Method for producing fluorine-containing olefin

Abstract

To provide a method for producing a fluorine-containing olefin that enables the fluorine-containing olefin to be produced at high yield.SOLUTION: The present invention provides a production method for producing a fluorine-containing olefin, comprising reacting a fluorine-containing first olefin and a second olefin with each other in the presence of a ruthenium compound represented by the following formula (X).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for producing a fluorinated olefin.

Background Art

[0002] A compound in which some or all of the hydrogen atoms in an olefin are substituted with fluorine atoms, that is, a fluorinated olefin, is known as an industrially useful compound.

[0003] As a method for producing a fluorinated olefin, for example, International Publication No. 2015 / 033927 describes a production method by a metathesis reaction of an olefin having at least two fluorine atoms and another olefin in the presence of a ruthenium compound.

Summary of the Invention

Problems to be Solved by the Invention

[0004] In International Publication No. 2015 / 033927, a ruthenium compound having a 5-membered N-heterocyclic carbene ligand is used as a catalyst, and the progress of the metathesis reaction has been confirmed, but an improvement in yield has been demanded.

[0005] The present disclosure has been made in view of such circumstances, and the problem to be solved by one embodiment of the present invention is to provide a method for producing a fluorinated olefin capable of obtaining a fluorinated olefin in a high yield.

Means for Solving the Problems

[0006] Specific means for solving the above problems include the following aspects. <1>A production method for producing a fluorinated olefin by reacting a first olefin represented by the following formula (1) with a second olefin different from the first olefin in the presence of a ruthenium compound represented by the following formula (X).

Chemical Formula

Advantages of the Invention

[0007] According to the present disclosure, a method for producing a fluorinated olefin capable of obtaining a fluorinated olefin in a high yield is provided.

Modes for Carrying Out the Invention

[0008] Hereinafter, the method for producing a fluorinated olefin of the present disclosure will be described in detail.

[0009] In this specification, a numerical range indicated using "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range of other stepwise descriptions. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0010] In this specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, provided that the intended purpose of the step is achieved.

[0011] [Method for producing fluorinated olefin] The method for producing a fluorinated olefin according to the present disclosure is a production method for producing a fluorinated olefin by reacting a first olefin represented by the following formula (1) with a second olefin different from the first olefin in the presence of a ruthenium compound represented by the following formula (X).

[0012] [Chemical formula] In formula (X), A represents a group of atoms necessary to form a 6- or 7-membered nitrogen-containing heterocycle containing two nitrogen atoms. The nitrogen-containing heterocycle may have an aromatic ring or an aliphatic ring condensed thereto, and A and the aromatic ring or aliphatic ring condensed to the nitrogen-containing heterocycle may have substituents. R 1 and R 2 each independently represent an alkyl group, an aryl group, or an aralkyl group. Y 1 and Y 2 each independently represent an anionic ligand. L 1 represents a neutral electron-donating ligand. p represents 0 or 1. Z 1 and Z 2 each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and Z 1 and Z 2 may be bonded to each other to form a ring. Z 1 and Z 2 Either or both of and L 1 may be chemically bonded.

[0013] [Chem.] In formula (1), A 1 , A 2 and A 3 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a fluorinated alkyl group having 1 to 10 carbon atoms.

[0014] In the method for producing a fluorinated olefin of the present disclosure, by using a ruthenium compound represented by formula (X) as a catalyst, the metathesis reaction between the first olefin represented by formula (1) and the second olefin proceeds, and it has been found that the yield is dramatically improved as compared with the conventional method. Although the reason for the improved yield is not clear, it is considered to be due to the fact that the nitrogen-containing heterocyclic ring bonded to ruthenium in formula (X) is a 6-membered ring or a 7-membered ring. Specifically, a complex having an N-heterocyclic carbene ligand of a 6-membered ring or a 7-membered ring has a higher electron-donating ability than a complex having an N-heterocyclic carbene ligand of a 5-membered ring. Therefore, the electron density on the ruthenium atom increases, and it is considered that the electron state becomes optimal for the metathesis reaction of the fluorinated olefin.

[0015] Hereinafter, each raw material used in the method for producing a fluorinated olefin of the present disclosure will be described.

[0016] [Ruthenium compound represented by formula (X)] The ruthenium compound used in the method for producing a fluorinated olefin of the present disclosure is represented by the following formula (X). In the method for producing a fluorinated olefin of the present disclosure, the ruthenium compound represented by formula (X) functions as a catalyst.

[0017] [Chem.]

[0018] [A] In formula (X), A represents a group of atoms necessary to form a 6- or 7-membered nitrogen-containing heterocycle containing two nitrogen atoms. A is preferably composed of a combination of atoms selected from the group consisting of carbon atoms, nitrogen atoms, and oxygen atoms, and more preferably composed of only carbon atoms. That is, A preferably represents a group of carbon atoms necessary to form a 6- or 7-membered nitrogen-containing heterocycle containing two nitrogen atoms.

[0019] When the 6- or 7-membered nitrogen-containing heterocycle consists of two nitrogen atoms and a group of carbon atoms, the group of carbon atoms may be saturated or unsaturated, but is preferably saturated. Also, the carbon atoms constituting the group of carbon atoms may be carbonyl carbons. A is preferably an alkylene group, and more preferably a trimethylene group or a tetramethylene group.

[0020] A may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an amino group, a nitrile group, a nitro group, a sulfo group, a carboxy group, and a hydroxy group. These substituents may further have the above substituents.

[0021] The alkyl group may be cyclic or chain-like. The chain-like alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 8. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a cyclopropyl group, a cyclohexyl group, and a 2-ethylhexyl group. Examples of the alkyl group having a substituent include a 2-hydroxyethyl group, a 2-carboxyethyl group, a 2-methoxyethyl group, and a 2-diethylaminoethyl group.

[0022] The alkenyl group may be cyclic or acyclic. The acyclic alkenyl group may be a linear alkenyl group or a branched alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 2-pentenyl group, and a 2-hexenyl group.

[0023] The alkynyl group may be cyclic or acyclic. The acyclic alkynyl group may be a linear alkynyl group or a branched alkynyl group. The number of carbon atoms of the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. Examples of the alkynyl group include an ethynyl group and a 2-propynyl group.

[0024] Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aryl group having a substituent include a 2,4,6-trimethylphenyl group, a 2,6-diisopropylphenyl group, an o-tolyl group, a 3,5-di-tert-butylphenyl group, a 2,6-dimethyl-4-methoxyphenyl group, and a 2,6-difluorophenyl group.

[0025] The alkyl portion of the aralkyl group is the same as the above alkyl group. The aryl portion of the aralkyl group is the same as the above aryl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0026] The heterocyclic ring of the heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic ring may be a monocyclic ring or a condensed ring. Examples of the heterocyclic ring include a pyridine ring, a piperidine ring, a furan ring group, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, a phenoxazine ring, an indoline ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring, and a thiadiazole ring.

[0027] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0028] The alkyl portion of the alkoxy group is the same as the above alkyl group. Examples of the alkoxy group include a methoxy group, a propyloxy group, a pentyloxy group, and a cyclohexyloxy group.

[0029] The aryl portion of the aryloxy group is the same as the above aryl group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

[0030] The nitrogen-containing heterocyclic ring may have an aromatic ring or an aliphatic ring condensed thereto, and the aromatic ring or aliphatic ring condensed to the nitrogen-containing heterocyclic ring may have a substituent. Examples of the substituent that the aromatic ring or aliphatic ring has are the same as those that A has above.

[0031] Examples of the aromatic ring that may be condensed to the nitrogen-containing heterocyclic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring that may be condensed to the nitrogen-containing heterocyclic ring include a cyclopentane ring and a cyclohexane ring.

[0032] [R 1 and R 2 In formula (X), R 1 and R 2 each independently represent an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, and aralkyl group may each have a substituent. Examples of the substituent are the same as those that A has above.

[0033] ​The alkyl group may be cyclic or linear. The linear alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, and even more preferably from 1 to 8. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a cyclopropyl group, a cyclohexyl group, and a 2-ethylhexyl group. Examples of the alkyl group having a substituent include a 2-hydroxyethyl group, a 2-carboxyethyl group, a 2-methoxyethyl group, and a 2-diethylaminoethyl group.

[0034] Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aryl group having a substituent include a 2,4,6-trimethylphenyl group, a 2,6-diisopropylphenyl group, an o-tolyl group, a 3,5-di-tert-butylphenyl group, a 2,6-dimethyl-4-methoxyphenyl group, and a 2,6-difluorophenyl group.

[0035] The alkyl moiety of the aralkyl group is the same as the above alkyl group. The aryl moiety of the aralkyl group is the same as the above aryl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0036] R 1 and R 2 From the viewpoint of improving the catalytic activity, it is preferably a sterically bulky group, more preferably a branched-chain alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group, even more preferably a cyclic alkyl group, an aryl group or an aralkyl group, and particularly preferably an aryl group.

[0037] Specifically, the branched-chain alkyl group is preferably a tert-butyl group. The cyclic alkyl group is preferably a cycloalkyl group. The aryl group is preferably a 2,4,6-trimethylphenyl group, a 2,6-diisopropylphenyl group, an o-tolyl group, a 3,5-di-tert-butylphenyl group, a 2,6-dimethyl-4-methoxyphenyl group or a 2,6-difluorophenyl group. The aralkyl group is preferably a benzyl group.

[0038] [Y 1 and Y 2 In formula (X), Y 1 and Y 2 each independently represents an anionic ligand. An anionic ligand is a ligand that has a negative charge when separated from the ruthenium atom. Y 1 and Y 2 include, for example, a halogen atom. Among them, Y 1 and Y 2 are more preferably chlorine atoms.

[0039] [L 1 In formula (X), L 1 represents a neutral electron-donating ligand. An electron-donating ligand is a ligand that has an effect of increasing the electron density of the ruthenium atom.

[0040] Examples of the electron-donating ligand include nitrogen-based ligands, phosphorus-based ligands and oxygen-based ligands.

[0041] Examples of the nitrogen-based ligand include bipyridine-based ligands, biquinoline-based ligands, phenanthroline-based ligands, pyridine-based ligands, quinoline-based ligands, benzoquinoline-based ligands, acridine-based ligands, tertiary aliphatic amine-based ligands and tertiary aromatic amine-based ligands. Examples of the phosphoric acid-based ligand include phosphine-based ligands. Examples of the oxygen-based ligand include ether-based ligands.

[0042] [p]​​ In formula (X), p represents 0 or 1. That is, L 1 is optionally present.

[0043] [Z 1 and Z 2 In formula (X), Z 1 and Z 2 each independently represents a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and Z 1 and Z 2 may be bonded to each other to form a ring. Z 1 and Z 2 either or both of them and L 1 may be chemically bonded.

[0044] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

[0045] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom include an alkyl group having 1 to 20 carbon atoms having a substituent containing the above atoms, an aryl group having 6 to 20 carbon atoms having a substituent containing the above atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent containing the above atoms include a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an amino group, an imino group, a nitrile group, an amide group, a carbamate group, a nitro group, a carboxy group, an ester group, a thioether group, a sulfo group, a phosphoric acid group, and a silyl group.

[0046] Z 1 、Z 2 and L 1 Examples of the combination of them include, for example, the following. Z 1 、Z 2 and L 1 ​Other ligands are omitted as [L].

[0047]

Chem.

[0048] From the viewpoint of availability, the ruthenium compound used in the method for producing the fluorinated olefin of the present disclosure is preferably a compound represented by the following formula (X1).

[0049]

Chem.

[0050] In formula (X1), R 1 , R 2 , Y 1 , Y 2 , L 1 , p, Z 1 and Z 2 are the same as R 1 , R 2 , Y 1 , Y 2 , L 1 , Z 1 and Z 2 in formula (X), respectively.

[0051] In formula (X1), n is 1 or 2, R 3 represents a hydrogen atom or a substituent, and the carbon atom constituting the nitrogen-containing heterocyclic ring having two nitrogen atoms may be a carbonyl carbon. Examples of the substituent represented by R 3 include the same ones as the substituents of A described above.

[0052] Examples of the ruthenium compound represented by formula (X) include the following compounds. Here, "Mes" means a 2,4,6-trimethylphenyl group, "o-tol" means an o-tolyl group, "Dipp" means a 2,6-diisopropylphenyl group, and "Cy" means a cyclohexyl group.

[0053]

Chem.

[0054] <The first olefin> The first olefin used in the method for producing a fluorinated olefin of the present disclosure is an olefin represented by formula (1).

[0055]

Chemical formula

[0056] Examples of the first olefin include the following compounds.

[0057]

Chemical formula

[0058] Among them, from the viewpoint of efficiently obtaining a fluorinated olefin with a high fluorine content, in formula (1), at least two of A 1 , A 2 and A 3 are preferably fluorine atoms. Further, the first olefin is preferably tetrafluoroethylene.

[0059] <The second olefin> The second olefin used in the method for producing a fluorinated olefin of the present disclosure is not particularly limited as long as it is an olefin different from the first olefin. From the viewpoint of improving the yield, the second olefin is preferably an olefin represented by formula (2).

[0060]

Chemical formula

[0061] However, when one of A 4 and A 5 is a halogen atom, the other represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. When one of A 6 and A 7 is a halogen atom, the other represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

[0062] Examples of the functional group AA having an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom at the linking position with the vinyl carbon include an alkoxy group, an aryloxy group, an acetoxy group, an amino group, an alkylthio group, an arylthio group, a dialkylphosphino group and a diarylphosphino group. Among them, from the viewpoint of improving the yield, the functional group AA is preferably a functional group having an oxygen atom, a nitrogen atom or a sulfur atom at the linking position with the vinyl carbon, and more preferably an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

[0063] From the viewpoint of improving the yield, the second olefin is preferably A 4 ~A 7 in which those other than the functional group AA are hydrogen atoms. Further, from the viewpoint of improving the yield, the second olefin is preferably a monosubstituted olefin or a 1,2-disubstituted olefin, and more preferably a monosubstituted olefin.

[0064] Examples of the second olefin include the following compounds.

Chemical formula

[0065] Hereinafter, the reaction conditions in the method for producing the fluorine-containing olefin of the present disclosure will be described.

[0066] From the viewpoint of improving the yield, the first olefin and the second olefin used in the production method of the present disclosure are preferably degassed or dehydrated in advance. The degassing method is not particularly limited, and examples thereof include ultrasonic degassing, vacuum degassing and freeze degassing. Further, the dehydration method is not particularly limited, and examples thereof include a method of contacting with a dehydrating agent such as a molecular sieve.

[0067] The mixing method of the first olefin, the second olefin and the ruthenium compound serving as a catalyst is not particularly limited. Examples of the mixing method include a method of dissolving the ruthenium compound in a solvent and then sequentially adding the first olefin and the second olefin.

[0068] The usage amounts of the first olefin and the second olefin are not particularly limited. For example, the amount of the second olefin can be 0.1 mol to 100 mol with respect to 1 mol of the first olefin.

[0069] From the viewpoint of improving the yield, the usage amount of the ruthenium compound is preferably 0.001 mol% to 1.0 mol%, and more preferably 0.005 mol% to 0.5 mol% with respect to the amount of substance of the second olefin. The ruthenium compound used in the method for producing the fluorine-containing olefin of the present disclosure has high catalytic activity. Therefore, the reaction can proceed with a very small usage amount as compared with the case where a ruthenium compound having a 5-membered N-heterocyclic carbene ligand is used as a catalyst.

[0070] Examples of the reaction solvent include aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; halogen solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate may be mentioned. The reaction solvent may be one kind or a combination of two or more kinds.

[0071] Among them, from the viewpoint of improving the yield, the reaction solvent is preferably an ether solvent or an ester solvent, and more preferably an ester solvent.

[0072] From the perspective of suppressing side reactions and improving the yield, the concentration of the second olefin in the reaction system is preferably low, and from the perspective of production efficiency and cost, it is preferably high. From both of these perspectives, the concentration of the second olefin in the reaction system is preferably from 0.01 mol / L to 2 mol / L, more preferably from 0.05 mol to 1 mol / L. When the concentration is from 0.01 mol / L to 2 mol / L, it is possible to produce the target product with high productivity and low cost while suppressing the generation of by-products due to excessive progress of the reaction.

[0073] The reaction temperature is not particularly limited, but from the perspective of the reaction rate, it is preferably from 0 °C to 150 °C, more preferably from 20 °C to 100 °C, and even more preferably from 30 °C to 70 °C. Usually, a temperature lower than the boiling point of the reaction solvent is set.

[0074] The reaction time is not particularly limited, but from the perspective of improving the yield, it is preferably from 1 hour to 15 hours, more preferably from 2 hours to 12 hours. Also, depending on the embodiment, the reaction time is preferably from 2 hours to 10 hours.

[0075] The reaction atmosphere is not particularly limited, but an inert gas atmosphere is preferred. Examples of the inert gas include nitrogen and argon. When using an olefin that is a gas under the reaction conditions, such as ethylene and tetrafluoroethylene, the reaction can be carried out in an olefin gas atmosphere.

[0076] The pressure in the reaction system is not particularly limited, but from the perspective of improving the yield, the reaction is preferably carried out under normal pressure or under pressure. In the case of under pressure, the upper limit value of the pressure is, for example, 4 atmospheres (atm).

[0077] In the method for producing a fluorine-containing olefin of the present disclosure, the target fluorine-containing olefin may be isolated by a known method. Examples of the isolation method include distillation, column chromatography, and recycling preparative HPLC, and these can be used alone or in combination as necessary.

[0078] The obtained fluorinated olefin can be identified by a generally known method. Examples of the analysis method include, for example, 1 H-NMR (proton nuclear magnetic resonance), 19 F-NMR (fluorine-19 nuclear magnetic resonance), 13 C-NMR (carbon-13 nuclear magnetic resonance), and GC-MS (gas chromatography-mass spectrometry). These can be used alone or in combination as necessary.

[0079] In the method for producing a fluorinated olefin of the present disclosure, the reaction between the first olefin and the second olefin is excellent in functional group tolerance. That is, even if the first olefin and the second olefin each have a functional group, or a compound having a functional group is added as an additive, the reactivity does not decrease, and the functional group is retained without being converted. Examples of the functional group include an alkyl group, an aromatic group, a carbonyl group, a hydroxyl group, a nitro group, an amino group, and a cyano group. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred. The aromatic group may be an aromatic hydrocarbon group or a heteroaromatic group, but an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. The carbonyl group is preferably a carbonyl group in a ketone, an aldehyde, or an amide. The hydroxyl group is preferably an alcoholic hydroxyl group. The nitro group is preferably a nitro group bonded to an aromatic ring. The amino group is preferably a tertiary amino group. The cyano group is preferably a cyano group bonded to an aliphatic group.

Examples

[0080] Hereinafter, the present disclosure will be described more specifically by way of examples. However, the present disclosure is not limited to the following examples as long as the gist thereof is not exceeded.

[0081] In the metathesis reaction, the reaction conversion rate, yield, and selectivity were all calculated using NMR. Basically, hexafluoroparaxylene was used as the internal standard substance. When the NMR peaks of hexafluoroparaxylene overlapped with those of the raw material or the target product, hexafluorobenzene and cyclohexane were used as the internal standard substances. When a heavy solvent was used as the measurement solvent, the name of the heavy solvent was described, and when the measurement was performed without using a heavy solvent, it was described as NONE. As the NMR apparatus, JNM-ECS400 (resonance frequency: 400 MHz) manufactured by JEOL Ltd. was used. 1 In 1H-NMR, tetramethylsilane was used as the reference value of 0 ppm, 19 In 19F-NMR, C6F6 was used as the reference value of -162 ppm. As the gas chromatography apparatus, Agilent 7890B GC System (manufactured by Agilent Technologies) was used.

[0082] The reaction conversion rate was calculated based on the following formula. Reaction conversion rate (%) = (1 - number of moles of unreacted raw material / number of moles of charged raw material) × 100

[0083] The yield was calculated based on the following formula. Yield (%) = (number of moles of target product / number of moles of charged raw material) × 100

[0084] The selectivity was calculated based on the following formula. Selectivity (%) = (number of moles of target product / number of moles of by-product) × 100

[0085] [Example 1] In the metathesis reaction of tetrafluoroethylene and phenyl vinyl ether, the results obtained using various ruthenium catalysts are shown below.

[0086] [Chemical formula]

[0087] (Example 1C) A solution was prepared by dissolving 0.005 mmol of ruthenium catalyst (Ru-7) in 7.5 mL of 1,2-dichloroethane. Under a nitrogen atmosphere, the prepared solution was placed in a 50 mL stainless steel reaction vessel equipped with a stir bar, a pressure gauge, a gas inlet tube, a raw material addition tube, and an exhaust tube with a back pressure valve. Next, tetrafluoroethylene was added to the reaction vessel from the inlet tube at a flow rate of 6 mL / min under normal pressure, and the inside of the reaction vessel was replaced with tetrafluoroethylene. After heating the reaction vessel to 60 °C, a solution prepared by dissolving 5 mmol of phenyl vinyl ether in 2 mL of 1,2-dichloroethane was added over 5 minutes. After 4 hours, the reaction vessel was cooled to room temperature, and nitrogen gas was passed through the inlet tube at a flow rate of 25 mL / min for 5 minutes to purge tetrafluoroethylene. The reaction vessel was opened, and hexafluorobenzene or hexafluoroparaxylene was added to the reaction solution as an internal standard substance, and then 1 1H-NMR and 19 19F-NMR analysis was performed to quantify the raw materials and products.

[0088] The NMR analysis results of the obtained (2,2-difluorovinyl)phenyl ether are shown below.

[0089] 1 1H-NMR (400 MHz, chloroform-d): δ 7.31 - 7.36 (m, 2H), 7.08 (t, J = 7.3 Hz, 1H), 7.01 - 7.03 (m, 2H), 6.07 (dd, J = 15.1, 3.2 Hz, 1H) 19 19F-NMR (376 MHz, chloroform-d): δ -97.92 (dd, J = 67.9, 18.8 Hz, 1F), -116.28 (d, J = 66.5 Hz, 1F)

[0090] The NMR analysis results of the obtained 1,2-diphenoxyethene are shown below. The mass ratio (E / Z) of the E-isomer and the Z-isomer was 37 / 63. 1 1H-NMR (400 MHz, chloroform-d): E isomer: δ 7.33 (m, 2H), 7.03 - 7.12 (m, 3H), 6.88 (s, 1H) Z isomer: δ 7.33 (m, 2H), 7.03 - 7.12 (m, 3H), 6.16 (s, 1H)

[0091] (Example 1A, Example 1B, Comparative Example 1) Instead of the ruthenium catalyst (Ru - 7) in Example 1C, in Example 1A, the ruthenium catalyst (Ru - 6) was used, in Example 1B the ruthenium catalyst (Ru - 6') was used, and in Comparative Example 1, the ruthenium catalyst (Ru - 5) was used. The metathesis reaction was carried out in the same manner as in Example 1C except for this

[0092] The ruthenium catalysts (Ru - 5), ruthenium catalysts (Ru - 6), ruthenium catalysts (Ru - 6'), and ruthenium catalysts (Ru - 7) are compounds having the following structures. Note that "Mes" means a 2,4,6 - trimethylphenyl group (also referred to as a "mesityl group").

[0093] [Chemical formula]

[0094] The reaction conversion rate (denoted as "conv." in the table) and the yield of the product in each metathesis reaction are shown in Table 1

[0095] [Table 1]

[0096] As shown in Table 1, it was found that in Examples 1A - 1C, the yield of the target product (2,2 - difluorovinyl)phenyl ether was higher compared to Comparative Example 1

[0097] [Example 2] In the metathesis reaction of tetrafluoroethylene and phenyl vinyl ether, the results of conducting the reaction under various conditions with respect to the type of solvent, the amount of solvent, the amount of catalyst, the pressure inside the reaction vessel, the reaction temperature, and the reaction time are shown below.

[0098] [Chemical formula]

[0099] (Example 2A) Example 2A is the same as Example 1C.

[0100] (Examples 2B to 2F) A metathesis reaction was carried out in the same manner as in Example 2A, except that 1,2-dichloroethane used as the solvent in Example 2A was changed to the solvents listed in Table 2.

[0101] (Example 2G) A metathesis reaction was carried out in the same manner as in Example 2F, except that the reaction temperature in Example 2F was changed from 60 °C to 40 °C.

[0102] (Example 2G') A metathesis reaction is carried out in the same manner as in Example 2G, except that the reaction temperature in Example 2G is changed from 40 °C to 30 °C.

[0103] (Example 2G") A metathesis reaction is carried out in the same manner as in Example 2G, except that the reaction temperature in Example 2G is changed from 40 °C to 5 °C.

[0104] In Examples 2G' and 2G", due to the decrease in the reaction temperature, it becomes easier to stop the reaction at a low conversion rate, and as a result, an improvement in selectivity is expected.

[0105] (Example 2H) A metathesis reaction was carried out in the same manner as in Example 2F, except that the back pressure valve was adjusted so that the pressure inside the reaction vessel became 2 atm in Example 2F.

[0106] (Example 2H’) In Example 2H, a metathesis reaction is carried out in the same manner as in Example 2H, except that the back pressure valve is adjusted so that the pressure in the reaction vessel becomes 4 atmospheres. In Example 2H’, an improvement in reaction conversion rate, yield, and selectivity is expected due to the increase in pressure.

[0107] (Example 2I) A solution was prepared by dissolving 0.005 mmol of ruthenium catalyst (Ru-7) in 38 mL of ethyl acetate. Under a nitrogen atmosphere, the prepared solution was placed in a 50 mL stainless steel reaction vessel equipped with a stir bar, a pressure gauge, a gas inlet tube, a raw material addition tube, and an exhaust tube with a back pressure valve. Next, tetrafluoroethylene was added to the reaction vessel from the inlet tube at a flow rate of 6 mL / min to replace the inside of the reaction vessel with tetrafluoroethylene. Then, the back pressure valve was adjusted so that the pressure in the reaction vessel became 2 atmospheres. After heating the reaction vessel to 60 °C, a solution prepared by dissolving 5 mmol of phenyl vinyl ether in 2 mL of ethyl acetate was added over 5 minutes. After 8 hours, the reaction vessel was cooled to room temperature, and nitrogen gas was flowed through the inlet tube at a flow rate of 25 mL / min for 5 minutes to purge tetrafluoroethylene. The reaction vessel was opened, and hexafluorobenzene or hexafluoroparaxylene was added to the reaction solution as an internal standard substance, and then 1 1H-NMR and 19 19F-NMR analysis was performed to quantify the raw materials and products.

[0108] (Example 2J) In Example 2I, a metathesis reaction was carried out in the same manner as in Example 2I, except that the amount of ruthenium catalyst (Ru-7) was changed to 0.0005 mmol and the reaction time was changed to 12 hours.

[0109] (Example 2J’) In Example 2J, a metathesis reaction is carried out in the same manner as in Example 2J, except that the amount of ruthenium catalyst (Ru-7) is changed to 0.05 mmol.

[0110] (Example 2J”) In Example 2J, a metathesis reaction is carried out in the same manner as in Example 2J, except that the amount of the ruthenium catalyst (Ru-7) is changed to 0.00025 mmol.

[0111] In Examples 2J' and 2J", due to the decrease in the amount of the ruthenium catalyst, it becomes easier to stop the reaction at a low conversion rate, and as a result, an improvement in the selectivity is expected.

[0112] The reaction conversion rate (denoted as "conv." in the table), the yield of the product, and the selectivity in each metathesis reaction are shown in Table 2. In Table 2, DCE means 1,2-dichloroethane, THF means tetrahydrofuran, iPr2O means diisopropyl ether, CPME means cyclopentyl methyl ether, and EtOAc means ethyl acetate. The selectivity was calculated based on the number of moles of 1,2-diphenoxyethene, which is a by-product, and the number of moles of (2,2-difluorovinyl)phenyl ether, which is the target product.

[0113] [Table 2]

[0114] As shown in Table 2, it was found that in Examples 2B to 2J, the yield of the target product, (2,2-difluorovinyl)phenyl ether, was as high as in Example 2A (Example 1C). In particular, when an ether-based solvent or an ester-based solvent was used, it was found that the yield and selectivity of the target product, (2,2-difluorovinyl)phenyl ether, were high. Also, when comparing Example 2G and Example 2H, it was found that the higher the pressure of tetrafluoroethylene, the higher the yield and selectivity of the target product, (2,2-difluorovinyl)phenyl ether. Furthermore, when comparing Example 2H and Example 2I, it was found that the lower the concentration of the second olefin, phenyl vinyl ether, the higher the yield and selectivity of the target product, (2,2-difluorovinyl)phenyl ether.

[0115] [Example 3] In the metathesis reaction of tetrafluoroethylene and a monosubstituted olefin, the results of using various monosubstituted olefins are shown below.

[0116]

Chemical formula

[0117] (Example 3A) Example 3A is the same as Example 2I.

[0118] (Examples 3B to 3E) The metathesis reaction was carried out in the same manner as in Example 3A, except that the phenyl vinyl ether used in Example 3A was changed to the monosubstituted olefins described in Table 3, and the amount of solvent, the amount of catalyst, and the reaction time were changed to the conditions in Table 3. In Example 3E, 2.5 mmol of the monosubstituted olefin was used.

[0119] The reaction conversion rate (denoted as "conv." in the table), the yield of the product (Compound 31), and the selectivity in each metathesis reaction are shown in Table 3. In Table 3, Ph means a phenyl group. The selectivity was calculated based on the number of moles of Compound 31, which is the target product, and the number of moles of Compound 32, which is the by-product.

[0120] The NMR analysis results of (2,2-difluorovinyl)dodecyl ether obtained in Example 3B are shown below.

[0121] 1 H-NMR (400 MHz, chloroform-d): δ 5.62 (dd, J = 16.7, 2.5 Hz, 1H), 3.68 (t, J = 6.6 Hz, 2H), 1.59 - 1.66 (m, 2H), 1.26 - 1.41 (m, 19H), 0.88 (t, J = 6.9 Hz, 3H) 19 F-NMR (376 MHz, chloroform-d): δ -101.28 (dd, J = 80.9, 17.3 Hz, 1F), -121.53 (d, J = 80.9 Hz, 1F).

[0122] The NMR analysis results of (2,2-difluorovinyl)phenyl sulfide obtained in Example 3C are shown below.

[0123] 1 1H-NMR (400 MHz, chloroform-d): δ 7.29 - 7.31 (m, 4H), 7.19 - 7.24 (m, 1H), 5.15 (d, J = 21.0 Hz, 1H) 19 19F-NMR (376 MHz, chloroform-d): δ -76.55 (d, J = 19.0 Hz, 1F), -79.48 (dd, J = 20.8, 19.0 Hz, 1F)

[0124] The NMR analysis results of (2,2-difluorovinyl)carbazole obtained in Example 3D are shown below. 19 19F-NMR (376 MHz, NONE): δ -103.37 (dd, J = 83.8, 14.4 Hz, 1F), -124.10 (d, J = 86.7 Hz, 1F)

[0125] The NMR analysis results of (2,2-difluorovinyl)tridecafluoroheptyl ether obtained in Example 3E are shown below. 19 19F-NMR (376 MHz, chloroform-d): δ -80.64 (s, 3F), -96.70 (dd, J = 72.2 Hz, 14.4 Hz, 1F), -117.59 (d, J = 75.1 Hz, 1F), -120.02 (s, 2F), -122.11 (s, 2F), -122.74 (s, 2F), -123.32 (s, 2F), -126.04 (s, 2F)

[0126] [Table 3]

[0127] As shown in Table 3, it was found that the metathesis reaction proceeded in any of the monosubstituted olefins shown in Examples 3A to 3E.

[0128] [Example 4] In the metathesis reaction of tetrafluoroethylene and 1,2-disubstituted olefins, the results of using various 1,2-disubstituted olefins are shown below.

[0129] [Chemical formula]

[0130] (Examples 4A to 4B) The metathesis reaction was carried out in the same manner as in Example 2F, except that the phenyl vinyl ether used in Example 2F was changed to the 1,2-disubstituted olefin described in Table 4, and the reaction time was changed to the time described in Table 4.

[0131] The reaction conversion rate (denoted as "conv." in the table) and the yield of the product (compound 42) in each metathesis reaction are shown in Table 4. In Table 4, Ph means a phenyl group, and n-Hep means an n-heptyl group.

[0132] [Table 4]

[0133] As shown in Table 4, it was found that the metathesis reaction proceeded in any of the 1,2-disubstituted olefins shown in Examples 4A and 4B.

[0134] [Example 5] The results of the metathesis reaction of tetrafluoroethylene and cyclic olefins are shown below.

[0135] [Chemical formula]

[0136] (Example 5A) The phenyl vinyl ether used in Example 2F was changed to 2,3 - dihydrofuran, and the metathesis reaction was carried out in the same manner as in Example 2F except that the amount of ruthenium catalyst (Ru - 7) used was changed to 0.5 mol% and the reaction time was changed to 5 hours.

[0137] 19 By performing 19F - NMR analysis, it was confirmed that Compound 51 was obtained. 19 19F - NMR (376 MHz, NONE): δ - 87.70 (d, J = 49.1 Hz, 1F), - 90.44 (dd, J = 46.2, 23.1 Hz, 1F), - 101.58 (dd, J = 86.7, 17.3 Hz, 1F), - 121.93 (d, J = 86.7 Hz, 1F)

[0138] [Example 6] In the metathesis reaction of tetrafluoroethylene and phenyl vinyl ether, a functional group tolerance test was carried out.

[0139] After filling a screw - cap NMR tube with 1 atm of tetrafluoroethylene, a ruthenium catalyst (Ru - 7) was added. A solution prepared by dissolving 220 μmol of phenyl vinyl ether and 1,4 - bis(trifluoromethyl)benzene as an internal standard substance in 0.6 mL of toluene was added. Then, the additives listed in Table 5 were added in an amount equivalent to 1 equivalent to phenyl vinyl ether, and the NMR tube was heated at 60 °C for 2 hours. After 2 hours, it was cooled to room temperature. In Example 5A, 1 1H - NMR and 19 By performing 19F - NMR analysis, the raw materials and products were quantified. In Examples 5B - 5H, the raw materials and products were quantified by using gas chromatography.

[0140] Table 5 shows the reaction conversion rate (denoted as "conv." in the table), the yield of the product, and the remaining amount of the additive in each metathesis reaction. In Table 5, MeCN means acetonitrile and EtOH means ethanol. The remaining amount of the additive was calculated based on the following formula. Remaining amount of additive (%) = (amount of additive after reaction / amount of additive charged) × 100 In Examples 5B to 5H, the amount (number of moles) of the additive after the reaction was calculated using a gas chromatography device.

[0141]

Chemical formula

[0142]

Table 5

[0143] As shown in Examples 5B to 5H, it was found that the metathesis reaction proceeds even when a compound having a functional group is added as an additive.

[0144] The disclosures of Japanese Patent Application No. 2020-034736 filed on March 2, 2020, and Japanese Patent Application No. 2020-132483 filed on August 4, 2020, are hereby incorporated by reference in their entirety. Further, all documents, patent applications, and technical standards described in this specification are incorporated by reference in this specification to the same extent as if each individual document, patent application, and technical standard was specifically and individually stated to be incorporated by reference.

Claims

1. A production method for producing a fluorine-containing olefin by reacting a first olefin represented by the following formula (1) with a second olefin different from the first olefin in the presence of a ruthenium compound represented by the following formula (X). 【Chemical 1】 In formula (X), A represents an atomic group necessary to form a 6- or 7-membered nitrogen-containing heterocyclic ring containing two nitrogen atoms. An aromatic ring or an aliphatic ring may be condensed with the nitrogen-containing heterocyclic ring. A and the aromatic ring or aliphatic ring condensed with the nitrogen-containing heterocyclic ring may have substituents. R １ and R ２ each independently represents an alkyl group, an aryl group or an aralkyl group, Y １ and Y ２ each independently represents an anionic ligand, L １ represents a neutral electron-donating ligand, p represents 0 or 1. Z １ and Z ２ each independently represents a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and Z １ and Z ２ may be bonded to each other to form a ring. Z １ and Z ２ either or both of them and L １ may be chemically bonded. 【Chemical 2】 In formula (1), A １ , A ２ and A ３ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a fluorine-containing alkyl group having 1 to 10 carbon atoms.

2. The production method according to claim 1, wherein the second olefin is represented by the following formula (2). [Chemical Formula 3] In formula (2), A ４ ~A ７ At least one of them represents a functional group AA having an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom at the bonding position with a vinyl carbon, and A ４ ~A ７ Other than the functional group AA among them each independently represents a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and A ４ and A ５ , A ４ and A ６ , A ５ and A ７ , and A ６ and A ７ may be bonded to each other to form a ring. However, A ４ and A ５ when one of them is a halogen atom, the other represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and A ６ and A ７ when one of them is a halogen atom, the other represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

3. The production method according to claim 2, wherein in the formula (2), the functional group AA is an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

4. In the formula (1), A １ , A ２ and A ３ The production method according to any one of claims 1 to 3, wherein at least two of are fluorine atoms.

5. The production method according to any one of claims 1 to 4, wherein the second olefin is a monosubstituted olefin or a 1,2-disubstituted olefin.

6. The production method according to any one of claims 1 to 5, wherein the usage amount of the ruthenium compound is 0.001 mol% to 1.0 mol% with respect to the amount of substance of the second olefin.

7. In the formula (X), R １ and R ２ are each independently a 2,4,6-trimethylphenyl group, 2,6-diisopropylphenyl group, o-tolyl group, 3,5-di-tert-butylphenyl group, 2,6-dimethyl-4-methoxyphenyl group or 2,6-difluorophenyl group, and the production method according to any one of claims 1 to 6.

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