[0069] The average pore diameter of the alkali metal fluoride supported on a carrier is preferably 5 to 20 μm, more preferably 8 to 15 μm, from the viewpoint of producing a vinyl fluoride compound with particularly high conversion, yield and selectivity. In the present disclosure, the average pore diameter of the alkali metal fluoride supported on a carrier is measured by the BET method.

[0070] (1-4) Fluorine-containing gases The above-mentioned alkali metal fluoride also functions as a catalyst, and can produce a vinyl fluoride compound with a particularly high conversion rate, yield, and selectivity. However, the alkali metal fluoride contains fluorine atoms, and the fluorine atoms may be extracted during the reaction to obtain the vinyl fluoride compound represented by the general formula (1). Therefore, the amount of the alkali metal fluoride that effectively functions as a catalyst may decrease as the reaction proceeds for a long time. Therefore, in order to replenish fluorine atoms, it is preferable to carry out the above reaction in the presence of a gas containing fluorine.

[0071] Such fluorine-containing gases are not particularly limited, and examples thereof include F2, HF, CFCl3, CF2Cl2, CFHCl2, CF2HCl, CF3H, NF3, IF5, IF7, FCl, and ClF3.

[0072] In the present disclosure, when the reaction is carried out in a gas phase, the above-mentioned fluorine-containing gas is preferably blown in a gaseous state (gas phase).

[0073] (1-5) Reaction temperature In the step of obtaining a vinyl fluoride compound by reacting a vinyl halide compound in the present disclosure, the reaction temperature is usually preferably 200 to 500°C, more preferably 250 to 450°C, and even more preferably 300 to 400°C, from the viewpoint of producing a vinyl fluoride compound with particularly high conversion rate, yield, and selectivity.

[0074] (1-6)Reaction time In the present disclosure, when the reaction is carried out in the gas phase, for example, when a gas-phase flow system is adopted, the reaction time (W / F) of the raw material compound (vinyl halide compound) to the catalyst (alkali metal fluoride) [W: weight of the catalyst including alkali metal fluoride (total weight including the carrier in the case of alkali metal fluoride supported on a carrier) (g), F: flow rate of the raw material compound (vinyl halide compound) (cc / sec)] is preferably 5 to 200 g·sec. / cc, more preferably 10 to 150 g·sec. / cc, and even more preferably 15 to 100 g·sec. / cc, from the viewpoint of particularly high conversion rate of the reaction and obtaining the vinyl fluoride compound in a higher yield and with a higher selectivity. The contact time means the time during which the raw material compound and the catalyst are in contact with each other.

[0075] The above contact times indicate conditions when the reaction is carried out in the gas phase, particularly in a gas phase continuous flow system, but can also be appropriately adjusted when the reaction is carried out in a batch system.

[0076] In the present disclosure, when the reaction step is carried out in the presence of a fluorine-containing gas, the content of the fluorine-containing gas is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, and even more preferably 1 to 2.5 mol, per mol of the raw material compound (vinyl halide compound), from the viewpoint of particularly high conversion rate of the reaction and capable of producing a vinyl fluoride compound in higher yield and higher selectivity.

[0077] (1-7) Reaction pressure In the present disclosure, the reaction pressure when the vinyl halide compound is reacted to obtain the vinyl fluoride compound 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 producing the vinyl fluoride compound with particularly high conversion, yield and selectivity. In the present disclosure, the pressure is a gauge pressure unless otherwise specified.

[0078] In the reaction of the present disclosure, the reactor in which the raw material compound (vinyl halide compound) is reacted in the presence of an alkali metal fluoride and, if necessary, a gas containing fluorine is present, is not particularly limited in shape and structure as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tube reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0079] (1-8) Reaction example The reaction step of the present disclosure for obtaining a vinyl fluoride compound by reacting a vinyl halide compound can be carried out by either a continuous gas phase flow method or a batch method in which a raw material compound (vinyl halide compound) is continuously charged into a reactor and a target compound (vinyl fluoride compound) is continuously withdrawn from the reactor. If the target compound remains in the reactor, the elimination reaction may proceed further, so it is preferable to carry out the reaction by a continuous gas phase flow method. In the present disclosure, the reaction step of obtaining a vinyl fluoride compound by reacting a vinyl halide compound is carried out in the gas phase, and in particular, it is preferable to carry out the reaction by a continuous gas phase flow method using a fixed bed reactor. When the reaction is carried out by a continuous gas phase flow method, the apparatus, operation, etc. can be simplified and it is economically advantageous.

[0080] In the present disclosure, the reaction step of reacting a vinyl halide compound to obtain a vinyl fluoride compound is preferably carried out under an inert gas atmosphere in order to suppress deterioration of the alkali metal fluoride. Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred in terms of reducing costs. The concentration of the inert gas is preferably 0 to 50 mol% of the gas components introduced into the reactor. When the reaction is carried out in the presence of a fluorine-containing gas, the reaction may be carried out under an atmosphere of the fluorine-containing gas or a mixed atmosphere of the inert gas and the fluorine-containing gas. The concentration of the fluorine-containing gas is preferably 0.1 to 90 mol% of the gas components introduced into the reactor.

[0081] After the reaction is completed, purification treatment can be carried out according to a conventional method, if necessary, to obtain the vinyl fluoride compound represented by the general formula (1).

[0082] (1-9) Target compound The target compound of the present disclosure thus obtained is represented by the general formula (1): CHR 1 =CFR 2 (1) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 2 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 2 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group. It is a vinyl fluoride compound represented by the formula:

[0083] The vinyl fluoride compound may include both cis and trans isomers. From the viewpoint of production with high conversion, yield and selectivity, the trans isomer is preferred.

[0084] [ka]

[0085] [In the formula, R 1 and R 2 is the same as above.] Preferred are vinyl fluoride compounds represented by the following formula:

[0086] R in general formula (1) and (1A) 1 and R 2 R in the above general formulas (2) and (2A) 1 and R 3 In addition, R in general formula (2) and (2A) corresponds to 3 is a halogen atom other than a fluorine atom, the target vinyl fluoride compound may include a compound in which the halogen atom is replaced with a fluorine atom and a compound in which the halogen atom remains as it is. Therefore, the vinyl fluoride compound represented by the general formulas (1) and (1A) to be produced may be, for example,

[0087] [ka]

[0088] etc.

[0089] The vinyl fluoride compounds thus obtained can be effectively used in various applications such as etching gases for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., cleaning gases, building blocks for organic synthesis, etc. Building blocks for organic synthesis will be described later.

[0090] 2. Composition In the manner described above, a vinyl fluoride compound can be obtained. The vinyl fluoride compounds represented by the general formulas (1) and (1A) and the vinyl fluoride compounds represented by the general formula (3): R 1 -C≡CR 2 (3) [In the formula, R 1 and R 2 is the same as above.] The compound may be obtained in the form of a composition containing an alkyne compound represented by the formula:

[0091] In this case, the content of the fluorinated vinyl compound represented by general formula (1) is preferably 60 to 99.9 mol%, more preferably 80 to 99 mol%, based on the total amount of the composition of the present disclosure being 100 mol%. The content of the alkyne compound represented by general formula (3) is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, based on the total amount of the composition of the present disclosure being 100 mol%. In addition, when the fluorinated vinyl compound represented by general formula (1) contains both general formulas (1A1) and (1A2) as described below, the above content is the total amount thereof.

[0092] As described above, R in general formulas (2) and (2A) 3 When is a halogen atom other than a fluorine atom, the target compound, that is, a fluorinated vinyl compound, may include a compound in which the halogen atom is replaced with a fluorine atom, and a compound in which the halogen atom remains as it is.

[0093] For this reason, the vinyl fluoride compounds represented by the general formulas (1) and (1A) include those represented by the general formula (1A1):

[0094] [ka]

[0095] [In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. and a difluorovinyl compound represented by the formula: General formula (1A2):

[0096] [ka]

[0097] [In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. 1represents a halogen atom other than a fluorine atom. and a vinyl fluoride compound represented by the formula:

[0098] In general formulas (1A) and (1B), R 1 The above-mentioned items can be used as X 1 Examples of halogen atoms other than fluorine atoms represented by the formula (I) include chlorine atoms, bromine atoms and iodine atoms.

[0099] In this case, the content of the difluorovinyl compound represented by formula (1A1) is preferably 40 to 98 mol%, more preferably 50 to 90 mol%, based on the total amount of the composition of the present disclosure being 100 mol%, and the content of the difluorovinyl compound represented by formula (1A2) is preferably 2 to 30 mol%, more preferably 3 to 20 mol%, based on the total amount of the composition of the present disclosure being 100 mol%.

[0100] According to the production method of the present disclosure, even when the above-mentioned composition is obtained, the vinyl fluoride compound represented by general formula (1) can be obtained in one step with a high reaction conversion rate, high yield and high selectivity. Therefore, it is possible to reduce components other than the vinyl fluoride compound represented by general formula (1) in the composition, thereby reducing the purification effort required to obtain the vinyl fluoride compound represented by general formula (1).

[0101] The composition of the present disclosure can be effectively used for a variety of applications, such as an etching gas for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., as well as a building block for organic synthesis, a cleaning gas, etc. 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 CF3Si(CH3)3, a fluoroalkyl group such as a CF3 group can be introduced to convert it into a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate.

[0102] Although the embodiment of the present disclosure has been described above, various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0103] The following examples will clarify the features of the present disclosure, but the present disclosure is not limited to these examples.

[0104] Synthesis example 1: 50% CsF / AC Activated carbon (specific surface area 1200m 2 The activated carbon was mixed with cesium fluoride in an amount of 50% by mass, with the total amount of activated carbon and cesium fluoride being 100% by mass, to obtain a 50% CsF / AC catalyst in which cesium fluoride is supported on activated carbon. The specific surface area of ​​the obtained catalyst was 600 cm. 2 / g, pore volume was 0.7 mL / g, and pore diameter was 10 μm.

[0105] Synthesis example 2: 5% CsF / AC Activated carbon (specific surface area 1200m 2 The activated carbon was mixed with cesium fluoride in an amount of 5% by mass, with the total amount of activated carbon and cesium fluoride being 100% by mass, to obtain a 5% CsF / AC catalyst in which cesium fluoride is supported on activated carbon. The specific surface area of ​​the obtained catalyst was 900 cm 2 / g, pore volume was 0.8 mL / g, and pore diameter was 10 μm.

[0106] Synthesis example 3: 5%KF / AC Activated carbon (specific surface area 1200m 2 The activated carbon was mixed with potassium fluoride in an amount of 5% by mass, with the total amount of activated carbon and potassium fluoride being 100% by mass, to obtain a 5% KF / AC catalyst in which cesium fluoride is supported on activated carbon. The specific surface area of ​​the obtained catalyst was 900 cm. 2 / g, pore volume was 0.8 mL / g, and pore diameter was 10 μm.

[0107] Examples 1 to 5 In the methods for producing a vinyl fluoride compound in Examples 1 to 5, the raw material compound is a vinyl halide compound represented by the general formula (2), in which R 1 and R 3 is a trifluoromethyl group, X is a chlorine atom, and the reaction is as follows:

[0108] [ka]

[0109] According to the procedure described above, a vinyl fluoride compound was obtained.

[0110] 10 g of the catalyst obtained in Synthesis Example 1, 2, or 3 was added to a stainless steel pipe (outer diameter: 1 / 2 inch) serving as a reaction tube. After drying at 200°C for 2 hours under a nitrogen atmosphere, CF3CH=CClCF3 (raw material compound) was circulated through the reaction tube at normal pressure so that the contact time (W / F) between CF3CH=CClCF3 (raw material compound) and the catalyst was 16.0 g sec / cc or 42.0 g sec / cc.

[0111] The reaction was carried out in a continuous gas phase flow mode.

[0112] The reaction tube was heated to 300°C or 400°C to initiate the reaction.

[0113] One hour after the start of the reaction, the distillate that had passed through the removal tower was collected.

[0114] Then, mass analysis was performed by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (manufactured by Shimadzu Corporation, product name "GC-2014"), and structural analysis was performed by NMR spectroscopy using an NMR (manufactured by JEOL, product name "400YH")

[0115] Mass spectrometry and structural analysis confirmed that the target compound, CF3CH=CFCF3, was produced. The results are shown in Table 1.

[0116] [Table 1]

[0117] Examples 6 to 8 In the methods for producing a vinyl fluoride compound in Examples 6 to 8, the raw material compound is a vinyl halide compound represented by the general formula (2), in which R 1 is a hydrogen atom, R 3 and X is a chlorine atom, the reaction is as follows:

[0118] [ka]

[0119] According to the procedure described above, a vinyl fluoride compound was obtained.

[0120] 10 g of the catalyst obtained in Synthesis Example 1 or 3 was added to a stainless steel pipe (outer diameter: 1 / 2 inch) serving as a reaction tube. After drying at 200°C for 2 hours under a nitrogen atmosphere, CH2=CCl2 (raw material compound) was circulated through the reaction tube at normal pressure so that the contact time (W / F) between CH2=CCl2 (raw material compound) and the catalyst was 10.0 g sec / cc or 20.0 g sec / cc.

[0121] The reaction was carried out in a continuous gas phase flow mode.

[0122] The reaction tube was heated to 400° C. to initiate the reaction.

[0123] One hour after the start of the reaction, the distillate that had passed through the removal tower was collected.

[0124] Then, mass analysis was performed by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (manufactured by Shimadzu Corporation, product name "GC-2014"), and structural analysis was performed by NMR spectroscopy using an NMR (manufactured by JEOL, product name "400YH")

[0125] Mass spectrometry and structural analysis confirmed that the target compounds were CH2=CClF and CH2=CF2. The results are shown in Table 2.

[0126]

Table 2

Claims

1. General formula (1): CHR 1 =CFR 2 (1) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 2 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 2 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group, In the presence of an alkali metal fluoride, General formula (2): CHR 1 =CXR 3 (2) [In the formula, R 1 R represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. 3 represents a halogen atom, an alkyl group, or a fluoroalkyl group. 3 When R is a fluoroalkyl group, 1 is a halogen atom, an alkyl group or a fluoroalkyl group. X is a halogen atom other than a fluorine atom. A reaction step of obtaining a vinyl fluoride compound represented by the general formula (1) by reacting a vinyl halide compound represented by the general formula (1) Equipped with the alkali metal fluoride is potassium fluoride and / or cesium fluoride; the reaction step is carried out in a gas-phase continuous flow system, the contact time (W / F) of the vinyl halide compound with the catalyst containing the alkali metal fluoride is 5 to 200 g·sec / cc, and the reaction temperature in the reaction step is 200 to 450° C.

2. The vinyl fluoride compound represented by the general formula (1) is represented by the general formula (1A): 【Chemistry 1】 [In the formula, R 1 and R 2 is the same as above.] The method according to claim 1, wherein the vinyl fluoride compound is represented by the formula:

3. The vinyl halide compound represented by the general formula (2) is represented by the general formula (2A): 【Chemistry 2】 [In the formula, R 1 , R 3 and X is the same as above. The method according to claim 1 or 2, wherein the vinyl halide compound is represented by the formula:

4. The method according to any one of claims 1 to 3, wherein the alkali metal fluoride is supported on a carrier.

5. The specific surface area of ​​the alkali metal fluoride supported on the carrier is 500 to 2000 m 2 The method according to claim 4, wherein the molecular weight of the polymer is 1 / g.

6. 6. The method according to claim 4, wherein the content of the alkali metal fluoride is 0.1 to 75 mass%, based on 100 mass% of the total amount of the support and the alkali metal fluoride.

7. The process according to any one of claims 1 to 6, wherein the reaction step is carried out in the presence of a fluorine-containing gas.

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