JP2016145174A - Method for producing fluorine-containing diene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily and efficiently produce fluorine-containing diene under mild conditions by ene-yne metathesis reaction between fluorine-containing olefin and acetylene.SOLUTION: Provided is a method for producing fluorine-containing diene as shown in formula by reacting a substituted acetylene compound and a fluorine-containing olefin compound in the presence of a metal-carbene complex compound having olefin metathesis reaction activity.SELECTED DRAWING: None

Description

  The present invention relates to a novel method for producing a fluorinated diene by an ene-in metathesis reaction.

  In the diene which is an olefin having two double bonds, industrially useful compounds are known as compounds in which some or all of the hydrogen atoms are substituted with fluorine atoms, that is, fluorine-containing dienes. A method for producing a compound simply and efficiently has not been established.

  On the other hand, an olefin metathesis reaction (hereinafter sometimes simply referred to as “olefin metathesis”), which is a double bond recombination reaction using a metal catalyst, is widely used as a method for producing olefins having various substituents. In addition, an ene-in metathesis reaction, which is one of olefin metathesis reactions, is known as an effective method for synthesizing conjugated dienes. However, since an electron-deficient olefin having an electron-withdrawing substituent has low reactivity, it is not easy to use it for olefin metathesis. For example, Non-Patent Document 1 examines the reactivity of olefins having various substituents, and describes that the reactivity of electron-deficient olefins is low. In fact, since olefins having halogen atoms such as fluorine atoms and chlorine atoms are also electron-deficient olefins, there are few reports used for olefin metathesis.

Chatterjee, A.M. K. et al. , Journal of American Chemical Society, 2003, 125, 11360-11370. Macnaughtan, M .; L. et al. , Journal of American Chemical Society, 2007, 129, 7708-7709.

  Thus, it is not practical to use an olefin having a halogen atom for olefin metathesis. Non-Patent Document 2 discloses a method for producing a diene in which a chlorine atom is introduced by an ene-in metathesis reaction using trimethylsilylacetylene and vinyl chloride as raw materials, but an olefin containing a fluorine atom (fluorinated olefin) is used. There have been no reports on the production of fluorine-containing dienes by an enyne metathesis reaction.

  Therefore, an object of the present invention is to provide a method for easily and efficiently producing a fluorinated diene under mild conditions by an ene-in metathesis reaction between a fluorinated olefin and acetylene. Furthermore, using a molecule that has both a carbon-carbon double bond (olefin unit) and a carbon-carbon triple bond (acetylene unit) in the molecule, a ring-closing reaction and an enyne metathesis reaction are performed in the molecule to produce a fluorinated diene. It is an object of the present invention to provide a method for performing the above.

  As a result of earnest study, the present inventors have found that a fluorine-containing olefin and acetylene give a fluorine-containing diene under mild conditions in the presence of a metal catalyst having a metal-carbon double bond. It came to complete.

That is, the present invention relates to the following <1> to <5>.
<1> In the presence of a metal-carbene complex compound (10) having olefin metathesis reaction activity, a compound represented by the following formula (21) and a compound represented by the following formula (31) or represented by the following formula (32) The compound represented by the following formula (51), the compound represented by the following formula (52), the compound represented by the following formula (53), and the following formula (54) A compound represented by the following formula (55), a compound represented by the following formula (56), a compound represented by the following formula (57), and a compound represented by the following formula (58) A method for producing at least one compound selected from the group consisting of:

However, the symbol in a formula represents the following meaning.
A ¹¹ and A ¹² are each independently a functional group selected from the group consisting of the following functional group (i), functional group (ii), functional group (iii), and functional group (iv). A ¹¹ and A ¹² may be bonded to each other to form a ring.
Functional group (i): hydrogen atom.
Functional group (ii): a halogen atom.
Functional group (iii): a monovalent hydrocarbon group having 1 to 20 carbon atoms.
Functional group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom.
R ¹¹ and R ¹² are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a (per) fluoroalkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 5 to 20 carbon atoms. And a functional group selected from the group consisting of (per) halogenated aryl groups having 5 to 20 carbon atoms.
R _F ′ is a group consisting of a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and a (per) fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. The functional group chosen.
X ^{11 to} X ¹³ are each independently a functional group selected from the group consisting of a hydrogen atom, a halogen atom, a (per) halogenated alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms.

<2> A compound represented by the following formula (61) is produced by reacting a compound represented by the following formula (22) in the presence of the metal-carbene complex compound (10) having olefin metathesis reaction activity. Method.

However, the symbol in a formula represents the following meaning.
R ¹³ is a functional group selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a C 1-15 perfluoroalkyl group, a C 1-12 alkyl group, and a C 5-20 aryl group.
R _F ′ is a group consisting of a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and a (per) fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. The functional group chosen.
X ¹⁴ is a functional group selected from the group consisting of a hydrogen atom, a halogen atom, a (per) halogenated alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms.
Z is a functional group selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms including a hetero atom, and the alkylene group and hetero atom having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms including may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group and an ester group.

<3> The method for producing a compound according to <1> or <2>, wherein the metal in the metal-carbene complex compound (10) is ruthenium, molybdenum, or tungsten.
<4> The method for producing a compound according to <1> or <3>, wherein the compound represented by the formula (31) is at least one compound selected from the group consisting of compounds represented by the following formula: .

However, R ^PF in formula is a functional group selected from the group consisting of perfluoroalkyl group having 1 to 12 carbon atoms and having an etheric oxygen atom between perfluoroalkyl groups and carbon atoms and carbon atoms of 1 to 12 carbon atoms is there.

<5> The method for producing a compound according to <1> or <3>, wherein the compound represented by the formula (32) is at least one compound selected from the group consisting of compounds represented by the following formula: .

However, the OR _F is (per) halogenated alkoxy group having 1 to 12 carbon atoms and having an etheric oxygen atom between (per) halogenated alkoxy group and carbon atoms and carbon atoms of 1 to 12 carbon atoms in the formula A functional group selected from the group consisting of

  According to the method for producing a fluorinated diene according to the present invention, a fluorinated diene can be produced simply and efficiently from a fluorinated olefin and acetylene by an ene-in metathesis reaction.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. Further, the present invention relates to enyne metathesis by a metal catalyst, and description of general features common to the prior art may be omitted.
In the present specification, the “compound represented by the formula (X)” may be simply referred to as “compound (X)”.
In the present specification, the monosubstituted olefin means an olefin in which one hydrogen atom or halogen atom and one organic group are bonded to one carbon atom of a double bond. The 1,2-disubstituted olefin means an olefin in which the same or different organic groups are bonded to each carbon atom of a double bond.
The perhalogenated alkyl group means a group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms. The perhalogenated alkoxy group means a group in which all hydrogen atoms of the alkoxy group are substituted with halogen atoms. The same applies to perhalogenated alkoxy groups and perhalogenated aryl groups.
The term “(per) halogenated alkyl group” is used as a general term that includes a halogenated alkyl group and a perhalogenated alkyl group. That is, the group is an alkyl group having one or more halogen atoms. The same applies to (per) halogenated alkoxy groups, (per) halogenated aryl groups, and (per) halogenated aryloxy groups.
An aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of carbon atoms forming an aromatic ring in an aromatic compound, and a carbocyclic compound The aryl group derived from is combined with the heteroaryl group derived from a heterocyclic compound.
The number of carbon atoms of the hydrocarbon group means the total number of carbon atoms contained in the whole hydrocarbon group, and when the group has no substituent, the number of carbon atoms forming the hydrocarbon group skeleton is When the group has a substituent, the total number is obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the hydrocarbon group skeleton.

<Reaction mechanism>
The present invention relates to a method for producing a fluorine-containing diene by an ene-in metathesis reaction. A fluorine diene compound can be obtained.

In the scheme (a), [L] is a ligand, M is ruthenium, molybdenum, or tungsten, and A ¹ and A ² are each independently a hydrogen atom, a halogen atom, or a carbon number of 1-20. A monovalent hydrocarbon group and a group consisting of a monovalent hydrocarbon group having 1 to 20 carbon atoms and 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 Is a functional group selected from A ¹ and A ² may be bonded to each other to form a ring. R ¹¹ and R ¹² are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a (per) fluoroalkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 5 to 20 carbon atoms. And a functional group selected from the group consisting of (per) halogenated aryl groups having 5 to 20 carbon atoms. R _F ′ is a group consisting of a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and a (per) fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. The functional group chosen. X ^{11 to} X ¹³ are each independently a functional group selected from the group consisting of a hydrogen atom, a halogen atom, a (per) halogenated alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms.

  The enyne metathesis reaction is reversible. That is, in Scheme (a), there is a reverse reaction (reaction represented by an arrow in the reverse direction). However, the details of this point will not be described. In addition, there is a possibility that geometric isomers exist for the diene produced. However, the details of this point are strongly dependent on the individual reactions, and the explanation is omitted.

  In scheme (a), two different fluorine-containing olefin compounds and acetylene are used as raw materials, and a fluorine-containing diene compound is obtained by carrying out an ene-in-metathesis reaction between molecules, but a carbon-carbon double bond (olefin unit). When a molecule having both a carbon-carbon triple bond (acetylene unit) is used as a raw material, an ene-in metathesis reaction proceeds in the molecule, and a fluorinated diene compound can be obtained.

In the present invention, as shown in the following scheme (b), for example, by reacting compound (21) with compound (31) in the presence of compound (11), compound (51), compound (52), compound ( 53) and at least one compound selected from the group consisting of compound (54).
In the scheme (b), the following compound (32) can be used instead of the compound (31). In that case, at least one compound selected from the group consisting of compound (55), compound (56), compound (57) and compound (58) shown below can be produced.
Further, instead of reacting the compound (21) with the compound (31) or the compound (32), the following compound (22) can also be used as a raw material compound. Compound (22) is a compound having both an olefin unit and an acetylene unit in the molecule. When compound (22) is used as a raw material, compound (61) shown below is produced.

  The enyne metathesis reaction proceeds as a complex in the presence of the compound (11). The compound (11) is described as a representative example of the metal-carbene complex compound (10). As the metal-carbene complex compound (10), a ruthenium-carbene complex, a molybdenum-carbene complex, or a tungsten-carbene complex ( Hereinafter, “metal-carbene complex” is also collectively referred to.). As the metal-carbene complex, in addition to the compound (11), the compound (12), the compound (13), the compound (14), the compound (15), the compound (16), the compound (17), or the compound (18) described later. In any case, it is considered that the enyne metathesis reaction proceeds by the same reaction mechanism as that of the above-described scheme (a). Hereinafter, the same applies to the metal-carbene complex.

In the present specification, symbols in the formula represent the following meanings.
[L] is a ligand.
M is ruthenium, molybdenum or tungsten.
A ¹ , A ² , A ¹¹ and A ¹² are each independently a functional group selected from the group consisting of the following functional group (i), functional group (ii), functional group (iii), and functional group (iv) It is. A ¹ and A ² may be bonded to each other to form a ring. A ¹¹ and A ¹² may be bonded to each other to form a ring. However, when ^one of A ¹ and A ² is a halogen atom, the other is a functional group selected from the group consisting of functional group (i), functional group (iii), and functional group (iv).
X ¹ and X ² are each independently a functional group selected from the group consisting of the following functional group (i) and functional group (ii).
However, functional group (i)-functional group (iv) mean the following, respectively.
Functional group (i): hydrogen atom.
Functional group (ii): a halogen atom.
Functional group (iii): a monovalent hydrocarbon group having 1 to 20 carbon atoms.
Functional group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom.
R ^{11 to} R ¹³ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a (per) fluoroalkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 5 to 20 carbon atoms. And a functional group selected from the group consisting of (per) halogenated aryl groups having 5 to 20 carbon atoms.
R _F ′ is a group consisting of a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and a (per) fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. The functional group chosen.
X ^{11 to} X ¹⁴ are each independently a functional group selected from the group consisting of a hydrogen atom, a halogen atom, (per) halogenation having 1 to 12 carbon atoms, an alkyl group, and an alkyl group having 1 to 12 carbon atoms. .
Z is a functional group selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms including a hetero atom, and the alkylene group and hetero atom having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms including may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group and an ester group.

<Metal-carbene complex compound (10) having olefin metathesis reaction activity>
The metal-carbene complex compound (10) having olefin metathesis reaction activity plays a role as a catalyst in the production method according to the present invention, but both the one added as a reagent and the one generated during the reaction (catalytically active species) are used. means. Here, the compound (10) is known to show catalytic activity when some of the ligands dissociate under the reaction conditions, and to show catalytic activity without dissociation of the ligands. However, any of them is not limited in the present invention. In general, the ene-in metathesis reaction proceeds while repeating the coordination and dissociation of the olefin to the catalyst, and therefore it is not always clear how many ligands other than the olefin are coordinated on the catalyst during the reaction. Therefore, in this specification, [L] does not specify the number or type of ligands. The metal in the metal-carbene complex compound (10) is preferably ruthenium, molybdenum or tungsten.

Hereinafter, the specific compound (11) will be described.
A ¹ and A ² in the compound (11) are as defined above. That is, A ¹ and A ² in the compound (11) are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and It is a C1-C20 monovalent hydrocarbon group containing 1 or more atoms selected from the group consisting of silicon atoms, and may be bonded to each other to form a ring. However, the compound (11) is excluded when both A ¹ and A ² are halogen atoms.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable from the viewpoint of availability.
The monovalent hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 5 to 20 carbon atoms, and may be linear, branched or cyclic.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom preferably includes the atom. Examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms containing the atom, and an aryloxy group having 5 to 20 carbon atoms. The monovalent hydrocarbon group may be linear, branched, or cyclic. In these preferred groups, halogen atoms may be bonded to at least some of the carbon atoms. That is, for example, it may be a (per) fluoroalkyl group or a (per) fluoroalkoxy group. Moreover, these preferable groups may have an etheric oxygen atom between carbon atoms. These preferred groups may have a substituent 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. Examples of the substituent include hydroxyl group, amino group, imino group, nitrile group, amide group (carbonylamino group), carbamate group (oxycarbonylamino group), nitro group, carboxyl group, ester group (acyloxy group or alkoxycarbonyl group). ), A thioether group, a silyl group, and the like. These groups may be further substituted with an alkyl group or an aryl group. For example, the amino group (—NH ₂ ) may be a monoalkylamino group (—NHR), a monoarylamino group (—NHAr), a dialkylamino group (—NR ₂ ), or a diarylamino group (—NAr ₂ ). .
Preferred examples of the compound (11) having a combination of A ¹ and A ² include those represented by the following formula from the viewpoint of availability. In the following formula, Cy means a cyclohexyl group.

Specifically, when M is ruthenium in the compound (11), it can be represented by the following formula (11-A). The ligand [L] in the formula (11) is represented by L ¹ , L ² , L ³ , Z ¹¹ and Z ¹² in the formula (11-A). There is no limitation on the positions of L ¹ , L ² , L ³ , Z ¹¹ and Z ¹² , and they may be interchanged in the formula (11-A). That is, for example, Z ¹¹ and Z ¹² may be in the trans position or the cis position.

In formula (11-A), L ¹ , L ² and L ³ are each independently a ligand having a neutral charge when being separated from the central metal (neutral electron donating ligand) It is. Specifically, carbonyl group, amines, imines, pyridines, ethers, nitriles, esters, phosphines, thioethers, sulfoxides, sulfones, aromatic compounds, olefins, isocyanides, thiocyanates And hetero atom-containing carbene compounds. Among these, phosphines, pyridines, and heteroatom-containing carbene compounds are preferable, and trialkylphosphine and N-heterocyclic carbene compounds are more preferable.
However, depending on the combination of the ligands, not all ligands can coordinate to the central metal due to steric factors and / or electronic factors, and as a result, some of the coordination sites may be empty. . For example, the following combinations are exemplified as L ¹ , L ² and L ³ . L ¹ : hetero atom-containing carbene compound, L ² : phosphines, L ³ : none (vacant coordination). L ¹ : hetero atom-containing carbene compound, L ² : pyridines, L ³ : pyridines

In Formula (11-A), Z ¹¹ and Z ¹² are each independently a ligand (anionic ligand) having a negative charge when pulled away from the central metal. Specifically, halogen atom, hydrogen atom, substituted diketonate group, substituted cyclopentadienyl group, alkyl group having 1 to 20 carbon atoms, aryl group having 5 to 20 carbon atoms, substitution having 1 to 20 carbon atoms Alkoxy group, substituted aryloxy group having 5 to 20 carbon atoms, substituted carboxylate group having 1 to 20 carbon atoms, substituted aryl carboxylate group having 6 to 20 carbon atoms, substituted alkylthiolate having 1 to 20 carbon atoms Groups, substituted arylthiolate groups having 6 to 20 carbon atoms, nitrate groups, and the like. Of these, a halogen atom is preferable, and a chlorine atom is more preferable.

Wherein (11-A), ^{A 1} and ^{A 2} are each same as ^{A 1} and ^{A 2} in formula (11).
Alternatively, ^{2 to 6 of} L ¹ , L ² , L ³ , Z ¹¹ , Z ¹² , A ¹ and A ² may be bonded to each other to form a multidentate ligand.

  Such catalysts are generally referred to as “ruthenium-carbene complexes” and are described in, for example, Vougioukalakis, G .; C. et al. , Chem. Rev. 2010, 110, 1746-1787. The ruthenium-carbene complex described in 1) can be used. Further, for example, a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.

Specific examples of the ruthenium-carbene complex include bis (triphenylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium dichloride, ( 1,3-diisopropylimidazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazole) -2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazole) 2-Ilidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1 , 3-bis (2-methylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-dicyclohexyl-4,5-dihydroimidazol-2-ylidene] ( Tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylide) ) (Tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [bis (3-bromopyridine)] benzylidene ruthenium dichloride, (1,3-dimesityl- 4,5-dihydroimidazol-2-ylidene) (2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl) methylidene ] Dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, Umicore M73 SIPr and the like, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) ) (2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl) methylidene] dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, and Umicore M73 SIPr are particularly preferable. Of the above complexes, the names beginning with “Umicore” are trade names of Umicore products.
In addition, the said ruthenium carbene complex may be used independently and may be used together 2 or more types. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.

In the compound (11), when M is molybdenum or tungsten, it can be represented by the following formula (11-B) or formula (11-C).
As the compound (11), a coordinating solvent (tetrahydrofuran, ethylene glycol dimethyl ether, etc.) may be further coordinated.

The ligand [L] in the formula (11) is represented by ═NR ¹ , —R ⁴ , —R ⁵ in the formula (11-B). There is no limitation on the positions of ═NR ¹ , —R ⁴ , and —R ⁵ , and they may be replaced with each other in the formula (11-B). M is molybdenum or tungsten, and examples of R ¹ include an alkyl group and an aryl group. Examples of R ⁴ and R ⁵ include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, sulfonate groups, amino groups (alkylamino groups, η ¹ -pyrrolide, η ⁵ -pyrrolide, etc.) and the like. R ⁴ and R ⁵ may be linked to form a bidentate ligand.

Further, in the formula (11-C), an olefin (C ₂ (R ⁶ ) ₄ ) is cycloadded to the metal-carbon double bond portion of the compound represented by the formula (11-B) ([2 + 2] cycloaddition). And a compound in which a metallacyclobutane ring is formed. However, four R ⁶ are monovalent functional groups which may be the same or different from each other, and examples thereof include a hydrogen atom, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, and an amino group. The compound represented by the formula (11-C) is considered to be equivalent to the compound represented by the formula (11-B).
In the formula (11-B) and formula (11-C), ^{A 1} and ^{A 2} are each same as ^{A 1} and ^{A 2} in formula (11).

The catalyst is generally referred to as “molybdenum-carbene complex” or “tungsten-carbene complex”. (Ed) Olefin Metathesis: Theory and Practice, Wiley, 2014. The molybdenum-carbene complex or tungsten-carbene complex described in 1) can be used. For example, a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich or Strem can be used.
The molybdenum-carbene complex or the tungsten-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.

  Specific examples of compound (11-B) are shown below. Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and Ph represents a phenyl group.

  Specific examples of the compound (11-C) include the following compounds.

<Acetylene>
R ¹¹ and R ¹² in the compound (21) used as a raw material are as defined above.
That is, R ¹¹ and R ¹² in the compound (21) are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a (per) fluoroalkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a carbon number. It is a functional group selected from the group consisting of 5 to 20 aryl groups and (per) halogenated aryl groups having 5 to 20 carbon atoms, but is a hydrogen atom, a fluorine atom, a chlorine atom, (per) having 1 to 8 carbon atoms. A fluoroalkyl group and an aryl group having 1 to 8 carbon atoms are preferred from the viewpoint of availability.
More specific examples of the compound (21) include the compounds shown below.

<Fluorine-containing olefin>
R _F ′, X ¹¹ , X ¹² and X ¹³ in the compound (31) used as a raw material are as defined above. That is, R _F ′ in the compound (31) is a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and (per) having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. It is a functional group selected from the group consisting of fluoroalkyl groups, and X ^{11 to} X ¹³ are each independently a hydrogen atom, a halogen atom, a (per) halogenated alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. A functional group selected from the group consisting of alkyl groups. Compound (31) can utilize both terminal and internal olefins.

R _F ′ is preferably a C 1-8 perfluoroalkyl group from the viewpoint of availability, and X ^{11 to} X ¹³ are preferably a hydrogen atom, a fluorine atom or a chlorine atom from the viewpoint of availability. As a combination of R _F ′ and X ^{11 to} X ¹³ , R _F ′ is preferably a C 6-8 perfluoroalkyl group, and X ^{11 to} X ¹³ are hydrogen atoms.

A ¹¹ and A ¹² in the compound (32) used as a raw material are as defined above. That is, A ¹¹ and A ¹² in the compound (32) are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, It is a functional group selected from the group consisting of C1-C20 monovalent hydrocarbon groups containing one or more atoms selected from the group consisting of phosphorus atoms and silicon atoms. A ¹¹ and A ¹² may be bonded to each other to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable from the viewpoint of availability.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, or an aryloxy having 5 to 20 carbon atoms. In particular, methyl, ethyl, propyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, (2-ethyl) hexyloxy, or dodecyloxy A group is preferred from the viewpoint of availability. Further, the hydrocarbon group skeleton may be linear, branched or cyclic.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom and silicon atom has 1 to 1 carbon atoms containing the atom. A 20-alkyl group, a C1-C20 alkoxy group, a C5-C20 aryl group containing the said atom, and a C5-C20 aryloxy group are preferable.

In compound (31) or compound (32), the number of substituents on the double bond is not particularly limited, but halogenated ethylene, monosubstituted olefin, 1,1-disubstituted olefin, 1,2-disubstituted olefin Is preferable in that it has high reactivity. The geometric isomerism on the double bond is not particularly limited.
More specific examples of the compound (31) or the compound (32) include the compounds shown below. In the present specification, the wavy line means one or a mixture of both isomers of E / Z.

R ^PF in the above formula is a functional group selected from the group consisting of a C 1-12 perfluoroalkyl group and a C 1-12 perfluoroalkyl group having an etheric oxygen atom between carbon atoms. OR _F is selected from the group consisting of a (per) halogenated alkoxy group having 1 to 12 carbon atoms and a (per) halogenated alkoxy group having 1 to 12 carbon atoms having an etheric oxygen atom between the carbon atoms. Functional group.

Compound (22) is a compound having both a carbon-carbon double bond (olefin unit) and a carbon-carbon triple bond (acetylene unit) in the molecule. Therefore, when compound (22) is used as a raw material compound, an ene-in metathesis reaction occurs in the molecule, and a fluorinated diene can be obtained.
In the compound (22), R _F ′, X ¹⁴ , R ¹³ and Z are as defined above. That is, R _F ′ in the compound (22) is a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and (per) having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. X ¹⁴ is a functional group selected from the group consisting of fluoroalkyl groups, and X ¹⁴ is selected from the group consisting of hydrogen atoms, halogen atoms, (per) halogenated alkyl groups having 1 to 12 carbon atoms, and alkyl groups having 1 to 12 carbon atoms. R ¹³ is selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a C 1-15 perfluoroalkyl group, a C 1-12 alkyl group, and a C 5-20 aryl group. Z is a functional group selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms and an alkylene group having 1 to 20 carbon atoms containing a hetero atom, The alkylene group having 1 to 20 carbon atoms and the alkylene group having 1 to 20 carbon atoms including a hetero atom may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, and an ester group. .

R _F ′ is preferably a C 1-10 perfluoroalkyl group from the viewpoint of reactivity, and X ¹⁴ is preferably a hydrogen atom from the viewpoint of reactivity. R ¹³ is preferably a hydrogen atom from the viewpoint of reactivity, and Z is preferably an alkylene group having 3 to 5 carbon atoms from the viewpoint of reactivity. As a combination of R _F ′, X ¹⁴ , R ¹³ and Z, R _F ′ is preferably a perfluoroalkyl group having 4 to 8 carbon atoms, X ¹⁴ is a hydrogen atom, R ¹³ is a hydrogen atom, and Z is 4 carbon atoms. More preferably, R _F ′ is a perfluoroalkyl group having 8 carbon atoms, X ¹⁴ is a hydrogen atom, R ¹³ is a hydrogen atom, and Z is an alkylene having 4 carbon atoms.

  In the compound (22), the number of substituents on the double bond is not particularly limited, but monosubstituted olefins and 1,2-disubstituted olefins are preferable in that they have high reactivity. The geometric isomerism on the double bond is not particularly limited.

  In addition, the compound (21), the compound (22), the compound (31), and the compound (32) described above may be collectively referred to as “raw material compounds” hereinafter.

<Fluorine-containing diene>
The fluorine-containing diene compound obtained by the ene-in metathesis of the present invention is selected from the group consisting of the compounds (51) to (58) shown below when an ene-in metathesis reaction is carried out between the molecules of the fluorine-containing olefin and acetylene. At least one compound is obtained. Moreover, when an ene-in metathesis reaction is carried out in a molecule | numerator using a compound (22), the compound (61) shown below will produce | generate.

  More specific examples of the compound (51) to the compound (58) or the compound (61) include the compounds shown below.

<Manufacturing method>
The present invention relates to a method for producing a fluorinated diene by enyne metathesis. Typically, the fluorinated olefin and acetylene are brought into contact with each other in the presence of a metal-carbene complex, or the fluorinated olefin structure is formed in the molecule. By bringing a molecule having an acetylene structure into contact with each other in the presence of a metal-carbene complex, enyne metathesis is performed to obtain a fluorinated diene.

Both the terminal and internal acetylene can be used for the compound represented by the above formula (21) which is acetylene as a raw material. From the viewpoint of improving the yield of the target product, it is preferable to use deaerated and dehydrated olefin as a raw material. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. For the olefin as a raw material, the degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.
Moreover, since the olefin used as a raw material may contain a trace amount impurity (for example, a peroxide etc.), you may refine | purify from the point of the target-product yield improvement. There is no particular limitation on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).

Of the fluorine-containing olefins used as raw materials, both the terminal and internal olefins can be used for the compound represented by the above formula (31). The compound represented by the above formula (32) is a terminal olefin. These are not particularly limited in the number of substituents on the double bond, but ethylene, monosubstituted olefin, and 1,2-disubstituted olefin are preferable in that they have high reactivity. The geometric isomerism on the double bond is not particularly limited. From the viewpoint of improving the yield of the target product, it is preferable to use deaerated and dehydrated olefin as a raw material. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. For the olefin as a raw material, the degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.
Moreover, since the olefin used as a raw material may contain a trace amount impurity (for example, a peroxide etc.), you may refine | purify from the point of the target-product yield improvement. There is no particular limitation on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).

The compound represented by the above formula (22), which is a raw material for performing an enyne metathesis reaction in a molecule, can be used regardless of whether the olefin unit is at the terminal or inside, and the acetylene unit is It can be used either at the end or inside. From the viewpoint of improving the yield of the target product, it is preferable to use a degassed and dehydrated compound as a raw material. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve. For the compound as a raw material, the degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.
Moreover, since the compound used as a raw material may contain a trace amount impurity (for example, a peroxide etc.), you may refine | purify from the point of the target-product yield improvement. There is no particular limitation on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).

When two or more kinds of raw material compounds are present, that is, when an ene-in metathesis reaction is performed between molecules, these raw material compounds may be added after mixing in the reaction vessel in advance or separately. Absent. In some cases, acetylene is brought into contact with a mixture obtained by bringing the fluorine-containing olefin into contact with the metal-carbene complex.
The molar ratio of the fluorine-containing olefin and acetylene used as a raw material is not particularly limited, but the other acetylene is used in an amount of about 0.01 to 100 mol, preferably 0.1 About 10 mol is used.

The metal-carbene complex may be added as a reagent or generated in the system.
When charging as a reagent, a commercially available metal-carbene complex may be used as it is, or a non-commercially available metal-carbene complex synthesized by a known method from a commercially available reagent may be used.
When it is generated in the system, a metal-carbene complex prepared from a metal complex as a precursor by a known method can be used in the present invention.

  Although there is no restriction | limiting in particular as the quantity of the metal-carbene complex to be used, About 0.0001-1 mol is normally used with respect to 1 mol of fluorine-containing olefin used as a raw material, Preferably it uses about 0.001-0.2 mol. .

  The metal-carbene complex to be used is usually charged into the reaction vessel as a solid, but may be charged after being dissolved or suspended in a solvent. There is no restriction | limiting in particular as a solvent used at this time in the range which does not exert a bad influence on reaction, An organic solvent, a fluorine-containing organic solvent, an ionic liquid, water etc. can be used individually or in mixture. In these solvent molecules, some or all of the hydrogen atoms may be substituted with deuterium atoms.

Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, glyme, diglyme, and the like can be used. Examples of the fluorine-containing organic solvent include hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, dichloropentafluoropropane, and the like. Can be used. As the ionic liquid, for example, various pyridinium salts, various imidazolium salts and the like can be used. Among the above solvents, benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF in terms of solubility of the metal-carbene complex. (Tetrahydrofuran), hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, and mixtures thereof are preferred.
In addition, it is preferable to use a degassed and dehydrated solvent for improving the yield of the target product. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. The degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.

The atmosphere in which the raw material compound and the metal-carbene complex are brought into contact is not particularly limited, but an inert gas atmosphere is preferable from the viewpoint of extending the life of the catalyst, and a nitrogen or argon atmosphere is particularly preferable. However, when a compound that becomes a gas under reaction conditions is used as a raw material, it can be carried out in these gas atmospheres.
The phase in which the raw material compound and the metal-carbene complex are brought into contact with each other is not particularly limited, but a liquid phase is usually used in terms of reaction rate. When the compound as a raw material is a gas under the reaction conditions, it is difficult to carry out in the liquid phase, and therefore it can be carried out in the gas-liquid two phase. In the case of carrying out in the liquid phase, a solvent can be used. As the solvent used at this time, the same solvents as those used for dissolving or suspending the metal-carbene complex can be used. In addition, when there are two or more compounds as raw materials, and at least one of these compounds is liquid under the reaction conditions, it may be carried out without a solvent.

  The container for bringing the raw material compound into contact with the metal-carbene complex is not particularly limited as long as it does not adversely affect the reaction. For example, a metal container or a glass container can be used. In addition, since the enyne metathesis concerning this invention may handle the olefin and / or acetylene of a gaseous state on reaction conditions, the pressure-resistant container in which high airtightness is possible is preferable.

Although there is no restriction | limiting in particular as temperature which makes a raw material compound and a metal carbene complex contact, Usually, it can implement in the range of -100-200 degreeC, and 0-150 degreeC is preferable at the point of reaction rate. Note that the reaction does not start at low temperatures, and the complex may be rapidly decomposed at high temperatures. Therefore, it is necessary to appropriately set the lower limit and the upper limit of the temperature. Usually, it is carried out at a temperature below the boiling point of the solvent used.
Although there is no restriction | limiting in particular as time to contact a raw material compound and a metal carbene complex, Usually, it implements in the range of 1 minute-48 hours.
The pressure for bringing the raw material compound into contact with the metal-carbene complex is not particularly limited, but it may be under pressure, under normal pressure, or under reduced pressure. Usually, it is about 0.001-10 MPa, preferably about 0.01-1 MPa.

When the raw material compound and the metal-carbene complex are brought into contact with each other, an inorganic salt, an organic compound, a metal complex, or the like may coexist within a range that does not adversely affect the reaction. The reaction rate may be accelerated by adding ethylene. When adding ethylene, it is preferable that it is 0.0001-1 mol with respect to 1 mol of fluorine-containing olefins used as a reference | standard.
Moreover, you may stir the mixture of a raw material compound and a metal carbene complex in the range which does not exert a bad influence on reaction. At this time, a mechanical stirrer, a magnetic stirrer, or the like can be used as a stirring method.

  After contacting the raw material compound and the metal-carbene complex, the target product is usually obtained as a mixture of a plurality of fluorine-containing dienes, and may be isolated by a known method. Examples of the isolation method include distillation, column chromatography, recycle preparative HPLC and the like, and these can be used alone or in combination as necessary.

The target product obtained in this reaction can be identified by a known method similar to that for ordinary organic compounds. For example, ¹ H-, ¹⁹ F-, ¹³ C-NMR, GC-MS and the like can be mentioned, and these can be used alone or in combination.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. <Commercially available reagents>
In this example, unless otherwise specified, a commercially available catalyst was used as it was for the reaction. The solvent (m-xylene-d ₁₀ ) and internal standard substance (p-bis (trifluoromethyl) benzene) were used in the reaction after freezing and degassing a commercially available product in advance and drying with molecular sieve 4A.
<Evaluation method>
In this example, the structure of the synthesized compound was identified by performing ¹ H-NMR and ¹⁹ F-NMR measurements using a nuclear magnetic resonance apparatus (JNM-AL300) manufactured by JEOL Ltd. Moreover, molecular weight was calculated | required by the electron ionization method (EI) using the Shimadzu Corporation gas chromatograph mass spectrometer (GCMS-QP2010Ultra).

<Example 1>
Enyne metathesis of 4-phenyl-1-butyne and C ₈ F ₁₇ —CH═CH ₂ with Umicore M73 SIPr catalyst 4-phenyl-1-butyne (0.1 mmol, 0.014 mL), Umicore M73 SIPr catalyst (50 mol%, under nitrogen atmosphere) 0.05 mmol), C ₈ F ₁₇ —CH═CH ₂ (0.2 mmol, 0.053 mL, 2 mmol equivalent) and m-xylene-d ₁₀ (0.6 mL) were weighed into an NMR measuring tube. The NMR tube was heated at 140 ° C. and reacted at that temperature for 3 hours. After completion of the reaction, NMR and GC-MS were measured to confirm the production of product A and / or product B shown below.
A series of these reactions is shown below.

GC-MS (CI) of product A, product B: = 577 (M + H ⁺ ).

<Example 2>
Enyne metathesis of 4-phenyl-1-butyne and tetrafluoroethylene by Umicore M73 SIPr catalyst Under nitrogen atmosphere, 4-phenyl-1-butyne (0.04 mmol, 0.0056 mL), Umicore M73 SIPr catalyst (100 mol%, 0.04 mmol), tetra Fluoroethylene (0.12 mmol, 3 mol equivalent) and m-xylene-d ₁₀ (0.6 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 140 ° C. and reacted at that temperature for 1 hour. After completion of the reaction, NMR and GC-MS are measured to confirm the expected reaction progress.
A series of these reactions is shown below.

  According to the present invention, a fluorine-containing diene can be easily and efficiently produced by an ene-in metathesis reaction between a fluorine-containing olefin and acetylene.

Claims (5)

In the presence of a metal-carbene complex compound (10) having olefin metathesis reaction activity, a compound represented by the following formula (21) and a compound represented by the following formula (31) or a compound represented by the following formula (32) And the compound represented by the following formula (52), the compound represented by the following formula (53), the compound represented by the following formula (54). , A compound represented by the following formula (55), a compound represented by the following formula (56), a compound represented by the following formula (57), and a compound represented by the following formula (58) A method for producing at least one compound selected.

However, the symbol in a formula represents the following meaning.
A ¹¹ and A ¹² are each independently a functional group selected from the group consisting of the following functional group (i), functional group (ii), functional group (iii), and functional group (iv). A ¹¹ and A ¹² may be bonded to each other to form a ring.
Functional group (i): hydrogen atom.
Functional group (ii): a halogen atom.
Functional group (iii): a monovalent hydrocarbon group having 1 to 20 carbon atoms.
Functional group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom.
R ¹¹ and R ¹² are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a (per) fluoroalkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 5 to 20 carbon atoms. And a functional group selected from the group consisting of (per) halogenated aryl groups having 5 to 20 carbon atoms.
R _F ′ is a group consisting of a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and a (per) fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. The functional group chosen.
X ^{11 to} X ¹³ are each independently a functional group selected from the group consisting of a hydrogen atom, a halogen atom, a (per) halogenated alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. A method for producing a compound represented by the following formula (61) by reacting a compound represented by the following formula (22) in the presence of the metal-carbene complex compound (10) having olefin metathesis reaction activity.

However, the symbol in a formula represents the following meaning.
R ¹³ is a functional group selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a C 1-15 perfluoroalkyl group, a C 1-12 alkyl group, and a C 5-20 aryl group.
R _F ′ is a group consisting of a fluorine atom, a (per) fluoroalkyl group having 1 to 20 carbon atoms, and a (per) fluoroalkyl group having 1 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms. The functional group chosen.
X ¹⁴ is a functional group selected from the group consisting of a hydrogen atom, a halogen atom, a (per) halogenated alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms.
Z is a functional group selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms including a hetero atom, and the alkylene group and hetero atom having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms including may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group and an ester group.   The method for producing a compound according to claim 1 or 2, wherein the metal in the metal-carbene complex compound (10) is ruthenium, molybdenum or tungsten. The method for producing a compound according to claim 1 or 3, wherein the compound represented by the formula (31) is at least one compound selected from the group consisting of compounds represented by the following formula.

However, R ^PF in formula is a functional group selected from the group consisting of perfluoroalkyl group having 1 to 12 carbon atoms and having an etheric oxygen atom between perfluoroalkyl groups and carbon atoms and carbon atoms of 1 to 12 carbon atoms is there. The method for producing a compound according to claim 1 or 3, wherein the compound represented by the formula (32) is at least one compound selected from the group consisting of compounds represented by the following formula.

However, the OR _F is (per) halogenated alkoxy group having 1 to 12 carbon atoms and having an etheric oxygen atom between (per) halogenated alkoxy group and carbon atoms and carbon atoms of 1 to 12 carbon atoms in the formula A functional group selected from the group consisting of