WO2002034723A1

WO2002034723A1 - Process for preparation of diaminocarbene-transition metal complexes, ruthenium compounds and their usage

Info

Publication number: WO2002034723A1
Application number: PCT/JP2001/009206
Authority: WO
Inventors: Seiji Okada; Kazunori Taguchi; Yasuo Tsunogae
Original assignee: Zeon Corporation
Priority date: 2000-10-23
Filing date: 2001-10-19
Publication date: 2002-05-02

Abstract

A process for preparing complexes of transition metals with diaminocarbene ligands, which comprises the step (A) of deprotonating a secondary amine, reacting the obtained anion with carbon disulfide, and then desulfurizing the obtained compound into an N,N,N',N'-tetrasubstituted amidinium salt, the step (B) of preparing a diaminocarbene from the salt by deprotonation, and the step (C) of bringing the diaminocarbene into contact with a transition metal complex bearing a neutral ligand to conduct ligand exchange and thereby obtaining a transition metal complex bearing a diaminocarbene ligand; ruthenium compounds and process for their preparation; a process for metathesis of olefinic compounds with the ruthenium compounds; and a process for producing polymers by ring-opening metathesis polymerization of cyclic olefins with the same.

Description

Description Method for producing diaminocarbene-coordinated transition metal complex

And ruthenium compound and method of using the same

Technical field

The present invention relates to a method for producing a transition metal complex coordinated with diaminocarbene, a novel ruthenium compound and a method for using the ruthenium compound, and particularly to a metathesis polymerization method for an olefin compound and a hydrogenation method for a polymer.

Background technology

The metathesis reaction of an olefin compound is a ring-opening metathesis polymerization, a ring-closing metathesis reaction, a cross-metathesis reaction of an acyclic olefin, a metathesis reaction of an acyclic gen, and the like, and is an industrially useful reaction. Heretofore, transition metal compounds such as tungsten, molybdenum, and titanium have been mainly used as these metathesis reaction catalysts.

Recently, a complex compound having a ruthenium carbene bond (hereinafter sometimes referred to as a ruthenium-carbene complex), which has the advantage of being less susceptible to water and alcohol, has been synthesized, and its application to metathesis reactions has been studied. ing. For example, Japanese Patent Application Laid-Open No. Hei 9-1152828 describes that a ruthenium-carbene complex having phosphine as a ligand shows a high catalytic activity for an olefin metathesis reaction. Japanese Patent Application Laid-Open No. H10-195182 discloses that after ring-opening metathesis polymerization of cyclic olefins using the ruthenium-carbene complex, the complex is also used as a hydrogenation catalyst. A method for hydrogenating a ring-opened polymer is disclosed.

Also, there are many reports on a method for hydrogenating an olefinic unsaturated bond of a polymer in the presence of a ruthenium complex compound (Japanese Patent Application Laid-Open Nos.

— 1 7 6 2 3 3, JP-A-11-138 009, JP-A-7-292 9, JP-A-7-

1 4 9 8 2 3, Japanese Patent Application Laid-Open No. Hei 11-1-5 8 25 56, Japanese Patent Application Laid-Open No. 11-193 3 1 1 -209460). In each report, a ruthenium compound having at least one phosphine as a ligand is used as a hydrogenation catalyst, but none of the catalytic activities is sufficiently high, and the activity is higher. The development of a hydrogenation catalyst was desired.

On the other hand, International Publications W099 / 51344 and WOO0Z1 5339 disclose that when substituted imidazoline-12-ylidene or substituted imidazolidin-12-ylidene is used as a ligand, the catalytic activity of the ruthenium complex compound for metathesis reaction is reduced. Further improvements are disclosed. However, the activity is still insufficient for industrial use, and there is a problem that the stability of the complex in a solution is not sufficient and the complex is easily decomposed. Furthermore, many of the substituted imidazolidine_2_ylidene ligands cannot be synthesized depending on the type of the substituent at the N-position, and it is difficult to obtain a ruthenium complex compound that is optimal for the target metathesis reaction. There was also a problem.

By the way, a benzimidazoline-2-ylidene compound having a structure in which a benzene ring and an imidazoline ring are fused by sharing two carbon atoms, and examples of their synthesis are described in Chem. Eur. J., Vol. 5, No. 6 1 931—reported in 1 935 (1 999). The synthesis method is as follows: First, N, N'-disubstituted 1,2-phenylenediamine is reacted with thiophosgene to synthesize 1,3-disubstituted benzimidazolysine 1-2-thione, and then Na-K By reacting with the alloy to remove sulfur, 1,3-disubstituted benzimidazolidine-12-ylidene is obtained.

However, this method requires the use of highly toxic thiophosgene for the synthesis of 1,3-disubstituted benzimidazolidin-12-thiones, and the 1,3-disubstituted benzimidazolidin-2-ylidene. There is a problem that a long time is required for the desulfurization reaction when synthesizing the compound. As described above, it is difficult to synthesize a benzimidazoline-12-ylidene compound, and thus, a ruthenium mono-lupene complex having the compound as a ligand has not been obtained.

On the other hand, heterocyclic carbene compounds having a nitrogen atom such as 1,3-diisopropylimidazoline_2-ylidene and 1.3-dimesitylimimidazoline-1-ylidene As another method for synthesizing a product, a method has been proposed in which a 1,3-disubstituted imidazolyl salt is used as a reaction intermediate. In addition, several methods for synthesizing the reaction intermediate have been reported.

In general, a method of reacting an imidazole with an organic halogen compound is widely known.Other than that, U.S. Pat.No. 5,077.44 discloses monosubstituted amines, paraformaldehyde and Glyoxal as a raw material; Org.LΘtt., Vol.1, No.6, 953-9556 (19999) has 2,4,6-trimethylaniline After reacting phosphorus and glyoxal, ethane 1.2-di (mesitylamine) is synthesized by a reduction reaction and then reacted with triethyl orthoformate: and 2-bromomesitylene and ethane-1,2-diamine Is reacted with a palladium catalyst to synthesize ethane-1,2-di (mesitylamine) and then reacted with triethyl orthoformate.

However, according to the study of the present inventors, the substituted imidazolium salts obtainable by the above synthesis method are 1,3,4,5-tetramethylimidazolium salt, 1,3,4,5-tetraphenylimidazolym salt Only those having very limited substituents, such as salts, 1,3-dimesityl-14,5-dihydroimidazolium salts (ie, 1,3-dimesitylimidazolidinium salts). For example, it has been extremely difficult to synthesize an imidazolium salt having an aromatic substituent at the 4-position or 5-position carbon atom, such as a benzimidazolyl salt, according to a known method.

Therefore, an object of the present invention is to provide a method for safely and easily producing a diaminocarbene-coordinated transition metal complex useful as a catalyst for various organic reactions represented by a metathesis reaction in a high yield. Another object of the present invention is to provide a novel ruthenium compound having a catalytic activity sufficient for industrial use. Another object of the present invention is to provide a method for using the ruthenium compound as a catalyst for a metathesis reaction of olefin or a hydrogenation reaction of a polymer.

Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, in the step of synthesizing diaminocarbene, which is a heterocyclic carbene having a nitrogen atom, It has been found that diaminophenol can be easily obtained by synthesizing the amidinium salt by a novel method using a method via an N, N, N ', N'-tetra-substituted amidinium salt as an intermediate. Was. In other words, the synthesis of N, N, N ′, N′-tetrasubstituted thiourea, which is a reaction intermediate of the above amidinium salt, is replaced with a conventional method using a thiophosgene, and a secondary amine is subjected to a deprotonation reaction. Next, the reaction is carried out by reacting carbon disulfide.Furthermore, the synthesis of diaminocarbene using the tetra-substituted thiourea as a raw material is changed to N, N, N ′. N'-tetrasubstituted amidinium salt allows a diaminocarbene to be obtained in a very simple operation and in a short time by a method via a amidinium salt. By reacting the diaminocarbene with a transition metal complex, diaminocarbene can be obtained. We have found that coordinated transition metal complexes can be easily synthesized.

In addition, we succeeded for the first time to synthesize a novel ruthenium-carbene complex having a substituted imidazoline-2-ylidene having an imidazoline ring sharing an aromatic ring structure and a carbon-carbon unsaturated bond as a ligand. Furthermore, they have found that the ruthenium-carbene complex is an extremely active and stable catalyst for the olefin metathesis reaction. Furthermore, when a carbene compound having a hetero atom is coordinated as a hydrogenation catalyst, a transition metal compound belonging to Groups 8 to 10 of the periodic table, in particular, a ruthenium compound having a carbene compound having a hetero atom coordinated is used. It was also found that the polymerizable unsaturated bond in the polymer could be hydrogenated very efficiently. The present invention has been completed based on such findings.

Thus, according to the present invention, N, N, N ', N'-tetrasubstituted thioureas are synthesized by reacting a secondary amine with deprotonation and then with carbon disulfide, followed by desulfurization. Step (A) of synthesizing N, N, N ', N'-tetra-substituted amidinium salt by reaction: N, N, N', N'-tetra-substituted amidinyl obtained in the above step (A) (B) synthesizing a diaminocarbene by deprotonating a thiol salt, and bringing the diaminocarbene obtained in the step (B) into contact with a transition metal complex having a neutral ligand to undergo a ligand exchange reaction. A process for synthesizing a lysaminocarbene-coordinated transition metal complex (C). In the step (A), diamine is preferred as the secondary amine. In the step (c), a ruthenium compound is preferably used as the transition metal complex having a neutral ligand. According to the present invention, (1) a substituted imidazoline is obtained by reacting an aromatic ring compound in which at least one amino group is bonded to each of adjacent carbon atoms with a deprotonation and then reacting with carbon disulfide. Synthesizing a 2-imion, followed by synthesizing a substituted imidazolium salt by a desulfurization yellow reaction, and (2) synthesizing a substituted imidazoline-12-ylidene by subjecting the obtained substituted imidazolium salt to a deprotonation reaction; 3) A method for producing a ruthenium compound in which the substituted imidazoline-2-ylidene is coordinated by a ligand exchange reaction by contacting the obtained substituted imidazoline-1-ylidene with a ruthenium compound is also provided.

Further, according to the present invention, there is also provided a ruthenium compound in which a substituted imidazoline-12-ylidene having a structure in which an aromatic ring and an imidazoline ring share two carbon atoms and are fused is coordinated. You. The ruthenium compound preferably has a ruthenium-carbene bond.

Further, according to the present invention, there is provided a method for performing a metathesis reaction of an olefin compound using the above ruthenium compound. Further, according to the present invention, there is also provided a method for obtaining a polymer by subjecting a cyclic olefin to a ring-opening metathesis polymerization reaction using the above ruthenium compound.

Furthermore, according to the present invention, the olefinic unsaturated bond in a polymer having a weight average molecular weight of 1,000 to 1,000,000 as measured by gel permeation chromatography. Is provided by using, as a catalyst, a transition metal compound belonging to Groups 8 to 10 of the periodic table in which a carbene compound having a hetero atom is coordinated. As the transition metal compound, a ruthenium compound is preferable.

BEST MODE FOR CARRYING OUT THE INVENTION

(Preparation of diaminocarbene coordinated transition metal complex)

The method for producing a diaminocarbene-coordinated transition metal complex of the present invention comprises the steps of: deprotonating a secondary amine and then reacting with carbon disulfide to obtain N, N.N ′, N ′.

—Synthesis of tetra-substituted thiourea, followed by desulfurization reaction of N, N, N ', N' Step of synthesizing a tetra-substituted amidinium salt (A): a step of synthesizing a diaminocarbene by deprotonating the N, N, N'.N'-tetra-substituted amidinium salt obtained in the above step (A) (B): and a step of contacting the diaminophenol obtained in the step (B) with a transition metal complex having a neutral ligand to synthesize a diaminocarbene coordinated transition metal complex by a ligand exchange reaction ( C): It is characterized by containing.

The deprotonation reaction in the step (A) is carried out by contacting a secondary amine with an alkali metal compound or an alkaline earth metal compound in the presence or absence of a solvent to form an alkali metal amide or an alkaline earth metal compound. This is a reaction to form a class of metal amides (abbreviated as metal amides).

Examples of the alkali metal compound include sodium hydride, lithium hydride, lithium diisopropylamide, n-butyl lithium, t-butoxy potassium, t-butoxide sodium, sodium methoxide, sodium ethoxide, potassium methoxide, and potassium. Ethoxide and the like can be mentioned. Examples of the alkaline earth metal compound include calcium hydride, magnesium hydride, magnesium methoxide, and magnesium ethoxide.

The use amount (molar ratio) of the alkaline metal compound or the alkaline earth metal compound to the secondary amine is preferably 0.1 to 5.0, more preferably 0.5 to 1.5. It is. If the amount is too large or too small, the yield of the target metal amide decreases. The solvent used for the deprotonation reaction is not particularly limited as long as it is inert to the reaction and dissolves the generated metal amide. Examples of the solvent include ethers, ketones, esters, and halogenated carbon. Examples include hydrogens, aromatic hydrocarbons, and aliphatic hydrocarbons. Among them, ethers and aromatic hydrocarbons are preferred.

The reaction temperature may be any temperature at which the generated metal amide is stable, and is usually from 180 ° C to 200 ° C, preferably from _50 ° C to 100 ° C. More preferably, the temperature is in the range of 110 ° C to 50 ° C.

As the secondary amine, diamine which forms a stable cyclic structure by reaction with carbon disulfide is preferably used. Such diamines are not particularly limited. For example, N, N'-dimethylethylenediamine (1,2-di (methylamino)) , N, N'-diethylethylenediamine, N, N'-di (i-propyl) ethylenediamine, N, N'-diphenylethylenediamine, N, N'dimesityl Ethylenediamine, N, N '—Diphenyl 1,2, -diphenyl Ethylenediamine, N, N' —Di (p-tolyl) ethylenediamine, N.N '— Di (2,6-diethylphenyl) , N'-di (2,6-dimethylphenyl) ethylenediamine, N, N'-di (2,6-diisopropylphenyl) ethylenediamine, N, N'-di (benzhydryl) ethylenediamine, N, N'-dinaphthyl Ethylenediamine, N, Ν 'dianthracenylethylendiamine, N, N' dineopentylethylenediamine, N, N'-di (tert-butyl) ethylenediamine, N, N 'ditritylethylenediamine Min, N, N'-di (1-phenylethyl) ethylenediamine, N.N'-diadamantylethylenediamine, N, N'-dicyclohexylethylenediamine, N, N'di (i-propyl ) 1 1, 1, 2, 2-tetrafluoroethylenediamine, N, N '-diphenyl 1,2-dimethylideneethylenediamine, N. N'-dimesityl 1, 2-di Cyanoethylenediamine, N, N'-dimesityl_1,2-cyclohexenediamine, N, N'-di [2,6-di (i-propylphenyl)]-1,2-cyclohexenediamine Ethylenediamines such as;

1,2-di (methylamino) ethylene, 1,2-di (ethylamino) ethylene, 1,2-di (i-propylamino) ethylene, 1,2-di (phenylamino) ethylene, 1,2-di (mesitylamino) Ethylene, 1,2-di (p-tolylamino) Ethylene, 1,2-di (2,6-diethylphenylamino) Ethylene, 1,2-di (2,6-dimethylphenylamino) Ethylene, 1,2-di (2,6-diisopropylphenylamino) ethylene, 1,2-di (benzhydrylamino) ethylene, 1,2-di (naphthylamino) ethylene, 1,2-di (anthracene) Nilamino) ethylene, 1,2-di (neopentylamino) ethylene, 1,2-di (tert-butylamino) ethylene, 1,2-di (tritylamino) ethylene, 1,2-di (1 Enilethylamino) Ethylene, 1,2-di (adamantylamino) ethylene, 1,2-di (cyclohexylamino) ethylene, 1,2

—Di (phenylamino) 1-1,2-diphenylethylene, 1,2-di (i-pro 1,2-Dimethylethylene, 1,2-di (i-propylamino) -1.2-difluoroethylene, 1,2-di (mesitylamino) 1,1,2-dichloroethylene —Diaminoethylenes:

N, N'-Dimethyl-1,2-phenylenediamine, N, N'-Diethyl-1,2-phenylenediamine, N, N'-Di (i-propyl) 1-1,2-phenylenediamine, N, N '—Dimesityl-3,4,5,6-tetrafluoro-1,2,2-phenylenediamine, N, N' —Dimesityl-3,6-tetrafluoro-1,2,2-phenylenediamine, N, N '—Dimesityl 3,5-tetrafluoro-1,2-phenylenediamine, N, N'-dimesityl-3,4,6-tetrafluorol 1.2-phenylenediamine, N, N'-dimesityl-1,4,5- Phenylenediamines such as tetrafluoro-1,2-phenylenediamine;

Diaminopyridines such as 3,4-di (ί-propylamino) pyridine and 2,3-di (i-propylamino) pyridine;

N, N—Dimethyl-1,3-propanediamine, N, N—Getyl-1,3-propanediamine, N, N—di (i-propyl) 1-1,3-propandiamine, N, N—diphenyl1, 3-propanediamine, N, N-dimesityl-1,3_propanediamine, N, N-di (p-tolyl) -1,1,3-propanediamine, N, N-di (2.6-getylphenyl) 1-1,3 —Propanediamine, N, N—di (2,6-dimethylphenyl) 1-1,3-propanediamine, N, N—di (2,6-diisopropylphenyl) 1-1,3-propanediamine, N.N—di (Benzhydryl) 1,3-propanediamine, N, N-dinaphthyl-1,3-propanediamine, N, N-dianthracenyl-1,3-propanediamine, N, N-dineopentyl-11,3-propanediamine, N, N— Di-tert-butyl-1 3-propanediamine, N, N-ditrityl-1,3-propanediamine, N, N-di (1-phenylethyl) 1-1,3-propanediamine, N, N-diadamantyl1-1,3-propanediamine, N, N-dicyclo 1.3-propanediamines such as hexyl-1,3-propanediamine; and the like. Of these diamines, phenylenediamines and diaminopyridines are preferably used. After deprotonating the secondary amine, the resulting metal amide is reacted with carbon disulfide to synthesize N, N, N ', N'-tetrasubstituted thiourea. The metal amide is contacted with carbon disulfide in the presence or absence of an organic solvent. The contacting method may be such that carbon disulfide is added to metal amide and mixed, or metal amide is added to carbon disulfide and mixed. It may be added separately and mixed. The organic solvent to be used is not particularly limited as long as it is inert to the reaction and dissolves the N, N. N ′, N′—tetraura-substituted thiourea to be formed. Similar ones can be mentioned.

The use amount (molar ratio) of carbon disulfide to the secondary amino group contained in the metal amide is usually 1 to 10,000, preferably 1 to 100. The reaction temperature is not particularly limited as long as the generated N, N, N ', N'-tetra-substituted thiourea is stably present, and is preferably from 180 to 200 ° C, more preferably from 150 to 100 ° C. Is more preferable, and 110 to 50 ° C is particularly preferable. Although the reaction time is not particularly limited, it is preferably 1 minute or more and 1 week or less, and 10 minutes or more in order to obtain N, N, N ', N'-tetrasubstituted thiourea in high yield. Particularly preferred is 5 hours or less.

The N, N. N ', N'-tetrasubstituted thiourea obtained by the above method has the following general formula

A compound having the structural unit of [1]. When diamine is used as the secondary amine, cyclic N, N, N ', N'-tetra-substituted thioureas are formed.

(Wherein, R ^{1 to} R ⁴ are each independently a substituent. R ² and R ³ may be bonded to each other to form a ring. The following formulas [2], [3] and The same applies to [4].) The N, N, N ', N'-tetrasubstituted thiourea formed may be isolated and purified for the next reaction, or the reaction solution obtained by the above method May be used as is, Next, the produced N, N, Ν ', N'-tetra-substituted thiourea is subjected to a desulfurization reaction to synthesize an N, N, N'.N'-tetra-substituted amidinium salt. The desulfurization reaction is carried out by contacting the N, NN.N ', N'-tetrasubstituted thiourea with a desulfurizing agent, such as a Bronsted acid. Specific examples of Bronsted acids, HC and _{HB r, HI, HN0 3,} H 2 S0 4, HBF 4, HP F 6, etc. HS b F ₆ and the like. Subsequent to the Brönsted acid treatment, a Brensted acid salt having a different anion is added and anion exchange is carried out, so that X— in the following general formula [2] can be converted to an anion of the Brönsted acid salt. . By doing so, the desulfurization reaction proceeds efficiently, and the resulting N, N, N ', N'-tetra-substituted amidinium salt may be stabilized.

The molar ratio of Bronsted acid to N, N, N ', N'-tetrasubstituted thiourea is usually from 0.1 to 100, preferably from 0.5 to 10. The reaction temperature, reaction time, reaction method, and reaction solvent are the same as in the above thiourea synthesis reaction.

By the above reaction, N, N, N ', N'-tetra-substituted amidinium salts are obtained. N, N, N ', N'-tetra-substituted amidinium salts are compounds having a structural unit represented by the following general formula [2].

(In the formula, X— is any anion, and is determined by the type of desulfurizing agent or salt thereof.)

In the step (Β), the Ν, Ν, Ν ′, N ′ tetra-substituted amidinium salt obtained in the step (Α) is subjected to a deprotonation reaction to form a Ν, Ν, Ν ′. This is the step of synthesizing Ruben. This deprotonation reaction is carried out by mixing Ν, Ν, Ν ′, N′—tetra substituted amidinium salt with a deprotonating agent. The deprotonating agent is an alkali metal compound or an alkaline earth metal compound. The same ones as mentioned in (A) can be used.

The deprotonation reaction can be performed in the presence or absence of an organic solvent. The mixing method may be such that a deprotonating agent may be added to N, N, N ', N'-tetra substituted amidinium salt, or vice versa. The addition method may be the whole amount at once, or may be added several times.

The organic solvent to be used is not particularly limited as long as it is inert to the reaction and dissolves the N, N, N ', N'-tetra substituted diaminocarbene to be formed. Examples thereof include ethers, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons. Among them, ethers and aromatic hydrocarbons are preferred.

The molar ratio of the alkali metal compound or alkaline earth metal compound to N, N, N ', N'-tetra-substituted amidinium salt is 0.1 to 100, preferably 0.5 to 5. Too much or too little will reduce the yield of the desired product.

The reaction temperature may be any temperature at which the generated N, N, N ', N'-tetrasubstituted diaminocarbene is stably present, and is preferably from _80 to 200 ° C, more preferably from 150 to 150 ° C. Preferably, 0 ° C to 100 ° C is particularly preferred. The reaction time is not particularly limited, but is preferably 1 minute or more and 1 week or less, particularly preferably 10 minutes or more and 5 hours or less, in order to obtain the desired product in high yield.

The resulting N, N, N ', N'-tetra-substituted diaminocarbene may be isolated and used for the next reaction. Alternatively, N, N, N', N'-tetra-substituted amidinium salt may be used in combination with May be used as it is.

The N.N, N ', N'-tetrasubstituted diaminocarbene obtained in the step (B) is a compound having a structural unit represented by the following general formula [3].

In the step (C), the N, N, N ', N'-tetra-substituted diaminocarbene (hereinafter also referred to as diaminocarbene) obtained in the step (B) is combined with a transition metal complex having a neutral ligand. This is a step of synthesizing a diaminocarbene-coordinated transition metal complex by contacting and performing a ligand exchange reaction. This reaction can be performed in the presence or absence of a solvent.

The transition metal complex having a neutral ligand is not particularly limited, but a transition metal complex having a transition metal of Groups 8 to 10 of the periodic table as a central metal is preferable. The transition metals of the 8th to 10th groups of the periodic table include iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), and nickel. (Ni), noradium (Pd), and platinum (Pt). Among these, Fe, Ru, Co, Rh, Ni, and Pd are preferable, and Ru is more preferable.

The neutral ligand coordinated to the transition metal may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples include oxygen atoms, water, carbonyl, amines, pyridines, ethers, nitrols, esters, phosphines, phosphinites, phosphites, stibines, sulfoxides, thioethers, Examples include amides, aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates, carbene compounds, and the like.

Normally, diaminocarbene and the transition metal complex react quantitatively, so that an equivalent amount of the diaminocarbene and the transition metal complex may be reacted.However, depending on the type of diaminocarbene, there is an excess relative to the transition metal complex. In some cases, the ligand exchange reaction proceeds more efficiently when used.

The reaction temperature may be any temperature at which the diaminocarbene-coordinated transition metal complex to be formed is stably present. The reaction temperature is preferably from 80 to 200 ° C, preferably from 70 to 150 ° C, more preferably from 50 to 140 ° C. The temperature is particularly preferably 100 ° C. The reaction time is not particularly limited, but is preferably 1 minute or more and 24 hours or less, particularly preferably 10 minutes or more and 5 hours or less, in order to obtain the desired product at a high yield.

The reaction solvent may be any solvent that is inert to the ligand exchange reaction and dissolves the diaminocarbene-coordinated transition metal complex to be formed. Examples thereof include ethers, ketones, and Examples include steles, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons. Among them, ethers and aromatic hydrocarbons are preferred.

As described above, the diaminocarbene-coordinated transition metal complex obtained in the step (C) is a compound having a structural unit represented by the following general formula [4].

[Four]

(In the formula, M represents a transition metal, Y represents an arbitrary ligand, and n is an integer of 0 to 6.)

The method for producing a diaminocarbene-coordinated transition metal complex of the present invention includes the steps (A) to (C) described above, and can be carried out in a very short time without using dangerous raw materials such as thiophosgene. You can get things.

(Method for Producing Ruthenium Compound) The method for producing a ruthenium compound of the present invention comprises the steps of (1) deprotonating an aromatic ring compound in which at least one amino group is bonded to each of adjacent carbon atoms, Substituted imidazoline 1-2-thione is synthesized by reacting carbon sulfide, followed by synthesis of substituted imidazolium salt by desulfurization reaction. (2) Deprotonation reaction of the obtained substituted imidazolium salt results in substitution imidazoline (2) A ruthenium compound in which the substituted imidazoline-12-ylidene is contacted with a ruthenium compound, and the substituted imidazoline-12-ylidene is coordinated by a ligand exchange reaction. Is manufactured.

Here, the above reaction steps (1) to (3) correspond to the steps (A) to (C) in the above-described method for producing a diaminocarbene-coordinated transition metal complex, respectively. Ie

As a starting material for the step (A), an aromatic cyclized compound represented by the following general formula [5] is used, and as a transition metal complex having a neutral ligand, which is a reaction material for the step (C): By performing ligand exchange using a ruthenium compound having a neutral ligand, a ruthenium compound to which a substituted imidazoline-1-ylidene is coordinated can be produced. Can be.

[Five]

(R ⁵ and R ⁶ are each independently a substituent, preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ⁷ and R ⁸ are bonded to each other to form an aromatic ring structure. The same applies to equations [6] to [8] below.)

The aromatic ring compound represented by the general formula [5] is, for example, R ^{1 of} the formula [5],

A method of reacting an aromatic primary diamine in which R ² is a hydrogen atom with a halogenated hydrocarbon to obtain an aromatic secondary amine, and reacting a 1,2-dihalogenated aromatic compound with a monoalkylamine to obtain an aromatic amine It can be synthesized using a known method such as a method for obtaining a secondary amine.

The reaction conditions and the like in the above-mentioned reaction steps (1) to (3) are the same as the steps (A) to (C) in the above-described method for producing a diaminocarbene-coordinated transition metal complex.

The substituted imidazoline-1-thione which is an intermediate in the reaction step (1) is, for example, a compound represented by the following general formula [6].

The substituted imidazolium salt formed in the reaction step (1) is, for example, a compound represented by the following general formula [7].

(Where X— is any anion.)

The substituted imidazoline-1-ylidene formed in the reaction step (2) is, for example, a compound represented by the following general formula [8].

Conventionally, as a method for obtaining substituted benzimidazoline 1-2-ylidene, thiourea is synthesized by reacting toxic amine with highly toxic thiophosgene, and then directly substituted benzimidazoline 1-2-ylidene without forming a substituted imidazolyl salt. The method of synthesis was adopted. However, the reaction was dangerous, and the synthesis required a long period of one month or more. According to the above reaction steps (1) and (2), substituted benzylimidazoline-1-ylidene can be obtained in a very short time without using dangerous thiophosgene.

The substituted imidazoline-12-ylidene thus obtained is brought into contact with a ruthenium compound having a neutral ligand, and ligand exchange between the neutral ligand and the substituted imidazoline-12-ylidene is performed. Thus, the intended ruthenium compound to which the substituted imidazoline-1-ylidene is coordinated can be synthesized. The neutral ligand may be any ligand having a neutral charge, that is, any Lewis base, and is exemplified in step (C) in the above-described method for producing a diaminocarbene-coordinated transition metal complex. Neutral ligands similar to those described above are used. (New ruthenium compound)

The ruthenium compound of the present invention is a compound in which a substituted imidazoline-1-ylidene having a structure in which an aromatic ring and an imidazoline ring are fused by sharing two carbon atoms is coordinated to a ruthenium atom. .

The substituted imidazoline-1-ylidene is a compound in which the carbon at position 2 of the substituted imidazoline ring is a methylene free radical. Here, the methylene free radical is an uncharged divalent carbon atom having a bond, and is represented by (> C :). Compounds having a methylene free radical are generally unstable and mostly exist only temporarily as reaction intermediates. However, the substituted imidazoline-1-ylidene has a methylene free radical having a 1-position of imidazoline. Since it is stabilized by the nitrogen atom at the 3-position, it can be isolated as a compound. Note that the substituted imidazoline-1-ylidene is a compound represented by the general formula [7].

In the formula [7], the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵ and R ⁶ is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, and an aryl group; However, it may be branched or annular. Further, one or more hydrogen atoms in the hydrocarbon group may be substituted with a functional group containing any of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, or a halogen atom. . Specific examples of such a functional group include a nitro group, a nitroso group, an alkoxy group, an aryloxy group, an amide group, a carbonyl group, a carbonyl group, a silyl group, and a sulfonyl group.

Among the above hydrocarbon groups, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable. Specifically, alkyl having no functional group such as methyl group, ethyl group, isopropyl group, cyclohexyl group, 1-phenylethyl group, 1-naphthylethyl group, 1-tert-butylethyl group, tert-butyl group, etc. Groups; hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-chloroethyl group, 3-fluoropropyl group, 2-aminoethyl group, 3-aminopropyl pill group, 2-acetyl Alkyl groups having a functional group, such as a tylaminoethyl group, an ethoxyshethyl group, an ethoxycetyl group, a methoxycarbonylethyl group, and an ethoxycarbonylethyl group; a phenyl group, a 2-methylphenyl group, and a 4-methylphenyl group; Aryl groups having no functional group, such as phenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, mesityl, and naphthyl: 2-aminophenyl, 4-aminophenyl, 2-hydroxyphenyl Group, 4-hydroxyphenyl group, 2-cyclophenyl group, 4-chlorophenyl group, 2-nitrophenyl group, 4-nitrophenyl group, 2-acetoxyphenyl group, 4-acetoxyphenyl group Aryl group having a functional group, such as an aryl group.

The aromatic ring structure formed by bonding R ⁷ and R ⁹ to each other is not particularly limited. For example, a benzene ring structure; a bonded benzene ring structure such as a naphthalene ring structure or a pyrene ring structure: a pyridine ring structure, Examples include heteroaromatic ring structures such as a pyrrole ring structure, a thiophene ring structure, and a furan ring structure, and a benzene ring structure and a bonded benzene ring structure because of the stability of substituted imidazoline-1-ylidene and the availability of raw materials. Is preferred.

The above substituted imidazoline-12-ylidene is more specifically represented by the following general formulas [9] to [17].

[9]

[1 5]

[1 7]

(In the formulas [9] and [17], R ⁵ R ⁶ is the same as described above. R ⁹ R ³² is each independently hydrogen or a substituent. The substituents are bonded to each other to form a ring. O)

Specific examples of the substituent represented by R ⁹ R ³² include a hydrocarbon group and a substituted hydrocarbon group. Hydrocarbon groups include alkyl, alkenyl, and alkynyl groups

, And an aryl group, which may be linear, branched or cyclic

. A substituted hydrocarbon group is a group in which at least one hydrogen in the hydrocarbon group is a group containing any of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, or a halogen atom. It is a substituted hydrocarbon group. Examples of the substituent include an alkoxy group, a carboxyl group, an alkynyl group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and an alkylamide. Groups, an arylamide group, an alkylsilyl group, an arylsilyl group, an alkylsulfonyl group, an alkylsulfinyl group, a halogen atom, a nitro group, a nitroso group, and a cyano group.

R ⁹ to R ^{3 2} is hydrogen, alkyl group, Ariru group, an alkoxy group, Ariruoki shea group, a halogen atom, preferably Shiano group, hydrogen, an alkyl group, an alkoxy group, a halogen atom particularly preferred. Specifically, hydrogen: an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group: an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; fluorine and chlorine And halogen atoms such as bromine and iodine. When bonded together to form a ring, a benzene ring is preferred.

Ruthenium compound of the present invention as long as it is a compound substituted Imidazorin 2 Iride emissions as described above is coordinated to the ruthenium, but also include any of those, methylene emissions radical (> _C:) is bound to the ruthenium metal A ruthenium complex compound having a ruthenium-carbene structure is preferred because of its high catalytic activity. Carbenes are generally unstable, but are stabilized by binding to ruthenium. The ruthenium compound can be represented by the following general formula [18].

(Wherein, R ^{5 to} R ⁸ are the same as described above. X ¹ and X ² are each independently an arbitrary α. L represents an neutral ligand, and L ¹ represents an arbitrary neutral ligand. R ³³ and R ³⁴ each independently represent hydrogen or a substituent, preferably hydrogen, or a hydrocarbon group having 1 to 20 carbon atoms, wherein the hydrocarbon group is a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, It may contain a phosphorus atom or a silicon atom. )

The anionic ligand (X ¹ and X ² ) may be any ligand having a negative charge when separated from the central metal (Ru), and a neutral ligand (L ¹ ) may be any ligand that has a neutral charge when separated from the central metal. L ¹ may be a substituted imidazoline-1-ylidene having a structure in which an aromatic ring and an imidazoline ring are fused by sharing two carbon atoms.

Specific examples of such anionic ligands (X ¹ and X ² ) include halogen atoms such as fluorine (F), bromine (Br), chlorine (CI) and iodine (I), hydrogen, and acetyl. Acetone, diketonate group, substituted cyclopentagenenyl group, substituted aryl group, alkenyl group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carboxyl group, alkyl or arylsulfonate group, alkylthio group Alkenylthio, arylthio, alkylsulfonyl, and alkylsulfinyl groups.

Other examples of the neutral ligand (L ¹ ) include oxygen atoms, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, and phosphites. , Sulfoxides, thioethers, amides, aromatic compounds, cyclic diolefins, olefins, isocyanides, thiosyanates, and carbene compounds.

Specific examples of R ³³ and R ³⁴ include hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carboxyl group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group. , An alkylsulfonyl group, and an alkylsulfinyl group. Specific examples of the ruthenium compound of the present invention represented by the general formula [18] include bis (N, N'-diisopropylbenzimidazoline- 1 -ylidene) benzylidene ruthenium dichloride and bis (N, N'-dicyclo) Hexylbenzimidazoline Benzylidene ruthenium dichloride, bis (N, N'-diphenyldibenzimidazoline-1-2-ylidene) benzylideneruthenium dichloride, bis (N, N'-dicyclopentylbenzimidazoline-1-2-ylidene) Ruthenium compounds, such as benzylidene ruthenium dichloride, in which two substituted imidazoline-1-ylidenes are coordinated;

(N, N'-dicyclohexylbenzimidazoline-1-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (N, N'-dimesitylbenzimidazoline-1-ylidene) (t Recycling mouth hexylphosphine) benzylidene ruthenium dichloride, [N, N'-di (1-phenylethyl) benzimidazoline-l2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [N, N'- Di (diphenylmethyl) benzimidazazoline-l 2-^^ pyridene] (tricyclohexylphosphine) benzylidene dimethyl dichloride, [N, N'-di (p-methylphenyl) benzimidazoline_2-ylidene] (tricyclo Xylphosphine) benzylidene ruthenium dichloride, [N, N'-di (1-si Lohexylethyl) benzimidazoline-l-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium diruthenium compound in which substituted imidazoline-2-ylidene and a neutral ligand are coordinated, respectively. Can be.

(Metathesis reaction)

The novel ruthenium compound of the present invention can be used as a highly active catalyst for an olefin metathesis reaction. In particular, it is used as a highly active catalyst in the metathesis reaction of an olefin compound having a functional group, which has been conventionally difficult. Examples of the functional group of the olefin compound 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, and more specifically, an alkoxy group, a carboxyl group and a carboxyl group. Group, alkenyloxy group, alkynyloxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, alkylamino group, arylamino group, alkylamide group, arylamide group, alkylsilyl group, arylsilyl group, alkylsulfonyl group , An alkylsulfinyl group, a halogen atom, a nitro group, a nitroso group, and a cyano group. Here, the metathesis reaction of an olefin compound includes a general reaction generally referred to as an olefin metathesis reaction (eg, KJ IV inand JC Mo I, Olefin Me tathesis and Me tathesis Pollymerization, Academia Press, Tokyo, etc.). See). Examples thereof include ring-opening metathesis polymerization, ring-closing metathesis reaction, cross-metathesis reaction of acyclic olefins, and acyclic gen metathesis reaction.

Such an olefin metathesis reaction may be performed without a solvent or in a solvent. The solvent to be used can be appropriately selected depending on the type of the olefin compound to be reacted. Since the ruthenium compound of the present invention is stable in polar solvents, it can be used not only in nonpolar solvents but also in reactions in polar solvents such as water and alcohol. The reaction temperature can be arbitrarily selected depending on the type of the reaction and the type of the olefin compound to be reacted, but generally, the lower limit is 180 ° C and the upper limit is 200 ° C. If the reaction temperature is too low, the reaction rate will be slow, and if it is too high, the ruthenium compound will decompose. The reaction time can be arbitrarily selected depending on the type of reaction, and is generally in the range of 1 minute to 1 week.

The ruthenium compound of the present invention is particularly suitable as a catalyst for ring-opening metathesis polymerization of cyclic olefins. Examples of the cyclic olefin include a cyclic olefin having a norbornene ring, such as a norbornene, a dicyclopentagene, and a tetracyclododecene; a monocyclic cyclic olefin, and the like. These cyclic olefins may be substituted by a hydrocarbon group such as an alkyl group, an alkenyl group, or an alkylidene group, or a polar group, and further have a double bond other than the double bond of the norbornene ring. You may.

. Norbornene Specific examples of the cyclic Orefin compound having an emission ring, dicyclopenta diene, methylcyclohexyl dicyclopentadiene, dihydro dicyclopentadiene (tricyclo [4.3.1 ² ^'5 0.] - Deka 3- E down ) And the like; tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene, 8-methylidenetetracyclododecene, 8—Echili Dentetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene, 8-phenyl Tetracyclododecene, 8-methoxycarbonylditetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-hydroxyloxytetracyclododecene, tetracyclododecene 1-8.9-dicarboxylic acid, tetracyclododecene-1,8,9-dicarboxylic anhydride, 8-cyanotetracyclododecene, tetracyclododecene-1,8,9-dicarboxylic imide, 8-cyclotetracyclododecene, 8- Tetracyclododecenes such as trimethoxysilyltetracyclododecene:

Norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5_decylnorbornene, 5-cyclohexylnorbornene, 5-cyclopentylnorbornene, 5-ethylidene norbornene, 5-vinyl norbornene, 5 _ propenyl norbornene, 5-cyclo to hexenyl norbornene-5-cyclopentenyl-norbornene, 5-phenylene Le norbornene, Te Bok Rashikuro ^{[6. 5. I 2 5. 0} 1 6 · 0 ⁸ · ¹³ ] Trideka 3,8,10,12-Tetraene (1,4-Methanol 1,4,4a, 9a-Tetrahydrofluorene), Tetracyclo [6. ^{^{6. I 2 5 · 0 1 6}} . 0 8 1 3] tetradec one 3, 8, 1 0, 1 2 Tetoraen (1.4 one methanol 1, 4, 4 a, 5, 1 0, 1 0 a- Hexahydroanthracene), 5-Methoxycarbonyl Norbornene, 5-Ethoxycarbonylnorbornene, 5-Methyl-5-methoxycarbonylnorbornene, 5-Methyl-15-ethoxycarbonylnorbornene, Norbornenyl-2-methylpropionite, Norbornenyl-2-Methyloctanate, Norbornene-1 5. 6-dicarboxylic anhydride, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norporene, 5,5-di (hydroxymethyl) norporene, 5-hydroxy-i-provirnorbornene, 5,6-dicarboxy Norbornenes, such as norbornene and 5-methoxycarbonyl 6;

Oxanolnorbornene, 5-methyloxanorbornene, 5-ethyloxanol Bornene, 5-butyloxanol norbornene, 5-hexyloxanorbornene, 5-decyloxanorbornene, 5-cyclohexyloxanorbornene, 5-cyclopentyloxanorbornene, 5-phenyloxanolnorbornene, 5- E Tylidenoxoxanorbornene, 5-vinyloxanolnorbornene, 5-propenyloxanolnorbornene, 5-cyclohexenyloxaxorbornene, 5-cyclopentenyloxoxanorbornene, 5-methoxycarbonyloxanolnorbornene , 5-ethoxycarbonyloxanorbornene, 5-methyl-5-methoxycarbonyloxonorbornene, 5-methyl-5 -ethoxycarbonyloxanorbornene, oxanolbornenyl-2-methylpropionate, oxa Norbornenyl-1 2-methyloctanate 5,6-dicarboxylic anhydride, 5-hydroxymethyloxanorbornene, 5,6-di (hydroxymethyl) oxanorbornene, 5.5-di (hydroxymethyl) oxanorbornene, 5-hydroxy- i-Propyloxanorbornene, 5,6-Dicarboxyoxanorbornene, 5-Methoxycarboxy-l-6-lipoxyxanolnorbornene, 5-Cyanoxanolnorbornene, Oxanolpolbornene-5,6-Dicarboxylic Oxanolpornes such as acid imides;

Hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-butylhexacycloheptadecene, 12-hexylhexacycloheptadecene, 12-decylhexacyclohepta Decene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacyclo Heptadecenes such as heptacene, 12-cyclohexenylhexacycloheptacene, and 12-cyclopentenyl hexadecene; and heptadecene.

The monocyclic cyclic olefins are usually cyclic monoolefins or cyclic diolefins having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms. Examples of cyclic monoolefins include cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene and the like. 16 are mentioned. Examples of the cyclic diolefin include those described in JP-A-7-258318, such as cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, and phenylcyclooctadiene.

These cyclic olefins can be used independently or in combination of two or more.

(Hydrogenation reaction)

The hydrogenation method of the present invention is characterized in that the polymer having a weight average molecular weight of 1,000 to 1,0000,000 in terms of polystyrene as measured by gel permeation chromatography is used. This is a method in which unsaturated bonds are hydrogenated using a transition metal compound belonging to Groups 8 to 10 of the periodic table, in which a carbene compound having a hetero atom is coordinated, as a catalyst. Conventionally known hydrogenation catalysts in which phosphines are coordinated with transition metal compounds belonging to Groups 8 to 10 of the periodic table have a weight-average molecular weight measured by gel permeation chromatography that is equivalent to polystyrene. Thus, the polymer had insufficient activity to selectively hydrogenate the olefinic carbon-carbon unsaturated bond in 1,000 or more polymers.

On the other hand, the hydrogenation catalyst used in the hydrogenation method of the present invention comprises a transition metal compound belonging to Group 8 to 10 of the periodic table in which a benzene compound having a hetero atom is coordinated. Very high activity.

Periodic Tables 8 to "! Group 0 transition metals include Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt. The hydrogenation catalytic activities of u, Rh and Pd are high and preferred, and Ru is particularly preferred.

A carbene compound containing a hetero atom is a compound having a hetero atom and a methylene free radical (an uncharged divalent carbon atom having a bond and represented by (> C :)). Compounds with methylene free radicals are generally unstable

Although most of them are only temporarily present as reaction intermediates, they can be isolated as compounds because they are stabilized by the bonding of two hetero atoms to the methylene carbon. Heteroatoms are atoms of Groups 15 and 16 of the Periodic Table.

. Specific examples include N, 0, P, S, As, and Se. Especially , N, 0, S, and P are preferred for obtaining a stable carbene compound, N and P are particularly preferred, and N is most preferred.

Specific examples of the carbene compound containing a nitrogen atom include a compound represented by the general formula [19].

R37 _R 38

[1 9]

(R ³⁵ to R ³⁸ are each independently a substituent, preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ³⁷ and R ³⁸ may be bonded to each other to form a ring structure. Good.)

R ^{35 to} R ³⁸ can be selected from the same substituents as R ⁵ described above. Further, a carbene compound in which R ³⁷ and R ³⁸ are bonded to each other to form a ring structure is the most stable and preferable.

Examples of the carbene compound containing a nitrogen atom represented by the general formula [19] include 1,3-diisopropylimidazolidine-12-ylidene, 1,3-dicyclohexyl imidazolidine-12-peridene, and 1,3-diene (Methylphenyl) imidazolidine 1-2-ylidene, 1.3-di (methylnaphthyl) imidazolidine-12-ylidene, 1,3-dimesitylimidazolidine 1-2-ylidene, 1,3-diadamantyl imidazolidine 1-2- 1,3-diphenylimidazolidin-1,2-ylidene, 1,3,4,5-tetramethylimidazolidin-1,2-ylidene, 1,3_diisopropyl-1,4-imidazoline-1,2_ylidene, 1,3 —Dicyclohexyl —4-Imidazoline-1-ylidene, 1,3-di (methylphenyl) 1-141 Γmidazoline-1-2-ylidene, 1,3-di (methylnaphthyl) _ 4-T-Midazoline-1 2-Ilidene, 1,3-Dimesityl-1-4-Imidazoline-1-2-Ilidene, 1,3 Diadamantyl- 4-Imidazoline-1 2-Ilidene, 1,3-Diphenyl-2-4-Imidazoline-1 2-Ilidene, 1,3,4,5-tetramethyl-4-1 ^ T-midazoline-2-ylidene, 1,3,4,5-tetraphenyru 4-1-imidazoline-2-1-ylidene, 1,3,4-trifure Lu 2,3,4,5-tetrahydro-1-H -1,2,4-Triazo-1-yl 5-ylidene, 3- (2,6-diisopropylphenyl) -1,2,3.4,5-tetrahydrothiazole-2-ylidene, 1,3-dicyclohexylhexa Hydropyrimidine_2-ylidene, Ν, Ν, N '. N' 1-tetraisopropylformamidinylidene, 1,3,4-triphenyl 2,5-dihydro-1Η-1,2,4-triazo 5-Ilidene, 3- (2,6-diisopropylphenyl) -1,2,3-dihydrothiazole-2-ylidene, and the like. In addition, the carbene compounds represented by the aforementioned general formulas [8] to [17] can also be mentioned as specific examples.

Among these, saturated cyclic compounds in which the hetero atom adjacent to the carbene has a bulky substituent, specifically 1,3-diisopropylimidazolidin-1-ylidene, 1,3-dicyclohexylimidazolidin-1- ^ Γylidene, 1,3-di (methylphenyl) imidazolidine-12-ylidene, 1,3-di (methylnaphthyl) imidazolidine-12-ylidene, 1,3-dimesitylimidazolidine1-2-ylidene , 1,3-Diadamantylimidazolidine-1-2-ylidene, 1,3-Diphenylimidazolidine-1-2-ylidene, 1,3,4,5-Tetraphenylimidazolidin-1-2-ylidene, 1,3 , 4-Triphenyl-1,2,3,4,5-tetrahydro 1 H—1,2,4-triazole _5—peridene, 3- (2,6-diisopropyl pyrphenyl) 1,2,3 4,5-tetrahydrothiazole-2 Ilidene, 1,3-dicyclohexylhexahydropyrimidine 12-ylidene, N, N 'dicyclohexylbenzimidazoline-12-ylidene, N, N'-dimesitylbenzimidazoline 1-2-ylidene, N, N '-Di (1-phenylethyl) benzimidazoline_2_ylidene is particularly preferred.

The group 8-10 transition metal compound of the periodic table obtained by coordinating a carbene compound containing a hetero atom is a carbene compound containing a hetero atom described above as a group 8-10 transition metal compound of the periodic table. Any coordinating metal complex may be used, but a transition metal compound represented by the general formula [20] and a ruthenium compound represented by the formula [21] or [22] are particularly preferable.

[(X ³ ) _rn (L ² ) _n (L ³ ) pM ¹ ] _z [20]

[twenty two]

(In the formula, M ¹ is a transition metal belonging to Group 8 to Group ¹⁰ of the periodic table, and X ³ to X ⁷ independently represent any anionic ligand. L ² , L ⁴ and L ⁶ represent to indicate the carbene compounds containing hetero atoms, L ^3, L ⁵ and L ⁷ are. R ³ ⁹ ~ R ⁴² are each independently indicate any neutral electron donor, hydrogen or a substituent, preferably hydrogen, Or a hydrocarbon group having 1 to 20 carbon atoms, wherein the hydrocarbon group may include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Where n and z are 1 or 2.

Specific examples of X ^{3 to} X ⁷ include halogen atoms such as F, Br, CI and I, hydrogen, acetylacetone, diketonate group, substituted cyclopentagenenyl group, substituted aryl group, alkenyl group, and alkyl. Group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carboxyl group, alkyl or arylsulfonate group, alkylthio group, alkenylthio group, arylthio group, alkylsulfonyl group and alkylsulfinyl group Can be.

Specific examples of L ³ , L ⁵ and L ⁷ include oxygen, water, carbonyl, nitrosyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, stibine , Sulfoxides, thioethers, amides, aromatic compounds, cyclic diolefins, olefins, isocyanides, thiosyanates and the like.

Specific examples of R ^{39 to} R ⁴² include a hydrogen, an alkenyl group, an alkynyl group, an alkyl group

, Aryl group, carboxyl group, alkenyloxy group, alkynyloxy group, Examples include a ryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, and an alkylsulfinyl group.

That is, examples of the general formula [20] include dichloro (1,3-diisopropyl-14-imidazoline-12-ylidene) (p-cymene) ruthenium and dihydrido (1,3-dimesitylimidazolidine 1-2). —Ilidene) (triphenylphosphine) ruthenium, carbonylchlorohydrido (1,3-diisopropyl-14-rmidazoline-12-ylidene) (triphenylphosphine) ruthenium, carbonylchlorohydrido (1,3, -dimesityl-4-imidazoline) I 2 -ylidene) (tricyclohexylphosphine) ruthenium, etc.

Examples of the general formula [21] include bis (1,3-diisopropylimidazolidine)

Benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazolidine-1-ylidene) benzylidene ruthenium dichloride, bis (1,3-diisopropyl-1-41-midazoline 1-2) Ruthenium compounds coordinated by two heteroatom-containing carbene compounds such as benzylidene ruthenium dichloride, benzylidene ruthenium dichloride, and bis (1,3-dicyclohexyl 4-imidazoline-12- ^ Γlidene) benzylidene ruthenium dichloride ;

(1,3-dicyclohexylimidazolidin-1-ylidene) (tricyclohexylphosphine) ethoxycarbene ruthenium dichloride, (1,3-dicyclohexyl hexyl_4_imidazoline-2-ylidene) (tricyclohexylphosphite) Benzylidene ruthenium dichloride, [1,3-bis (2,4,6-trimethylphenyl) imidazolidine-1-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3—bis ( 2,4.6-trimethylphenyl) imidazolidin-1-2-ylidene] (pentamethylcyclopentadienyl) benzylideneruthenium dichloride, [1,3-bis (2,4,6-trimethylphenyl) 14-imidazoline One 2-ylidene] (tricyclohexyl phosphine) benzylidene ruthenium di Carbene compounds such as [1,3_bis (2,4,6-trimethylphenyl) -14-imidazoline-12-ylidene] (pentamethylcyclopentagenenyl) benzylideneruthenium dichloride Ruthenium compounds coordinated with neutral electron donating compounds, Examples of the general formula [22] include bis (1,3-diisopropylimidazolidine-2-ylidene) phenylvinylidene ruthenium dichloride and bis (1,3-dicyclohexylimidazolidin-2-ylidene) ) T-butylvinylidene ruthenium dichloride, bis (1,3-diisopropyl-14-imidazoline-12-ylidene) phenylvinylidene ruthenium dichloride, bis (1,3-dicyclohexyl-lu-imidazoline) Ruthenium compound in which two heteroatom-containing carbene compounds such as t-butylvinylidene ruthenium dichloride are coordinated; (1,3-dicyclohexylimidazolidine 1-2-ylidene) (tricycloide Xylphosphine) t-butylvinylidene ruthenium dichloride, (1,3-dicyclohexyl-41-imidazoline-2) Peridene) (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, [1,3-bis (2,4,6-trimethylphenyl) imidazolidine-1-ylidene] (tricyclohexylphosphine ) T-butylvinylidene ruthenium dichloride, [1,3-bis (2,4,6-trimethylphenyl) imidazolidine_2_ylidene] (pentamethylcyclopentadenyl) phenylvinylidene ruthenium dichloride , [1,3-bis (2,4,6-trimethylphenyl) -14-imidazoline-12-ylidene] (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, [1,3— Bis (2,4,6-trimethylphenyl) -14-imidazoline-12-ylidene] (pentamethylcyclopentagenenyl) t-butylvinylidenetenidium dichloride Examples thereof include ruthenium compounds in which a hetero atom-containing carbene compound and a neutral electron donating compound are coordinated.

As a measure for further improving the hydrogenation catalytic activity of a transition metal belonging to Groups 8 to 10 of the periodic table formed by coordinating a carbene compound containing a hetero atom, a activating agent may be added. Specific examples include organometallic reducing agents such as organolithium, organomagnesium, organozinc, organoaluminum, and organotin, or amine compounds.

Preferred examples of the organometallic reducing agent include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, and neofillithium as the organic lithium: butylethylmagnesium, and petitethyl as the organic magnesium. Octyl magnesium chloride, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, aryl magnesium bromide, neopentyl magnesium chloride, neophyl magnesium chloride, etc .: The organic zinc is dimethyl Zinc, getyl zinc, diphenyl zinc, etc .; organoaluminum includes trimethylaluminum, triethylaluminum, triisobutylaluminum, getylaluminum chloride, ethylaluminum sesquique lid, ethylaluminum dichloride, etc .: organotin Examples thereof include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. Preferred examples of the amine compound include methylamine, ethylamine, and anily. Primary amine compounds such as dimethylamine, ethylenediamine and 1.3-diaminocyclobutane; secondary amine compounds such as dimethylamine, methylisopropylamine and N-methylaniline; trimethylamine, triethylamine, triphenylamine, N, N-dimethyl Tertiary amine compounds such as aniline, pyridine and monopicoline can be exemplified.

The amount of the activator to be added, such as an organometallic reducing agent or an amine compound, is 0 to the transition metal compound belonging to Group 8 to Group 10 of the periodic table formed by coordinating a carbene compound containing a hetero atom. 0.1 to 1000 equivalents are preferred, 0.2 to 500 equivalents are more preferred, and 0.5 to 200 equivalents are particularly preferred. If the addition amount is less than 0.1 equivalent, there is no effect of addition, and if it is more than 100 equivalent, a side reaction easily occurs.

The polymer having a weight average molecular weight of 1,000 to 1,000,000 in terms of polystyrene as measured by gel permeation chromatography used in the hydrogenation method of the present invention is an olefinic carbon. There is no particular limitation as long as the polymer has a one-carbon unsaturated bond in the polymer.However, a polymer having an olefinic unsaturated bond in the polymer main chain has significant weatherability and heat resistance due to hydrogenation. It is preferable because it is improved. Specific examples of these include ring-opening metathesis polymers of cyclic olefins and polymers of conjugated genes.

Examples of ring-opening metathesis polymers of cyclic olefins include ring-opening metathesis polymers having a norbornene ring and monocyclic olefins as described above. Polymers may be mentioned. In the present invention, the olefin polymer produced by the olefin metathesis reaction can be hydrogenated. When the ruthenium compound of the present invention is used as a metathesis reaction catalyst, the ruthenium compound can be used as it is as a hydrogenation catalyst.

Examples of the polymer of a conjugated diene include a random, block, alternating or graft copolymer with a polymer such as butadiene, isoprene or piperylene and other monomers. Examples of other monomers include aromatic vinyl compounds such as styrene and polymethylstyrene; acrylonitriles such as acrylonitrile and methacrylonitrile: acrylonitrile and acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. , ^ Monounsaturated carboxylic acids and their carboxylic esters. The polymerization method is not particularly limited, and is not limited to polymerization modes such as radical polymerization, anion polymerization, cationic polymerization, and coordination polymerization, and polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization. Specific examples of the polymer polymerized by these methods and usable in the hydrogenation reaction of the present invention include polybutadiene, polyisoprene, butadiene-styrene random copolymer, butadiene-styrene block copolymer, and isoprene-styrene. Examples thereof include a block copolymer and a butadiene-acrylonitrile copolymer.

The polymer used in the hydrogenation method of the present invention is a polymer having a weight-average molecular weight of 1,000 to 1,000,000 in terms of polystyrene, as measured by gel permeation chromatography. is there. The hydrogenation catalyst of the present invention is a polymer having a molecular weight of 1,000 or more, preferably 2.0000 or more, and a molecular weight of 1,000 or less, preferably 500 or less. Can be particularly efficiently hydrogenated.

The hydrogenation reaction is carried out by bringing the above polymer and hydrogen into contact with each other in the presence of the ruthenium compound of the present invention, if necessary, in the presence of a high activator. The hydrogenation reaction may be performed without a solvent or in a solvent. The solvent can be appropriately selected depending on the type of the polymer to be hydrogenated, and not only a non-polar solvent but also a polar solvent such as water or alcohol can be used. The reaction temperature and the reaction time can also be appropriately selected, but the ranges are the same as in the case of the above-mentioned olefin metathesis reaction. The hydrogen pressure during the reaction is usually 0 to 10 MPa, preferably 0.01 to 8 MPa. It is preferably 0.05 to 5 MPa.

According to the method of the present invention, hydrogenation can be performed to any hydrogenation rate of 50% or more, preferably 80% or more, more preferably 900/0 or more of the olefinic unsaturated bond.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

(1) The generated ruthenium compound was identified by measurement of ¹ H-NMR and ¹³ C-NMR spectra.

(2) The polymerization conversion of the ring-opening metathesis polymerization was determined by a solid content weighing method.

(3) The molecular weight of the ring-opening metathesis polymer was measured as a polystyrene equivalent value by gel-permeation chromatography (GPC) using tetrahydrofuran as a solvent. The molecular weight of the hydride of the ring-opening polymer was cyclohexane Was measured as a polyisoprene conversion value by GPC using as a solvent.

(4) The hydrogenation rate of the unsaturated unsaturated bond was measured by ¹ H-NMR spectrum.

(5) The products of the ring-closing metathesis reaction and the cross-metathesis reaction of acyclic olefins were analyzed by gas chromatography-mass spectroscopy (GC-MS).

(Example 1)

N, N'-Dimesityl-1,2-phenylenediamine 1.57 parts by weight was placed in a NASFRASCO, purged with nitrogen, 45 parts by weight of ether was added, and the mixture was cooled to _78 ° C. There, a solution of n-butyllithium in cyclohexane (concentration: 1.54moI

ZI) 6.0 parts by weight were added, and the mixture was stirred for 5 minutes, and then gradually returned to room temperature. After stirring for 30 minutes, 2 parts by weight of carbon disulfide (CS ₂ ) was added, and stirring was further continued for 30 minutes, and then the solvent was removed under reduced pressure. The obtained powder is washed with methanol and dried to give a white powder (N,

N′-dimesitylbenzimidazoline-1-thione) was obtained (yield 1.37 parts by weight, yield 78%). 1.3 parts by weight of the obtained white powder was weighed into an eggplant flask, and after purging with nitrogen, 18 parts by weight of tetrahydrofuran (THF) was added. Immerse the flask in an ice bath and dilute nitric acid (3.61 mol THF solution) in the flask.

After adding 4 parts by weight and stirring for 5 minutes, the temperature was returned to room temperature, and stirring was continued as it was. Half an hour After stirring, 0.53 parts by weight of sodium borofluoride was added, and the mixture was further stirred for 1 hour. The reaction solution was filtered to remove solids. After the obtained filtrate was concentrated under reduced pressure, ether was added to precipitate a reaction product, which was separated by filtration and dried to obtain a white powder (yield 0.925 parts by weight, yield 62). %). When the white powder was measured by ¹ H-NMR spectrum (solvent: CDCl ₃ , temperature: 25 ° C.), the following proton peak was observed. Mesityl benzimidazolym) Tetrafluoroborate was identified.

6 = 9.67 (1 H, s, NC〃N), 7.7 2 to 7.74 (2 H, m, 〃 on the benzene ring of benzimidazole), 7.38 to 7.40 ( 2 H, m, 〃 on the benzene ring of benzimidazole), 7.12 (4 H, s, H at / 77 position of mesityl group), 2.40 (6H, s. ₃ ), 2.05 (1 2 H, s, C-position at o-position of mesityl group

3 parts by weight of the product A O thus obtained was weighed in an eggplant flask, and after substituting with nitrogen, 9 parts by weight of THF was added, and the mixture was cooled to 178 ° C. Thereto was added 0.50 parts by weight of n-butyllithium (1.54moI hexane solution), and the mixture was stirred for 5 minutes and then gradually returned to room temperature.

After stirring at room temperature for 15 minutes, bis (tricyclohexylphosphine) benzylidin ruthenium (IV) dichloride 0.372 parts by weight dissolved in 9 parts by weight of toluene is added to the reaction solution and stirred for 1 hour did. The reaction solution was depressurized to remove the solvent, and the remaining solid portion was dissolved in 4.5 parts by weight of toluene, which was added dropwise to 17 parts by weight of n-pentane. The solution was filtered, the filtrate was concentrated, washed with n-pentane three times at 178 ° C and dried to give a pink-brown powder (yield 0.152 wt. Rate 3 7%). The ¹ H-NMR spectrum (solvent: CDCI ₃ , temperature: 25 ° C) of the peach-brown powder was measured and found that at 19.37 ppm, the Ru = CH proton (1 H, s ), 6.62 to 7.41 The aromatic proton (13H, aromatic) was observed at 1 ppm, and the proton of P—CH (3H, m) was observed at 2.35 ppm. This powder was identified as (N, N'-dimesitylbenzimidazoline-1-ylidene) (cyclohexylphosphine) benzylidine ruthenium (IV) dichloride. The intermediate product A obtained by reacting the product A with n-butyllithium is as follows: (1) The raw material is (NN'-dimesitylbenzimidazolym) tetrafluoroborate And (2) the final product obtained using the intermediate product A is (N, N'-dimesitylbenzimidazoline-2-ylidene) (cyclohexylphosphine) benzylidene ruthenium ( IV) Because it is dichloride, it was presumed to be N, Ν'-dimesitylbenzimidazoline_2-ylidene.

(Comparative Example 1)

1, No. 6, 953—956 (1 999), according to the method described in Org. Lett.. Vol. 1, 953-956 (1 999). N, N′—dimesityl-1,2—phenylenediamine 0.5.500 weight Parts were weighed into an eggplant-shaped flask, replaced with nitrogen, added with 0.236 parts by weight of NH ₄ PF ₆ and 0.242 parts by weight of triethyl orthoformate, heated to 120 ° C, and stirred for 2 hours. The product (N, N'-dimesityl-benzimidazolium) hexafluorophosphate was not obtained.

(Example 2)

N, N'-Dimesityl-1,2-ethylenediamine 1. Transfer 34 parts by weight to a NASA flask, replace with nitrogen, add 45 parts by weight of ether, and place the eggplant flask in a flask.

Cooled to 8 ° C. There, a solution of n-butyllithium in cyclohexane (concentration: 1

. 54mo I / 1) 6.0 parts by weight was added, and the mixture was stirred for 5 minutes, and then gradually returned to room temperature. After stirring for 30 minutes, 2 parts by weight of carbon disulfide (CS ₂ ) was added, and stirring was further continued for 30 minutes, and then the solvent was removed under reduced pressure. The obtained powder was washed with methanol and then dried to obtain a white powder (NNN-dimesitylimidazolidine-1-thione) (yield 1.16 parts by weight, yield 75%). 1.1.4 parts by weight of the obtained white powder was weighed into an eggplant-shaped flask, and after purging with nitrogen, tetrahydrofuran (THF) 1

8 parts by weight were added. Immerse the flask in an ice bath and add diluted nitric acid (3.61 mo

(THF solution with IZI concentration) 1. Add 4 parts by weight, stir for 5 minutes, return to room temperature, and continue stirring. After stirring for 30 minutes, sodium hexafluorophosphate 0.8

06 parts by weight were added, and the mixture was further stirred for 1 hour. The reaction solution was filtered to remove solids

. After concentrating the obtained filtrate under reduced pressure, ether was added to precipitate a reaction product. The precipitate was separated by filtration and dried to obtain a white powder (yield 0.989 parts by weight, yield 65%). When the ¹ H-NMR spectrum (solvent: d-acetone, temperature: 25 ° C.) of the obtained powder was measured, the following proton peaks were confirmed. Mesityl imidazolidum) Hexafluorophosphate was identified.

δ = 8.82 (1 Η, s, NC ΗΝ), 7.10 (4 Η, s, aromatic), 4.71 (4 H, s, NCC〃 ₂ N), 2.45 ( 1 2 H, s, p-C〃 ₃ ) of mesityl group, 2.32 (6 H. s, o-

CH ₃ )

308 parts by weight of the product B O thus obtained was weighed into an eggplant flask, and after purging with nitrogen, 9 parts by weight of THF was added, and the mixture was cooled to −78 ° C. Thereto was added 0.50 parts by weight of n-butyllithium (1.54 MoIZI hexane solution), and the mixture was stirred for 5 minutes and then gradually returned to room temperature.

After stirring at room temperature for 15 minutes, 0.11 parts by weight of chromium (1.5-cyclooctane) rhodium (I) dimer dissolved in 9 parts by weight of toluene is added to the reaction solution, and the mixture is added for 1 hour. Stirred. The reaction solution was depressurized to remove the solvent, the remaining solid was dissolved in 5 parts by weight of toluene, and the solution was added dropwise to 18 parts by weight of n-pentane. The resulting solution was filtered, and the filtrate was concentrated, washed three times with n-pentane at 178 ° C, and dried to obtain a pink-brown powder. A result of measuring the powder peach brown ¹ H- NMR and ¹³ C-NMR spectrum, (N, N '- dimesityl imidazolidine one 2 _ ylidene) (1, 5-cyclopropyl O Kuta Zhen) rhodium (I) It was found to be chloride (yield 0.245 parts by weight, yield 96 <½).

The intermediate product B obtained by reacting the product B with n-butyllithium was prepared from the starting material and the final product in the same manner as in Example 1, except that N, Ν ′ dimesitylimimidazolidine was used. It was estimated that it was one 2-ylidene.

(Example 3)

To an autoclave equipped with a stirrer, 300 parts by weight of cyclohexane and 66.9 parts by weight of dicyclopentadiene were added, and 0.64 parts by weight of 1-hexene was further added as a chain transfer agent. The (N, N'-dimesitylben) obtained in Example 1 was added to this solution. A catalyst solution obtained by dissolving 0.222 parts by weight of diimidazoline-1- (r-ridene) (cyclohexylphosphine) benzylidene ditenium (IV) dichloride in 9 parts by weight of THF was added. After the solution was stirred at 60 ° C. for 1 hour, 0.30 parts by weight of ethyl vinyl ether was added to stop the polymerization reaction. When a part of the polymerization reaction solution was sampled and analyzed, the polymerization conversion was 99 <½ or more, the number average molecular weight (Mr was 9,200, and the weight average molecular weight (Mw) was 18,900).

Next, hydrogen was supplied into the autoclave, and the mixture was stirred at 150 ° C and a hydrogen pressure of 5. OMPa for 6 hours to perform a hydrogenation reaction. The hydrogenation rate of the obtained hydride was 99.9% or more, Mn was 14,200, and Mw was 29,300.

(Comparative Example 2)

(N, N'-dimesitylbenzimidazoline-1-ylidene) (cyclohexylphosphine) benzylideneruthenium (IV) 1,3-bis (mesityl) -14 in place of dichloride —Ilidene] (tricyclohexylphosphine) A polymerization reaction was carried out in the same manner as in Example 3 except that benzylidene ruthenium (IV) dichloride was used. When a part of the polymerization reaction solution was sampled and analyzed, the yield was 67%, the number average molecular weight (Mn) was 8,200, and the weight average molecular weight (Mw) was 16,600.

Next, hydrogen was supplied into the autoclave, and the mixture was stirred at 150 ° C and a hydrogen pressure of 5.0 MPa for 6 hours to perform a hydrogenation reaction. The hydrogenation rate of the obtained hydride was 20%.

(Comparative Example 3)

(N, N'-dimesitylbenzimidazoline-l- 2-ylidene) (cyclohexylphosphine) benzylidineruthenium (IV) 1,3-bis (mesityl) -imidazolidine-l-ylidene instead of dichloride (Tricyclohexylphosphine) A polymerization reaction was carried out in the same manner as in Example 3, except that benzylidene ruthenium (IV) dichloride was used. When a part of the polymerization reaction solution was sampled and analyzed, the yield was 88%, the number average molecular weight (Mn) was 9,100, and the weight average molecular weight (Mw) was 18,800.

Then, supply hydrogen into the autoclave, 150 ° C, hydrogen pressure 5.0MP The mixture was stirred at a for 6 hours to carry out a hydrogenation reaction. The hydrogenation rate of the obtained hydride was 10%.

(Example 4)

0.0054 parts by weight of (N, N'-dimesitylbenzimidazolin-1-ylidene) (cyclohexylphosphine) benzylidene ruthenium (IV) dichloride obtained in Example 1 was added to a glass container. Then, the mixture was dissolved in 2 parts by weight of 1,2-dichloromouth ethane, and subsequently, 0.05 parts by weight of 1.7-year-old kutadiene was added and mixed.

After reaction at 45 ° C for 3 hours, analysis by GC-MS showed that cyclohexene was produced at a reaction conversion of 98% or more due to the closed metathesis reaction of 1,7-octagedene.

(Example 5)

In a glass container, 0.0054 parts by weight of (N, N'-dimesitylbenzimidazoline-2-^^ lidene) (cyclohexylphosphine) benzylidine ruthenium (IV) dichloride obtained in Example 1 was added. And dissolved in 2 parts by weight of 1,2-dichloroethane. Subsequently, 0.336 parts by weight of 1-octene was added and mixed. After reacting at 45 ° C for 3 hours, analysis by GCZMS revealed that 7-tetradecene was formed at a reaction conversion of 65% by the cross-metathesis reaction of 1-octene.

(Example 6)

To a glass reactor equipped with a stirrer, 0.016 parts of 2,6-diisopropylphenylimide neophylidenemolybdenum (VI) bis (hexafluoro-t-butoxide) was added, and then 40 parts of cyclohexane, Dicyclopentadiene (10 parts) and 1-hexene (0.092 parts) were added, and a polymerization reaction was performed at room temperature. After the reaction for 3 hours, the polymerization reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer. The polymer was separated by filtration, washed, and dried under reduced pressure at 40 ° C for 40 hours. The yield of the obtained ring-opened polymer was 9.2 parts, and the molecular weight (in terms of polystyrene) was such that the number average molecular weight (Mn) was 8,900 and the weight average molecular weight (Mw) was 17.000.

To an autoclave equipped with a stirrer, 5.0 parts of the obtained ring-opening metathesis polymer and 35 parts of hexane were added. Then, OrganomeTafFies20

0 1, 2 O, carbonyl chlorohydride synthesized according to 794-797 ( 1, 3-diisopropyl one 4 one imidazoline one 2- ylidene) (Bok Rishikuro to key sills phosphine) was added ruthenium 6.0 1 0 ³ hydrogenation catalyst solution in 1 0 parts of tetrahydrofuran, and hydrogen pressure 1 The hydrogenation reaction was performed at OMPa and 120 ° C for 10 hours. The hydrogenation reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer. After washing by filtration, the polymer was dried under reduced pressure at 40 ° C for 40 hours. The hydrogenation rate was over 99%.

(Example 7)

Nitrile rubber Nipo I 1042 (Acrylonitrile content 33.5% by weight, Mooney viscosity 77) manufactured by Nippon Zeon Co., Ltd. 5 parts together with 90 parts of benzene benzene were added to a photoclave equipped with a stirrer and dissolved. carbonyl chloro hydride (1. 3-diisopropylamino one 4 one imidazoline one 2-^ gamma isopropylidene) (tricyclo to carboxymethyl Le) ruthenium 6. 0 X 1 0 ³ parts of water hydrogenation catalyst dissolved in black port benzene 5 parts The solution was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and 140 ° C. for 10 hours. The hydrogenation reaction solution was poured into a large amount of methanol to completely precipitate the polymer. The polymer was separated by filtration, washed, and dried under reduced pressure at 40 ° C for 40 hours. The hydrogenation rate is 99 Q /. Was more than

Industrial applicability

According to the method for producing an N, N, N ', N'-tetra-substituted diaminocarbene-coordinated transition metal complex of the present invention, a safe and short time using secondary amine and carbon disulfide which are easy to handle, The desired product can be obtained in high yield. Further, according to the method for producing a ruthenium compound of the present invention, a desired ruthenium compound can be synthesized safely and easily.

The ruthenium compound of the present invention exhibits high activity in the metathesis reaction of an olefin compound, and can be applied particularly to the metathesis reaction of an olefin compound having a functional group and the hydrogenation reaction of a polymer, which have been difficult in the past. Moreover, this ruthenium compound has excellent stability even in polar solvents, and has a wide range of usable reaction solvents.

According to the hydrogenation method of the present invention, even a polymer having a high molecular weight can be hydrogenated at a high hydrogenation rate, and the heat resistance and weather resistance of the polymer can be greatly improved.

Claims

The scope of the claims

1. Deprotonate the secondary amine and then react with carbon disulfide to synthesize N, N, N'.N'—tetra-substituted thiourea, followed by the desulfurization reaction. (A) for synthesizing N, N, N ', N'—tetra-substituted amidinium salt; Reacting to obtain a diaminocarbene (B); and contacting the diaminocarbene obtained in the step (B) with a transition metal complex having a neutral ligand to form a diaminocarbene by a ligand exchange reaction. Step of synthesizing coordination transition metal complex (C)

A method for producing a diaminocarbene-coordinated transition metal complex comprising:

2. The method according to claim 1, wherein diamine is used as the secondary amine in the step (A).

3. The production method according to claim 1, wherein in the step (C), a ruthenium compound is used as a transition metal complex having a neutral ligand.

4. (1) After deprotonating an aromatic ring compound in which at least one amino group is bonded to each of the adjacent carbon atoms, substituted imidazoline-2-thione is reacted by reacting with carbon disulfide. Synthesis, followed by synthesis of substituted imidazolium salt by desulfurization reaction. A method for producing a ruthenium compound in which a substituted imidazoline-1-ylidene is coordinated by a ligand exchange reaction by bringing a substituted imidazoline-2-ylidene into contact with a ruthenium compound.

5. A ruthenium compound coordinated with a substituted imidazoline-2-ylidene having a structure in which an aromatic ring and an imidazoline ring share two carbon atoms and are fused.

6. The ruthenium compound according to claim 5, which has a ruthenium-carbene bond.

7. A method for performing a metathesis reaction of an olefin compound using the ruthenium compound according to claim 5 or 6.

8. A method for obtaining a polymer by subjecting a cyclic olefin to a ring-opening metathesis polymerization reaction using the ruthenium compound according to claim 5 or 6.

9. The weight average molecular weight measured by gel permeation chromatography The olefinic unsaturated bond in the polymer having a molecular weight of 1,000 to 1,000,000 is formed by using a transition metal compound belonging to Group 8 to Group 10 of the Periodic Table in which a carbene compound having a hetero atom is coordinated. How to hydrogenate.

10. The hydrogenation method according to claim 9, wherein a ruthenium compound obtained by coordinating a carbene compound having a hetero atom is used.