Method for producing vinyl compound

Abstract

The present invention provides a method for producing a vinyl compound in which a hydrogen atom is bonded to an SP2 carbon atom of an alkenyl group, by reacting a halogenated vinyl compound in which a halogen atom is bonded to an SP2 carbon atom of an alkenyl group with a hydrogen-containing compound in the presence of a nickel-containing catalyst to obtain the vinyl compound, a vinyl compound in which a hydrogen atom is bonded to an SP2 carbon atom of an alkenyl group can be obtained with high conversion rate and high selectivity without diluting a halogenated vinyl compound.

Description

[0001] This case is a divisional application with an application date of July 7, 2020, application number 202010644422.8, and invention name "Method for producing vinyl compounds". Technical Field

[0002] The present invention relates to a method for preparing a vinyl compound. Background Art

[0003] Vinyl compounds in which a hydrogen atom is bonded to the sp2 carbon atom of the alkenyl group are represented by trifluoroethylene, and are expected to be used in various applications such as cleaning gas, etching gas, refrigerant, and building blocks for organic synthesis.

[0004] As a method for producing the vinyl compound, for example, a method is known in which a mixed gas obtained by diluting a halogenated vinyl compound having a halogen atom bonded to the SP2 carbon atom possessed by an alkenyl group with nitrogen as a starting material is reacted with hydrogen in the presence of a palladium catalyst (for example, refer to Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application No. 2013-534529 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] An object of the present invention is to provide a method for obtaining a vinyl compound having a hydrogen atom bonded to the SP2 carbon atom of an alkenyl group with high conversion rate and high selectivity without diluting the halogenated vinyl compound.

[0010] Technical solutions for solving technical problems

[0011] The present invention includes the following configurations.

[0012] Item 1. A method for producing a vinyl compound in which a hydrogen atom is bonded to an SP2 carbon atom possessed by an alkenyl group, comprising:

[0013] In the presence of a nickel-containing catalyst,

[0014] A step of obtaining the above vinyl compound by reacting a halogenated vinyl compound in which a halogen atom is bonded to the sp2 carbon atom of the alkenyl group with a compound containing hydrogen.

[0015] Item 2. The manufacturing method according to Item 1, wherein:

[0016] The above vinyl compound is a vinyl compound represented by the general formula (1),

[0017]

[0018] [Where R 1 , R 2 and R 3 are the same or different and represent a fluorine atom, an alkyl group or a fluoroalkyl group. ].

[0019] Item 3. The production method according to Item 2, wherein R in the general formula (1) is 1 , R 2 and R 3 is a fluorine atom or a fluoroalkyl group.

[0020] Item 4. The production method according to any one of Items 1 to 3, wherein

[0021] The above-mentioned halogenated vinyl compound is a halogenated vinyl compound represented by the general formula (2),

[0022]

[0023] [Where R 1 , R 2 and R 3 are the same or different and represent a fluorine atom, an alkyl group or a fluoroalkyl group. X represents a halogen atom. ].

[0024] Item 5. The production method according to Item 4, wherein X in the general formula (2) is a halogen atom other than a fluorine atom.

[0025] Item 6. A production method as described in any one of Items 1 to 5, wherein, in the above-mentioned reaction, the contact time (W / F) of the above-mentioned halogenated vinyl compound with the above-mentioned nickel-containing catalyst (the total amount of the carrier and the nickel-containing catalyst when supported on a carrier) is 4 to 200 g·sec / cc.

[0026] Item 7. The production method according to any one of Items 1 to 6, wherein the reaction temperature in the above reaction is 200 to 600°C.

[0027] Item 8. The production method according to any one of Items 1 to 7, wherein the presence ratio of the hydrogen-containing compound to the halogenated vinyl compound in the reaction field is 0.5 to 1.5 mol of the hydrogen-containing compound per 1 mol of the halogenated vinyl compound.

[0028] Item 9. The production method according to any one of Items 1 to 8, wherein the content of the inert gas in the raw material gas is 0 to 1% by volume.

[0029] Item 10. A composition comprising a vinyl compound represented by the general formula (1) and a vinyl compound represented by the general formula (3),

[0030]

[0031] [Where R 1 , R 2 and R 3 are the same or different and represent a fluorine atom, an alkyl group or a fluoroalkyl group. ];

[0032]

[0033] [Where R 1 and R 2 has the same meaning as above. ],

[0034] The content of the vinyl compound represented by the above general formula (1) is 90.0 to 97.0 mol % based on 100 mol % of the total composition.

[0035] Item 11. The composition according to Item 10, which is used as a cleaning gas, an etching gas, a refrigerant, or a building block for organic synthesis.

[0036] Effects of the Invention

[0037] According to the present invention, a vinyl compound having a hydrogen atom bonded to the SP2 carbon atom of an alkenyl group can be obtained with a high conversion rate and a high selectivity without diluting the halogenated vinyl compound. DETAILED DESCRIPTION

[0038] In this specification, "comprising" is a concept including "including", "consisting essentially of", and "consisting only of". In addition, in this specification, when a numerical range is indicated as "A to B", it means A or more and B or less.

[0039] In the present invention, the "selectivity" means the ratio (mol %) of the total molar amount of the target compound contained in the outflow gas from the reactor outlet to the total molar amount of the compounds other than the raw material compounds in the outflow gas.

[0040] In the present invention, the “conversion rate” means the ratio (mol %) of the total molar amount of compounds other than the raw material compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0041] In the present invention, the term "yield" refers to the ratio (mol %) of the total molar amount of the target compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0042] 1. Method for producing vinyl compounds

[0043] The method for producing a vinyl compound of the present invention is a method for producing a vinyl compound in which a hydrogen atom is bonded to an SP2 carbon atom possessed by an alkenyl group, which comprises: in the presence of a nickel-containing catalyst, reacting a halogenated vinyl compound in which a halogen atom is bonded to an SP2 carbon atom possessed by an alkenyl group with a compound containing hydrogen to obtain the above-mentioned vinyl compound.

[0044] At present, as shown in patent documentation 1, utilize nitrogen dilution on the sp2 carbon atom that alkenyl group has and be combined with the mixed gas obtained of halogenated vinyl compound and react with hydrogen under the existence of palladium catalyst as starting material.Utilize this method, think that the maximum conversion rate is 91%, but, because must carry out the dilution of raw material compound, under the situation that needs to improve yield, become drawback.In addition, selectivity also can not be said to be high.In addition, the catalyst life of palladium catalyst as catalyst is short, is not suitable for long-term reaction, and, expensive, has the trend of increasing cost.

[0045] According to the present invention, as described above, a halogenated vinyl compound having a halogen atom bonded to the SP2 carbon atom possessed by an alkenyl group is reacted with a compound containing hydrogen in the presence of a nickel-containing catalyst, thereby obtaining a vinyl compound having a hydrogen atom bonded to the SP2 carbon atom possessed by the alkenyl group with a high conversion rate and a high selectivity without diluting the raw material compound. In addition, the nickel catalyst used has a long catalyst life and can be used for a long-term reaction.

[0046] (1-1) Halogenated vinyl compounds

[0047] The halogenated vinyl compound that can be used as a substrate in the production method of the present invention is a halogenated vinyl compound in which a halogen atom is bonded to the SP2 carbon atom possessed by the alkenyl group, and is preferably a halogenated vinyl compound represented by the general formula (2):

[0048]

[0049] [Where R 1 , R 2 and R 3 are the same or different and represent a fluorine atom, an alkyl group or a fluoroalkyl group. X represents a halogen atom. ].

[0050] In the general formula (2), R 1 , R 2 and R 3Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and other groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms. The alkyl group may have 1 to 6, particularly 1 to 3, substituents such as halogen atoms described below.

[0051] In the general formula (2), R 1 , R 2 and R 3 Examples of the fluoroalkyl group include fluoroalkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms (particularly perfluoroalkyl groups), such as trifluoromethyl and pentafluoroethyl groups.

[0052] Among them, as R 1 , R 2 and R 3 From the viewpoints of reaction conversion rate, selectivity of the target product, catalyst life, etc., a fluorine atom or a fluoroalkyl group is preferred, and a fluorine atom or a perfluoroalkyl group is more preferred.

[0053] In the general formula (2), the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, from the viewpoints of the conversion rate of the reaction, the yield and selectivity of the target product, the life of the catalyst, etc., preferably, it is a halogen atom other than a fluorine atom (chlorine atom, bromine atom and iodine atom), and more preferably, a chlorine atom.

[0054] As the halogenated vinyl compound as the raw material compound, R is preferred from the viewpoint that the vinyl compound as the target can be produced with particularly high conversion, yield and selectivity and the catalyst life is particularly excellent. 1 , R 2 and R 3 All of them are fluorine atoms, and X is preferably a chlorine atom.

[0055] The above R 1 , R 2 , R 3 and X may be the same or different.

[0056] Specific examples of the halogenated vinyl compounds that are raw material compounds satisfying the above conditions include:

[0057]

[0058] wait.

[0059] These halogenated vinyl compounds may be used alone or in combination of two or more. As such halogenated vinyl compounds, known or commercially available products may be used.

[0060] In addition, in the method of the present invention, when the reaction is carried out by the gas phase flow continuous method described later, the supplied raw material gas may contain an inert gas such as nitrogen and argon in addition to the above-mentioned halogenated vinyl compound serving as the raw material compound. However, since the method of the present invention does not require dilution of the above-mentioned halogenated vinyl compound serving as the raw material compound and can also react with a hydrogen-containing gas to obtain a vinyl compound, the total amount of the raw material gas is set to 100% by volume, the amount of the inert gas present is preferably 0 to 1% by volume, and the raw material gas is most preferably composed only of the above-mentioned halogenated vinyl compound.

[0061] (1-2) Compounds containing hydrogen

[0062] As the compound containing hydrogen, in addition to hydrogen, it also includes compounds of hydrogen and other elements (for example, oxygen hydrogen as a compound of oxygen and hydrogen, etc.). However, since the reaction of the present invention is a reaction in which the halogen atoms of the halogenated vinyl compound are replaced with hydrogen atoms, the compound containing hydrogen preferably does not contain hydrogen halides (hydrogen fluoride, hydrogen chloride) or contains a very small amount (for example, less than 5 volume % relative to the total amount of the compound containing hydrogen). In addition, from the viewpoint of the conversion rate, yield and selectivity of the reaction, it is preferred to use hydrogen. These compounds containing hydrogen can be used alone or in combination with two or more.

[0063] The compound containing hydrogen generally uses a gas containing hydrogen, preferably together with the halogenated vinyl compound (raw material compound), and is supplied to the reactor in a gas phase state. Regarding the presence of the compound containing hydrogen, in the reaction field, it is preferably 0.5 to 1.5 moles, more preferably 0.6 to 1.4 moles, and further preferably 0.7 to 1.3 moles relative to 1 mole of the halogenated vinyl compound (raw material compound). In addition, when the reaction is carried out in a continuous gas phase flow described later, the supply amount of the compound containing hydrogen is preferably 0.5 to 1.5 moles, more preferably 0.6 to 1.4 moles, and further preferably 0.7 to 1.3 moles relative to 1 mole of the supply amount of the halogenated vinyl compound (raw material compound). By setting it to this range, the reaction based on the compound containing hydrogen can be better carried out, the generation of impurities can be further reduced, the selectivity of the vinyl compound of the product is high, and it can be recovered with a high yield.

[0064] (1-3) Reaction

[0065] In the step of reacting a halogenated vinyl compound represented by the general formula (2) with a hydrogen-containing compound of the present invention, for example, as a raw material compound, among the halogenated vinyl compounds represented by the general formula (2), R 1 , R 2 and R 3 All of them are fluorine atoms, and X is preferably a chlorine atom.

[0066] In other words, it is preferably according to the following reaction formula:

[0067]

[0068] A vinyl compound is obtained through a single step.

[0069] (1-3) Catalyst

[0070] The step of reacting the halogenated vinyl compound represented by the general formula (2) with a hydrogen-containing compound of the present invention is a step of reacting the halogenated vinyl compound having a halogen atom bonded to the sp2 carbon atom of the alkenyl group with a hydrogen-containing compound in the presence of a nickel-containing catalyst.

[0071] The nickel-containing catalyst is not particularly limited, and examples thereof include nickel metal, nickel oxide, nickel nitrate, a homogeneous nickel catalyst coordinated with a ligand, Raney nickel, etc. These nickel-containing catalysts may be used alone or in combination of two or more.

[0072] From the viewpoint of being able to produce vinyl compounds with particularly high conversion, yield and selectivity, the specific surface area of ​​the nickel-containing catalyst is preferably 500 to 2000 m 2 / g, more preferably 800 to 1500 m 2 / g. In the present invention, the specific surface area of ​​the nickel-containing catalyst is measured by the BET method. When the specific surface area of ​​the nickel-containing catalyst is in such a range, the density of the particles of the nickel-containing catalyst will not be too small, and therefore, the target compound can be obtained with a higher selectivity. In addition, the conversion rate of the raw material compound can be further improved. In addition, when the nickel-containing catalyst is supported on a carrier as described later, the specific surface area of ​​the nickel-containing catalyst supported on the carrier is also preferably within the above range.

[0073] Such a nickel-containing catalyst can react a halogenated vinyl compound with a hydrogen-containing compound to obtain a vinyl compound with particularly high conversion, yield and selectivity. The catalyst also has a long life and can withstand long-term or repeated reactions.

[0074] The nickel-containing catalyst may be a known or commercially available product, or may be synthesized with reference to CHEMISTRY LETTERS (1990) P879-880 or the like.

[0075] In the present invention, when the reaction is carried out in a gas phase, the raw material compound is contacted with a hydrogen-containing compound in the presence of a catalyst. In this case, from the viewpoint of reactivity, the catalyst is preferably in contact with the raw material compound in a solid state (solid phase).

[0076] In the present invention, for example, when a gas phase continuous flow reaction is carried out, from the viewpoint of reactivity, the nickel-containing catalyst may also be in powder form, but is preferably in pellet form. In addition, the above-mentioned nickel-containing catalyst may be used directly or may be supported on a carrier and used. Thus, the specific surface area of ​​the catalyst is increased, the reaction efficiency is improved, and vinyl compounds can be manufactured with particularly high conversion, yield and selectivity. There is no particular limitation on the carrier used for support, for example, carbon, aluminum oxide, zirconium oxide, silicon dioxide, titanium dioxide, silicon dioxide aluminum oxide, chromium oxide, etc. may be cited. As carbon, activated carbon, amorphous carbon, graphite, diamond, etc. may be cited. These carriers may be used alone or in combination of two or more. Among them, from the viewpoint that the specific surface area is large and nickel is easily supported, preferably carbon and silicon dioxide, more preferably carbon, and further preferably activated carbon.

[0077] When a nickel-containing catalyst is supported on a carrier, the supported amount is not particularly limited. From the viewpoint of being able to produce vinyl compounds with particularly high conversion rate, yield and selectivity, the total amount of the nickel-containing catalyst and the carrier is set to 100 mass %, and the nickel-containing catalyst preferably contains 0.1 to 75 mass %, more preferably 1 to 60 mass %.

[0078] From the viewpoint of being able to manufacture vinyl compounds with particularly high conversion, yield and selectivity, the bulk density of the nickel-containing catalyst supported on the carrier is preferably 0.01 to 10 g / mL, more preferably 0.1 to 5 g / mL. In the present invention, the bulk density of the nickel-containing catalyst supported on the carrier is measured using a bulk density measuring device. When the bulk density of the nickel-containing catalyst supported on the carrier is in such a range, the density of the particles of the nickel-containing catalyst supported on the carrier will not be too small, and therefore, the target compound can be obtained with a higher selectivity. In addition, the conversion rate of the raw material compound can be further improved.

[0079] From the viewpoint of being able to manufacture vinyl compounds with particularly high conversion, yield and selectivity, the pore volume of the nickel-containing catalyst supported on the carrier is preferably 0.1 to 1.5 mL / g, more preferably 0.25 to 1.0 mL / g. In the present invention, the pore volume of the nickel-containing catalyst supported on the carrier can be measured using the BET method. When the pore volume of the nickel-containing catalyst supported on the carrier is in such a range, the density of the particles of the nickel-containing catalyst supported on the carrier will not be too small, and therefore, the target compound can be obtained with a higher selectivity. In addition, the conversion rate of the raw material compound can be further improved.

[0080] From the viewpoint of being able to produce vinyl compounds with particularly high conversion rate, yield and selectivity, the average pore diameter of the nickel-containing catalyst supported on the carrier is preferably 5 to 20 μm, more preferably 8 to 15 μm. In the present invention, the average pore diameter of the nickel-containing catalyst supported on the carrier is measured by the BET method.

[0081] When the nickel-containing catalyst is supported on a carrier, the supporting method is not particularly limited. For example, the carrier can be supported by adding the carrier to an aqueous solution containing a nickel compound (nickel oxide, nickel nitrate, a homogeneous nickel catalyst coordinated with a ligand, Raney nickel, etc.), heating and removing the water. Various conditions can be in accordance with conventional methods.

[0082] (1-4) Reaction temperature

[0083] In the step of obtaining a vinyl compound by reacting a halogenated vinyl compound with a hydrogen-containing compound of the present invention, the reaction temperature is usually preferably 200 to 600° C., more preferably 250 to 500° C., and further preferably 300 to 400° C., from the viewpoint of being able to produce a vinyl compound with particularly high conversion, yield, and selectivity. In addition, from the viewpoint of conversion, yield, and selectivity, when the reaction time described later is short (for example, when W / F is 4 g·sec. / cc or more and less than 5 g·sec. / cc), it is preferred to set the reaction temperature to a higher level (for example, 400 to 600° C.). In addition, when the reaction time described later is long (for example, when W / F is 5 g·sec. / cc or more), there is no problem even if the reaction temperature is low (for example, 200 to 400° C.).

[0084] (1-5) Reaction time

[0085] In the present invention, when the reaction is carried out in the gas phase, the reaction time is, for example, when the gas phase flow method is adopted, the contact time (W / F) of the raw material compound (halogenated vinyl compound) with the catalyst (nickel-containing catalyst; when supported on a carrier, it is the total amount of the carrier and the nickel-containing catalyst) [W: the weight (g) of the catalyst (nickel-containing catalyst; when supported on a carrier, it is the total amount of the carrier and the nickel-containing catalyst), F: the flow rate (cc / sec) of the raw material compound (halogenated vinyl compound)] is set longer, the higher the conversion rate is; the shorter it is set, the higher the selectivity of the vinyl compound is. Therefore, from the viewpoint that the conversion rate of the reaction is particularly high and the vinyl compound can be obtained with a higher yield and a high selectivity, it is preferably 4 to 200 g·sec. / cc, more preferably 4.5 to 100 g·sec. / cc, and further preferably 5 to 50 g·sec. / cc. In addition, the above contact time means the time for the raw material compound and the catalyst to contact.

[0086] The above-mentioned contact time indicates the conditions when the reaction is carried out in a gas phase, particularly in a gas phase continuous flow system, but can be appropriately adjusted when the reaction is carried out in a batch system.

[0087] (1-6) Reaction pressure

[0088] From the viewpoint of being able to produce vinyl compounds with particularly high conversion, yield and selectivity, the reaction pressure when the halogenated vinyl compound and the hydrogen-containing compound are reacted to obtain the vinyl compound in the present invention is preferably -0.05 to 2 MPa, more preferably -0.01 to 1 MPa, and still more preferably normal pressure to 0.5 MPa. In addition, in the present invention, when there is no special mark about the pressure, it is set as the gauge pressure.

[0089] In the reaction of the present invention, as a reactor for reacting a raw material compound (halogenated vinyl compound) with a compound containing hydrogen in the presence of a nickel-containing catalyst, the shape and structure are not particularly limited as long as it is a reactor that can withstand the above-mentioned temperature and pressure. As the reactor, for example, a vertical reactor, a horizontal reactor, a multi-tube reactor, etc. can be listed. As the material of the reactor, for example, glass, stainless steel, iron, nickel, iron-nickel alloy, etc. can be listed.

[0090] (1-7) Example of reaction

[0091] The process of making a halogenated vinyl compound react with a compound containing hydrogen to obtain a vinyl compound of the present invention can be implemented by continuously supplying a raw material compound (halogenated vinyl compound) and a compound containing hydrogen to a reactor, and continuously releasing the target compound (vinyl compound) from the reactor in any of a gas phase continuous flow type and an intermittent type. When the target compound accumulates in the reactor, a hydrogenation reaction will be further carried out, and therefore, it is preferably implemented in a gas phase continuous flow type. In the process of making a halogenated vinyl compound react with a compound containing hydrogen to obtain a vinyl compound of the present invention, it is preferably carried out in a gas phase, particularly in a gas phase continuous flow type using a fixed bed reactor. When carried out in a gas phase continuous flow type, it is possible to simplify the device, operation, etc., and it is economically advantageous.

[0092] Regarding the atmosphere when the step of reacting the halogenated vinyl compound with the compound containing hydrogen to obtain the vinyl compound in the present invention is carried out, from the viewpoint of the efficiency of the reaction, preferably under an inert gas atmosphere, under a hydrogen atmosphere, etc. The inert gas can include nitrogen, helium, argon, etc. Among these inert gases, nitrogen is preferably used from the viewpoint of suppressing cost.

[0093] After the reaction is completed, the vinyl compound represented by the general formula (1) can be obtained by performing purification treatment according to a conventional method as required.

[0094] (1-8) Target compound

[0095] The target compound of the present invention obtained in this way is a vinyl compound having a hydrogen atom bonded to the sp2 carbon atom possessed by the alkenyl group, preferably a vinyl compound represented by the general formula (1):

[0096]

[0097] [Where R 1 , R 2 and R 3 are the same or different and represent a fluorine atom, an alkyl group or a fluoroalkyl group. ].

[0098] R in the general formula (1) 1 , R 2 and R 3 R in the above general formula (2) 1 , R 2 and R 3 Therefore, the vinyl compound represented by the general formula (1) to be produced can be specifically listed as follows:

[0099] wait.

[0100] The vinyl compound obtained in this way can be effectively used in various applications such as etching gas, cleaning gas, and building blocks for organic synthesis for forming the most advanced microstructures of semiconductors, liquid crystals, etc. The building blocks for organic synthesis will be described later.

[0101] 2. Composition

[0102] The vinyl compound can be obtained in the above manner, but can also be obtained in the form of a composition containing the vinyl compound represented by the general formula (1).

[0103] For example, the composition may also contain a vinyl compound represented by the general formula (3), a vinyl compound represented by the general formula (4), etc.:

[0104]

[0105] [Where R 1 and R 2 has the same meaning as above. ];

[0106]

[0107] [Where R 1 The meaning is the same as above. ].

[0108] In this case, when the total amount of the composition of the present invention is 100 mol%, the content of the fluorinated vinyl compound represented by the general formula (1) is preferably 90.0 to 97.2 mol%, more preferably 90.5 to 97.1 mol%. In addition, when the total amount of the composition of the present invention is 100 mol%, the content of the vinyl compound represented by the general formula (3) is preferably 1.0 to 5.0 mol%, more preferably 1.4 to 4.0 mol%. In addition, when the total amount of the composition of the present invention is 100 mol%, the content of the vinyl compound represented by the general formula (4) is preferably 0.1 to 2.5 mol%, more preferably 0.2 to 2.2 mol%.

[0109] Furthermore, according to the production method of the present invention, even when the vinyl compound represented by the general formula (1) is obtained in the form of the above-mentioned composition, the vinyl compound represented by the general formula (1) can be obtained with a high reaction conversion rate, high yield and high selectivity, thereby reducing the components other than the vinyl compound represented by the general formula (1) in the composition, thereby reducing the labor for purification for obtaining the vinyl compound represented by the general formula (1).

[0110] Such a composition of the present invention can be effectively used not only in the use of etching gas for forming the most advanced microstructures such as semiconductors and liquid crystals, but also in various uses such as organic synthesis building blocks and cleaning gases. In addition, organic synthesis building blocks refer to substances that can become precursors of compounds having a highly reactive skeleton. For example, when the composition of the present invention is reacted with a fluorinated organosilicon compound such as CF3Si(CH3)3, a fluoroalkyl group such as a CF3 group can be introduced to convert it into a cleaning agent, which can become a fluorinated pharmaceutical intermediate.

[0111] Although the embodiments of the present invention have been described above, various modifications of the embodiments and details may be made without departing from the spirit and scope of the claims.

[0112] [Example]

[0113] Hereinafter, examples will be described to clarify the features of the present invention, but the present invention is not limited to these examples.

[0114] Synthesis Example 1: Ni-AC

[0115] 5 g of nickel nitrate was dissolved in 25 g of pure water, and activated carbon (specific surface area 1200 m 2 / g) to make the amount of nickel nitrate relative to the total amount of carbon and nickel nitrate reach 20% by mass, then heating at 80°C under reduced pressure for 1 hour to remove water, then drying at 200°C under reduced pressure, and calcining at 400°C for 3 hours to obtain a catalyst in which nickel is supported on activated carbon.

[0116] Synthesis Example 2: Ni-SiO2

[0117] 5 g of nickel nitrate was dissolved in 25 g of pure water, and silicon dioxide (specific surface area 800 m 2 / g) to make the amount of nickel nitrate relative to the total amount of silica and nickel nitrate reach 20% by mass, then heating at 80°C under reduced pressure for 1 hour to remove water, then drying at 200°C under reduced pressure, and calcining at 400°C for 3 hours to obtain a catalyst in which nickel is supported on silica.

[0118] Examples 1 to 9

[0119] In the methods for producing vinyl compounds of Examples 1 to 9, the raw material compound is a halogenated vinyl compound represented by the general formula (2) wherein R 1 , R 2 and R 3 is a fluorine atom, X is a chlorine atom, according to the following reaction formula:

[0120]

[0121] A vinyl compound is obtained.

[0122] 10 g of the catalyst obtained in Synthesis Example 1 or 2 was added to a SUS pipe (outer diameter: 1 / 2 inch) serving as a reaction tube. After drying at 200° C. for 2 hours under a nitrogen atmosphere, the pressure was brought to normal pressure, the supply amount of hydrogen was set to 1 mol relative to 1 mol of CF2=CFCl (raw material compound), and CF2=CFCl (raw material compound) and hydrogen were circulated in the reaction tube in such a manner that the contact time (W / F) between CF2=CFCl (raw material compound) and the catalyst was 3 g·sec / cc, 5 g·sec / cc, or 10 g·sec / cc.

[0123] The reaction was carried out in a gas phase continuous flow system.

[0124] The reaction tube was heated at 300°C or 400°C to initiate the reaction.

[0125] One hour after the start of the reaction, the fractions passing through the detoxification tower were collected.

[0126] Thereafter, mass analysis 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 based on NMR spectra using NMR (manufactured by JEOL, trade name "400YH").

[0127] From the results of mass spectrometry and structural analysis, it was confirmed that CF2=CFH was generated as the target compound. Table 1 shows the conditions and results of the catalyst, temperature, and contact temperature.

[0128]

Table 1

[0129]

Claims

1. A method for producing a vinyl compound in which a hydrogen atom is bonded to an SP2 carbon atom possessed by an alkenyl group, characterized in that: include: In the presence of a nickel-containing catalyst, A step of obtaining the vinyl compound by reacting a halogenated vinyl compound in which a halogen atom is bonded to the sp2 carbon atom of an alkenyl group with a compound containing hydrogen.

2. The manufacturing method according to claim 1, characterized in that: The vinyl compound is a vinyl compound represented by the general formula (1), In the formula, R 1 , R 2 and R 3 The same or different groups represent a fluorine atom, an alkyl group or a fluoroalkyl group.

3. The manufacturing method according to claim 2, characterized in that: In the general formula (1), R 1 , R 2 and R 3 is a fluorine atom or a fluoroalkyl group.

4. The manufacturing method according to any one of claims 1 to 3, characterized in that: The halogenated vinyl compound is a halogenated vinyl compound represented by the general formula (2), In the formula, R 1 , R 2 and R 3 are the same or different and represent a fluorine atom, an alkyl group or a fluoroalkyl group; X represents a halogen atom.

5. The manufacturing method according to claim 4, characterized in that: X in the general formula (2) is a halogen atom other than a fluorine atom.

6. The manufacturing method according to any one of claims 1 to 5, characterized in that: In the reaction, The contact time (W / F) of the halogenated vinyl compound with the nickel-containing catalyst is 4 to 200 g·sec / cc, or, When the nickel-containing catalyst is supported on a carrier, the contact time (W / F) of the halogenated vinyl compound with respect to the total amount of the nickel-containing catalyst and the carrier is 4 to 200 g·sec / cc.

7. The manufacturing method according to any one of claims 1 to 6, characterized in that: The reaction temperature in the reaction is 200-600°C.

8. The manufacturing method according to any one of claims 1 to 7, characterized in that: In the reaction field, the existence ratio of the hydrogen-containing compound to the halogenated vinyl compound is: the hydrogen-containing compound is 0.5 to 1.5 moles relative to 1 mole of the halogenated vinyl compound.

9. The manufacturing method according to any one of claims 1 to 8, characterized in that: The content of the inert gas in the raw material gas is 0 to 1 volume %.

10. A composition, characterized in that: Containing a vinyl compound represented by the general formula (1) and a vinyl compound represented by the general formula (3), In formula (1), R 1 , R 2 and R 3 are the same or different, representing a fluorine atom, an alkyl group or a fluoroalkyl group, In formula (3), R 1 and R 2 The meaning is the same as above, When the total amount of the composition is 100 mol %, the content of the vinyl compound represented by the general formula (1) is 90.0 to 97.0 mol %.

11. The composition according to claim 10, characterized in that: It is used as a cleaning gas, etching gas, refrigerant or building block for organic synthesis.

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