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  • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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  • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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  • C07C41/01—Preparation of ethers
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  • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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  • C07D—HETEROCYCLIC COMPOUNDS
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  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
  • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
  • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
  • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
  • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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  • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
  • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
  • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/821—Ruthenium
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  • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
  • B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen

Definitions

• the present disclosure relates to a method for producing a fluorine-containing olefin.
• a compound in which a part or all of hydrogen atoms in an olefin is replaced with a fluorine atom, that is, a fluorine-containing olefin is known as an industrially useful compound.
• 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 a method for producing a fluorine-containing olefin capable of obtaining a fluorine-containing olefin in a high yield. To provide.
• 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).
• Manufacturing method to manufacture A represents a group of atoms required to form a 6- or 7-membered nitrogen-containing heterocycle containing two nitrogen atoms, even if an aromatic ring or an aliphatic ring is condensed on the nitrogen-containing heterocycle. Often, A and the aromatic or aliphatic rings fused to the nitrogen-containing heterocycle may have substituents.
• R 1 and R 2 independently represent an alkyl group, an aryl group or an aralkyl group, respectively.
• Y 1 and Y 2 independently represent anionic ligands, respectively.
• L 1 represents a neutral electron donating ligand.
• p represents 0 or 1 and represents Z 1 and Z 2 are independently composed of a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.
• a 1 , A 2 and A 3 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a fluorine-containing alkyl group having 1 to 10 carbon atoms.
• the second olefin is the production method according to ⁇ 1> represented by the following formula (2).
• At least one of A 4 ⁇ A 7 is an oxygen atom to the connecting position with the vinyl carbon, nitrogen atom, a functional group AA having a sulfur atom or a phosphorus atom
• one of A 4 and A 5 is a halogen atom
• the other is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus atom, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms containing 1 or more than atoms selected the group consisting of a silicon atom
• the other is a hydrogen atom, a carbon number 1
• ⁇ 3> The production method according to ⁇ 2>, wherein the functional group AA is an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms in the formula (2).
• ⁇ 4> The production method according to any one of ⁇ 1> to ⁇ 3>, wherein at least two of A 1 , A 2 and A 3 are fluorine atoms in the formula (1).
• ⁇ 5> The production method according to any one of ⁇ 1> to ⁇ 4>, wherein the second olefin is a mono-substituted olefin or a 1,2-di-substituted olefin.
• R 1 and R 2 are independently 2,4,6-trimethylphenyl group, 2,6-diisopropylphenyl group, o-tolyl group, and 3,5-di-tert-.
• a method for producing a fluorine-containing olefin capable of obtaining a fluorine-containing olefin in a high yield.
• the numerical range indicated by using "-" in the present specification means a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
• 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 another numerical range described stepwise.
• 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.
• the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means. In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment. In the present specification, the term "process" is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in the case where it cannot be clearly distinguished from other processes. Is done.
• a first olefin represented by the following formula (1) and a second olefin different from the first olefin are used in the presence of a ruthenium compound represented by the following formula (X).
• a ruthenium compound represented by the following formula (X) This is a production method for producing a fluorine-containing olefin by reacting.
• A represents a group of atoms required to form a 6- or 7-membered nitrogen-containing heterocycle containing two nitrogen atoms.
• An aromatic ring or an aliphatic ring may be condensed on the nitrogen-containing heterocycle, and A and the aromatic ring or the aliphatic ring condensed on the nitrogen-containing heterocycle may have a substituent.
• R 1 and R 2 independently represent an alkyl group, an aryl group or an aralkyl group, respectively.
• 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 are independently composed of a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. It represents a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group, and Z 1 and Z 2 may be bonded to each other to form a ring. Either or both of Z 1 and Z 2 and L 1 may be chemically bonded.
• a 1 , A 2 and A 3 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a fluorine-containing alkyl group having 1 to 10 carbon atoms.
• the metathesis reaction between the first olefin represented by the formula (1) and the second olefin proceeds by using the ruthenium compound represented by the formula (X) as a catalyst.
• the yield was dramatically improved as compared with the conventional case. The reason for the improvement in yield is not clear, but it is considered that the nitrogen-containing heterocycle bonded to ruthenium in the formula (X) is a 6-membered ring or a 7-membered ring.
• a complex having a 6-membered ring or a 7-membered ring N-heterocyclic carbene ligand has a higher electron donating ability than a complex having a 5-membered ring N-heterocyclic carbene ligand. Therefore, it is considered that the electron density on the ruthenium atom has increased and the electron state has become optimal for the metathesis reaction of the fluorine-containing olefin.
• the ruthenium compound used in the method for producing a fluorine-containing olefin of the present disclosure is represented by the following formula (X).
• the ruthenium compound represented by the formula (X) functions as a catalyst.
• A represents a group of atoms required 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 required to form a 6- or 7-membered nitrogen-containing heterocycle containing two nitrogen atoms.
• the carbon atom group may be saturated or unsaturated, but is preferably saturated. .. Further, the carbon atom constituting the carbon atom group may be a carbonyl carbon.
• A is preferably an alkylene group, more preferably a trimethylene group or a tetramethylene group.
• A may have a substituent.
• substituents 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 and a carboxy group. And a hydroxy group and the like.
• substituents may further have the above-mentioned substituents.
• the alkyl group may be cyclic or chain-like.
• the chain alkyl group may be a linear alkyl group or a branched chain alkyl group.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms.
• 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.
• the alkenyl group may be cyclic or chain.
• the chain alkenyl group may be a linear alkenyl group or a branched chain alkenyl group.
• the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms.
• 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.
• the alkynyl group may be cyclic or chain-like.
• the chain alkynyl group may be a linear alkynyl group or a branched chain alkynyl group.
• the alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms. Examples of the alkynyl group include an ethynyl group and a 2-propynyl group.
• 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 and a 2,6-dimethyl-.
• Examples include 4-methoxyphenyl group and 2,6-difluorophenyl group.
• 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 that of the above aryl group.
• Examples of the aralkyl group include a benzyl group and a phenethyl group.
• the heterocycle of the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
• the heterocycle may be a monocyclic ring or a condensed ring.
• Heterocycles include pyridine ring, piperidine ring, furan ring group, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenoxazine ring, and indole ring. Examples thereof include a ring, a thiazole ring, a pyrazine ring, a thiaziazine ring, a benzoquinoline ring and a thiazizole ring.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the alkyl moiety 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.
• 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.
• An aromatic ring or an aliphatic ring may be condensed on the nitrogen-containing heterocycle, and the aromatic ring or the aliphatic ring condensed on the nitrogen-containing heterocycle may have a substituent.
• substituent contained in the aromatic ring or the aliphatic ring include the same substituents contained in the above-mentioned A.
• Examples of the aromatic ring that may be condensed with the nitrogen-containing heterocycle include a benzene ring and a naphthalene ring.
• Examples of the aliphatic ring that may be condensed with the nitrogen-containing heterocycle include a cyclopentane ring and a cyclohexane ring.
• R 1 and R 2 independently represent an alkyl group, an aryl group or an aralkyl group, respectively.
• the alkyl group, aryl group and aralkyl group may each have a substituent. Examples of the substituent include those similar to the substituent contained in A.
• the alkyl group may be cyclic or chain-like.
• the chain alkyl group may be a linear alkyl group or a branched chain alkyl group.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms.
• 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.
• 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 and a 2,6-dimethyl-.
• Examples include 4-methoxyphenyl group and 2,6-difluorophenyl group.
• 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 that of the above aryl group.
• Examples of the aralkyl group include a benzyl group and a phenethyl group.
• R 1 and R 2 are preferably sterically bulky groups, more preferably branched chain alkyl groups, cyclic alkyl groups, aryl groups or aralkyl groups, and cyclic groups. It is more preferably an alkyl group, an aryl group or an aralkyl group, and particularly preferably an aryl group.
• the branched chain alkyl group is preferably a tert-butyl group.
• the cyclic alkyl group is preferably a cycloalkyl group.
• Aryl groups are 2,4,6-trimethylphenyl group, 2,6-diisopropylphenyl group, o-tolyl group, 3,5-di-tert-butylphenyl group, 2,6-dimethyl-4-methoxyphenyl group. Alternatively, it is preferably a 2,6-difluorophenyl group.
• the aralkyl group is preferably a benzyl group.
• Y 1 and Y 2 each independently represent an anionic ligand.
• An anionic ligand is a ligand that has a negative charge when separated from the ruthenium atom.
• Examples of Y 1 and Y 2 include halogen atoms. Above all, it is more preferable that Y 1 and Y 2 are chlorine atoms.
• L 1 represents a neutral electron donating ligand.
• the electron donating ligand is a ligand having an effect of increasing the electron density of the ruthenium atom.
• electron-donating ligands include nitrogen-based ligands, phosphorus-based ligands, and oxygen-based ligands.
• nitrogen-based ligand examples include a bipyridine-based ligand, a biquinolin-based ligand, a phenanthroline-based ligand, a pyridine-based ligand, a quinoline-based ligand, a benzoquinolin-based ligand, and an acrydin-based ligand. Examples thereof include a position, a tertiary aliphatic amine-based ligand and a tertiary aromatic amine-based ligand.
• Examples of the phosphoric acid-based ligand include a phosphine-based ligand.
• oxygen-based ligand examples include an ether-based ligand.
• Z 1 and Z 2 are independently hydrogen atom, halogen atom, monovalent hydrocarbon group having 1 to 20 carbon atoms, or halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom.
• a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of silicon atoms, and Z 1 and Z 2 may be bonded to each other to form a ring. Either or both of Z 1 and Z 2 and L 1 may be chemically bonded.
• 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.
• a substituent containing the above atom As 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, a substituent containing the above atom is used. Examples thereof include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms having a substituent containing the above atom, 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 atom 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 and a sulfo group.
• Examples include groups, phosphate groups and silyl groups.
• Examples of the combination of Z 1 , Z 2 and L 1 include the following. Ligands other than Z 1 , Z 2 and L 1 are omitted as [L].
• the ruthenium compound used in the method for producing a fluorine-containing olefin of the present disclosure is preferably a compound represented by the following formula (X1) from the viewpoint of easy availability.
• R 3 represents a hydrogen atom or a substituent, and the carbon atom constituting the nitrogen-containing heterocycle having two nitrogen atoms may be a carbonyl carbon.
• R 3 examples include the same substituents as those of A.
• Examples of the ruthenium compound represented by the formula (X) include the following compounds.
• Mes means 2,4,6-trimethylphenyl group
• o-tol means o-tolyl group
• dipp means 2,6-diisopropylphenyl group
• Cy means 2,6-diisopropylphenyl group
• Cy means a cyclohexyl group.
• the first olefin used in the method for producing a fluorine-containing olefin of the present disclosure is an olefin represented by the formula (1).
• a 1 , A 2 and A 3 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a fluorine-containing alkyl group having 1 to 10 carbon atoms.
• Examples of the first olefin include the following compounds.
• the first olefin is preferably tetrafluoroethylene.
• the second olefin used in the method for producing a fluorine-containing olefin of the present disclosure is not particularly limited as long as it is an olefin different from the first olefin.
• the second olefin is preferably an olefin represented by the formula (2) from the viewpoint of improving the yield.
• At least one of A 4 ⁇ A 7 represents a functional group AA having a coupling position to an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom with vinyl carbon.
• the functional group AA of A 4 ⁇ A 7 are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus
• a 4 and A 5 when one of A 4 and A 5 is a halogen atom, the other is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus atom, and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms containing 1 or more than atoms selected the group consisting of a silicon atom, when one of a 6 and a 7 is a halogen atom, the other is a hydrogen atom, a carbon number 1 A monovalent hydrocarbon having 1 to 20 carbon atoms or having 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. Represents an atom.
• the functional group AA having an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom at the connection position with the vinyl carbon include an alkoxy group, an aryloxy group, an acetoxy group, an amino group, an alkylthio group, an arylthio group and a dialkylphosphino. Examples include groups and diallylphosphino groups.
• the functional group AA is preferably a functional group having an oxygen atom, a nitrogen atom or a sulfur atom at the connection position with the vinyl carbon, and is an alkoxy group having 1 to 20 carbon atoms or a carbon number of carbon atoms. More preferably, it is 6 to 20 aryloxy groups.
• the second olefin from the viewpoint of improving the yield, than the functional group AA of A 4 ⁇ A 7 is preferably a hydrogen atom.
• the second olefin is preferably a mono-substituted olefin or a 1,2-di-substituted olefin, and more preferably a mono-substituted olefin, from the viewpoint of improving the yield.
• Examples of the second olefin include the following compounds.
• the first olefin and the second olefin used in the production method of the present disclosure are preferably degassed or dehydrated in advance from the viewpoint of improving the yield.
• the degassing method is not particularly limited, and examples thereof include ultrasonic degassing, vacuum decompression degassing, and freeze degassing.
• the dehydration method is not particularly limited, and examples thereof include a method of contacting with a dehydrating agent such as a molecular sieve.
• 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 in which the ruthenium compound is dissolved in a solvent, and then the first olefin and the second olefin are sequentially added.
• the amount of the first olefin and the second olefin used is not particularly limited, but 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.
• the amount of the ruthenium compound used is preferably 0.001 mol% to 1.0 mol%, preferably 0.005 mol% to 0.5 mol%, based on the amount of the substance of the second olefin. Is more preferable.
• the ruthenium compound used in the method for producing a fluorine-containing olefin of the present disclosure has high catalytic activity. Therefore, the reaction can proceed with a very small amount of use as compared with the case where a ruthenium compound having a 5-membered ring N-heterocyclic carbene ligand is used as a catalyst.
• reaction solvent examples 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, o-dichlorobenzene; Ether-based solvents such as tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; Examples thereof include ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate.
• the reaction solvent may be one kind or a combination of two or more kinds.
• the reaction solvent is preferably an ether solvent or an ester solvent, and more preferably an ester solvent from the viewpoint of improving the yield.
• the concentration of the second olefin in the reaction system is preferably low from the viewpoint of suppressing side reactions and improving the yield, and preferably high from the viewpoint of production efficiency and cost. From both viewpoints, the concentration of the second olefin in the reaction system is preferably 0.01 mol / L to 2 mol / L, more preferably 0.05 mol to 1 mol / L. When the concentration is 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 the excessive progress of the reaction. be.
• the reaction temperature is not particularly limited, but from the viewpoint of the reaction rate, it is preferably 0 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C., and even more preferably 30 ° C. to 70 ° C. Usually, a temperature lower than the boiling point of the reaction solvent is set.
• the reaction time is not particularly limited, but from the viewpoint of improving the yield, 1 hour to 15 hours is preferable, and 2 hours to 12 hours is more preferable. Further, depending on the embodiment, the reaction time is preferably 2 hours to 10 hours.
• the reaction atmosphere is not particularly limited, but an inert gas atmosphere is preferable.
• the inert gas include nitrogen and argon.
• an olefin that is a gas under reaction conditions such as ethylene and tetrafluoroethylene, it can be carried out in the gas atmosphere of the olefin.
• the pressure in the reaction system is not particularly limited, but from the viewpoint of improving the yield, the reaction is preferably carried out under normal pressure or pressure. Under pressure, the upper limit of pressure is, for example, 4 atmospheres (atm).
• the target fluorine-containing olefin may be isolated by a known method.
• the isolation method include distillation, column chromatography, and recycled preparative HPLC, and these can be used alone or in combination as required.
• the obtained fluorine-containing olefin can be identified by a commonly known method.
• analysis methods include 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 chromatograph mass analysis). ), And these can be used alone or in combination as needed.
• 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 if a compound having a functional group is added as an additive, the reactivity is not lowered and the functional group is not converted. Is held in.
• 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 chain alkyl group, or a cyclic alkyl group, but is preferably a linear alkyl group.
• the aromatic group may be an aromatic hydrocarbon group or a heteroaromatic group, but is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
• the carbonyl group is preferably a carbonyl group in ketones, aldehydes and amides.
• 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.
• Hexafluoroparaxylene was basically used as an internal standard substance. When the NMR peak of hexafluoroparaxylene overlaps with the raw material or the target product, hexafluorobenzene and cyclohexane were used as internal standard substances. When a deuterated solvent was used as the measurement solvent, the name of the deuterated solvent was described, and when the measurement was performed without using the deuterated solvent, it was described as NONE.
• JNM-ECS400 resonance frequency: 400 MHz
• reaction conversion rate (1-number of moles of unreacted raw material / number of moles of charged raw material) x 100
• Yield (%) (number of moles of target product / number of moles of raw material to be charged) x 100
• Example 1 The results of the metathesis reaction between tetrafluoroethylene and phenyl vinyl ether using various ruthenium catalysts are shown below.
• Example 1C A solution was prepared in which 0.005 mmol of ruthenium catalyst (Ru-7) was dissolved in 7.5 mL of 1,2-dichloroethane.
• the prepared solution was placed in a stainless steel reaction vessel having a volume of 50 mL equipped with a stirrer, a pressure gauge, a gas insertion tube, a raw material addition tube, and an exhaust tube with a back pressure valve under a nitrogen atmosphere.
• tetrafluoroethylene was added to the reaction vessel from the insertion tube at a flow rate of 6 mL / min under normal pressure, and the inside of the reaction vessel was replaced with tetrafluoroethylene.
• reaction vessel 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 flowed from the insertion tube at a flow rate of 25 mL / min for 5 minutes to purge tetrafluoroethylene. The reaction vessel was opened, hexafluorobenzene or hexafluoroparaxylene as an internal standard substance was added to the reaction solution, and then 1 H-NMR and 19 F-NMR analysis were performed to quantify the raw materials and products.
• Example 1A Example 1A, Example 1B, Comparative Example 1
• a ruthenium catalyst (Ru-6) was used in Example 1A
• a ruthenium catalyst (Ru-6') was used in Example 1B
• Comparative Example 1 a ruthenium catalyst (Ru-6') was used.
• the metathesis reaction was carried out in the same manner as in Example 1C except that a ruthenium catalyst (Ru-5) was used.
• the ruthenium catalyst (Ru-5), the ruthenium catalyst (Ru-6), the ruthenium catalyst (Ru-6') and the ruthenium catalyst (Ru-7) are compounds having the following structures.
• “Mes” means 2,4,6-trimethylphenyl group (also referred to as “mesitylene group”).
• Table 1 shows the reaction conversion rate (indicated as “conv.” In the table) and the yield of the product in each metathesis reaction.
• Example 2 The results of the metathesis reaction between tetrafluoroethylene and phenyl vinyl ether under various conditions of the type of solvent, the amount of the solvent, the amount of catalyst, the pressure in the reaction vessel, the reaction temperature and the reaction time are shown below.
• Example 2A is the same as Example 1C.
• Example 2B to Example 2F The metathesis reaction was carried out in the same manner as in Example 2A, except that 1,2-dichloroethane used as a solvent in Example 2A was changed to the solvent shown in Table 2.
• Example 2G The 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.
• Example 2G' The 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.
• Example 2G The 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.
• Example 2G' and Example 2G' it is easy to stop the reaction at a low conversion rate due to the decrease in the reaction temperature, and as a result, the selectivity is expected to be improved.
• Example 2F In Example 2F, the 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 in the reaction vessel became 2 atm.
• Example 2H' In Example 2H, the 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 atm. In Example 2H', an increase in pressure is expected to improve the reaction conversion rate, yield, and selectivity.
• Example 2I A solution was prepared in which 0.005 mmol of ruthenium catalyst (Ru-7) was dissolved in 38 mL of ethyl acetate.
• the prepared solution was placed in a stainless steel reaction vessel having a volume of 50 mL equipped with a stirrer, a pressure gauge, a gas insertion tube, a raw material addition tube, and an exhaust tube with a back pressure valve under a nitrogen atmosphere.
• tetrafluoroethylene was added to the reaction vessel from the insertion tube at a flow rate of 6 mL / min, and the inside of the reaction vessel was replaced with tetrafluoroethylene.
• the back pressure valve was adjusted so that the pressure in the reaction vessel became 2 atm.
• reaction vessel After heating the reaction vessel to 60 ° C., a solution of 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 from the insertion tube at a flow rate of 25 mL / min for 5 minutes to purge tetrafluoroethylene. The reaction vessel was opened, hexafluorobenzene or hexafluoroparaxylene as an internal standard substance was added to the reaction solution, and then 1 H-NMR and 19 F-NMR analysis were performed to quantify the raw materials and products.
• Example 2J In Example 2I, the 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.
• Ru-7 ruthenium catalyst
• Example 2J' In Example 2J, the 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 0.05 mmol.
• Example 2J In Example 2J, the 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.
• Example 2J'and Example 2J' the decrease in the amount of the ruthenium catalyst makes it easy to stop the reaction at a low conversion rate, and as a result, the selectivity is expected to be improved.
• Table 2 shows the reaction conversion rate (denoted as “conv.” In the table), the yield of the product, and the selectivity in each metathesis reaction.
• DCE means 1,2-dichloroethane
• THF means tetrahydrofuran
• iPr 2 O means diisopropyl ether
• CPME means cyclopentyl methyl ether
• EtOAc means ethyl acetate.
• the selectivity was calculated based on the number of moles of the by-product 1,2-diphenoxyetene and the number of moles of the target product (2,2-difluorovinyl) phenyl ether.
• Example 2B to 2J 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, it was found that the yield and selectivity of the target product (2,2-difluorovinyl) phenyl ether were high when an ether solvent or an ester solvent was used. Further, when Example 2G and Example 2H were compared, 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. ..
• Example 2H and Example 2I are compared, the lower the concentration of the second olefin phenylvinyl ether, the higher the yield and selectivity of the target product (2,2-difluorovinyl) phenyl ether. It turned out.
• Example 3 The results of using various mono-substituted olefins in the metathesis reaction between tetrafluoroethylene and mono-substituted olefins are shown below.
• Example 3A is the same as Example 2I.
• Example 3B to Example 3E The same method as in Example 3A except that the phenylvinyl ether used in Example 3A was changed to the monosubstituted olefin shown in Table 3 and the amount of solvent, the amount of catalyst and the reaction time were changed to the conditions shown in Table 3. A metathesis reaction was performed. In Example 3E, 2.5 mmol of monosubstituted olefin was used.
• Table 3 shows the reaction conversion rate (indicated as “conv.” In the table), the yield of the product (Compound 31), and the selectivity in each metathesis reaction.
• 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 a by-product.
• Example 4 The results of using various 1,2-disubstituted olefins in the metathesis reaction between tetrafluoroethylene and 1,2-disubstituted olefins are shown below.
• Example 4A-4B Metathesis 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 olefins shown in Table 4 and the reaction time was changed to the time shown in Table 4. The reaction was carried out.
• Table 4 shows the reaction conversion rate (indicated as “conv.” In the table) and the yield of the product (Compound 42) in each metathesis reaction.
• Ph means a phenyl group
• n-Hep means an n-heptyl group.
• Example 5 The results of the metathesis reaction between tetrafluoroethylene and cyclic olefin are shown below.
• Example 5A Example 2F except that the phenyl vinyl ether used in Example 2F was changed to 2,3-dihydrofuran, the amount of ruthenium catalyst (Ru-7) used was changed to 0.5 mol%, and the reaction time was changed to 5 hours.
• the metathesis reaction was carried out in the same manner as in the above.
• Example 6 A functional group tolerance test was performed in the metathesis reaction between tetrafluoroethylene and phenyl vinyl ether.
• a ruthenium catalyst (Ru-7) was added. After adding a solution of 220 ⁇ mol of phenylvinyl ether and 1,4-bis (trifluoromethyl) benzene as an internal standard in 0.6 mL of toluene, the additives shown in Table 5 were added to phenylvinyl ether. It was added in an amount of 1 equivalent, and the NMR tube was heated at 60 ° C. for 2 hours. After 2 hours, it was cooled to room temperature.
• Example 5A the raw materials and products were quantified by performing 1 H-NMR and 19 F-NMR analysis.
• Examples 5B-5H the raw materials and products were quantified by using gas chromatography.
• Table 5 shows the reaction conversion rate (indicated as "conv.” In the table), the yield of the product, and the remaining amount of the additive in each metathesis reaction.
• 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 to be charged) x 100
• the amount (number of moles) of the additive after completion of the reaction was calculated using a gas chromatography apparatus.

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