JP2003089689A - Ruthenium complex compound, method for producing the same, catalyst for metathesis reaction and catalyst for hydrogenation reaction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a ruthenium complex compound in which a heterogeneous atom-containing carbene compound having a six-membered ring structure is bound to ruthenium and which is useful as an olefin compound metathesis reaction catalyst or a hydrogenation reaction catalyst, and to provide a method for producing the ruthenium complex compound. SOLUTION: The ruthenium complex compound in which the heterogeneous atom-containing carbene compound having the six-membered ring structure is bound to ruthenium is obtained, and the method for producing the ruthenium complex compound is characterized by reacting the heterogeneous atom- containing carbene compound having the six-membered ring structure with a ruthenium complex compound having one or more neutral ligands to exchange the ligands.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ruthenium complex compound useful as a catalyst for a metathesis reaction and a hydrogenation reaction of an olefin compound, and a method for producing the same.

[0002]

BACKGROUND ART Metathesis reactions such as ring-opening metathesis polymerization of olefin compounds, ring-closing metathesis reaction, cross-metathesis reaction of acyclic olefins, and metathesis reaction of acyclic dienes are industrially useful reactions. This metathesis reaction is carried out in the presence of a catalyst. As a catalyst to be used, conventionally, a transition metal compound such as tungsten, molybdenum or titanium is combined with an organometallic reducing agent such as an organoaluminum compound or an organotin compound. Catalyst systems are known. However, in these catalyst systems, it is difficult to control the metathesis reaction because a plurality of catalytically active species are produced, and the produced catalytically active species are unstable and deactivate immediately.

On the other hand, in recent years, it has been reported that a transition metal-carbene complex in which a carbene compound is bonded to a transition metal exhibits a high catalytic activity, and further various metathesis reactions can be highly controlled. For example, European Published Patent No. 2181
No. 38 publication and "Metathesis Polymer"
ization of Offices and Po
lymerization of Alkynes ”,
1996, page 1, Kluwer Academic
In Publisher and Boston, a carbene complex of molybdenum or tungsten having a bulky alkoxide ligand and an imide ligand serves as a highly active catalyst for a metathesis reaction, and when this complex is used, stereospecificity is relatively high. It is described that ring-opening metathesis polymerization of high cyclic olefin is possible.

Further, recently, a ruthenium complex compound (hereinafter sometimes referred to as "ruthenium-carbene complex") in which a carbene compound is bonded to ruthenium, which has an advantage of being less susceptible to water and alcohol, has been attracting attention. . For example, Japanese Patent Publication No. 9-512828 discloses a ruthenium-carbene complex having phosphine as a ligand as a catalyst for a metathesis reaction of a highly active olefin compound. In addition, JP-A-10-195182
In the publication, ring-opening metathesis polymerization of cyclic olefins is carried out in the presence of a ruthenium-carbene complex compound having phosphine as a ligand, and then olefinic property in the ring-opening polymer is added without adding a catalyst for hydrogenation reaction. A method of hydrogenating a double bond is disclosed.

Further, WO99 / 51344 and WO0
0/15339 discloses a ruthenium-carbene complex having, as a ligand, a substituted imidazoline-2-ylidene or a substituted imidazolidine-2-ylidene, which is a heterocyclic carbene compound having a 5-membered ring structure in place of phosphine. It has been reported that this compound has an extremely high catalytic activity, and an example in which a metathesis reaction is carried out using a ruthenium-carbene complex having a substituted imidazoline-2-ylidene as a ligand having different 1,3-position substituents Has been done.

However, since ruthenium is a rare and expensive metal, high activation of the ruthenium-carbene complex catalyst is required.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a novel and highly active ruthenium complex compound, a process for producing the same, a catalyst for metathesis reaction of an olefin compound containing the complex compound, and a hydrogenation reaction of the olefin compound. An object is to provide a catalyst.

[0008]

The present inventors have succeeded for the first time in obtaining a ruthenium complex compound in which a hetero atom-containing carbene compound having a 6-membered ring structure is bonded to ruthenium. Then, they have found that the ruthenium complex compound serves as a highly active catalyst for the metathesis reaction and hydrogenation reaction of an olefin compound, and have completed the present invention.

Thus, according to the first aspect of the present invention, there is provided a ruthenium complex compound in which a hetero atom-containing carbene compound having a 6-membered ring structure is bonded to ruthenium. According to a second aspect of the present invention, there is provided a method for producing a ruthenium complex compound, which comprises reacting a hetero atom-containing carbene compound having a 6-membered ring structure with a ruthenium complex compound having a neutral ligand. It According to a third aspect of the present invention, there is provided a catalyst for metathesis reaction of an olefin compound, which comprises the ruthenium complex compound of the present invention. The metathesis reaction catalyst of the present invention can be suitably used as a ring-opening metathesis polymerization catalyst. According to a fourth aspect of the present invention, there is provided a catalyst for hydrogenation reaction of an olefin compound, which comprises the ruthenium complex compound of the present invention.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 1) Ruthenium Complex Compound The ruthenium complex compound of the present invention is a novel compound and is characterized in that at least one heteroatom-containing carbene compound having a 6-membered ring structure is bonded to ruthenium.

The hetero atom-containing carbene compound having a 6-membered ring structure is a compound having at least one hetero atom and at least one methylene radical in the 6-membered ring structure. A methylene free radical is an uncharged divalent carbon atom having a bond and is represented by (> C :).

Here, the hetero atom means the 15th periodic table.
It refers to an atom belonging to Group 16 and Group 16, and specifically includes N atom, O atom, P atom, S atom, As atom, Se atom and the like. Among these heteroatoms, N atom, O
Atoms, P atoms and S atoms are preferable for obtaining a stable carbene compound, N atoms and P atoms are more preferable, and N atoms are particularly preferable.

Among the N atom-containing carbene compounds having a 6-membered ring structure, a particularly preferable compound is a hexahydropyrimidine-2-ylidene derivative represented by the following general formula [1].

[0014]

[Chemical 1]

In the formula, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group. Also, R ¹
At least two of R ⁸ may be bonded to each other to form a ring. Examples of the halogen atom include fluorine, chlorine, bromine and the like. Moreover, as a hydrocarbon group, a C1-C20 hydrocarbon group is mentioned.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group and an aryl group. The alkyl group, alkenyl group and alkynyl group may be linear, branched or cyclic, and one or more hydrogen atoms in the hydrocarbon group are, for example, nitro group, nitroso group, alkoxy group, aryloxy group. Group, amide group, carboxyl group, carbonyl group,
It may be substituted with a functional group such as a silyl group or a sulfonyl group, or a halogen atom.

Among the above hydrocarbon groups, the number of carbon atoms is 1 to 20.
Is preferably an alkyl group or an aryl group having 6 to 20 carbon atoms. Specifically, methyl group, ethyl group, isopropyl group, sec-butyl group, tert-butyl group, n-butyl group, n-pentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, etc. 1-2 carbon atoms
An alkyl group of 0; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a benzyl group, 1
-Phenylethyl group, 1- (α-naphthyl) ethyl group,
Aralkyl group having 7 to 20 carbon atoms such as 1- (β-naphthyl) ethyl group; 1- (1,2,2-trimethylpropoxycarbonyl) ethyl group, 2- (1,2,2-trimethylpropoxycarbonyl) ethyl Group, 1- (ethoxycarbonyl) ethyl group, 2- (ethoxycarbonyl) ethyl group, or other functional group-containing alkyl group having 1 to 20 carbon atoms;

Phenyl group, 2-methylphenyl group, 3-
Methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,6-diethylphenyl group, 2,
6-diisopropylphenyl group, mesityl group, 3,5-
Dimethoxyphenyl group, 2-aminophenyl group, 4-aminophenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2-nitrophenyl group, 4-nitrophenyl group, Examples thereof include an aryl group which may have a substituent such as a 2-acetoxyphenyl group, a 4-acetoxyphenyl group, an α-naphthyl group and a β-naphthyl group.

The carbene compound represented by the general formula [1] can be prepared by a known method, for example, Chemical Com.
communications, 1999, 241-242.
It can be synthesized by the method described on the page. Also, W
It can also be synthesized by a method similar to the method for synthesizing a heterocyclic carbene compound having a 5-membered ring structure described in O00 / 15339. In general, a carbene compound having a methylene free group is unstable and only temporarily exists as a reaction intermediate, but a hetero atom-containing carbene compound having a 6-membered ring structure used in the present invention is stable and is isolated. be able to.

In the present invention, among the above-mentioned ruthenium complex compounds, the ruthenium complex compound represented by the following general formula [2] is preferable.

[0021]

[Chemical 2]

In the formula, R ^{1 to} R ⁸ have the same meanings as in the above formula [1]. X ¹ and X ² each independently represent any anionic ligand, and L represents any neutral ligand. R ⁹
And R ¹⁰ independently of each other represent a hydrogen atom or an organic group. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms.
Alkynyl group, C6-20 aryl group, C1-20 carboxylate group, C1-20 alkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy. Group, C6-20 aryloxy group, C2-20 alkoxycarbonyl group, C1-20 alkylthio group, C6-2
Examples thereof include an arylthio group having 0, an alkylsulfonyl group having 1 to 20 carbon atoms, and an alkynylsulfinyl group having 1 to 20 carbon atoms. In addition, these organic groups are oxygen atoms,
It may be substituted with a group containing any atom selected from the group consisting of a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom, or a halogen atom. Among these, it is preferable that one of R ⁹ and R ¹⁰ is a hydrogen atom and the other is the above organic group.

The anionic ligands (X ¹ and X ² )
May be any ligand as long as it has a negative charge when separated from the central metal (Ru). Further, the neutral ligand (L) may be any ligand as long as it has a neutral charge when separated from the central metal,
It may be a hetero atom-containing carbene compound having a 6-membered ring structure represented by the above formula [1].

Specific examples of the anionic ligands (X ¹ and X ² ) include halogen atoms such as fluorine, chlorine, bromine and iodine; hydrogen atoms; diketonate groups such as acetylacetonate; and substituents. May be cyclopentadienyl group, allyl group optionally having a substituent, alkenyl group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carboxyl group,
Examples thereof include an alkyl sulfonate group, an aryl sulfonate group, an alkylthio group, an alkenylthio group, an arylthio group, an alkylsulfonyl group and an alkylsulfinyl group. Of these, a halogen atom is preferable.

Specific examples of the neutral ligand (L) include:
Oxygen atom, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, aromatic compounds, cyclic diolefins, Examples thereof include olefins, isocyanides, thiocyanates, and a hetero atom-containing carbene compound having a 6-membered ring structure represented by the above formula [1]. Among these, pyridines and phosphines are preferable.

Specific examples of the ruthenium complex compound represented by the general formula [2] include (1,3-diisopropylhexahydropyrimidine-2-ylidene) (benzylidene).
(Tricyclohexylphosphine) ruthenium dichloride, (1,3-dibenzylhexahydropyrimidine-2
-Ylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-diphenylhexahydropyrimidine-2-ylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride, [1,3-di (4'-methyl (Phenyl) hexahydropyrimidine-2-ylidene] (benzylidene)
(Tricyclohexylphosphine) ruthenium dichloride, 1,3-di (2 ', 4'-dimethylphenyl) hexahydropyrimidine-2-ylidene] (benzylidene)
(Tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl hexahydropyrimidine-2
-Ylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dicyclohexylhexahydropyrimidine-2-ylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride,

(1,3-diphenylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, [1,
3-di (4'-methylphenyl) hexahydropyrimidine-2-ylidene] (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, [1,3
-Di (2 ', 4'-dimethylphenyl) hexahydropyrimidine-2-ylidene] (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride,
(1,3-Dimesityl hexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, [1,3-di (2 '
-Propenyl) hexahydropyrimidine-2-ylidene] (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, [1,3-di (1'-phenylethyl) isopropylhexahydropyrimidine-
2-ylidene] (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dicyclohexylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride and the like can be mentioned.

2) Production of Ruthenium Complex Compound The ruthenium complex compound of the present invention is prepared by reacting a ruthenium complex compound having a neutral ligand with the carbene compound having a 6-membered ring hetero atom. It can be manufactured by exchanging the particles.

As the neutral ligand of the ruthenium complex compound having the neutral ligand, a ligand having a neutral charge,
That is, any Lewis base may be used. Specific examples thereof include oxygen atom, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, stibines, sulfoxides, thioethers, amides, Examples thereof include aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates and carbene compounds.

The amount of the hetero atom-containing carbene compound having a 6-membered ring structure used in the ligand exchange reaction is usually 1 mol or more per 1 mol of the ruthenium complex compound (raw material) having a neutral ligand. There is no particular limitation. The ligand exchange reaction between the neutral ligand and the hetero atom-containing carbene compound having a 6-membered ring structure usually proceeds quantitatively. Therefore, a hetero atom-containing carbene compound having one 6-membered ring structure can be obtained by using the hetero atom-containing carbene compound in an approximately equimolar amount of the raw material. When used in a double amount (mol) or more, a ruthenium complex compound in which a hetero atom-containing carbene compound having one or two 6-membered ring structures is bonded to ruthenium can be obtained. The hetero atom-containing carbene compound having a 6-membered ring structure may be isolated and purified, or the reaction crude product may be directly used for the ligand exchange reaction without isolation and purification. .

The temperature of the ligand exchange reaction is not particularly limited as long as it is within a temperature range in which the desired ruthenium complex compound can stably exist, but is usually -100 ° C to 200 ° C, preferably -80 ° C to 150 ° C. , More preferably -40 ° C
Is in the range of -100 ° C The reaction time is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours.

The ligand exchange reaction is usually carried out in an inert solvent. Any solvent may be used as long as it is inert and can dissolve the ruthenium complex compound to be produced, and examples thereof include ethers, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons. Hydrogen or the like can be used. Among these, use of ethers or aromatic hydrocarbons is particularly preferable from the viewpoint of obtaining the desired ruthenium complex compound in good yield.

3) Catalyst for Metathesis Reaction The ruthenium complex compound of the present invention is useful as a catalyst for metathesis reaction of an olefin compound. Here, the olefin compound is not particularly limited as long as it has at least one carbon-carbon double bond in the molecule. Also,
The ruthenium complex compound of the present invention exhibits high activity also to an olefin compound having a functional group. Examples of the functional group of the olefin compound having a functional group include a functional group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom and the like.

More specifically, alkoxy group, carboxyl group, alkenyloxy group, alkynyloxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, alkylamino group, arylamino group, alkylamido group, aryl. Examples of the substituent include an amide group, an alkylsilyl group, an arylsilyl group, an alkylsulfonyl group, an alkylsulfinyl group, a nitro group, a nitroso group and a cyano group.

The metathesis reaction of an olefin compound is
It includes all reactions generally called olefin metathesis reaction (KJ Ivin and J.
C. Mol, Olefin Metathesis a
nd Metathesis Polymerizati
on, Academic Press, Tokyo, etc.). For example, ring-opening metathesis polymerization, ring-closing metathesis reaction, cross-metathesis reaction of acyclic olefin, acyclic diene metathesis reaction and the like can be mentioned.

The metathesis reaction can be carried out without solvent or in a solvent. The solvent to be used can be appropriately selected depending on the kind of the olefin compound to be reacted, but the ruthenium complex compound of the present invention is stable not only in the non-polar solvent but also in the polar solvent, so that not only the non-polar solvent but also the polar solvent is used. You can

Examples of the non-polar solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane and diethylcyclohexane. Alicyclic hydrocarbons such as decahydronaphthalene, bicycloheptane, tricyclodecane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene, and tetrahydronaphthalene can be used. Examples of the polar solvent include nitro compounds such as nitromethane and nitrobenzene; nitrile compounds such as acetonitrile and benzonitrile; ethers such as diethyl ether and tetrahydrofuran; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol. , T-butyl alcohol and other alcohols;
Water or the like can be used. Among these, industrially widely used chain aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, alcohols, and water are preferably used.

In the metathesis reaction, the mixing ratio of the olefin compound and the solvent is not particularly limited, but the concentration of the olefin compound in the reaction solution is usually 1 to 100% by weight,
Preferably 2-100% by weight, more preferably 5-10
It is in the range of 0% by weight. When the concentration of the olefin compound is 1% by weight or less, the productivity of the reaction product decreases.

The amount of the ruthenium complex compound used with respect to the olefin compound is not particularly limited, but in terms of the molar ratio of (metal ruthenium in the catalyst) / (olefin compound), it is usually 1: 100 to 1: 2,000,000, It is preferably in the range of 1: 500 to 1,000,000, more preferably 1: 1,000 to 1: 500,000. When the amount of catalyst used is too large, it becomes difficult to remove the catalyst, while when the amount of catalyst is too small, sufficient reaction activity cannot be obtained.

The reaction temperature of the metathesis reaction can be arbitrarily selected depending on the kind of the metathesis reaction and the kind of the olefin compound to be reacted, but it is usually from -80 ° C to 200 ° C.
It is in the range of ° C. If the reaction temperature is too low, the reaction rate will be slow, while if the reaction temperature is too high, the ruthenium complex compound may decompose. The reaction time can be arbitrarily set depending on the type of reaction, but is usually in the range of 1 minute to 1 week.

The metathesis reaction can be initiated by mixing an olefin compound (a reaction solution optionally containing a solvent) and a ruthenium complex compound.

Among these metathesis reactions, the ruthenium complex compound of the present invention is particularly suitable as a catalyst for the ring-opening metathesis polymerization reaction of cyclic olefins (hereinafter, simply referred to as "polymerization reaction").

Examples of the cyclic olefin include monocyclic cyclic olefin monomers; norbornene-based monomers such as norbornenes, dicyclopentadiene and tetracyclododecene. These cyclic olefins may be used alone or in combination of two or more. These cyclic olefins are alkyl groups,
It may be substituted with a hydrocarbon group such as an alkenyl group, an alkylidene group or an aryl group, or a polar group. Also,
When a norbornene-based monomer is used, it may have a double bond in addition to the double bond of the norbornene ring.

Examples of the monocyclic olefin include cyclic monoolefins or cyclic diolefins having usually 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms. Specific examples of the cyclic monoolefin include cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene and the like. Specific examples of the cyclic diolefin include cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, phenylcyclooctadiene and the like.

As the norbornene-based monomer, a substituted or unsubstituted bicyclic or tricyclic or more polycyclic norbornene can be used, and specific examples thereof include norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene and chlorine. Norcyclene, ethylidene norbornene, chloromethyl norbornene, trimethylsilyl norbornene, phenyl norbornene, cyano norbornene, dicyano norbornene, methoxycarbonyl norbornene, pyridyl norbornene, nadic acid anhydride, bicyclic ring which may have a functional group such as nadic acid imide Norbornenes;

Tricyclonorbornenes such as dicyclopentadiene, dihydrodicyclopentadiene and their alkyl, alkenyl, alkylidene, aryl, hydroxy, acid anhydride groups, carboxyl and alkoxycarbonyl substitution products; dimethanohexahydronaphthalene, dimethanooctane Tetracyclic norbornenes such as hydronaphthalene and its alkyl, alkenyl, alkylidene, aryl, hydroxy, acid anhydride groups, carboxyl and alkoxycarbonyl substitution products; pentacyclic norbornenes such as tricyclopentadiene; hexacycles such as hexacycloheptadecene Norbornenes; dinorbornene, compounds in which two norbornene rings are bonded by a hydrocarbon or an ester group, and compounds containing a norbornene ring such as an alkyl- or aryl-substituted product thereof.

In the polymerization reaction, a polymer molecular weight modifier may be used. Examples of the molecular weight modifier include compounds having a vinyl group. Specifically, 1-butene, 1-pentene, 1-hexene, 1-
Α-olefins such as octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; vinyl esters such as allyl acetate and glycidyl methacrylate. Vinyl alcohols such as allyl alcohol; nitrogen-containing vinyl compounds such as acrylamide; The amount of the vinyl compound used can be appropriately selected according to the molecular weight of the target polymer, but is usually 0.001 to 10 with respect to the cyclic olefins.
It is in the range of mol%.

At the end of the polymerization reaction, the vinyl compound may be added again to release the ruthenium complex compound from the growth end of the polymer, if desired, to terminate the polymerization. This polymerization termination method is particularly useful for improving the activity of the catalyst used in the hydrogenation step of hydrogenating the obtained polymer subsequent to the polymerization reaction.

4) Hydrogenation Reaction Catalyst The ruthenium complex compound of the present invention also exhibits high activity as a catalyst for selectively hydrogenating the carbon-carbon double bond of an olefin compound. The olefin compound is not particularly limited as long as it has at least one carbon-carbon double bond in the molecule, and can be arbitrarily selected according to the purpose.

The hydrogenation reaction is carried out by bringing the olefin compound and hydrogen into contact with each other in the presence of the ruthenium complex compound of the present invention. This hydrogenation reaction can be carried out without solvent or in a solvent. The solvent can be appropriately selected depending on the kind of the olefin compound to be hydrogenated, and not only a non-polar solvent but also a polar solvent such as water or alcohol can be used.

Examples of the non-polar solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane and diethylcyclohexane. Alicyclic hydrocarbons such as decahydronaphthalene, bicycloheptane, tricyclodecane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene, and tetrahydronaphthalene can be used. Examples of the polar solvent include nitro compounds such as nitromethane and nitrobenzene; nitrile compounds such as acetonitrile and benzonitrile; ethers such as diethyl ether and tetrahydrofuran; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol. , T-butyl alcohol and other alcohols;
Water or the like can be used. Among these, industrially widely used chain aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, alcohols, and water are preferably used.

The amount of the ruthenium complex compound used in the hydrogenation reaction is not particularly limited, but when expressed by the molar ratio of (metal ruthenium in the catalyst) / (olefin compound),
Usually 1: 100 to 1: 2,000,000, preferably 1: 500 to 1,000,000, more preferably 1 :.
It is in the range of 1,000 to 1: 500,000. The pressure of hydrogen used in the hydrogenation reaction is usually 10 MPa or less, preferably 0.01 to 8 MPa, more preferably 0.05 to
It is 5 MPa. The reaction temperature and reaction time of the hydrogenation reaction can be appropriately selected, but the range is the same as in the case of the metathesis reaction of the olefin compound described above.

It is also possible to carry out ring-opening metathesis polymerization of an olefin compound using the ruthenium complex compound of the present invention, and subsequently hydrogenate the produced polymer. In that case, the ruthenium complex compound of the present invention used as a catalyst in the polymerization step can be directly used as a catalyst for hydrogenation reaction.

The ruthenium complex compound of the present invention is subjected to ring-opening metathesis polymerization using dicyclopentadiene (DCP) as a cyclic olefin and then subjected to a hydrogenation reaction to obtain a hydrogenated DCP polymer. In this case, it can be used particularly preferably. The obtained DCP ring-opening polymer hydride has a polystyrene-equivalent weight average molecular weight of 1,000 to 500,000 as measured by gel permeation chromatography (GPC).
And the iodine value is 20 or less.

[0055]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified.

(1) The synthesized ruthenium complex compound is
^The structure was identified by measurement of ¹ H-NMR, ¹³ C-NMR and ^{3 1} P-NMR spectra. (2) The polymerization conversion rate in ring-opening metathesis polymerization was determined by the solid content weight measurement method. (3) The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer are determined by gelling with tetrahydrofuran as a solvent.
It was measured as a polystyrene conversion value by permeation chromatography (GPC, manufactured by Tosoh Corp., HLC-8020). Moreover, the molecular weight of the hydride of the ring-opening polymer was measured as a polystyrene conversion value by gel permeation chromatography (GPC, Tosoh Corp., HLC-8121, 135 ° C.) using orthodichlorobenzene as a solvent. . (4) The hydrogenation rate of carbon-carbon double bonds in the polymer is ¹
It was measured by 1 H-NMR spectrum. (5) Analysis of the reaction product by the ring-closing metathesis reaction and the cross-metathesis reaction of the acyclic olefin was performed by using a gas chromatography-mass spectrum (GC-MS) analysis method.

Example 1 Synthesis of (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride 1,3-diisopropyl-1,4,5,6-tetrahydropyrimidi Titanium tetrafluoroborate (Tetr
ahedron Letters Vol. 32, N
o. 38, 5031-5034 (1991). ) 2.8 parts and 3 parts of sodium hydride are put into a Schlenk tube, and tetrahydrofuran (TH
F) 130 parts and 240 parts of ammonia were added. The mixture was stirred at ammonia reflux temperature for 3 hours. To the residue obtained by removing the solvent under reduced pressure, 200 parts of n-hexane was added and stirred sufficiently. The filtrate obtained by separating the solid components by filtration was used to prepare separately prepared bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride (RuCl
_{2 (= CH (OEt))} (P (C 6 H 11) 3) 2) 1
Part and tetrahydrofuran (130 parts) were added to the homogeneous mixture, and the mixture was stirred at room temperature for 2 hours. The residue obtained by removing the reaction solvent under reduced pressure was washed 5 times with 70 parts of n-hexane,
It was dried under reduced pressure. The obtained powder was recrystallized from hot n-hexane to obtain 0.3 part of the target compound. In addition,
All operations were performed under an argon atmosphere.

Physical property data of the obtained ruthenium complex compound are shown below. Elemental analysis value of target compound (C ₃₁ H
₅₉ ON ₂ Cl ₂ PRu); Calcd; C: 54.85, H: 8.76, N: 4.13.
(%) Measured value; C: 54.73, H: 8.74, N: 4.09
(%) ¹ H-NMR (CD ₂ Cl _2, room temperature) δ ppm: 14.
77 (d, 1H, J = 1.1 Hz, CH (OEt)) ³¹ P-NMR (CD ₂ Cl ₂ , room temperature) δ ppm: 3
8.5 (P (C ₆ H ₁₁ ) ₃ )) ¹³ C-NMR (CD ₂ Cl ₂ , room temperature) δppm: 20
7.9 (d, J = 82.2 Hz, NCN)

[0059]Example 2  (1,3-diisopropylhexe
Sahydropyrimidine-2-ylidene) (benzylidene)
(Tricyclohexylphosphine) ruthenium dichlorine
Synthesis of code 1,3-diisopropyl-1,4,5,6-tetrahydr
1.3 parts of ropyrimidinium tetrafluoroborate
Put it in a Schlenk tube, and add 23 parts of THF and lithium diisoprene.
0.53 parts of lopyramide was added. Stir at room temperature for 1 hour
did. This solution is filtered through Celite and the solution part is prepared separately.
Bis (tricyclohexylphosphine) benzylidene
Ruthenium dichloride (RuCl_Two(= CHC₆H₅)
(P (C ₆H₁₁)_Three)_Two) 1 part and 45 parts toluene
The mixture was added to the homogeneous mixture and stirred at room temperature for 1 hour. Reaction solvent
Concentrate under reduced pressure, add 41 parts of n-pentane, insoluble matter
Was removed by filtration through Celite and then dried under reduced pressure. Got
The powder obtained is cooled to -30 ° C and washed with n-pentane.
Thus, 0.3 part of the target compound was obtained. In addition, everything
All the operations were performed under an argon atmosphere.

Physical property data of the obtained ruthenium complex compound are shown below. ¹ H-NMR (C ₆ D ₆ , room temperature) δppm: 20.76
(D, 1H, J = 3.7 Hz, CHC ₆ H ₅ )) ³¹ P-NMR (C ₆ D ₆ , room temperature) δ ppm: 35.0
^{_{(P (C 6 H 11)}} 3)) 13 C-NMR (C 6 D 6, room temperature) [delta] ppm: 208.
9 (d, J = 85Hz, NCN)

Example 3 Ring-Opening Metathesis Polymerization and Hydrogenation Reaction of DCP 300 parts of cyclohexane and 66.9 parts of dicyclopentadiene were added to an autoclave equipped with a stirrer, and 0.64 part of 1-hexene was added as a molecular weight modifier. did. To this solution was added a solution prepared by dissolving 0.02 part of (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride obtained in Example 1 in 9 parts of THF. . This mixture was stirred at 60 ° C. for 1 hour, and then 0.3 part of ethyl vinyl ether was added to stop the polymerization reaction. When a part of the polymerization reaction liquid was sampled and analyzed, the polymerization conversion rate was 99% or more, Mn was 12,300, and Mw was 2
It was 4,900.

Then, hydrogen was supplied into the autoclave, and hydrogenation reaction was carried out by stirring at 150 ° C. and hydrogen pressure of 5 MPa for 6 hours. The hydrogenation rate of the obtained DCP polymerized hydride was 99.9% or more, the iodine value was 1.2, and Mn was 1
5,300 and Mw were 32,300.

Example 4 Ring-Opening Metathesis Polymerization and Hydrogenation Reaction of DCP 300 parts of cyclohexane and 74.8 parts of dicyclopentadiene were added to an autoclave equipped with a stirrer, and 0.48 part of 1-hexene as a molecular weight modifier was added. To this solution was added the catalyst solution prepared by dissolving 0.016 parts of (1,3-diisopropylhexahydropyrimidine-2-ylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride obtained in Example 2 in 9 parts of THF. . The solution was stirred at 60 ° C. for 1 hour, and then 0.16 part of ethyl vinyl ether was added to stop the polymerization reaction. When a part of the polymerization reaction liquid was sampled and analyzed, the polymerization conversion was 99% or more, Mn was 23,300, and Mw was 5
It was 3,500.

Next, hydrogen was supplied into the autoclave and hydrogenation reaction was carried out by stirring at 150 ° C. and hydrogen pressure of 5 MPa for 6 hours. The hydrogenation rate of the obtained DCP polymerized hydride was 99.9% or more, the iodine value was 2.4, and Mn was 2
It was 8,900 and Mw was 67,300.

Example 5 Ring-closing metathesis reaction of 1,7-octadiene The (1,3-diisopropylhexahydropyrimidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium obtained in Example 1 was placed in a glass container. A solution in which 0.05 part of dichloride was dissolved in 2 parts of 1,2-dichloroethane was added, and 0.5 part of 1,7-octadiene was added thereto. This mixture was reacted at 45 ° C. for 3 hours and then analyzed by GC-MS to find that it was 1,7
-Conversion rate of 98 due to ring-closing metathesis reaction of octadiene
It was found that cyclohexene was obtained at a percentage of more than 100%.

Example 6 Cross metathesis reaction of 1-octene A reaction was carried out in the same manner as in Example 3 except that 3.36 parts of 1-octene was used in place of 0.5 part of 1,7-octadiene. When analyzed by GC-MS, it was found that 7-at a conversion rate of 65% due to the 1-octene cross metathesis reaction.
It was found that tetradecene was obtained.

[0067]

As described above, according to the present invention, 6
Provided is a novel ruthenium complex compound having a hetero atom-containing carbene compound having a membered ring structure bonded thereto. According to the production method of the present invention, the ruthenium complex compound of the present invention can be produced simply and efficiently. In addition, the ruthenium complex compound of the present invention exhibits excellent catalytic activity for the metathesis reaction and hydrogenation reaction of an olefin compound.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C07B 61/00 300 C07B 61/00 300 C07F 15/00 C07F 15/00 A (72) Inventor Yasuo Kakujo Kanagawa Prefecture 1-2-1, Yokou, Kawasaki-ku, Kawasaki City, Japan Zeon Corporation R & D Center (72) Inventor Shintaro Ikeda 1-2-1, Yokou, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Zeon Corporation, R & D Center (72) Inventor Wolfgang A. Hermann Alexander von Humboldt Vuegg 11 D-85354 Freising Germany (72) Inventor Karl Ehuele La Orenza Vegg 12 82334 Puchheim by Munich German Republic F Term (reference) 4G069 AA06 AA08 BA27A BA27B BC70A BC70B BE02A BE02B BE05A BE05B BE13A BE13B BE26A BE26B BE33A BE33B CB02 CB04 CB38 CB44 DA02 4H006 AA02 AC28 AC29 BA23 BA46 BA48 BA81 4H039 CA2 9 CA40 CF10 CG50 CH20 4H050 AB40 WB11 WB16 WB21 4J032 CA25 CA34 CA38 CA43 CA45 CA68 CB01 CB03 CD02

Claims (5)

[Claims] 1. A ruthenium complex compound comprising a hetero atom-containing carbene compound having a 6-membered ring structure bonded to ruthenium. 2. The method for producing a ruthenium complex compound according to claim 1, wherein the ruthenium complex compound having a neutral ligand is reacted with a hetero atom-containing carbene compound having a 6-membered ring structure. 3. A catalyst for metathesis reaction of an olefin compound, which comprises the ruthenium complex compound according to claim 1. 4. The catalyst according to claim 3, which is for ring-opening metathesis polymerization. 5. A catalyst for hydrogenation reaction of an olefin compound, which comprises the ruthenium complex compound according to claim 1.