Process for producing vinyl fluoride compounds

Abstract

To provide a method capable of obtaining a vinyl fluoride compound with high yield and high selectivity.SOLUTION: A method for producing a vinyl fluoride compound includes: reacting a vinyl halide compound represented by CHR1=CXR3 (where, R1 is a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group, R3 is a halogen atom, an alkyl group, or a fluoroalkyl group, however, when R3 is a fluoroalkyl group, R1 is a halogen atom, an alkyl group, or fluoroalkyl group, and X is a halogen atom excluding a fluorine atom) in the presence of an alkali metal fluoride to obtain a vinyl fluoride compound represented by CHR1=CFR2 (where, R1 is a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group, R2 is a halogen atom, an alkyl group, or a fluoroalkyl group, however, when R2 is a fluoroalkyl group, R1 is a halogen atom, an alkyl group, or fluoroalkyl group.)SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] When substituting a halogen atom other than a fluorine atom bonded to an sp2 carbon atom in a vinyl halide compound with a fluorine atom, for example, a method of fluorinating a chlorine atom of tetrachloroethylene (PCE) with hydrogen fluoride and boron trifluoride (BF3) is also known (see, for example, Non-Patent Document 1).

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a method capable of obtaining a vinyl fluoride compound in a high yield and with a high selectivity.

Means for Solving the Problems

[0005] The present disclosure includes the following configurations.

[0006] Item 1. General formula (1): CHR 1 =CFR 2 (1) [In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. R 2 represents a halogen atom, an alkyl group, or a fluoroalkyl group. However, when R 2 is a fluoroalkyl group, R1 is a halogen atom, an alkyl group or a fluoroalkyl group. A method for producing a vinyl fluoride compound represented by in the presence of an alkali metal fluoride, General formula (2): CHR 1 =CXR 3 (2) [wherein, R 1 represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R 3 represents a halogen atom, an alkyl group or a fluoroalkyl group. However, when R 3 is a fluoroalkyl group, R 1 is a halogen atom, an alkyl group or a fluoroalkyl group. X represents a halogen atom other than a fluorine atom. reacting a vinyl halide compound represented by to obtain a vinyl fluoride compound represented by the general formula (1) reaction step A production method comprising.

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

[0008]

Chemical formula

[0009] [wherein, R 1 and R 2 are the same as defined above. The production method according to Item 1, which is a vinyl fluoride compound represented by.

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

[0011]

Chemical formula

[0012] [wherein, R1 , R 3 and X are the same as described above.] The production method according to claim 1 or 2, which is a vinyl halide compound represented by

[0013] Item 4. The specific surface area of the alkali metal fluoride is 500 to 2000 m 2 / g, and the production method according to any one of Items 1 to 3 is as described.

[0014] Item 5. The production 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 total amount of the carrier and the alkali metal fluoride is 100% by mass, and the content of the alkali metal fluoride is 0.1 to 75% by mass.

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

[0017] Item 8. The production method according to any one of Items 1 to 7, wherein in the reaction step, 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.

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

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

[0020]

Chemical formula

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

[0022] Item 11. Based on the total amount of the composition being 100 mol%, 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%. The composition according to Item 10.

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

[0024]

Chemical formula

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

[0026]

Chemical formula

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

[0028] Item 13. With the total amount of the composition being 100 mol%, the content of the difluorobinyl compound represented by the general formula (1A1) is 40 to 98 mol%, and the content of the vinyl fluoride compound represented by the general formula (1A2) is 2 to 30 mol%. The composition according to Item 12.

[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.

Advantages of the Invention

[0030] According to the present disclosure, a vinyl fluoride compound can be obtained in a high yield and with a high selectivity.

Modes for Carrying Out the Invention

[0031] In this specification, "containing" is a concept that includes any of "comprise", "consist essentially of", and "consist of". Also, in this specification, when a numerical range is indicated as "A to B", it means A or more and B or less.

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

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

[0034] In the present disclosure, the "yield" means 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 compound supplied to the reactor.

[0035] 1. Process for producing vinyl fluoride compound The method for producing a vinyl fluoride compound of the present disclosure is General formula (1): CHR 1 =CFR 2 (1) [In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R 2 represents a halogen atom, an alkyl group or a fluoroalkyl group. However, when R 2 is a fluoroalkyl group, R 1 is a halogen atom, an alkyl group or a fluoroalkyl group.] It is a method for producing a vinyl fluoride compound represented by in the presence of an alkali metal fluoride, General formula (2): CHR 1 =CXR 3 (2) [In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R 3 represents a halogen atom, an alkyl group or a fluoroalkyl group. However, when R 3 is a fluoroalkyl group, R 1 is a halogen atom, an alkyl group or a fluoroalkyl group. X is a halogen atom other than a fluorine atom.] reacting a vinyl halide compound represented by to obtain a vinyl fluoride compound represented by the general formula (1) compound, and comprises a reaction step.

[0036] Conventionally, a hydrogen fluoride addition reaction was first carried out, and then a dehydrohalogenation reaction was carried out to introduce a fluorine atom. According to this method, not only are two separate reaction steps required, but when the dehydrohalogenation reaction is carried out, a dehydrofluorination reaction also occurs simultaneously, and a large amount of by-products are generated, so the selectivity of the target product was low. Also, as in Non-Patent Document 1, a method of fluorinating a chlorine atom in tetrachloroethylene (PCE) with hydrogen fluoride and boron trifluoride (BF3 )) is also known, but the yield in this case was only about 20%.

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

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

[0039] This vinyl halide compound may contain both the cis form and the trans form, but from the viewpoint of being able to produce a vinyl fluoride compound particularly with a high conversion rate, yield and selectivity, the trans form is preferred, and the general formula (2A):

[0040] [Chemical formula]

[0041] [In the formula, R 1 , R 3 and X are the same as defined above.] The vinyl halide compound represented by the formula is preferred.

[0042] In General Formulas (2) and (2A), the halogen atoms represented by R 1 and R 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0043] In General Formulas (2) and (2A), the alkyl groups represented by R 1 and R 3 include, for example, an alkyl group 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 have 1 to 6, particularly 1 to 3, substituents such as the above-described halogen atoms.

[0044] In General Formulas (2) and (2A), the fluoroalkyl groups represented by R 1 and R 3 include, for example, a fluoroalkyl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as a trifluoromethyl group and a pentachloroethyl group (particularly a perfluoroalkyl group).

[0045] However, when R 1 is a hydrogen atom and R 3 is a fluoroalkyl group, it is not a vinyl fluoride compound represented by General Formula (1), but General Formula (3): R 1 -C≡C-R 2 (3) [In the formula, R 1 and R2 is the same as described above.] The alkyne compound represented by is easily synthesized. Therefore, R 3 When is a fluoroalkyl group, R 1 is a halogen atom, an alkyl group or a fluoroalkyl group.

[0046] In the general formulas (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, in terms of being able to produce a vinyl fluoride compound with particularly high conversion rate, yield and selectivity, R 1 and R 3 are both preferably fluoroalkyl groups (particularly perfluoroalkyl groups), and X is preferably a chlorine atom. is preferable.

[0048] Incidentally, when both R 3 and X are halogen atoms other than fluorine atoms, by the reaction of the vinyl halide compound represented by the above general formula (2) and (2A), CHR in which only one halogen atom is substituted with a fluorine atom 1 =CFX 1 , particularly the general formula (1A2):

[0049]

Chemical formula

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

[0051]

Chemical formula

[0052] [In the formula, R 1 is the same as described above.] Both of the difluorovinyl compounds represented by can be synthesized. The difluorovinyl compounds represented by these general formulas (1A1) and the vinyl fluoride compounds represented by the general formula (1A2) are all target compounds.

[0053] The above-mentioned R 1 , R 3 and X may be the same or different from each other.

[0054] Specific examples of the vinyl halide compound as a substrate satisfying the above conditions include

[0055] [Chemical formula]

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

[0057] (1-2) Substitution reaction In the reaction step of reacting the vinyl halide compound represented by the general formula (2) in the present disclosure , for example, as the substrate, in the vinyl halide compound represented by the general formula (2), R 1 and and R 3 are both preferably trifluoromethyl groups, X is preferably a chlorine atom, and the trans form is preferred. Also, as the substrate, in the vinyl halide compound represented by the general formula (2), R 1 is a hydrogen atom, and it is also preferable that R 3 and X are chlorine atoms.

[0058] That is, the following reaction formula:​

[0059]

Chem.

[0060] Preferably, a vinyl fluoride compound is obtained in one step according to [specific conditions].

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

[0062] The alkali metal fluoride is not particularly limited, but from the perspective of being able to produce a vinyl fluoride compound, particularly with high conversion, yield, and selectivity, fluorides of alkali metals in the 4th to 7th periods are preferred. For example, potassium fluoride (KF), cesium fluoride (CsF), etc. 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.

[0063] From the perspective of being able to produce a vinyl fluoride compound, particularly with high conversion, yield, and selectivity, the specific surface area of the alkali metal fluoride is preferably 500 - 2000 m 2 / g, more preferably 800 - 1500 m 2 / g. 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 within such a range, the density of the particles of the alkali metal fluoride 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. Incidentally, as will be 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 preferably within the above-mentioned range.

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

[0065] In the present disclosure, for example, when a gas-phase continuous flow reaction is carried out, from the viewpoint of reactivity, the alkali metal fluoride may be in powder form, but pellets are preferred. Further, the above-mentioned alkali metal fluoride can be used as it is, or can be used after being supported on a carrier (hereinafter, the alkali metal fluoride supported on a carrier may be referred to as "carrier-supported alkali metal fluoride"). Thereby, the specific surface area of the fluorine source is increased to improve the reaction efficiency, and vinyl fluoride compounds can be produced particularly with high conversion rates, yields and selectivities. The carrier to be supported is not particularly limited, and examples thereof include carbon, alumina, zirconia, silica, titania, zeolite, silica alumina, chromium oxide, etc. Examples of carbon include activated carbon, amorphous carbon, graphite, diamond, etc. These carriers can be used alone or in combination of two or more. Among them, carbon is preferable and activated carbon is more preferable from the viewpoint of having a large specific surface area and being easy to support the alkali metal fluoride. When it is a carrier-supported alkali metal fluoride, the loading amount is not particularly limited, but from the viewpoint of being able to produce vinyl fluoride compounds particularly with high conversion rates, yields and selectivities, taking the total amount of the carrier-supported alkali metal fluoride as 100% by mass, the alkali metal fluoride is 0.1 to 75 mass

[0066] When it is a carrier-supported alkali metal fluoride, the loading amount is not particularly limited, but from the viewpoint of being able to produce vinyl fluoride compounds particularly with high conversion rates, yields and selectivities, taking the total amount of the carrier-supported alkali metal fluoride as 100% by mass, the alkali metal fluoride is 0.1 to 75 mass It is preferably contained in an amount of %, and more preferably contained in an amount of 1 to 60% by mass.

[0067] From the viewpoint of being able to produce a vinyl fluoride compound with particularly high conversion rate, yield and selectivity, the bulk density of the carrier-supported alkali metal fluoride is preferably 0.01 to 10 g / mL, and more preferably 0.1 to 5 g / mL. In the present disclosure, the bulk density of the carrier-supported alkali metal fluoride is measured by a bulk density measuring instrument. When the bulk density of the carrier-supported alkali metal fluoride is within such a range, the density of the particles of the carrier-supported alkali metal fluoride 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] From the viewpoint of being able to produce a vinyl fluoride compound with particularly high conversion rate, yield and selectivity, the pore volume of the carrier-supported alkali metal fluoride is preferably 0.1 to 1.5 mL / g, and more preferably 0.25 to 1.0 mL / g. In the present disclosure, the pore volume of the carrier-supported alkali metal fluoride is measured by the BET method. When the pore volume of the carrier-supported alkali metal fluoride is within such a range, the density of the particles of the carrier-supported alkali metal fluoride 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] From the viewpoint of being able to produce a vinyl fluoride compound with particularly high conversion rate, yield and selectivity, the average pore diameter of the carrier-supported alkali metal fluoride is preferably 5 to 20 μm, and more preferably 8 to 15 μm. In the present disclosure, the average pore diameter of the carrier-supported alkali metal fluoride is measured by the BET method more.

[0070] (1-4) A gas containing fluorine The above-mentioned alkali metal fluoride also functions as a catalyst and can produce a vinyl fluoride compound with particularly high conversion rate, yield and selectivity. However, the alkali metal fluoride contains fluorine atoms, and the vinyl fluoride compound represented by the general formula (1) During the reaction to obtain the product, fluorine atoms can be abstracted. Therefore, as the reaction proceeds for a long time, the amount of alkali metal fluoride that functions effectively as a catalyst may decrease. For this reason, the above reaction is preferably carried out in the presence of a fluorine-containing gas with the intention of replenishing fluorine atoms.

[0071] Such a fluorine-containing gas is not particularly limited. For example, F2, HF, CFCl3 , CF2Cl2, CFHCl2, CF2HCl, CF3H, NF3, IF5, IF7, FCl, ClF3, etc. can be mentioned.

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

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

[0074] (1-6) Reaction time In the present disclosure, when the reaction is carried out in the gas phase, the reaction time, for example, when adopting a gas-phase flow type, is the contact time (W / F) of the raw material compound (vinyl halide compound) with respect to the catalyst (alkali metal fluoride) [W: the weight of the catalyst containing alkali metal fluoride (the total amount including the carrier in the case of carrier-supported alkali metal fluoride) (g), F: the flow rate of the raw material compound (vinyl halide compound) (cc / sec)]. The conversion rate of the reaction is particularly high, and the vinyl fluoride compound can be obtained in a higher yield metal fluoride including the carrier) (g), F: the flow rate of the raw material compound (vinyl halide compound) (cc / sec)] is such that the conversion rate of the reaction is particularly high, and the vinyl fluoride compound can be obtained in a higher yield From the viewpoint of being able to obtain a high conversion rate, 5 to 200 g·sec. / cc is preferable, 10 to 150 g·sec. / cc is more preferable, and 15 to 100 g·sec. / cc is even more preferable. The contact time mentioned above means the time during which the raw material compound and the catalyst are in contact.

[0075] The above contact time indicates the conditions when the reaction proceeds in the gas phase, particularly in the gas-phase continuous flow system, but it can also be appropriately adjusted when the reaction proceeds in the batch system.

[0076] In the present disclosure, when the reaction step is carried out in the presence of a gas containing fluorine, the content of the gas containing fluorine is, from the viewpoint of obtaining a particularly high conversion rate of the reaction and being able to obtain the vinyl fluoride compound in a higher yield and higher selectivity, based on 1 mole of the raw material compound (vinyl halide compound). 0.1 to 10 moles is preferable, 0.5 to 5 moles is more preferable, and 1 to 2.5 moles is even more preferable.

[0077] (1-7) Reaction pressure The reaction pressure when reacting the vinyl halide compound in the present disclosure 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 being able to produce the vinyl fluoride compound with particularly high conversion rate, yield and selectivity. In the present disclosure, when there is no particular notation about the pressure, it is a gauge pressure.

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

[0079] (1-8) Examples of the reaction ​In the reaction step of reacting a vinyl halide compound to obtain a vinyl fluoride compound in the present disclosure, the reaction can be carried out by either a gas-phase continuous flow type or a batch type in which a raw material compound (vinyl halide compound) is continuously charged into a reactor and the target compound (vinyl fluoride compound) is continuously withdrawn from the reactor. Since the elimination reaction can further proceed if the target compound remains in the reactor, it is preferably carried out by the gas-phase continuous flow type. In the reaction step of reacting a vinyl halide compound to obtain a vinyl fluoride compound in the present disclosure, it is preferably carried out in the gas phase, particularly by the gas-phase continuous flow type using a fixed-bed reactor. When carried out by the gas-phase continuous flow type, the apparatus, operation, etc. can be simplified and it is economically advantageous.

[0080] Regarding the atmosphere when carrying out the reaction step of reacting a vinyl halide compound to obtain a vinyl fluoride compound in the present disclosure, an inert gas atmosphere is preferred from the viewpoint of suppressing the deterioration of the alkali metal fluoride. Examples of the inert gas include nitrogen, helium, argon, etc. Among these inert gases, nitrogen is preferred from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas components introduced into the reactor. When the above reaction is carried out in the presence of a fluorine-containing gas, it can also be carried out in the atmosphere of the fluorine-containing gas or in a mixed atmosphere of the above 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 completion of the reaction, purification treatment is carried out according to a conventional method as necessary to obtain a vinyl fluoride compound represented by the general formula (1).

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

[0083] This vinyl fluoride compound can contain both the cis form and the trans form. However, from the viewpoint of being able to be produced with high conversion rate, yield and selectivity, the trans form is preferred, and the general formula (1A):

[0084]

Chemical formula

[0085] [In the formula, R 1 and R 2 are the same as those described above.] The vinyl fluoride compound represented by

[0086] In general formulas (1) and (1A), R 1 and R 2 correspond to R 1 and R 3 in the above-described general formulas (2) and (2A). Note that when R 3 in general formulas (2) and (2A) is a halogen atom other than a fluorine atom, the target vinyl fluoride compound may include a compound in which the halogen atom is substituted with a fluorine atom and a compound in which the halogen atom remains as it is. Therefore, the vinyl fluoride compound represented by general formulas (1) and (1A) to be produced, for example, specifically, is

[0087]

Chemical formula

[0088] include the following.

[0089] The vinyl fluoride compound thus obtained can be effectively used for various purposes such as an etching gas, a cleaning gas, and a building block for organic synthesis for forming state-of-the-art fine structures such as semiconductors and liquid crystals. The building block for organic synthesis will be described later.

[0090] 2. Composition As described above, a vinyl fluoride compound can be obtained. However, the vinyl fluoride compound represented by the general formulas (1) and (1A ) and the alkyne compound represented by the general formula (3): R 1 -C≡C-R 2 (3) [wherein R 1 and R 2 are the same as defined above.] may be obtained in the form of a composition containing the alkyne compound represented by the general formula (3):

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

[0092] Further, as described above, when R 3 in the general formulas (2) and (2A) is a halogen atom other than a fluorine atom, the target vinyl fluoride compound may include a compound in which the halogen atom is substituted with a fluorine atom and a compound in which the halogen atom remains as it is.

[0093] Therefore, the vinyl fluoride compounds represented by the general formulas (1) and (1A) may include a difluorovinyl compound represented by the general formula (1A1):

[0094] [Chemical formula]

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

[0096] [Chemical formula]

[0097] [In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. X 1 represents a halogen atom other than a fluorine atom.] may be included.

[0098] In the general formulas (1A) and (1B), R 1 can be the ones described above, and examples of the halogen atom other than the fluorine atom represented by X 1 include a chlorine atom, a bromine atom and an iodine atom.

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

[0100] According to the production method of the present disclosure, even when obtained as the above-described composition, the vinyl fluoride compound represented by the general formula (1) can be obtained in one step with a high conversion rate of the reaction, and high yield and high selectivity, so that the components other than the vinyl fluoride compound represented by the general formula (1) in the composition can be reduced, and thus the purification effort for obtaining the vinyl fluoride compound represented by the general formula (1) can be reduced. Since the components other than the vinyl fluoride compound represented by the general formula (1) can be reduced, the purification effort for obtaining the vinyl fluoride compound represented by the general formula (1) can be reduced. For obtaining the vinyl fluoride compound represented by the general formula (1), the purification effort can be reduced.

[0101] Such a composition of the present disclosure can be effectively used for various applications such as an etching gas for forming state-of-the-art fine structures such as semiconductors and liquid crystals, a building block for organic synthesis, and a cleaning gas. 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, it is possible to introduce a fluoroalkyl group such as a CF3 group and convert it into a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate. For obtaining a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate by introducing a fluoroalkyl group such as a CF3 group.

[0102] As described above, the embodiments of the present disclosure have been described, but various changes in form and details are possible without departing from the spirit and scope of the claims.

Examples

[0103] Examples are shown below to clarify the features of the present disclosure. The present disclosure is not limited to these examples.

[0104] Synthesis Example 1: 50% CsF / AC Activated carbon (specific surface area: 1200 m 2 / g) and cesium fluoride were mixed so that the total amount of activated carbon and cesium fluoride was 100% by mass and the amount of cesium fluoride used was 50% by mass, and a 50% CsF / AC catalyst in which cesium fluoride was supported on the activated carbon was obtained. The specific surface area of the obtained catalyst was 600 cm / g, 2 / g, The pore volume was 0.7 mL / g and the pore diameter was 10 μm.

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

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

[0107] Examples 1 to 5 In the method for producing a vinyl fluoride compound of Examples 1 to 5, the starting compound was a vinyl halide compound represented by the general formula (2), in which R and R 1 and R 3 were trifluoromethyl groups and X was a chlorine atom and, according to the following reaction formula:

[0108]

Chemical formula

[0109] a vinyl fluoride compound was obtained.

[0110] To a SUS pipe (outer diameter: 1 / 2 inch) serving as a reaction tube, 10 g of the catalyst obtained in Synthesis Example 1, 2, or 3 was added. After drying at 200 °C for 2 hours under a nitrogen atmosphere, CF3CH=CClCF3 (raw material compound) was passed through the reaction tube so that the pressure was normal pressure and 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 gas-phase continuous flow system.

[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 passing through the purification column was collected.

[0114] Thereafter, mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and structural analysis was performed by NMR spectrum using an NMR (manufactured by JEOL, trade name "400YH"). manufactured by JEOL, trade name "400YH") to perform structural analysis by NMR spectrum. Based on the results of mass spectrometry and structural analysis, it was confirmed that CF3CH=CFCF3 was produced as the target compound. The results are shown in Table 1.

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

[0116]

Table 1

[0117] Examples 6 to 8 In the method for producing a vinyl fluoride compound according to Examples 6 to 8, the raw material compound is a vinyl halide compound represented by the general formula (2), where R is a hydrogen atom, R 1 is a hydrogen atom, R 3 and X are chlorine atoms, and the following Reaction formula:

[0118] [Chemical formula]

[0119] Accordingly, a vinyl fluoride compound was obtained.

[0120] 10 g of the catalyst obtained in Synthesis Example 1 or 3 was added to a SUS pipe (outer diameter: 1 / 2 inch) which is a reaction tube. After drying at 200 °C for 2 hours under a nitrogen atmosphere, CH2=CCl2 (raw material compound) was passed through the reaction tube so that the pressure was normal pressure and 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 gas-phase continuous flow system.

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

[0123] One hour after starting the reaction, the distillate passing through the purification column was collected.

[0124] Thereafter, gas chromatography (manufactured by Shimadzu Corporation, product name "GC-2014") was used for mass spectrometry by gas chromatography / mass spectrometry (GC / MS), and structural analysis by NMR spectrum was performed using NMR (manufactured by JEOL, product name "400YH").

[0125] From the results of mass spectrometry and structural analysis, it was confirmed that CH2=CClF and CH2=CF2 were produced as the target compounds. The results are shown in Table 2.

[0126] [Table 2]

Claims

1. An alkyne compound represented by the general formula (1A): 【Chemical 1】 [In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R 2 represents a halogen atom, an alkyl group or a fluoroalkyl group. However, when R 2 is a fluoroalkyl group, R 1 is a halogen atom, an alkyl group or a fluoroalkyl group.], a vinyl fluoride compound represented by the formula, and a general formula (3): R 1 -C≡C-R 2 (3) [wherein, R selected in general formula (1A) 1 and R 2 are the same as those above.] and containing the same, and a composition in which, taking the total amount of the composition as 100 mol%, the content of the vinyl fluoride compound represented by the general formula (1A) is 60 to 99.9 mol%.

2. The composition according to claim 1, wherein, taking the total amount of the composition as 100 mol%, the content of the alkyne compound represented by the general formula (3) is 0.1 to 20 mol%.

3. The vinyl fluoride compound represented by the general formula (1A) is a difluoro vinyl compound represented by the general formula (1A1): 【Chemical 2】 [wherein, R 1 is the same as described above.] and a vinyl fluoride compound represented by the general formula (1A2): The composition according to claim 1 or 2, containing the same. 【Chemical Formula 3】 [wherein, R 1 is the same as described above. X 1 represents a halogen atom other than a fluorine atom. ]

4. The composition according to claim 3, wherein, taking the total amount of the composition as 100 mol%, the content of the difluoro vinyl compound represented by the general formula (1A1) is 40 to 98 mol%, and the content of the vinyl fluoride compound represented by the general formula (1A2) is 2 to 30 mol%.

5. The composition according to any one of claims 1 to 4, which is used as a cleaning gas, an etching gas, a refrigerant, or a building block for organic synthesis. ​

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