JP6759760B2 - Method for producing fluorine-containing olefin - Google Patents

Description

The present invention relates to a novel method for producing a fluorine-containing olefin by olefin metathesis.

Industrially useful compounds are known as fluorine-containing olefins, in which some or all of the hydrogen atoms in the olefin are replaced with fluorine atoms. An olefin metathesis reaction is known as a method for producing the fluorine-containing olefin (see, for example, Patent Document 1).

International Publication No. 2015/033927

However, in the examples described in Patent Document 1, the catalyst rotation speed is not sufficiently high, and practically, even a little higher reaction efficiency is required.
Therefore, an object of the present invention is to provide a method for producing a fluorine-containing olefin by olefin metathesis with high reaction efficiency.

In view of the above problems, the present invention has focused on the reaction conditions and found the conditions under which the reaction can proceed with high efficiency. That is, the present invention relates to the following [1] to [7].
[1] In the presence of a metal-carbene complex compound catalyst, an olefin metathesis reaction is carried out in a state where the first fluorine-containing olefin compound, which is a gas at normal temperature and pressure, is liquefied under pressure to produce a second fluorine-containing olefin compound. how to.
[2] The production method according to [1], wherein the first fluorine-containing olefin compound is 1,1-difluoroolefin or 1,2-difluoroolefin.
[3] The production method according to [1] or [2], which does not use a solvent.
[4] The production method according to any one of [1] to [3], wherein the olefin metathesis reaction is a cross metathesis reaction.
[5] The production method according to [4], which uses an olefin compound represented by the following formula (31) as a raw material.
(However, in the formula (31), R ^{11 to} R ¹⁴ are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, monovalent hydrocarbon group having 1 to 20 carbon atoms, or halogen atom, oxygen atom, respectively. It is a monovalent organic group having 1 to 20 carbon atoms and containing one or more atoms selected from the group consisting of nitrogen atom, sulfur atom, phosphorus atom and silicon atom.)

[6] The production method according to [5], wherein the compound represented by the formula (31) is a liquid under the reaction conditions.
[7] The production method according to [5] or [6], wherein the compound represented by the formula (31) is a compound having a hetero atom at the vinyl position.

According to the method for producing a fluorine-containing olefin compound of the present invention, high reaction efficiency can be obtained.

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 and carried out without departing from the gist of the present invention. Further, the present invention relates to olefin metathesis using a metal catalyst, and the 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)".
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 the hydrogen atoms of the alkoxy group are substituted with halogen atoms. The same applies to the perhalogenated alkoxy group and the perhalogenated aryl group.
Further, the (pel) alkyl halide group is used as a general term for a combination of an alkyl halide group and an alkyl halide group. That is, the group is an alkyl group having one or more halogen atoms. The same applies to the (pel) halogenated alkoxy group, the (pel) aryl halide group, and the (pel) halide aryloxy group.
The aryl group means a monovalent group corresponding to a residue from which one hydrogen atom bonded to any one of the carbon atoms forming an aromatic ring in an aromatic compound has been removed, and is a carbocyclic compound. It is used as a general term for a combination of an aryl group derived from and a heteroaryl group derived from a heterocyclic compound.
The number of carbon atoms of a hydrocarbon group means the total number of carbon atoms contained in the entire hydrocarbon group, and when the group does not have a substituent, the number of carbon atoms forming a hydrocarbon group skeleton is used. When the group has a substituent, it represents the total number obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the hydrocarbon group skeleton. The same applies to the number of carbon atoms of the organic group.
The hetero atom means an atom other than a carbon atom and a hydrogen atom, and is preferably one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom. Yes, more preferably an oxygen atom or a nitrogen atom.
Also, the metathesis reaction is reversible. However, the details on this point will be omitted. In addition, the produced fluorine-containing olefin may have geometrical isomers. However, the details of this point are strongly dependent on individual reactions and will not be described.

In the present specification, the symbols in the formula have the following meanings.
[L] is a ligand.
M is ruthenium, molybdenum or tungsten.
A ¹ and A ² are groups independently selected from the group consisting of the following groups (i), groups (ii), groups (iii), and groups (iv), respectively. A ¹ and A ² may be combined with each other to form a ring.
X ¹¹ , X ¹² and X ¹³ are independently selected from the group consisting of the following groups (i), groups (ii), and groups (v).
R ^{11 to} R ¹⁴ are groups independently selected from the group consisting of the following groups (i), groups (ia), groups (iii), and groups (iv). Any two of R ^{11 to} R ¹⁴ may be combined with each other to form a ring.
Group (i): Hydrogen atom.
Group (ii): Halogen atom.
Group (ia): chlorine atom, bromine atom or iodine atom.
Group (iii): A monovalent hydrocarbon group having 1 to 20 carbon atoms.
Group (iv): A monovalent organic group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and silicon atoms.
Group (v): Alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, (pel) alkyl halide group having 1 to 3 carbon atoms, and (pel) halogenated alkoxy group having 1 to 3 carbon atoms. A group selected from the group consisting of groups.

<Metal-carbene complex compound catalyst>
In the present invention, the metal-carbene complex compound (10) is used as a catalyst for the olefin metathesis reaction.

As the metal-carbene complex compound (10), compound (11) will be described as an example. Compound (11) plays a role as a catalyst in the production method according to the present invention, but means both those added as reagents and those produced during the reaction (catalytically active species). Here, it is known that the compound (11) exhibits catalytic activity by dissociating some of the ligands under reaction conditions, and exhibits catalytic activity without dissociation of the ligands. However, in the present invention, none of them is limited. Further, in general, olefin metathesis proceeds while repeatedly coordinating and dissociating the olefin to the catalyst, so it is not always clear how many ligands other than the olefin are coordinated on the catalyst during the reaction. Therefore, in the present specification, [L] does not specify the number or type of ligand. The metal in the metal-carbene complex compound (10) is preferably ruthenium, molybdenum, or tungsten.

In the present invention, the reaction is carried out in the presence of at least one metal-carbene complex compound selected from the group consisting of compound (11), compound (12), compound (13), compound (14) and compound (15). Is preferable. As the metal-carbene complex compound, compound (11) is preferable at the start of the reaction from the viewpoint of availability and reaction efficiency.

The specific compound (11) will be described below.
A ¹ and A ² in compound (11) 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. , And a monovalent organic group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of silicon atoms. A ¹ and A ² may be bonded to each other to form a ring as a divalent group in which one hydrogen atom or one halogen atom is removed from each of A ¹ and A ² .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the fluorine atom and the chlorine atom are preferable from the viewpoint of easy 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 organic group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and silicon atoms is preferably carbon containing the atoms. Examples thereof include an alkyl group having a number of 1 to 20, an alkoxy group having 1 to 20 carbon atoms including the atom, an aryl group having 5 to 20 carbon atoms including the atom, and an aryloxy group having 5 to 20 carbon atoms including the atom. .. The monovalent organic group may be linear, branched, or cyclic. These preferred groups may have halogen atoms bonded to at least some carbon atoms. That is, for example, it may be a (pel) fluoroalkyl group or a (pel) fluoroalkoxy group. Moreover, these preferable groups may have an ether oxygen atom between carbon atoms. Further, these preferable groups may have a substituent containing one or more atoms selected from the group consisting of halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and silicon atoms. Examples of the substituent include a hydroxyl group, an amino group, an imino group, a nitrile group, an amide group (carbonylamino group), a carbamate group (oxycarbonylamino group), a nitro group, a carboxyl group, and an ester group (acyloxy group or alkoxycarbonyl group). ), A thioether group, a silyl group and the like can be exemplified. 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 ). .. However, R is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms having an ether oxygen atom between carbon atoms, and Ar is an aryl group having 5 to 12 carbon atoms.

As the compound (11) having a combination of A ¹ and A ^2, the compound (11) represented by the following formula can be preferably exemplified in terms of availability. In the following formula, Cy means a cyclohexyl group.

In the present invention, the metal of the metal carbene complex compound is preferably ruthenium.
Specifically, when M is ruthenium in 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). The positions of L ¹ , L ² , L ³ , Z ¹¹ and Z ¹² are not limited and 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 independent ligands that have a neutral charge when separated from the central metal (neutral electron donating ligand). Is. Specifically, carbonyl groups, amines, imines, pyridines, ethers, nitriles, esters, phosphines, thioethers, sulfoxides, sulfones, aromatic compounds, olefins, isocyanides, thiosianates. , Heteroatom-containing carbene compound and the like. 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 be coordinated to the central metal due to steric factors and / or electronic factors, and as a result, some coordination constellations may be emptied. .. For example, examples of L ¹ , L ² and L ³ include the following combinations.
L ¹ : Heteroatom-containing carbene compound, L ² : Phosphines, L ³ : None (empty coordination).
L ¹ : Heteroatom-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 separated from the central metal. Specifically, a halogen atom, a hydrogen atom, a substituted diketonate group, a substituted cyclopentadienyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, and a substituent having 1 to 20 carbon atoms. Alkoxy group, substituted aryloxy group with 5 to 20 carbon atoms, substituted carboxylate group with 1 to 20 carbon atoms, substituted arylcarboxylate group with 6 to 20 carbon atoms, substituted alkylthiolate with 1 to 20 carbon atoms Examples thereof include a substituted arylthiolate group having 6 to 20 carbon atoms and a nitrate group. 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).

Further, ^{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 polydentate ligand.

The catalyst is generally referred to as a "ruthenium-carbene complex", for example, Vougioukarakis, G. et al. C. et al. Chem. Rev. , 2010, 110, 1746-1787. The ruthenium-carbene complex described in the above can be utilized. Further, for example, a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.

Specific examples of the rutenium-carben complex include bis (triphenylphosphine) benzylphosphine dichloride, bis (tricyclohexylphosphine) benzylphosphenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenilidene ruthenium dichloride, (tricyclohexylphosphine). 1,3-Diisopropylimidazol-2-iriden) (tricyclohexylphosphine) benzylidene lutenium dichloride, (1,3-dicyclohexylphosyl-2-iriden) (tricyclohexylphosphine) benzylidene lutenium dichloride, (1,3-dimeshyl imidazole) -2-Ilidene) (Tricyclohexylphosphine) benzylidene lutenium dichloride, (1,3-dimesityl-4,5-dihydroimidazole-2-iriden) (tricyclohexylphosphine) benzylidene lutenium dichloride, [1,3-bis (2,) 6-Diisopropylphenyl) -4,5-dihydroimidazol-2-iriden] (tricyclohexylphosphine) benzylidene lutenium dichloride, [1,3-bis (2-methylphenyl) -4,5-dihydroimidazol-2-iriden] (Tricyclohexylphosphine) benzylphosphine dichloride, [1,3-dicyclohexyl-4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylphosphine dichloride, bis (tricyclohexylphosphine) ethoxymethylphositenium dichloride, (1) , 3-Dimesityl-4,5-dihydroimidazol-2-iriden) (tricyclohexylphosphine) ethoxymethylphositenium dichloride, (1,3-dimesityl-4,5-dihydroimidazole-2-iriden) [bis (3-) Bromopyridine)] benzylidene lutenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-iriden) (2-isopropoxyphenylmethylidene) lutenium dichloride, (1,3-dimesityl-4,5-dihydro) Imidazole-2-iriden) [(Tricyclohexylphosyl) methylidene] Dichlorolutenium tetrafluoroborate, UmicoreM2, UmicoreM51, UmicoreM52, UmicoreM71SIMs, UmicoreM71SITr, UmicoreM73SIMs, UmicoreM73 SIPr and the like include (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) [(tricyclohexylphosyl) methylidene] dichlorolutenium tetrafluoroborate, UmicoreM2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, and Umicore M73 SIPr are particularly preferable. Among the above complexes, the name starting with "Umicore" is a trade name of a product of Umicore.

The ruthenium-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.

In the present invention, it is preferable that the metal of the metal carbene complex compound is molybdenum or tungsten from the viewpoint of availability of the catalyst.

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

When the metal of the metal catalyst is molybdenum or tungsten, as ligands [L] of the metal catalyst preferably having an imide ligand (R 1 ^-N = M). However, examples of R ¹ include an alkyl group and an aryl group. Further, as the ligand [L] of the metal catalyst, it is preferable to have a ligand in which oxygen atoms are coordinated in a bidentate. However, a ligand in which an oxygen atom is bidentate is a ligand having two or more oxygen atoms and coordinated with two of the oxygen atoms, and oxygen. This includes both cases where two monodentate ligands having atoms are coordinated (in this case, the monodentate ligands may be the same or different).

The ligand [L] in the formula (11) is represented by = NR ¹ , -R ⁴ , and -R ⁵ in the formula (11-B). = The positions of NR ¹ , -R ⁴ , and -R ⁵ are not limited, and may be interchanged 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 -pyrrolid, η ⁵ -pyrrolid, etc.) and the like. R ⁴ and R ⁵ may be linked to form a bidentate ligand.

In the formula (11-C), an olefin (C ₂ (R ⁶ ) ₄ ) is cycloadditioned ([2 + 2] cycloaddition) to the metal-carbon double bond portion of the compound represented by the formula (11-B). It is a compound that forms a metallacyclobutane ring. However four R ⁶ is also different are also good monovalent radical the same as each other, a hydrogen atom, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an amino group and the like. 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 a "molybdenum-carbene complex" or a "tungsten-carbene complex", for example, Grela, K. et al. (Ed) Olefin Mathesis: Theory and Practice, Wiley, 2014. The molybdenum-carbene complex or the tungsten-carbene complex described in the above can be used. Further, for example, a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich, Strem, or Ximo 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. In addition, Me means a methyl group, i-Pr means an isopropyl group, t-Bu means a tertiary butyl group, and Ph means a phenyl group.

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

<Compounds (12) to (15)>
Compounds (12) to (15) play a role as a catalyst in the production method according to the present invention in the same manner as the above compound (11), but those added as reagents and those produced during the reaction (catalytically active species). Means both.

<First Fluorine-Containing Olefin: Compound (21)>
In the present invention, the first fluorine-containing olefin compound is a gas at normal temperature and pressure. Here, normal temperature and pressure means 30 ° C. and 1 atm.
The olefin compound represented by the following formula (21) is the first fluorine-containing olefin compound used as a raw material, and X ¹¹ , X ¹² and X ¹³ in the compound (21) are the same as the above definitions.

That is, X ¹¹ , X ¹² and X ¹³ in compound (21) independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. It is a group selected from the group consisting of (pel) alkyl halide groups and (pel) halogenated alkoxy groups having 1 to 3 carbon atoms. In X ¹¹ and X ¹² , hydrogen atoms and halogen atoms are preferable from the viewpoint of availability. Further, X ¹³ is preferably a halogen atom or a perhalogenated alkyl group having 1 to 3 carbon atoms. Any two of X ¹¹ , X ¹² and X ¹³ may be bonded to each other to form a ring as a divalent group from which one hydrogen or halogen atom has been removed from each of the two groups. ..

Compound (21) as the 1,1-difluoro-olefin or 1,2-difluoro-olefin are preferred, 1,1-difluoro-olefin or a C 3 or more 1,2-difluoro-olefins are more preferred, ^{X 13} is a fluorine atom Compounds, ie 1,1-difluoroolefins, are preferred. The number of carbon atoms of compound (21) is preferably 2 or more and 5 or less.

Specific examples of the compound (21) include the following compounds. However, if there is an E / Z isomer, either one may be used. As the compound (21), only one kind may be used, or two or more kinds may be used in combination. However, only one type is preferable because the amount of by-products tends to increase.

Specific examples of the compound (21) include the compounds shown below.

<Compound (31)>
The olefin compound represented by the following formula (31) is a compound that may be used as a raw material, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the compound (31) are the same as the above definitions. When the olefin metathesis reaction is a cross metathesis reaction, compound (21) and compound (31) are used as raw materials.

R ^{11 to} R ¹⁴ in compound (31) are the same as those defined above. That is, R ^{11 to} R ¹⁴ are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, monovalent hydrocarbon group having 1 to 20 carbon atoms, or halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus. It is a monovalent organic group having 1 to 20 carbon atoms and containing one or more atoms selected from the group consisting of an atom and a silicon atom.

Any two of R ^{11 to} R ¹⁴ may be combined with each other to form a ring. As the ring, a ring in which the skeleton is composed of only carbon atoms or a carbon atom and a hetero atom is preferable. The size of the ring can be exemplified by a 3-membered ring to a 10-membered ring. As the partial structure of the ring, the structure of the following equation can be exemplified.

As the monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 5 to 20 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, or a phenyl group is particularly easily available. It is preferable from the viewpoint of sex. Further, the organic skeleton may be linear, branched, or cyclic.

The monovalent organic group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and silicon atoms is preferably carbon containing the atoms. Alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms including the atom, aryl group having 5 to 20 carbon atoms including the atom, aryl having 5 to 20 carbon atoms. An oxy group or an aryloxy group having 5 to 20 carbon atoms containing the atom can be exemplified.
Preferred examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, a (2-ethyl) hexyloxy group, and a dodecyloxy group.
These preferred groups may have halogen atoms bonded to at least some carbon atoms. That is, for example, it may be a (pel) fluoroalkyl group or a (pel) fluoroalkoxy group. Moreover, these preferable groups may have an ether oxygen atom between carbon atoms. Further, these preferable groups may have a substituent having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Examples of the substituent include an amino group, a nitrile group, a carboxyl group, an ester group (acyloxy group or an alkoxycarbonyl group), a thioalkyl group, and a silyl group.

Among them, R ^{11 to} R ¹⁴ are independently hydrogen atom, phenyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butyl group, tert-butoxy group, (2-ethyl) hexyloxy group and dodecyl. An oxy group, an acetyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group are preferable from the viewpoint of availability. Among the compounds (31), a compound having a hetero atom at the vinyl position (a compound in which an atom other than a carbon atom or a hydrogen atom exists next to a carbon atom of an olefin) has an effect of stabilizing an intermediate generated during the reaction. Therefore, it is considered that olefin metathesis is likely to proceed. Therefore, as the compound (31), a compound having a hetero atom at the vinyl position is preferable. As the hetero atom preferably present next to the carbon atom of the olefin, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, a phosphorus atom or a silicon atom is preferable, and an oxygen atom, a nitrogen atom or a halogen atom is more preferable. , Oxygen atom or nitrogen atom is particularly preferable.

As compound (31), both terminal and internal olefins can be used. The number of substituents on the double bond is not particularly limited, but ethylene, monosubstituted olefins, and 1,2-disubstituted olefins are preferable because they have high reactivity. The geometric isomerism on the double bond is also not particularly limited.

Specific examples of the compound (31) include the olefin compounds shown below.

R in the above formula is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms having an etheric oxygen atom between carbon atoms. When a plurality of Rs are present in the same molecule, they may be the same or different from each other. Ar is an aryl group having 5 to 12 carbon atoms. When a plurality of Ars are present in the same molecule, they may be the same or different from each other.

Among these, as the compound (31), a particularly preferable specific example is an olefin compound shown below.

<Second fluorine-containing olefin: compound (51) and compound (52)>
By the reaction between the compound (21) and the compound (31), at least one of the fluorine-containing olefin compound represented by the following formula (51) and the fluorine-containing olefin compound represented by the following formula (52) is produced. Fluorine. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and X ¹³ in compound (51) and compound (52) are similar to those defined above, and preferred groups are also R ¹¹ , R in compound (21) or compound (22). ^This is similar to the preferred groups of ¹² , R ¹³ , R ¹⁴ and X ¹³ , respectively.

Compound (51) and / or compound (52) is a fluorine-containing olefin compound in which a fluorine atom is directly bonded to a carbon atom constituting a carbon-carbon double bond.

The reaction between the compound (21) and the compound (31) may also produce an olefin compound represented by the following formula (53) or an olefin compound represented by the following formula (54), but in the present invention. Since the purpose is to produce a fluorine-containing olefin compound of at least one of compound (51) and compound (52), the description of compound (53) and compound (54) will be omitted.

<Manufacturing method>
The present invention relates to a method for producing a fluorine-containing olefin compound by olefin metathesis. For example, a first fluorine-containing olefin (compound (21)) and another olefin (compound (31)) are used as a raw material compound, and a metal-. In the presence of the carben complex compound (10), olefin metathesis is performed by contacting the raw material compound, and a second fluorine-containing olefin having a partial structure of the two raw material compounds (compound (51) and / or compound (52). )) Is obtained. In this case, the olefin metathesis is a cross metathesis reaction.

Further, as another example of the present invention, olefin metathesis is performed by using the first fluorine-containing olefin (compound (21)) as a raw material compound and contacting the raw material compound in the presence of the metal-carbene complex compound (10). It may be carried out to obtain a second fluorine-containing olefin (polymer). In this case, olefin metathesis is a metathesis polymerization reaction.

Both the compound (21) and the compound (31), which are the raw material compounds, can utilize both terminal and internal olefins. From the viewpoint of improving the yield of the target product, it is preferable to use a degassed and dehydrated raw material compound. The degassing operation is not particularly limited, but freeze degassing and the like may be performed. The dehydration operation is not particularly limited, but is usually brought into contact with a molecular sieve or the like. For the raw material compound, the degassing and dehydrating operations are usually performed before contact with the metal-carbene complex compound (10).

Further, since the olefin as a raw material may contain a trace amount of impurities (for example, peroxide), it may be purified from the viewpoint of improving the yield of the target product. There are no particular restrictions on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, LF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).

The compound (21) and the compound (31), which are the raw material compounds, may be mixed in advance and then charged into the reaction vessel, or may be charged separately. In some cases, the other raw material compound is brought into contact with the mixture obtained by contacting the compound (21) or the compound (31) with the metal-carbene complex compound as the raw material compound. The molar ratio of the raw material compound (21) and the compound (31) is not particularly limited, but it is preferable to use about 0.01 to 100 mol of the other olefin with respect to 1 mol of the standard olefin compound. Use about 0.1 to 10 mol.

In the present invention, the olefin metathesis reaction is carried out in a state where the first fluorine-containing olefin compound (21), which is a gas at normal temperature and pressure, is liquefied by pressurization. The reaction efficiency is improved by liquefying the compound (21) under pressure. In this case, it is preferable not to use a solvent in the reaction. Further, it is preferable that the metal-carbene complex compound is dissolved in the liquefied olefin compound (21). The term “liquefied by pressurization” refers to a state in which the pressure of the reaction system exceeds the vapor pressure of compound (21) at the reaction temperature. Of these, it is preferable that the partial pressure of the compound (21) in the reaction system exceeds the vapor pressure of the compound (21).

When the compound (31) is liquid under the reaction conditions (including the case where it is liquefied by heating), it is preferable not to use a solvent for the metathesis reaction. In this case, it is preferable that the metal-carbene complex compound is dissolved in the olefin compound. When compound (21) and compound (31) are incompatible, a solvent having an affinity for both may be used. Examples of such a solvent include a fluorine-containing solvent such as trifluoromethylbenzene.

The metal-carbene complex compound may be charged as a reagent or generated in the system. When charged as a reagent, a commercially available metal-carbene complex compound may be used as it is, or a non-commercially available metal-carbene complex synthesized from a commercially available reagent by a known method may be used. When generated in a system, a metal-carbene complex compound prepared from a metal complex as a precursor by a known method can be used in the present invention. The amount of the metal-carbene complex compound to be used is not particularly limited, but is usually about 0.0001 to 1 mol, preferably about 0.001 to 0.2 mol, based on 1 mol of the reference olefin compound. ..

The metal-carbene complex compound to be used is usually charged as a solid into the reaction vessel, but may be dissolved or suspended in a solvent before being charged. The solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, and an organic solvent, a fluorine-containing organic solvent, an ionic liquid, water and the like can be used alone or in combination. In these solvent molecules, some or all hydrogen atoms may be replaced 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-based solvents such as −dichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, glyme and diglyme 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, etc., in terms of solubility of the metal-carbene complex, etc. (Diethyl), hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene and the like, and mixtures thereof are preferable.

From the viewpoint of improving the yield of the target product, it is preferable to use a degassed and dehydrated solvent. The degassing operation is not particularly limited, but freeze degassing and the like may be performed. The dehydration operation is not particularly limited, but is usually brought into contact with a molecular sieve or the like. The degassing and dehydrating operations are usually performed prior to contact with the metal-carbene complex compound.

The atmosphere in which the raw material compound and the metal-carbene complex compound are brought into contact with each other is not particularly limited, but is preferably in an inert gas atmosphere, particularly preferably in a nitrogen or argon atmosphere, in terms of extending the life of the catalyst.

The phase in which the raw material compound and the metal-carbene complex compound are brought into contact with each other is a liquid phase. Since the raw material compound (21) is a liquid under the reaction conditions, it may be carried out without a solvent, but a solvent can be used if necessary. As the solvent used at this time, the same solvent as that used for dissolving or suspending the metal-carbene complex compound can be used.

The container for bringing the raw material compound into contact with the metal-carbene complex compound is not particularly limited as long as it does not adversely affect the reaction, and for example, a metal container or a glass container can be used. As a specific example, a metal pressure-resistant container capable of high airtightness is preferable.

The temperature at which the raw material compound and the metal-carbene complex compound are brought into contact with each other is not particularly limited, but can usually be carried out in the range of 30 to 200 ° C., and 30 to 150 ° C. is preferable in terms of the reaction rate. Since the reaction does not start at a low temperature and the complex may be rapidly decomposed at a high temperature, it is necessary to appropriately set the lower and upper limits of the temperature. When a solvent is used, it is preferably carried out at a temperature equal to or lower than the boiling point of the solvent.

The time for contacting the raw material compound and the metal-carbene complex compound is not particularly limited, but is usually carried out in the range of 1 minute to 48 hours.

The pressure at which the raw material compound and the metal-carbene complex compound are brought into contact with each other is not particularly limited, but is carried out under pressure. It is usually about 0.1 to 100 MPa, preferably about 0.1 to 10 MPa.

When the raw material compound and the metal-carbene complex compound are brought into contact with each other, an inorganic salt, an organic compound, a metal complex or the like may coexist as long as the reaction is not adversely affected.

Further, the mixture of the raw material compound and the metal-carbene complex compound may be stirred as long as it does not adversely affect the reaction. At this time, as a stirring method, a mechanical stirrer, a magnetic stirrer, or the like can be used.

After contacting the raw material compound with the metal-carbene complex compound, the target product is usually obtained as a mixture of a plurality of fluorine-containing olefins, and thus may be isolated by a known method. Examples of the isolation method include distillation, column chromatography, recycled preparative HPLC, and the like, and these can be used alone or in combination as required.
The target product obtained by this reaction can be identified by a known method similar to that of 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 as required.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
<Commercial reagent>
In this example, as the catalyst, unless otherwise specified, a commercially available product was used as it is in the reaction. The solvent (benzene-d ₆ ) and the internal standard substance (p-bis (trifluoromethyl) benzene) were used in the reaction after the commercially available product was frozen and degassed in advance and then dried with molecular sieve 4A.
<Evaluation method>
In this example, the structure of the synthesized compound was identified by performing ¹⁹ F-NMR measurement with a nuclear magnetic resonance apparatus (JNM-AL300) manufactured by JEOL Ltd.

<Example 1>
Metathesis of dodecyl vinyl ether and liquefied hexafluoropropylene catalyzed by Umicore M73 SIPr
Under a nitrogen atmosphere, Umicore M73 SIPr catalyst (5 mol%, 0.05 mmol, 41.3 mg), benzene (10.0 mL) and dodecyl vinyl ether (1.0 mmol, 212.4 mg) previously dried with potassium hydroxide were placed in a 125 mL pressure resistant reaction vessel. Weighed in. The internal solution was frozen by cooling with an acetone-dry ice bath, and the inside was depressurized to about 1 mmHg. Then, hexafluoropropylene (15 g, 100 mmol) was introduced at 0 ° C.
The reaction vessel was heated at 60 ° C. and reacted at that temperature for 1 hour. Under the present reaction conditions, the raw material hexafluoropropylene was liquefied and existed as a liquid in the reaction vessel. After completion of the reaction, p-bis (trifluoromethyl) benzene (internal standard substance, 1.0 mmol, 214.1 mg) was added to the obtained crude product, and then 0.1 mL was withdrawn. Withdrawn solution by measuring the NMR was diluted with _C 6 _{D 6,} dodecyl (2,3,3,3-tetrafluoropropene-1-yl) ether (E / Z mixture) confirmed the formation.
A series of these reactions is shown below. The catalyst rotation speed (catalyst rotation frequency per hour) calculated from the ¹⁹ F-NMR spectrum (internal standard substance p-bis (trifluoromethyl) benzene) was 4.3.

<Comparative example 1>
Metathesis of dodecyl vinyl ether and hexafluoropropylene catalyzed by Umicore M73 SIPr
Under a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.10 mmol, 82.6 mg), benzene (10.0 mL) and dodecyl vinyl ether (1.0 mmol, 212.4 mg) previously dried with potassium hydroxide were placed in a 125 mL pressure resistant reaction vessel. Weighed in. The internal solution was frozen by cooling with an acetone-dry ice bath, and the inside was depressurized to about 1 mmHg. Then, hexafluoropropylene (1.5 g, 10 mmol) was introduced at room temperature.
The reaction vessel was heated at 60 ° C. and reacted at that temperature for 1 hour. Under the present reaction conditions, the raw material hexafluoropropylene was not liquefied and existed as a gas in the reaction vessel. After completion of the reaction, p-bis (trifluoromethyl) benzene (internal standard substance, 1.0 mmol, 214.1 mg) was added to the obtained crude product, and then 0.1 mL was withdrawn. Withdrawn solution by measuring the NMR was diluted with _C 6 _{D 6,} dodecyl (2,3,3,3-tetrafluoropropene-1-yl) ether (E / Z mixture) confirmed the formation.
A series of these reactions is shown below. The catalyst rotation speed (catalyst rotation frequency per hour) calculated from the ¹⁹ F-NMR spectrum (internal standard substance p-bis (trifluoromethyl) benzene) was 2.4.

Claims (6)

In the presence of a metal-carbene complex compound catalyst, the reaction represented by the following formula (21) is represented by the following formula (31) in a state where the first fluorine-containing olefin compound which is a gas at normal temperature and pressure is liquefied by pressurization. A method for producing a second fluorine-containing olefin compound by carrying out an olefin cross metathesis reaction in which a liquid olefin compound is reacted under conditions .

(However, in the formula (21), X ¹¹ , X ¹² and X ¹³ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, and 1 to 1 carbon atoms. A group selected from the group consisting of 3 (pel) alkyl halide groups and 1 to 3 (pel) halogenated alkoxy groups. Any two of X ¹¹ , X ¹² and X ¹³ are , As a divalent group in which one hydrogen atom or halogen atom is removed from each of the two groups, they may be bonded to each other to form a ring.)

(However, in the formula (31), R ^{11 to} R ¹⁴ are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, monovalent hydrocarbon group having 1 to 20 carbon atoms, or halogen atom, oxygen atom, respectively. It is a monovalent organic group having 1 to 20 carbon atoms and containing one or more atoms selected from the group consisting of nitrogen atom, sulfur atom, phosphorus atom and silicon atom.) The production method according to claim 1 , wherein the olefin compound represented by the formula (21) has 2 or more and 5 or less carbon atoms. The production method according to claim 1 or 2 , wherein the first fluorine-containing olefin compound is 1,1-difluoroolefin or 1,2-difluoroolefin. The production method according to any one of claims 1 to 3 , wherein the phase in which the raw material compound containing the first fluorine-containing olefin compound and the metal-carbene complex compound catalyst are brought into contact with each other is a liquid phase. The production method according to any one of claims 1 to 4 , which does not use a solvent. The production method according to claim 5 , wherein the compound represented by the formula (31) is a compound having a hetero atom at the vinyl position.