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WO2002034723A1 - Methode de preparation de complexes de metaux de transition a base de diaminocarbene - Google Patents

Methode de preparation de complexes de metaux de transition a base de diaminocarbene Download PDF

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WO2002034723A1
WO2002034723A1 PCT/JP2001/009206 JP0109206W WO0234723A1 WO 2002034723 A1 WO2002034723 A1 WO 2002034723A1 JP 0109206 W JP0109206 W JP 0109206W WO 0234723 A1 WO0234723 A1 WO 0234723A1
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group
compound
reaction
ruthenium
ylidene
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Seiji Okada
Kazunori Taguchi
Yasuo Tsunogae
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Zeon Corp
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Zeon Corp
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Priority claimed from JP2001126970A external-priority patent/JP2002201180A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/28—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium

Definitions

  • 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.
  • 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.
  • transition metal compounds such as tungsten, molybdenum, and titanium have been mainly used as these metathesis reaction catalysts.
  • 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.
  • a ruthenium-carbene complex having phosphine as a ligand shows a high catalytic activity for an olefin metathesis reaction.
  • 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.
  • 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.
  • heterocyclic carbene compounds having a nitrogen atom such as 1,3-diisopropylimidazoline_2-ylidene and 1.3-dimesitylimimidazoline-1-ylidene
  • a method for synthesizing a product a method has been proposed in which a 1,3-disubstituted imidazolyl salt is used as a reaction intermediate.
  • several methods for synthesizing the reaction intermediate have been reported.
  • 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).
  • substituents such as salts, 1,3-dimesityl-14,5-dihydroimidazolium salts (ie, 1,3-dimesitylimidazolidinium salts).
  • 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.
  • 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.
  • N, N, N ′, N′-tetrasubstituted thiourea which is a reaction intermediate of the above amidinium salt
  • a conventional method using a thiophosgene and a secondary amine is subjected to a deprotonation reaction.
  • 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.
  • diaminocarbene By reacting the diaminocarbene with a transition metal complex, diaminocarbene can be obtained.
  • a transition metal complex 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.
  • N, N, N ', N'-tetrasubstituted thioureas are synthesized by reacting a secondary amine with deprotonation and then with carbon disulfide, followed by desulfurization.
  • diamine is preferred as the secondary amine.
  • a ruthenium compound is preferably used as the transition metal complex having a neutral ligand.
  • 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.
  • 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.
  • 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.
  • the ruthenium compound preferably has a ruthenium-carbene bond.
  • a method for performing a metathesis reaction of an olefin compound using the above ruthenium compound 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.
  • 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.
  • a transition metal compound a ruthenium compound is preferable.
  • 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 ′.
  • 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).
  • alkali metal compound examples 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.
  • alkaline earth metal compound examples 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.
  • diamine which forms a stable cyclic structure by reaction with carbon disulfide is preferably used.
  • diamines are not particularly limited.
  • 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, N
  • Ethylenediamines such as;
  • Diaminopyridines such as 3,4-di ( ⁇ -propylamino) pyridine and 2,3-di (i-propylamino) pyridine;
  • phenylenediamines and diaminopyridines are preferably used.
  • 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.
  • 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
  • diamine is used as the secondary amine, cyclic N, N, N ', N'-tetra-substituted thioureas are formed.
  • 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 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, ⁇ ', 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.
  • a desulfurizing agent such as a Bronsted acid.
  • Bronsted acids such as HC and HB r, HI, HN0 3, H 2 S0 4, HBF 4, HP F 6, etc. HS b F 6 and the like.
  • 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. .
  • 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.
  • N, N, N ', N'-tetra-substituted amidinium salts are compounds having a structural unit represented by the following general formula [2].
  • X— is any anion, and is determined by the type of desulfurizing agent or salt thereof.
  • the ⁇ , ⁇ , ⁇ ′, N ′ tetra-substituted amidinium salt obtained in the step ( ⁇ ) is subjected to a deprotonation reaction to form a ⁇ , ⁇ , ⁇ ′.
  • This deprotonation reaction is carried out by mixing ⁇ , ⁇ , ⁇ ′, 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.
  • N, N, N ', N'-tetra-substituted diaminocarbene may be isolated and used for the next reaction.
  • 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].
  • 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).
  • 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.
  • 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.
  • 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].
  • M represents a transition metal
  • Y represents an arbitrary ligand
  • 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.
  • 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.
  • 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.
  • 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):
  • a transition metal complex having a neutral ligand which is a reaction material for the step (C):
  • 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.
  • 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].
  • the substituted imidazoline-1-ylidene formed in the reaction step (2) is, for example, a compound represented by the following general formula [8].
  • 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.
  • 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.
  • 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.
  • 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.
  • the substituted imidazoline-1-ylidene is a compound represented by the general 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. .
  • 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.
  • alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable.
  • 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.
  • the aromatic ring structure formed by bonding R 7 and R 9 to each other is not particularly limited.
  • 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].
  • 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)
  • substituent represented by R 9 R 32 include a hydrocarbon group and a substituted hydrocarbon group.
  • Hydrocarbon groups include alkyl, alkenyl, and alkynyl groups
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • methylene emissions radical > C:
  • 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].
  • R 5 to R 8 are the same as described above.
  • X 1 and X 2 are each independently an arbitrary ⁇ .
  • 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.
  • anionic ligands include halogen atoms such as fluorine (F), bromine (Br), chlorine (CI) and iodine (I), hydrogen, and acetyl.
  • halogen atoms such as fluorine (F), bromine (Br), chlorine (CI) and iodine (I), hydrogen, and acetyl.
  • neutral ligand (L 1 ) examples 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.
  • 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.
  • 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;
  • the novel ruthenium compound of the present invention can be used as a highly active catalyst for an olefin metathesis reaction.
  • 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.
  • 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.
  • 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).
  • olefin metathesis reaction eg, KJ IV inand JC Mo I, Olefin Me tathesis and Me tathesis Pollymerization, Academia Press, Tokyo, etc.
  • 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.
  • 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.
  • 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.
  • 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-cyclohexenyltetracyclododo
  • 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.
  • 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;
  • 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.
  • cyclic diolefin examples include those described in JP-A-7-258318, such as cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, and phenylcyclooctadiene.
  • cyclic olefins can be used independently or in combination of two or more.
  • 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.
  • the polymer had insufficient activity to selectively hydrogenate the olefinic carbon-carbon unsaturated bond in 1,000 or more polymers.
  • 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.
  • 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
  • Heteroatoms are atoms of Groups 15 and 16 of the Periodic Table.
  • N examples include N, 0, P, S, As, and Se.
  • N, 0, S, and P are preferred for obtaining a stable carbene compound, N and P are particularly preferred, and N is most preferred.
  • carbene compound containing a nitrogen atom examples include a compound represented by the general formula [19].
  • 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,
  • 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- ⁇ ⁇ ylidene, 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
  • 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.
  • M 1 is a transition metal belonging to Group 8 to Group 10 of the periodic table
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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- ⁇ ⁇ lidene) benzylidene ruthenium dichloride ;
  • a activating agent may be added.
  • organometallic reducing agents such as organolithium, organomagnesium, organozinc, organoaluminum, and organotin, or amine compounds.
  • organometallic reducing agent examples include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, and neofillithium as the organic lithium: butylethylmagnesium, and petitethyl as the organic magnesium.
  • 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 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.
  • the polymer has a one-carbon unsaturated bond in the polymer.
  • 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.
  • 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.
  • the olefin polymer produced by the olefin metathesis reaction can be hydrogenated.
  • 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.
  • 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.
  • the generated ruthenium compound was identified by measurement of 1 H-NMR and 13 C-NMR spectra.
  • 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.
  • 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
  • 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.
  • 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, ⁇ '-dimesitylbenzimidazoline_2-ylidene.
  • N, N′ diimesityl-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.
  • N, N'-Dimesityl-1,2-ethylenediamine 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.
  • ⁇ 8.82 (1 ⁇ , s, NC ⁇ ), 7.10 (4 ⁇ , 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-
  • 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, ⁇ ′ dimesitylimimidazolidine was used. It was estimated that it was one 2-ylidene.
  • Example 2 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.
  • Example 1 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.
  • 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.
  • 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.
  • 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 /.
  • 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.
  • 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.

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Abstract

L'invention concerne une méthode de préparation de complexes de métaux de transition avec des ligands de diaminocarbène, qui consiste, dans une étape A: à effectuer une déprotonation d'une amine secondaire, à mettre en réaction l'anion obtenu avec un disulfure de carbone, et à désulfurer le composé obtenu en un sel d'amidinium N,N,N',N'-tétrasubstitué; dans une étape B: à préparer par déprotonation un diaminocarbène à partir dudit sel; et dans une étape C: à placer le diaminocarbène au contact d'un complexe de métaux de transition comportant un ligand neutre afin de réaliser un échange de ligands et obtenir ainsi un complexe de métaux de transition comportant un ligand de diaminocarbène. L'invention concerne des composés de ruthénium et une méthode de préparation de ces composés; une méthode de métathèse de composés oléfiniques avec des composés de ruthénium; et une méthode de production de polymères par polymérisation d'oléfines cycliques par métathèse avec ouverture du noyau.
PCT/JP2001/009206 2000-10-23 2001-10-19 Methode de preparation de complexes de metaux de transition a base de diaminocarbene Ceased WO2002034723A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2000-322554 2000-10-23
JP2000322554A JP2002128764A (ja) 2000-10-23 2000-10-23 Ｎ，ｎ，ｎ’，ｎ’−テトラ置換アミジニウム塩、ジアミノカルベンおよびジアミノカルベン配位遷移金属錯体の合成方法
JP2000324452 2000-10-24
JP2000-324452 2000-10-24
JP2001-126970 2001-04-25
JP2001126970A JP2002201180A (ja) 2000-10-24 2001-04-25 新規なルテニウム化合物及びその使用方法

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WO2010003226A1 (fr) * 2008-07-08 2010-01-14 Thadani Avinash N Ligands diaminocarbènes acycliques chiraux, précurseurs associés et leur utilisation dans des réactions de synthèse organique
CN112480175A (zh) * 2020-11-27 2021-03-12 吉林师范大学 一种具有低效率滚降特性的绿色高效有机电致磷光材料及其制备方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010003226A1 (fr) * 2008-07-08 2010-01-14 Thadani Avinash N Ligands diaminocarbènes acycliques chiraux, précurseurs associés et leur utilisation dans des réactions de synthèse organique
US8759541B2 (en) 2008-07-08 2014-06-24 Avinash N. Thadani Chiral acyclic diaminocarbene ligands, precursors therefore and their use in organic synthesis reactions
CN112480175A (zh) * 2020-11-27 2021-03-12 吉林师范大学 一种具有低效率滚降特性的绿色高效有机电致磷光材料及其制备方法

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