Metal complexes for use in metathesis

The present invention relates to metal complexes useful as catalytic components in olefin metathesis reactions, radical polymerization or addition reactions of atomic or group transitions, and vinylization reactions. The present invention also relates to preferably with respect to the subclass of the metal complex, its use as a catalytic component for the polymerization of α-olefins having high activity at moderate temperatures and optionally conjugated diene.

The present invention also relates to obtaining a polymer having an extremely narrow molecular weight distribution by a living polymerization reaction. The present invention also relates to a method for producing the metal complex and a novel intermediate involved in such a method. Furthermore, the present invention relates to specific derivatives of the metal complex suitable for covalent bonding to a carrier. The covalent product is useful as a supported catalyst for heterogeneous catalytic reactions.

The present invention also relates to the direct one-step synthesis of pyrrole, furan, and thiophene compounds from diallyl compounds. Finally, the present invention relates to a dendrimer material containing a metal complex attached to a core molecule, which is a catalyst that can be removed from the reaction mixture by ultrafiltration. In particular, the present invention relates to a Schiff base derivative of a ruthenium alkylidene complex carrying an N-heterocyclic carbene ligand, a method for producing the same, and many unsaturated hydrocarbons such as acyclic monoolefins, dienes, cyclic olefins, and alkynes. Regarding its use as a catalyst for metathesis.

Olefin metathesis involves a reaction between the first olefin and the first transition metal alkylene complex as an important step according to formula (1) below, thereby forming an unstable intermediate metallocyclobutane ring. Then, it is a catalytic process involving the conversion of this into a second olefin and a second transition metal alkylene complex. Because this type of reaction is reversible and competitive with each other, the overall result is the rate of each of them and the shift of equilibrium if the formation of volatile or insoluble products occurs. It depends heavily on.

<chemistry num="1"><img file="JP5100728B2_D0001.tif" /></chemistry>

Some non-limiting examples of the metathesis reaction of monoolefin or diolefin are shown in the following formulas (2) to (5). Removal of a product such as ethylene in formula (2) from the system dramatically changes the process and / or rate of the desired metathesis reaction, which is the reaction of ethylene with the alkylidene complex to methylene (M = CH).₂This is because it forms a complex, which is the most reactive and least stable of the alkylidene complexes.

<chemistry num="2"><img file="JP5100728B2_D0002.tif" /></chemistry>

A potential advantage over homocoupling (Equation 2) is cross-coupling between two different terminal olefins. Coupling reactions involving diene result in chain or cyclic dimers, oligomers, and ultimately chain or cyclic polymers (Equation 3). The latter reaction is commonly referred to as acyclic diene metathesis (hereinafter referred to as "ADMET"), which is advantageous in very high concentrations of solution or bulk, whereas cyclization , Convenient at low concentrations. When the intramolecular coupling of a diene occurs to produce a cyclic alkene, the process is called ring-closing metathesis (hereinafter referred to as "RCM") (Equation 4).

The cyclic olefin can be ring-opened to form an oligomer or a polymer [ring-opening metathesis polymerization represented by the formula 5 (hereinafter referred to as "ROMP")]. "Living ring-opening metathesis polymerization" occurs when the alkylidene catalyst reacts more rapidly with cyclic olefins (eg, norbornene or cyclobutane) than with respect to carbon-carbon double bonds in the growing polymer chain. .. That is, almost no termination occurs during or after the polymerization reaction.

Numerous catalytic systems consisting of well-defined single component metal carbene complexes have been prepared and used in olefin metathesis. One major development in olefin metathesis was the discovery of ruthenium and osmium carbene complexes by Grabs et al.

U.S. Pat. No. 5,977,393 discloses Schiff base derivatives of such compounds. It is useful as an olefin metathesis catalyst, where the metal is coordinated with a neutral electron donor [eg, triarylphosphine or tri (cyclo) alkylphosphine] and an anionic ligand. Such catalysts exhibit improved thermal stability while maintaining metathesis activity even in polar protic solvents. They can also cyclize diallylamine hydrochloride to dihydropyrrole hydrochloride.

The problems to be solved with respect to the Grabs carbene complex are (i) improving both catalyst stability (ie, delaying degradation) and metathesis activity at the same time, and (ii) such catalysts. The use is to extend the range of achievable organic products (eg, to give the ability to ring highly substituted diene into tri- and tetra-substituted olefins).

On the other hand, living polymerization systems have been reported for anionic and cationic polymerization, but their industrial applications are limited because they require high purity monomers and solvents, reaction initiators, and anhydrous conditions. It had been. In contrast, free radical polymerization is the most well-known commercial method for obtaining high molecular weight polymers. A wide variety of monomers can be radically polymerized and copolymerized under relatively simple experimental conditions that require the absence of oxygen but can be performed in the presence of water. However, free radical polymerization methods often form polymers with uncontrolled molecular weight and high polydispersity. Therefore, the combination of living polymerization and radical polymerization is extremely convenient, and the atom (or or) of US Pat. No. 5,763,548 containing (1) the transfer pathway of the atom or group and (2) the radical intermediate. It is achieved by the transfer radical polymerization method (hereinafter referred to as "ATRP").

In this type of living polymerization, there are virtually no chain break reactions such as transitions and terminations, and it is possible to control various parameters of the polymer structure such as molecular weight, molecular weight distribution, and terminal functionality. This also allows the preparation of various copolymers, such as block and star copolymers. Living / controlled radical polymerization requires a low constant concentration of radicals in equilibrium with various latent species. It utilizes a new polymerization initiation system based on the reversible formation of growing radicals in redox reactions between various transition metal compounds and polymerization initiators (eg alkyl halides, aralkyl halides or haloalkyl esters). To do. ATRP is based on the dynamic equilibrium between growth radicals and latent species established by reversible transition metal-catalyzed cleavage of carbon-halogen covalent bonds in the latent species. Polymerization systems utilizing this concept have been developed using, for example, complexes of copper, ruthenium, nickel, palladium, rhodium, and iron to establish the required equilibrium.

With the development of ATRP, interest in the Kharash reaction has increased in recent years, and this is due to the following mechanism:

<chemistry num="3"><img file="JP5100728B2_D0003.tif" /></chemistry>

It consists of the addition of polyhalogenated alkanes to both ends of the olefin by a radical mechanism according to the above.

ATRP is also called atom transfer radical addition (hereinafter referred to as "ATRA") because it is very similar to the color reaction.

The efficiency of the ruthenium alkenidene complex in the olefin metathesis reaction is inversely proportional to its activity in ATRP and ATRA, i.e. the most efficient catalyst for the olefin metathesis reaction shows the lowest activity in ATRP and ATRA. It is known from experiments. Therefore, there is a need in the art for catalytic components capable of exhibiting high efficiencies in both the olefin metathesis reaction and ATRP and ATRA. Further, there is a need in the art for a catalytic component capable of initiating an olefin metathesis reaction under extremely mild conditions, for example at room temperature. Finally, catalytic components capable of initiating the vinylization reaction with high efficiency are also needed in the art.

In addition, currently available synthetic pathways for obtaining the catalyst of US Pat. No. 5,977,393 have equal or even better performance properties because they proceed via the conversion of ruthenium bisphosphan carbene, but other transition metals. There is still a need in the art for the development of catalysts that can be synthesized directly from cheaper and more readily available raw materials, including.

<p><patcit num="1"><text>U.S. Pat. No. 5,977,393</text></patcit><patcit num="2"><text>U.S. Pat. No. 5,763,548</text></patcit><patcit num="3"><text>WO 02/02649</text></patcit></p>

<p> Poly-α-olefins such as polyethylene, polypropylene, and copolymers of ethylene with propylene and / or 1-butene are extremely widespread in various fields such as all types of extrusions, coextrusions and mold moldings. It is used. The need for poly-α-olefins with various physical properties is increasing. Also, in order to improve the productivity, increasing the yield of polyolefin per amount of catalyst and maintaining the catalytic activity over the period of continuous production are also important requirements.</p><p> WO02 / 02649 has (A) a bidentate ligand containing an imine structural moiety and reacts with (B-1) compound (A), a transition metal compound preferably in which the transition metal is titanium, zirconium or hafnium. Disclosed is an olefin polymerization catalyst system containing a compound having a reducing ability capable of converting the imine structure portion into a metal amine structure, and a compound (B-2) that reacts with the compound (A) to form an ion pair. There is. However, WO02 / 02649 does not teach transition metal compounds in which the metal is coordinated to the carbene ligand. With respect to the teaching of WO 02/02649, there is still a need to improve olefin polymerization activity and its maintenance in the art.</p><p> All of the above needs constitute various objectives to be achieved by the present invention.</p>

<p> In the present invention, an improved olefin metathesis catalyst modifies pK by modifying prior art ruthenium and osmium Schiff base derivatives or corresponding derivatives of other transition metals._aBy giving as a ligand a constrained steric hindrance group of at least 15, and / or by giving a carbene ligand that forms a fused aromatic ring system, and / or by giving a cumrylidene group as a carbene ligand. It is based on the unpredictable finding that it can be obtained. Conveniently, modified Schiff base derivatives of such ruthenium, osmium and other transition metals can be produced directly from cheaper and more readily available raw materials than prior art catalysts.</p><p> Also in the present invention, such modified Schiff base derivatives of ruthenium, osmium and other transition metals are not only efficient olefin metathesis catalysts, but also ATRP or ATRA and vinylization reactions such as enol-esters. It is based on the unpredictable finding that it is a highly efficient component in catalyzing or initiating radical reactions of atom (or group) transitions such as synthesis.</p><p> Another unpredictable finding of the present invention is that certain Schiff base derivatives of ruthenium and osmium in the prior art and corresponding derivatives of other transition metals are ATRP or ATRA and vinylization reactions, such as enol-ester synthesis, etc. It can also be used in catalyzing or initiating a radical reaction of an atom (or group) transition.</p><p> Furthermore, the present invention includes novel intermediates used in methods for preparing novel catalytically modified Schiff base derivatives. Yet another feature of the present invention includes a supported catalyst for use in a heterogeneous catalytic reaction comprising a catalytically active Schiff base derivative and a carrier suitable for carrying it.</p><p> In particular, the present invention is a porous inorganic solid (eg, a modified layered material such as an amorphous or semi-crystalline material, a crystalline molecular sieve, or an inorganic oxide) by further chemically modifying the metal complex of the Schiff base. Alternatively, a derivative suitable for covalent bonding to a carrier such as an organic polymer resin is provided.</p><p> Another feature of the present invention includes dendrimer materials in which two or more catalytically active Schiff base derivatives are attached to core molecules in order to successfully remove the catalyst from the reaction mixture by ultrafiltration.</p><p> Finally, another finding of the invention is that certain dimetal Schiff base derivatives of transition metals, unlike the corresponding monometal Schiff base catalysts, do not terminate the reaction with dihydropyrrole, dihydrofuran or dihydrothiophene compounds. , The point is that the direct one-step synthesis of pyrrole, furan, and thiophene compounds from diallyl compounds can be catalyzed. Yet another finding of the present invention is that a particular metal compound can be used as a component of the catalytic system for the polymerization of α-olefins and conjugated diene, which have high activity at moderate temperatures.</p>

<figref num="1">FIG. 1 shows a synthetic route for producing a ruthenium catalytic compound having the general formula (IA) according to an embodiment of the present invention.</figref><figref num="2">FIG. 2 shows a synthetic route for producing a ruthenium catalytic compound having the general formula (IC) according to another embodiment of the present invention.</figref><figref num="3">FIG. 3 shows the general formulas (IA) and (IB) of a one-metal complex, the general formulas (IVA) and (IVB) of a two-metal complex of the present invention, and their free radicals R in formulas (IA) and (IB).₃And R₄The equation (VI) of the condensed ring system in which is combined is shown.</figref><figref num="4">FIG. 4 shows the formulas (IIA), (IIB), (IIIA), and (IIIB) of a single metal intermediate complex, as well as the general formulas (IC) and (ID) of other single metal complexes of the present invention.</figref><figref num="5">FIG. 5 shows the formulas (IIIC) and (IIID) of the monometal intermediate complex of the present invention.</figref><figref num="6">FIG. 6 is a schematic view showing anchoring of a derivative of the one metal complex of the present invention into a mesoporous crystalline molecular sieve.</figref><figref num="7">FIG. 7 shows two alternative synthetic routes for producing derivatives of the monometal complex of the invention that can be covalently attached to a carrier.</figref><figref num="8">FIG. 8 shows the development of polystyrene produced by atomic transfer radical polymerization in the presence of the heterogeneous catalyst of the present invention as a function of time or conversion of molecular weight and dispersity.</figref><figref num="9">FIG. 9 shows the development of polystyrene produced by atomic transfer radical polymerization in the presence of the heterogeneous catalyst of the present invention as a function of time or conversion of molecular weight and dispersity.</figref><figref num="10">FIG. 10 is a schematic diagram showing a synthetic route for producing the dimetal complex of the present invention.</figref><figref num="11">FIG. 11 is a schematic diagram showing the preparation of cation species of the ruthenium monometal complex of the present invention.</figref>

(Definition) As used herein, the term complex or coordinating compound is used between a metal (acceptor) and several neutral molecules or ionic compounds (donors) called ligands, each containing a non-metal atom or ion. Refers to the result of a donor-acceptor mechanism or a Lewis acid-base reaction. A ligand having one or more atoms having a lone pair of electrons is called a polydentate ligand.

In the present specification, C_1-6The term alkyl means the monovalent free group of a linear or branched saturated hydrocarbon having 1 to 6 carbon atoms, eg, methyl, ethyl, propul, n-butyl, 1-methylethyl, 2-Methylpropyl, 1,1-dimethylethyl, 2-Methylbutyl, n-pentyl, dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, etc .; C_2-6Alkyl means a similar free radical having 2 to 6 carbon atoms and the like.

In the present specification, C_1-6The term alkylene refers to C as defined above._1-6It means a divalent hydrocarbon free radical corresponding to alkyl.

In the present specification, C_3-10The term cycloalkyl is a monocyclic aliphatic radical having 3 to 8 carbon atoms (eg, cyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, etc.). , Or C with 7-10 carbon atoms_7-10It means a polycyclic aliphatic radical (for example, norbornyl or adamantyl).

In the present specification, C_3-10The term cycloalkylene is defined above as C_3-10It means a divalent hydrocarbon free radical corresponding to cycloalkyl.

As used herein, the term aryl refers to mono- and polyaromatic monovalent radicals (eg, phenyl, benzyl, naphthyl, anthracenyl, adamantyl, phenanthrasyl, fluoranthenyl, chrysenyl, pyrenyl, biphenylyl, pisenyl) Etc.), for example, condensed benzo-C such as indanyl, 1,2,3,4-tetrahydronaphthalenyl, fluorenyl, etc._5-8Contains cycloalkyl radicals.

As used herein, the term heteroaryl refers to mono- and polyheteroaromatic monovalent radicals containing one or more heteroatoms independently selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus. Means, for example, pyridyl, pyrazinyl, pyrimidinyl, pyridadinyl, triazinyl, triazolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, pyrrolyl, furyl, thienyl, indrill, indazolyl, benzofuryl, benzothienyl, quinolyl, quinazolinyl, quinoxalinyl, , Phenoxazinyl, phenothiazine, xanthenyl, prynyl, benzothienyl, naphthophenyl, thiantrenyl, pyranyl, isobenzofuranyl, chromenyl, phenoxatiinyl, indridinyl, quinolidinyl, isoquinolyl, phthalazinyl, naphthylidineyl, cinnolinyl, pteridinyl, carborinyl, , Phenanthrolinyl, phenazinyl, phenothiazinyl, imidazolinyl, imidazolidinyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, etc., and all possible isomer forms thereof.

In the present specification, C_1-6The term alkoxy refers to C bonded to an oxygen atom._1-6It means an alkyl radical, and examples thereof include methoxy, ethoxy, propoxy, butoxy, etc .; C._2-6Alkoxy means a similar free radical having 2 to 6 carbon atoms and the like.

As used herein, the term halogen means an atom selected from the group consisting of fluorine, chlorine, bromine, and iodine.

In the present specification, C_1-20The term alkyl is C_1-6Includes alkyl (as defined above) and higher analogs thereof with 7-20 carbon atoms (eg, heptyl, ethylhexyl, octyl, nonyl, decyl, dodecyl, octadecyl, etc.).

As used herein, Polyhalo C_1-20The term alkyl refers to C in which each hydrogen atom is independently substituted with a halogen (preferably fluorine or chlorine)._1-20It is defined as alkyl and is, for example, difluoromethyl, trifluoromethyl, trifluoroethyl, octafluoropentyl, dodecafluoroheptyl, heptadecafluorooctyl and the like.

In the present specification, C_2-20The term alkenyl is defined as a straight or branched hydrocarbon radical containing one double bond and having 2 to 20 carbon atoms, eg, vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 2-pentenyl, 3-pentenyl, 3-methyl-2-butenyl, 3-hexenyl, 2-hexenyl, 2-octenyl, 2-decenyl, and all possible isomers of these, and further C_4-20Cycloalkenyl, a cyclic hydrocarbon radical containing one or more double bonds and having 4 to 20 carbon atoms (eg, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclooctadienyl, cyclopentadi) Enyl, cyclooctadienyl, norbornadienyl, indenyl, etc.) are also included.

In the present specification, C_2-20The term alkynyl is defined as a straight or branched hydrocarbon radical containing one or more triple bonds and having 2 to 20 carbon atoms, eg, acetylenyl, 2-propynyl, 3-butynyl. , 2-butynyl, 2-pentynyl, 3-pentynyl, 3-methyl-2-butynyl, 3-hexynyl, 2-hexynyl and the like, and all possible isomers of these.

In the present specification, C_1-20The term alkoxy refers to C, which has up to 20 carbon atoms._1-6It means a higher analog of alkoxy (as defined above) and includes, for example, octyloxy, decyloxy, dodecyloxy, octadecyloxy and the like.

As used herein, the terms alkylammonium and arylammonium are defined as described above, respectively._1-6Alkyl, C_3-10Means a 4-coordinated nitrogen atom attached to a cycloalkyl, aryl or heteroaryl group.

As used herein, the term "constraint steric hindrance" refers to a group or ligand whose movement is constrained, usually a branched or substituted group or ligand. A group whose size causes measurable molecular strain (angular strain or bond elongation) by X-ray diffraction.

As used herein, the term "enantiomer" refers to an optical purity of at least 80%, preferably at least 90%, more preferably at least 98% (as measured by standard methods in the art). It means each independent optically active form of the compound of the present invention.

As used herein, the term "solvate" refers to protic and aprotic solvents, and non-polar solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, etc. Refers to the association of a solvent molecule selected from the group consisting of esters, ketones, amides and water with the metal complex of the present invention.

In its broadest interpretation, the invention comprises a carbene ligand, a polydentate ligand, and one or more other ligands, at least one of the other ligands having a pK of 15 or more._aWith respect to a pentacoordinated metal complex, a salt thereof, a solvate thereof, or an enantiomer thereof, which is a constrained steric hindrance ligand having.

The five-coordinated metal complex may be a one-metal complex or a two-metal complex, with respect to one or more neutral ligands and one or more anionic ligands. The metal of is 5-coordinated and the other is 4-coordinated. In the latter case, the two metals may be the same or different. The polydentate ligand may be a bidentate ligand, in which case the metal complex of the invention may contain two other ligands or may be a tridentate ligand. , In that case, the metal complex comprises one other ligand.

The metal in the pentacoordinated metal complex of the present invention is preferably a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11, and 12 of the periodic table. The metal is from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, renium, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel, and cobalt. More preferably selected.

The polydentate ligand of the pentacoordinated metal complex of the present invention preferably contains at least two heteroatoms used for metal coordination. More preferably, at least one of the two heteroatoms is a nitrogen atom. Most preferably, one of the two heteroatoms is a nitrogen atom and the other heteroatom is an oxygen atom.

The carbene ligand of the pentacoordinated metal complex of the present invention may be an arenilidene ligand or a cumrenylidene ligand, for example, tetra-1,2,3-trienylidene, penta-1,2,3, 4-It may be tetranylidene or the like.

In one feature that is particularly useful when the metal complex is used in the presence of an organic solvent, one of the other ligands present in the pentacoordinated metal complex of the present invention is an anionic ligand. Is. The meaning of the term anionic ligand is conventional in the art and preferably conforms to the definition of US Pat. No. 5,977,393.

In another feature that is particularly useful when the metal complex is used in the presence of water, one of the other ligands is a solvent and the metal complex is a cationic species associated with an anion. Suitable anions for the latter purpose are selected from the group consisting of tetrafluoroborate, tetra (pentafluorophenyl) borate, alkyl sulfonates in which the alkyl group may be substituted with one or more halogen atoms, and aryl sulfonate. .. In such cationic species, suitable solvents for coordinating with metals are selected from protic and aprotic solvents, and non-polar solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers. , Aliphatic hydrocarbons, alcohols, esters, ketones, amides, and water.

More specifically, a pK of 15 or more, which is a central feature of the metal complex of the present invention._aConstrained sterically damaging ligands with are nonionic prophosphatran superstrong bases or imidazol-2-iriden, dihydroimidazol-2-iriden, oxazole-2-iriden, triazole-5-iriden, thiazole-2- N-heterocycle selected from the group consisting of iriden, bis (imidazolin-2-iriden), bis (imidazolidine-2-iriden), pyrrolidene, pyrazolylidene, dihydropyrrolilidene, pyrrolidinilidene, and benzo-condensed derivatives thereof. A derivative of carbene in which one or more hydrogen atoms are replaced by a group that causes constrained steric hindrance.

Further, the present invention includes (i) a polydentate ligand and one or more other ligands, and at least one of the other ligands has a pK of 15 or more._aA tetra-coordinated metal complex, which is a constrained sterically-damaged ligand having Provided is a method for producing a 5-coordinated metal complex disclosed above, which comprises a step of producing a 5-coordinated 1-metal complex by reacting. The present invention also provides another method for producing a pentacoordinated metal complex, which is described in the following step: -(i) Polydentate ligand and pK of 15 or more_aA tetracoordinated metal complex containing one or more other ligands other than the constrained sterically impaired ligand having a carbene ligand, (ii) an alkynyl compound, a diazo compound, and a dialkynyl. A first step of producing a 5-coordinated 1-metal complex containing a carbene ligand by reacting with a reactant selected from the group consisting of compounds and capable of imparting a carbene ligand to the metal; , -The 5-coordinated 1-metal complex obtained in the first step has a pK of 15 or more._aSpecies containing constrained steric hindrance groups with, and said 15 or more pK_aSecond step of reacting under conditions that allow the species containing the constrained steric hindrance group to coordinate to the metal in place of one other ligand other than the carbene ligand; Including.

Both methods apply to all metal complexes of the invention, whether one metal or two metals.

When the 5-coordinated metal complex of the present invention is a di-metal complex in which one metal is 5-coordinated and the other metal is 4-coordinated, each of the above methods is preferably further prepared in advance. It further comprises the step of reacting the 5-coordinated 1-metal complex with the 2-metal complex in which each metal is 4-coordinated. Such a reactive tetracoordinated dimetal complex is, for example, [RuCl.₂(p-cumene)]₂Alternatively, it may have a dimer structure such as an analog thereof. Alternatively, the reactive tetracoordinated dimetal complex can be formed in situ by contacting the terpenen with a trichloride of ruthenium, rhodium or cobalt. The metal of the reactive 4-coordinated 2-metal complex may be the same as or different from the metal of the 5-coordinated metal complex.

In all the methods described above, each metal is independently selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11, and 12 of the Periodic Table.

In certain embodiments, the five-coordinated metal complex used in the first step of the general method described above comprises one anionic ligand, thereby comprising one anionic ligand. Gives a 1-metal complex. Further, the method comprises the step of separating the anionic ligand from the 5-coordinated 1-metal complex by reacting the 5-coordinated 1-metal complex with a salt in the presence of a solvent. , A 5-coordinated 1-metal complex, which is a cationic species associated with an anion, is formed, in which the metal coordinates with respect to the solvent.

In another embodiment, the invention is a tetracoordinated 1 metal complex comprising a polydentate ligand and one or more other ligands, at least one of the other ligands. Is 15 or more pK_aProvided is the above-mentioned metal complex which is a constrained steric hindrance ligand having. Such a tetracoordinated 1 metal complex is not only surprisingly useful as an intermediate for producing catalytic components, but also has catalytic activity in itself in ROMP, ATRP, ATRA, and vinylization reactions. doing.

More specifically, the present invention is a pentacoordinated metal complex selected from metal complexes having one of the general formulas (IA) and (IB) shown in FIG. --M is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the periodic table.<u style="single">However, M is a transition metal except ruthenium and osnium (</u>Preferably<u style="single">,iron</u>, Molybdenum, Tungsten, Titanium, Renium, Copper, Chromium, Manganese, Rodium, Vanadium, Zinc, Gold, Silver, Nickel, and Cobalt.<u style="single">)</u>; --Z is selected from the group consisting of oxygen, sulfur, selenium, NR'''', PR'''', AsR'''', and SbR''''; --R'', R'''and R'''' are hydrogen atoms and C, respectively._1-6Alkyl, C_3-8Cycloalkyl, C_1-6Alkyl-C_1-6Alkoxysilyl, C_1-6Alkyl-aryloxysilyl, C_1-6Alkyl-C_3-10Selected from the group consisting of cycloalkoxysilyl, aryl, and heteroaryl, or R and R together form an aryl or heteroaryl free radical, each of the free radicals (hydrogen). (If different from the atom) is optionally a halogen atom, C_1-6Alkyl, C_1-6Alkoxy, aryl, alkyl sulfonate, aryl sulfonate, alkyl phosphonate, aryl phosphonate, C_1-6Alkyl-C_1-6Alkoxysilyl, C_1-6Alkyl-aryloxysilyl, C_1-6Alkyl-C_3-10Substituents R independently selected from the group consisting of cycloalkoxysilyl, alkylammonium, and arylammonium₅Is replaced by one or more, preferably one to three; --R'is defined the same as R'', R'''and R'''' when contained in a compound having the general formula (IA), or in a compound having the general formula (IB). If included in, C_1-6Alkylene and C_3-8Selected from the group consisting of cycloalkylenes (the alkylene or cycloalkylene group is optionally one or more substituents R₅Replaced by); --R₁Is over 15 pK_aIs a constrained steric hindrance group with; --R₂Is an anionic ligand; --R₃And R₄Are hydrogen atoms or C, respectively_1-20Alkyl, C_2-20Alkenyl, C_2-20Alkyne, C_1-20Carboxylate, C_1-20Alkoxy, C_2-20Alkenyloxy, C_2-20Alkynyloxy, aryl, aryloxy, C_1-20Alkoxycarbonyl, C_1-8Alkylthio, C_1-20Alkylsulfonyl, C_1-20Alkyl sulfinyl, C_1-20Alkyl sulfonate, aryl sulfonate, C_1-20Alkylphosphonate, arylphosphonate, C_1-20A free radical selected from the group consisting of alkylammonium and arylammonium; --R'and R₃And R₄One can be coupled to each other to form a bidentate ligand; --R'''and R'''' can combine with each other to form an aliphatic ring system containing heteroatoms selected from the group consisting of nitrogen, phosphorus, arsenic, and antimony; --R₃And R₄Can together form a fused aromatic ring system, as well as --y is M and R₃And R₄Sp between the carbon atoms that carry₂Indicates the number of carbon atoms and contains an integer from 0 to 3. Provided are a pentacoordinated metal complex, a salt thereof, a solvate, and an enantiomer.

In the above definition of the compounds of the invention, the group R₁Is the ability to give restraint steric hindrance and its pK_aOnly limited by the value, the latter is what is traditionally defined and measured in the art. R like this₁A suitable and non-limiting example of a group is the following high pK in which one or more hydrogen atoms are substituted with a constraining steric hindrance group._aDerivatives of the group are included.

--Imidazole-2-iriden (pK)_a= 24), --Dihydroimidazol-2-ylidene (pK higher than 24)_a), --Oxazole-2-iriden, --Triazole-5-Iliden, --Thiazole-2-iriden, --Pyrroliliden (pK)_a= 17.5), --Pyrazoliliden, --Dihydropyrroliliden, --Pyloriridiniriden (pK)_a= 44), --Bis (imidazolin-2-iriden) and bis (imidazolidine-2-iriden), --Benzodiazepine derivatives such as indolilidene (pK)_a= 16), and --Nonionic prophosphatran superstrong base [For example, those described in US Pat. No. 5,698,737, preferably Trimethyritriaza prophosphatran P (CH) known as Verkade superstrong base.₃NCH₂CH₂)₃N].

The constrained steric hindrance group is, for example, a branched chain or a substituted R'group, for example, a t-butyl group, a substituted C._3-10Cycloalkyl group, C_1-6Aryl groups with two or more alkyl substituents [eg, 2,4,6-trimethylphenyl (mesityl), 2,6-dimethylphenyl, 2,4,6-triisopropylphenyl or 2,6-diisopropylphenyl] , Or two or more Cs_1-6It is a heteroaryl group having an alkyl substituent (eg, pyridinyl).

In the above definition of the compound of the present invention, the group R₂Is an anionic ligand, preferably C_1-20Alkyl, C_2-20Alkenyl, C_2-20Alkyne, C_1-20Carboxylate, C_1-20Alkoxy, C_2-20Alkenyloxy, C_2-20Alkynyloxy, aryl, aryloxy, C_1-20Alkoxycarbonyl, C_1-8Alkylthio, C_1-20Alkylsulfonyl, C_1-20Alkyl sulfinyl, C_1-20Alkyl sulfonate, aryl sulfonate, C_1-20Alkylphosphonate, arylphosphonate, C_1-20It is selected from the group consisting of alkylammonium, arylammonium, halogen (preferably chlorine), and cyano.

The carbene ligand of the present invention will be described in detail below. First, unlike the Schiff bases of the prior art, 1 to 3 sps₂Carbon atoms are metals M and R₂And R₃The synthetic pathways for each of these species of compounds, present between the carbon atoms that support the group, differ with respect to the manufacturing process, as described below in the specification. That is, unsaturated carbon chains such as arenilidene or cumlenilidene (eg, pig-1,2,3-trienylidene, penta-1,2,3,4-tetraenylidene, etc.) may be present in the carbene ligand. it can. For simplification of the manufacturing route, a preferred embodiment consists of a carbene ligand with y = 2.

However, methods for making compounds with carbene ligands with y = 1 or y = 3 are also provided. As in the case of the Schiff base derivative of the prior art, y may be 0. The first preferred embodiment is R₃And R₄Each of which is a phenyl group. In the second preferred embodiment, R₄And R₅Together form a fused aromatic ring system having formula (IV) of FIG.

In the above definition of the compounds of the invention having formula (IA), the group R'is preferably selected from methyl, phenyl and substituted phenyl (eg, dimethylbromophenyl or diisopropylphenyl). For compounds of the invention having formula (IB), the group R'is preferably methylene or benzylidene.

In a more specific embodiment of the invention, M is selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, and rhenium, especially if the compound is intended for use in an olefin metathesis reaction. It is preferable to be done.

The present invention is also the first method for the production of a pentacoordinated metal complex having one of the formulas (IA) and (IB), which has one of the general formulas (IIA) or (IIB) 4 Coordinating metal complexes [in these formulas, M, Z, R, R', R'', R''', R'''' and R₂Is defined above for the general formulas (IA) and (IB), and R₆Is a leaving group. ], Equation R₁Compound with Y [R in the formula₁Is defined as described above, and Y is a leaving group. ] To form an intermediate having the general formula (IIIA) or (IIIB) shown in FIG. --Equation R₃R₄R₇Alkynyl compound with CCCH [in the formula, R₃And R₄Is defined above for the general formulas (IA) and (IB), and R₇Is a hydrogen atom, hydroxyl and R₃It is selected from the group consisting of (when y = 2)], --Expression N₂CR₃R₄Diazo compound with [in the formula, R₃And R₄Is defined as described above (if y is 0)], --Equation R₃Alkynyl compound having CCH [in the formula, R₃Is defined as described above (when y is 1)], and --Equation R₂₁CCCCR₂₂Dialkynyl compound having [in the formula, R₂₁And R₂₂Are independently selected from hydrogen atom and trialkylsilyl (when y is 3)], Provided are methods comprising reacting with a reactant selected from the group consisting of.

To carry out the above method, the leaving group Y is as commonly defined in the art (eg, Organic Chemistry, Structure and Function (1999), 3rd ed., WH Freeman &amp; Co., New- York, p.216-217, 227), preferably a hydrogen atom, C_1-6Alkoxy (eg t-butoxy), PR₃And NR₃[In the formula, R₃Is defined as described above. ] Is selected from the group consisting of.

As mentioned above, the reactants used in the second step of the method will vary from species to species depending on the value of y. For example, if y is 2, a suitable alkynyl compound is R₃And R₄Each of them is a phenyl group, as well as R₇Is a compound in which is hydroxy. If y is 3, then a suitable dialquinyl compound is butaziin or trimethylsilylbutadiine.

Further, the present invention is a second method for preparing a pentacoordinated metal complex having one of the general formulas (IA) and (IB), and in the first step, the general formula shown in FIG. 4 ( Compounds with either IIA) or (IIB) [in these formulas, M, Z, R, R', R'', R''', R'''' and R₂Is defined above for equations (IA) and (IB), and R₆Is a leaving group. ], --Equation R₃R₄R₇Alkynyl compound with CCCH [in the formula, R₃And R₄Is defined above for equations (IA) and (IB), and R₇Is a hydrogen atom, hydroxyl and R₃It is selected from the group consisting of (when y = 2). ], --Expression N₂CR₃R₄Diazo compound with [in the formula, R₃And R₄Is defined as described above (if y is 0)], --Equation R₃Alkynyl compound having CCH [in the formula, R₃Is defined as described above (when y is 1). ], And --Equation R₂₁CCCCR₂₂Dialkynyl compound having [in the formula, R₂₁And R₂₂Are independently selected from hydrogen atom and trialkylsilyl (when y is 3). ], It is reacted with a reactant selected from the group consisting of, and then in the second step, the reaction product of the first step is subjected to the formula R.₁Compound with Y [R in the formula₁Is defined as described above, and Y is a leaving group. ] And further react with. A suitable example of the leaving group Y in this second method is as disclosed for the first method.

In the above method, R₆Is preferably an aromatic and unsaturated alicyclic group group (eg, cyclooctadienyl, norbornadienyl, cyclopentadienyl, and cyclooctatrienyl), preferably one group. Above C_1-6It is substituted with an alkyl group. A suitable example of such a group is methylisopropylphenyl, where the methyl and isopropyl substituents of the phenyl group are in the para position.

The present invention also presents a tetracoordinated metal complex having one of the general formulas (IIIA) or (IIIB) shown in FIG. --M is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the periodic table, preferably ruthenium, osmium, iron, molybdenum, tungsten. , Titanium, ruthenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, cobalt, and nickel. --Z is selected from the group consisting of oxygen, sulfur, selenium, NR'''', PR'''', AsR'''', and SbR''''; --R'', R'''and R'''' are hydrogen atoms and C, respectively._1-6Alkyl, C_3-8Selected from the group consisting of cycloalkyl, aryl, and heteroaryl free radicals, or R and R together to form an aryl or heteroaryl group, each of which is the case. By halogen atom, C_1-6Alkyl, C_1-6Substituents R independently selected from the group consisting of alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium, and arylammonium.₅Is replaced by one or more, preferably one to three; --R'is defined in the same manner as R'', R'''and R'''' when contained in a compound having the general formula (IIIA), or in a compound having the general formula (IIIB). If included in, C_1-6Alkylene and C_3-8Selected from the group consisting of cycloalkylenes, the alkylene or cycloalkylene group may optionally be a substituent R.₅Replaced by one or more of; --R₁Is over 15 pK_aIs a constrained steric hindrance group with; --R₂Is an anionic ligand. ], The salt, solvate, and enantiomer are provided.

The present invention also presents a tetracoordinated metal complex having one of the general formulas (IIA) or (IIB) shown in FIG. --M is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the periodic table, preferably ruthenium, osmium, iron, molybdenum, tungsten, A metal of choice from titanium, ruthenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, cobalt, and nickel; --Z is selected from the group consisting of oxygen, sulfur, selenium, NR'''', PR'''', AsR'''' and SbR''''; --R'', R'''and R'''' are hydrogen atoms and C, respectively._1-6Alkyl, C_3-8A free radical selected from the group consisting of cycloalkyl, aryl and heteroaryl, or R and R together to form an aryl or heteroaryl free radical, each said free radical. Is a halogen atom, C, if desired_1-6Alkyl, C_1-6Substituents R independently selected from the group consisting of alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium, and arylammonium.₅Is substituted with one or more, preferably one to three, or R and R together to form an aryl or heteroaryl free radical, the free radical of which is bromine, Iodine, C_2-6Alkyl, C_2-6Substituent R selected from the group consisting of alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium and arylammonium₅One of them, or a halogen atom, C_1-6Alkyl, C_1-6Substituents R independently selected from the group consisting of alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium, and arylammonium.₅Replaced by two or more of; --R'is defined in the same manner as R'', R'''and R'''' when contained in a compound having the general formula (IIA), or a compound having the general formula (IIB). If included, C_1-6Alkylene and C_3-8Selected from the group consisting of cycloalkylenes, the alkylene or cycloalkylene group may optionally be a substituent R.₅Replaced by one or more of; --R₂Is an anionic ligand; --R₆Are aromatic and unsaturated alicyclics, preferably aryl and C_4-20A cycloalkenyl (eg, cyclooctadienyl, norbornadienyl, cyclopentadienyl, and cyclooctadienyl) group, the group of which is C._1-6It is optionally substituted with one or more alkyl groups. ] , The salt, the solvate, and the enantiomer.

R for the above classes of intermediate compounds₁And R₂More typical definitions of are already described for compounds of general formulas (IA) and (IB), respectively. All such compounds having the general formulas (IIA), (IIB), (IIIA) and (IIIB) are useful as intermediates for producing compounds having one of the general formulas (IA) and (IB). Is.

The intermediate having the formula (IIA) is first described in the following general formula: R'''C (OH) = C (R'') CHO Hydroxyaldehydes with, for example, salicylaldehyde (if Z is oxygen) or equivalent thioaldehyde (if Z is sulfur), aminoaldehyde (if Z is NR''''), phosphinaldehyde (if Z is PR) ''''), Aldehyde (if Z is AsR''''), or stibinoaldehyde (if Z is SbR'''') [however, hydroxy, thio, amino, phosphino, The alcino or stibino group is at the β position with respect to the aldehyde group. ] Is condensed with a primary aliphatic or aromatic amine, and then the resulting alkoxide is subjected to, for example, any metal of Group IA, IIA or IIIA of the Periodic Table (eg, sodium, potassium, magnesium or thallium). Is converted to its salt by reaction with the alkoxide of, and then the salt is converted to, for example, [RuCl.₂(p-cumene)]₂It can be prepared by a method similar to a known method including reacting with a metal complex having an unstable ligand (for example, halogen) such as.

The second class of intermediates having formula (IIB) is to first obtain an aldehyde such as benzaldehyde, o-hydroxyaniline (when Z is oxygen), aminothiol in order to obtain the desired 5-membered chelate ligand. (If Z is sulfur), diamine (if Z is NR''''), aminophosphine (if Z is PR''''), aminoarsin (if Z is AsR''''), or Aminostibin (when Z is SbR'''') [However, the hydroxy, thio, secondary amino, phosphino, arcino or stybino group is at the β-position with respect to the primary amino group. ] Is condensed with an amino alcohol such as, then the resulting alkanol is converted to its salt, and then the salt is subjected to an unstable coordination in the same manner as shown for compound (IIA) above. It can be prepared by reacting with a metal complex having children.

In addition, the present invention (a) The above-mentioned catalytically active 5-coordinated metal complex and (b) The amount of carrier supported on which the catalytically active pentacoordinated metal complex (a) is supported, Provided is a supported catalyst for use in a heterogeneous catalytic reaction containing.

In such supported catalysts, the carrier is a porous inorganic solid (including silica, zirconia, aluminosilica), eg, amorphous or semi-crystalline material, crystalline molecular sieve and modified layered material (eg, 1). It can be selected from the group consisting of more than a kind of inorganic oxides) and organic polymer resins (eg, polystyrene resins and derivatives thereof).

The porous inorganic solid that can be used with the catalyst of the present invention has an open microstructure that allows molecules to come into contact with the relatively large surface area of these substances that enhance their catalytic and sorption activity. These porous materials can be classified into three broad categories using the microstructure details on which they are based. These categories are amorphous or semi-amorphous materials, crystalline molecular sieves, and modified layered materials.

The detailed differences in the microstructure of these materials are important differences in the catalytic and sorption behavior of the materials, as well as the various observable properties used to characterize them, such as their surface area, pore size and These variations in pore size, the presence or absence of X-ray diffraction patterns, the details of such patterns, and their microstructures appear as differences in the appearance of materials when examined by transmission electron microscopy and electron diffraction.

Amorphous or semi-amorphous materials are an important class of porous inorganic solids that have been used for many years in industrial applications. Typical examples of such materials are amorphous silica commonly used in catalyst compositions and semi-amorphous transition alumina used as solid acidic catalyst and petroleum refining catalyst carriers. is there. The term "amorphous" refers to substances that do not have a long range order herein, because almost all substances have some degree of order, at least on a local scale. It can be somewhat misleading. Another term used to describe these substances is "X-ray neutrality (in different)". The ultrastructure of silica consists of 100-250 angstrom particles of dense amorphous silica (Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd.ed., Vol.20, 766-781 (1982)), and the porosity is It arises from the voids between the particles.

Semi-amorphous materials such as transition alumina also have a wide pore size distribution, but usually have a clear X-ray diffraction pattern consisting of several broad peaks. The microstructure of these materials consists of small crystalline regions of the concentrated alumina phase, and the porosity of the materials is due to the irregular voids between these regions (K. Wefers and Chanakya Misra, Oxides). and Hydroxides of Aluminum, Technical Paper No.19 Revised, Alcoa Research Laboratories, 54-59 (1987)). For any material, the diversity of pore sizes is typically very high because there is no long-range order to control the pore size of the material. The pore size of these materials belongs, for example, to a region called the mesoporous range, which includes pores in the range of about 15 to about 200 angstroms.

In stark contrast to these, structurally uncertain solids are materials with a very narrow pore size distribution because they are controlled by the strictly repetitive crystalline nature of the microstructure of the material. These substances are called "molecular sieves", the most important example of which is zeolite. Both natural and synthetic zeolites have long been shown to have catalytic properties for various forms of hydrocarbon conversion.

A particular zeolite material is an ordered, porous crystalline aluminosilicate with a well-defined crystal structure, as measured by X-ray diffraction, with a number of smaller cavities inside, which are even more. They are connected to each other by smaller channels or holes. These cavities or pores have a uniform pore size within a particular zeolitic material. The dimensions of these pores are such that adsorbed molecules of a particular size are accepted, but larger ones are rejected, and these materials are known as "molecular sieves" and have these properties. It is used in many types of methods to utilize. Such molecular sieves, both natural and synthetic, contain a wide range of cation-containing crystalline silicates.

These silicates are SiO₄And oxides of Group IIIB elements of the Periodic Table, such as AlO₄Can be described as a three-dimensional skeleton of the rigidity of, in which the tetrahedrons are cross-bonded by sharing oxygen atoms, which results in all Group IIIB elements (eg aluminum) and Group IVB elements (eg silicon). The ratio of the atom of) to the oxygen atom is 1: 2. The electron valence of tetrahedrons containing Group IIIB elements (eg, aluminum) is balanced by the inclusion of cations (eg, alkali metal or alkaline earth metal cations) in the crystal.

This is shown when the ratio of Group IIIB elements (eg aluminum) to various cations (eg Ca, Sr, Na, K or Li) is equal to 1. One type of cation can be completely or partially exchanged for another type of cation using the ion exchange method of conventional methods. By such cation exchange, the properties of a silicate can be changed by selecting an appropriate cation.

Many of these zeolites are named by letters or other convenient codes, such as zeolite A (US Pat. No. 2,882,243); X (US Pat. No. 2,882,244); Y (US Pat. No. 3,130,007); ZK. -5 (US Patent No. 3,247,195); ZK-4 (US Patent No. 3,314,752); ZSM-5 (US Patent No. 3,702,886); ZSM-11 (US Patent No. 3,709,979); ZSM-12 (US Patent No. 3,709,979) 3,832,449); ZSM-20 (US Patent No. 3,972,983); ZSM-35 (US Patent No. 4,016,245); ZSM-23 (US Patent No. 4,076,842); MCM-22 (US Patent No. 4,954,325); MCM- 35 (US Pat. No. 4,981,663); MCM-49 (US Pat. No. 5,236,575); and PSH-3 (US Pat. No. 4,439,409). The latter also contains a crystalline molecular sieve composition of a substance called PSH-3, and hexamethyleneimine, an organic compound that acts as a directing substance for the synthesis of stratified MCM-56. It refers to its synthesis from the reaction mixture.

Similar compositions with different structural elements are described in European Patent Application No. 293,032. Hexamethyleneimine is also crystalline molecular sieve MCM-22 in U.S. Pat. No. 4,954,325; MCM-35 in U.S. Pat. No. 4,981,663; MCM-49 in U.S. Pat. No. 5,236,575; and ZSM- in U.S. Pat. No. 5,021,141. Described for use in 12 synthesis. The molecular sieve composition SSZ-25 is described in US Pat. No. 4,826,667 and European Patent Application No. 231,860, wherein the zeolite is synthesized from a reaction mixture containing adamantane quaternary ammonium ions.

Zeolites, REY, USY, REUSY, dealuminated Y, superhydrophobic Y, silicon-rich dealuminated Y, ZSM-20, Beta, L, silicoaluminophosphate SAPO-5, SAPO-37, SAPO-40, MCM A molecular sieve material selected from the group consisting of -9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5, and mesoporous crystal MCM-41 is suitable for inclusion in the supported catalyst of the present invention.

By pillaring a particular stratified material, including a layer that can be isolated with a swelling agent, a material with a high level of porosity can be obtained. An example of such a stratified material is clay. Such clays are swollen with water, which separates the clay layer by water molecules.

Other stratified materials cannot be swollen with water, but can be swollen with certain organic swelling agents (eg amine and quaternary ammonium compounds). Examples of such non-water-swellable stratified materials are described in US Pat. No. 4,859,648, which includes stratified silicates, magadites, kenyaites, trititanates, and perovskite. Another example of a non-water-swellable stratified material is one that can be swollen with a particular organic swelling agent and includes the pore-containing titanometallate material described in US Pat. No. 4,831,006.

Once the stratified material swells, the material is strutged by intervening thermostable materials such as silica between the isolated layers. U.S. Pat. Nos. 4,831,006 and 4,859,648 described above describe methods for columnarizing non-water-swellable stratified materials described therein and refer to the definitions of columnarized and columnarized materials. Is incorporated herein by. Other patents describing columnarization and columnarized products of stratified material include US Pat. No. 4,216,188; 4,248,739; 4,176,090; and 4,367,163, and European Patent Application No. 205,711. Will be done.

The X-ray diffraction pattern of columnarized stratified material varies considerably depending on the extent to which swelling and columnarization usually disrupt well-ordered stratified microstructures. The microstructure regularity in some columnarized material is so extreme that only one peak in the low angle region of the X-ray diffraction pattern is observed at d intervals corresponding to the interlayer iterations in the columnarized material. Will be destroyed. Low-destructive material generally exhibits several peaks in this region, which is the order of this basic repeat. X-ray reflection due to the crystal structure of the layer is also observed in some cases. The pore size distribution within these columnarized stratified materials is narrower than that of amorphous and semi-amorphous materials, but wider than that of crystalline skeleton materials.

The present invention is a pentacoordinated metal complex within the broad permissible range described above or a pentacoordinated metal complex having one of the general formulas (IA) and (IB), preferably the metal M is ruthenium. Metathesis reactions, atomic transfer radical reactions, addition polymerization reactions, and carrier-type catalysts containing a pentacoordinated metal complex selected from the group consisting of osmium, iron, molybdenum, tungsten, and ruthenium, or the carriers defined above. It also provides for use as a catalytic component in a reaction selected from the group consisting of vinylization reactions.

In the first embodiment, the reaction transforms the first olefin into at least one of the second olefins (different from the first olefin), or linear olefin oligomers or polymers or cyclic olefins. It is a metathesis reaction to convert to. That is, the present invention comprises contacting at least one of the first olefins with a catalytically active metal carbene compound having one of the general formulas (IA) and (IB), optionally supported on a suitable carrier. The present invention relates to a method for carrying out a metathesis reaction.

The high levels of metathesis activity of the metal carbene compounds of the present invention coordinate these compounds to all types of olefins and catalyze metathesis reactions between these olefins. Examples of reactions made possible by the metal carben compounds of the present invention include, for example, ring-opening metathesis polymerization of cyclic olefins, ring-closing metathesis of acyclic diene, cross metathesis reactions involving at least one acyclic or cyclic olefin, and. Depolymerization of olefinic polymers, but not limited to these.

In particular, the catalyst of the present invention can catalyze a ring-sized cyclic olefin having at least three atoms. Examples of cyclic olefins that can be used in such metathesis reactions include norbornene and its functional derivatives (eg, those described in the examples below), cyclobutene, norbornadiene, cyclopentene, dicyclopentadiene, cycloheptene, cyclooctene. , 7-Oxanolbornene, 7-Oxanolbornadiene, Cyclooctane, and Cyclododecene.

The metathesis reaction of the present invention is carried out by dissolving a catalytic amount of a metal carben catalyst in a solvent in an inert atmosphere, and then, if desired, adding a cyclic olefin dissolved in the solvent to the carben solution with stirring. be able to. Solvents that can be used to carry out the metathesis reaction include not only aqueous solvents but also all kinds of organic solvents that are inert under polymerization conditions such as protic and aprotic solvents and non-polar solvents. Include.

More specific examples include not only supercritical solvents such as carbon dioxide (reactions are carried out under supercritical conditions), but also aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, etc. Included are ketones, amides, water, and mixtures thereof. Preferred solvents include benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof.

The solubility of the polymer formed during the metathesis polymerization reaction depends on the solvent selected and the molecular weight of the resulting polymer. The reaction temperature can typically vary from about 0 to about 100 ° C, preferably from 20 to 50 ° C. The reaction time is from about 1 to about 600 minutes. The molar ratio of catalysts to olefins is not exact and ranges from about 1: 100 to about 1: 1,000,000, preferably 1: 100 to about 1: 300,000, more preferably 1: 200 to 1: 10,000. Antioxidants and / or polymerization inhibitors (or chain transfer agents) can be added to the reaction mixture before the formed polymer solidifies or optionally when the desired molecular weight of the polymer is achieved. The choice of polymerization terminator to use is that the polymerization terminator may react with the catalytic carbene metal compound (IA) or (IB) under normal temperature conditions and be inert to further the reaction. It is not important to the present invention as long as it produces another Carben metal compound that cannot. Suitable examples of such polymerization inhibitors include vinyl compounds such as phenylvinyl sulfide, ethyl vinyl ether, vinyl acetate, and N-vinylpyrrolidone.

The pentacoordinated metal complexes of the present invention, in particular the (IA) and (IB) pentacoordinated metal complexes, are stable in the presence of various functional groups and therefore are of a wide variety under a wide variety of manufacturing conditions. Can be used to catalyze olefins. In particular, the first olefin compound to be converted in the metathesis reaction can contain one or more functional atoms or groups.

One or more functional atoms or groups include, for example, hydroxyl, thiol (mercapto), ketone, aldehyde, ester (carboxylate), thioester, cyano, cyanate, epoxy, silyl, silyloxy, silanyl, siloxazanyl, boronato, Boryl, stanyl, disulfide, carbonate, imine, carboxyl, amine, amide, carboxyl, isocyanate, thioisocyanate, carbodiimide, ether (preferably C)_1-20Alkoxy or aryloxy), thioether (preferably C)_1-20Thioalkoxy or thioaryloxy), nitro, nitroso, halogen (preferably chloro), ammonium, phosphonate, phosphoryl, phosphino, phosphanyl, C_1-20Alkyl sulfanyl, aryl sulfanyl, C_1-20Alkyl sulphonyl, aryl sulphonyl, C_1-20Examples include those selected from the group consisting of alkylsulfinyl, arylsulfinyl, sulfonamides, and sulfonates (preferably paratoluenesulfonates, methanesulfonates or trifluoromethanesulfonates). The functional atom or group of the first olefin may be either a substituent portion of the first olefin or a portion of the carbon chain of the first olefin compound.

The high level metathesis activity of the pentacoordinating metal complex of the present invention is, for example, a diallyl compound [diallyl ether, diallylthioether, diallylphthalate, diallylamino compound (for example, diallylamine, diallylaminophosphonate, diallylglycine ester, etc.)]. When catalyzing ring-closing metatheses of acyclic diene, such as 1,7-octadiene, substituted 1,6-heptadiene, in the presence or absence of a solvent at relatively low temperatures (about 20-80 ° C). Is useful. In the case of the above-mentioned diallyl compound, if the 5-coordinated metal complex to be used is a di-metal complex in which one metal is 5-coordinated and the other is 4-coordinated, the reaction proceeds unexpectedly further, and the pyrrolyl compound, A furanyl compound or a thiophenyl compound, that is, a dehydrogenating compound is given.

The pentacoordinated metal complex of the present invention contains one reactive end group which is a useful substance for a telechelic polymer, that is, a chain extension step, block copolymer synthesis, reaction injection molding, and polymer network formation. It can also be used for the preparation of macromolecules having the above. An example is hydroxyl telechelic polybutadiene, which can be obtained from 1,5-cyclooctadiene, 1,4-diacetoxy-cis-2-butene and vinyl acetate.

Most applications require highly functional polymers, i.e., polymers with at least two functional groups per chain. Reaction schemes for the synthesis of telechelic polymers by ring-opening metathesis polymerization are well known in the art. In such a scheme, the acyclic olefin acts as a chain transfer agent for adjusting the molecular weight of the telechelic polymer produced. When α, ω-2 functional olefins are used as chain transfer agents, bifunctional telechelic polymers can actually be synthesized.

In summary, the metathesis reaction method of the present invention can be carried out when the first olefin compound is an acyclic monoolefin. For example, the method for olefin coupling by cross-metathesis involves a first acyclic olefin or a functionalized olefin (eg, one described above) with a second olefin or a functionalized olefin. In the presence, it includes the step of contacting with the metal carbene compound of the present invention. More preferably, the cross metathesis reaction is of formula R.₈CH = CHR₁₀Monoolefin with and formula R₉CH = CHR₁₁A mixture of monoolefins having (in the formula, R)₈, R₉, R₁₀And R₁₁Independently, C_1-20Selected from alkyl groups, said C_1-20The alkyl group optionally supports one or more of the functional atoms or groups described above. ), Equation R₈CH = CHR₉Monoolefin with and formula R₁₁CH = CHR₁₀Can be for conversion to a mixture of monoolefins having.

Alternatively, the first olefin compound may be a diolefin or a cyclic monoolefin having a ring size of at least 3 atoms, and the metathesis reaction may be the diolefin or cyclic. It is preferably carried out under suitable conditions for the conversion of monoolefins to linear olefin oligomers or polymers. When the first olefin compound is a diolefin, the metathesis reaction is also carried out under conditions suitable for converting the diolefin into a mixture of a cyclic monoolefin and an aliphatic alpha olefin.

Depending on the selection of the starting material for the metathesis reaction and the intended use of the final organic molecule produced, the metathesis reaction can provide a very wide range of final products, including bioactive compounds. For example, the reaction is for the conversion of a mixture of two different olefins, one of which is (i) a cyclodiene containing 5-12 carbon atoms, and (ii) the following formula:

<chemistry num="4"><img file="JP5100728B2_D0004.tif" /></chemistry>

An alpha olefin selected from olefins having the following formula:

<chemistry num="5"><img file="JP5100728B2_D0005.tif" /></chemistry>

It may be for conversion to an unsaturated bioactive compound having.

In the above formula, a is an integer from 0 to 2 b is selected from 1 and 2 c is selected from 0 and 1 m and p indicate that the hydrocarbon chain of formula (V) contains 10 to 18 carbon atoms. r and t have a total of 12 to 40 carbon atoms in the hydrocarbon chains of the two different olefins of formula (IV). z is an integer from 1 to 10 X, X'and X'' are hydrogen atoms, halogens, methyls, acetyls, -CHO and -OR₁₂An atom or group that is selected independently of. R₁₂Is a hydrogen atom, as well as tetrahydropyranyl, tetrahydrofuranyl, t-butyl, trityl, ethoxyethyl, and SiR.₁₃R₁₄R₁₅It is selected from the alcohol protecting groups selected from the group consisting of. R₁₃, R₁₄And R₁₅Are independent of each other, C_1-6It is selected from alkyl and aryl groups.

Unsaturated bioactive compounds having formula (V) are pheromones or pheromone precursors, pesticides or pesticide precursors, pharmaceutically active compounds or pharmaceutical intermediates, fragrances or fragrance precursors. Some examples of the unsaturated bioactive compounds are 7,11-hexadecadienyl acetate, 1-chloro-5-decene, trans, trans-8,10-dodeca-dienol, 3,8, 10-Dodecatorienol, 5-decenyl acetate, 11-tetradecenyl acetate, and 1,5,9-tetradecatorien can be mentioned.

Gossyplure, which contains a mixture of 7,11-hexadecadienyl acetate stereoisomers, is a pest control, especially in view of its effectiveness in disrupting the mating and reproductive cycle of targeted insect species. It is a commercially available pheromone useful in. It can be conveniently made from 1,5,9-tetradecatriene, the latter from cyclooctadiene and 1-hexene according to the present invention.

When carrying out the metathesis reaction of the present invention, in most cases the reaction proceeds very rapidly, but for certain olefins, further to improve the reaction rate and / or the yield of the metathesis reaction. , The first olefin compound and optionally the second olefin compound are conveniently contacted with an organic or inorganic acid or an aluminum, titanium or boron based Lewis acid well known in the art.

Conversely, as described by some of the examples below, the ring-opening metathesis polymerization (ROMP) reaction using the catalyst of the present invention is norbornene such that the control of the polymerization becomes a problem in the absence of appropriate means. And for monomers such as substituted norbornene, it can proceed in a very rapid manner. This kind of problem is as in reactive injection molding (RIM) techniques, where the liquid olefin monomer and catalyst are mixed, then injected, cast or injected into the mold, and the polymerization is complete (ie, ie). During product "curing"), it is likely to occur during the molding of thermosetting polymers, where the molded portion is removed from the mold, if necessary, prior to the post-curing process.

The ability to control the reaction rate, the pot life of the reaction mixture, becomes more important in the molding of larger parts. The use of the catalysts of the present invention, prolonging the pot life, and / or controlling the rate of the metathesis polymerization reaction can be, for example, increasing the ratio of catalyst / olefin and / or to the reaction mixture of the polymerization retarder. It can be carried out by various methods such as addition.

Furthermore, this is (a) A first contact of the aforementioned metathesis catalyst (supported as desired) with an olefin in a reactor at a first temperature at which the metathesis catalyst is substantially inert (inactive). Process and (b) A second step of setting the temperature of the reactor to a second temperature above the first temperature at which the catalyst is active (eg, heating the reactor). It can be achieved by an improved embodiment including.

In a more typical embodiment, thermal activation occurs explosively rather than persistently, for example by repeating steps (a) and (b).

In the controlled polymerization method, the non-reactivity of the catalyst in the first step depends not only on the first temperature, but also on the olefin / catalyst ratio of the olefin / catalyst mixture. Preferably, the first temperature is about 20 ° C (room temperature), but for a particular olefin and a particular olefin / catalyst ratio, the olefin / catalyst mixture is cooler than room temperature, eg about 0 ° C. Cooling down to C may be appropriate. The second temperature is preferably about 40 ° C and may be up to about 90 ° C.

As described in the Examples below, the ring-opening metathesis polymerization reaction using the catalyst of the present invention has a molecular weight (number average) in the range of about 25,000 to 600,000 and a range of about 1.2 to 3.5, preferably about 1.3 to about 2.5. A polymer such as polynorbornene and a functional derivative thereof having well-controlled properties such as the dispersity (Mw / Mn) of the above is easily achieved.

When the ring-opening metathesis polymerization reaction using the catalyst of the present invention is carried out in a mold as in the RIM method, as is known in the art, an antioxidant, an antioxidant, ceramics, a light stabilizer, and a plasticizer. It occurs in the presence of compounding aids such as agents, dyes, pigments, fillers, reinforcing fibers, lubricants, adhesion promoters, viscosity enhancers, and mold release agents.

The metal carben compound of the present invention having one of the general formulas (IA) and (IB) and in which the metal M is preferably selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium, and rhenium. Yet another use is as a catalyst for the radical addition reaction of polyhalogenated alkenes to olefins (so-called colori reaction).

Such a reaction is preferably carried out in the presence of an organic solvent in a molar excess of polyhalogenated alkanes and in a temperature range of about 30-100 ° C. Suitable examples of polyhalogenated alkanes used in this embodiment of the invention are carbon tetrachloride, chloroform, trichlorophenylmethane, and carbon tetrabromide. Examples of suitable olefins are vinyl aromatic monomers (eg, styrene or vinyltoluene), α, β-ethylenically unsaturated acid esters (eg, C)._1-10Alkyl acrylate and methacrylate), acrylonitrile, etc.

Further, the present invention is as desired as disclosed above as a catalytic component of a catalytic system for atomic or group transfer radical polymerization of radical (co) polymerizable monomers, or for ATRA or vinylization reactions. A pentacoordinated metal complex supported on a carrier, a pentacoordinated metal compound having one of the general formulas (IC) and (ID) shown in FIG. 4, or a cationic species thereof (anionic ligand) is extracted. (Obtained), optionally in combination with the amount of carrier carried.

Here, in the general formulas (1C) and (1D), --M , Z, R', R'', R''', R'''', R₂, R₃, R₄And y are defined above for equations (IA) and (IB). --R₁₆Is a neutral electron donor.

Constrained steric hindrance group R for compounds (IA) and (IB)₁Unlike the compound (IC) and (ID) neutral electron donors R₁₆Is less than about 15 pK_aHave. R₁₆A good example of is the expression PR₁₇R₁₈R₁₉Phosphine (in the formula, R₁₇, R₁₈And R₁₉Are independent of each other, C_1-10Alkyl, C_3-8It is selected from the group consisting of cycloalkyl and aryl. ), For example, tricyclohexylphosphine (pK)_a= 9.7), tricyclopentylphosphine, triisopropylphosphine and triphenylphosphine (pK)_a= 2.7), as well as phosphine, arsine, stilbene, allen, heteroallene, etc. to which functionality has been imparted.

Compounds (IC) and (ID) are less effective than compounds (IA) and (IB) in catalysis of olefin metathesis reactions, but they are efficient in catalysis of AATRP, ATRA and vinylization reactions. Has been found to be.

Some of the compounds having one of the general formulas (IC) and (ID), especially those in which y is 0 and M is ruthenium or osmium, are well known in the art and are known as metathesis catalysts in the United States. It is described in Pat. No. 5,977,393. y is 1 to 3 or y is 0, but M is selected from the group consisting of iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, cobalt or nickel. Compounds having one of the general formulas (IC) and (ID), which are metals, are not yet known in the art, but as the second and third embodiments of the present invention, the methods described herein. Can be appropriately prepared by any of the above, in which case, in the raw material of the process of the corresponding method, R₁And R₁₆Simply replace with.

As already mentioned above, in order to successfully perform the living / controlled radical polymerization intended as the seventh embodiment of the present invention, a low steady state concentration (about 10).^-8Mol / l to 10^-6Growing radicals present in mol / l) and higher concentrations (typically about 10)^-4It is important to achieve rapid exchange with the inert chains present at molars / l to 1 mol / l). Therefore, it is desirable to adjust the respective amounts of the catalytic component and the radical (co) polymerization monomer of the present invention so that these concentration ranges are achieved.

The concentration of growing radicals is about 10^-6Above mol / l, the amount of active species present during the reaction is excessive, which results in an undesired increase in the reaction rate of side reactions (eg, radical-radical quenching, from non-catalytic species). Radical extraction etc.). The concentration of growing radicals is about 10^-8If it is less than a molar, an undesired decrease in polymerization rate will occur. Similarly, the concentration of the inactive chain is 10.^-4If it is less than mol / l, the molecular weight of the polymer produced may increase dramatically and its polydispersity may not be controlled. On the other hand, when the concentration of the Inactive Species is greater than 1 mol / l, the molecular weight of the reaction product tends to be undersized, resulting in oligomeric properties not greater than about 10 monomeric units. Approximately 10 in a lump^-2A molar / l concentration of the Inactive Chain gives a polymer with a molecular weight of approximately 100,000 g / mol.

The various catalytic components of the present invention are also suitable for radical polymerization of any rapidly polymerizing alkene, including (meth) acrylate, styrene and diene. They can provide controlled copolymers with a variety of structures, including block, random, gradient, star, graft, comb, superbranched, and dendritic (co) polymers. it can.

More typically, a monomer suitable for living radical polymerization according to the seventh embodiment of the present invention is of formula R.₃₁R₃₂C = CR₃₃R₃₄Includes. In the formula, --R₃₁And R₃₂Are independent of each other, hydrogen atom, halogen atom, CN, CF₃, C_1-20Alkyl (preferably C_1-6Alkyl), α, β-unsaturated C_2-20Alkynyl (preferably acetylenyl), α, β-unsaturated C_2-20Alkenyl (preferably vinyl) [optionally (preferably at the α-position) halogen, C_3-8Selected from the group consisting of cycloalkyl, phenyl (substituted with 1-5 substituents if desired)]; --R₃₃And R₃₄Independently, hydrogen atom, halogen atom (preferably fluorine or chlorine), C_1-6Alkyl and COOR₃₅(In the formula, R₃₅Is a hydrogen atom, alkali metal or C_1-6Selected from the group consisting of (selected from alkyl); --R₃₁, R₃₂, R₃₃And R₃₄At least two of them are hydrogen or halogen atoms.

Therefore, suitable vinyl heterocycles that can be used as the monomer of the present invention are 2-vinylpyridine, 6-vinylpyridine, 2-vinylpyrrole, 5-vinylpyrrole, 2-vinyloxazole, 5-vinyloxazole, 2-. Vinylthiazole, 5-vinylthiazole, 2-vinylimidazole, 5-vinylimidazole, 3-vinylpyrazole, 5-vinylpyrazole, 3-vinylpyrimidine, 6-vinylpyrimidine, 3-vinylisoxazole, 3-vinylisoxazole, It includes 2-vinylpyrimidine, 4-vinylpyrimidine, 6-vinylpyrimidine, and any vinylpyrimidine, most preferably 2-vinylpyridine.

Other preferred monomers are: --C_1-20Alcoholic (meth) acrylic acid ester, --Acrylonitrile, --C_1-20Alcoholic cyanoacrylic acid ester, --C_1-6Alcoholic didehydromalonate diester, --Vinyl ketone in which the α carbon atom of the alkyl group does not carry a hydrogen atom, and --C on the vinyl moiety (preferably α carbon atom) if desired_1-6Styrene with 1 to 5 substituents on the alkyl group and phenyl ring [The substituent is C_1-6Alkyl, C_1-6Alkenyl (preferably vinyl), C_1-6Alkynyl (preferably acetylenyl), C_1-6Alkoxy, halogen, nitro, carboxy, C_1-6Alkoxycarbonyl, C_1-6Selected from the group consisting of acyl-protected hydroxy, cyano, and phenyl], Including.

The most preferred monomers are methyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, and styrene.

In the seventh embodiment of the present invention, the catalyst component of the present invention is based on the reversible formation of growing radicals in the redox reaction between the metal component and the polymerization initiator. More preferably, it is used in combination with a polymerization initiator having an atom or group capable of radical transfer.

As a suitable polymerization initiator, formula R₃₅R₃₆R₃₇CX₁Those having In the formula, --X₁Is a halogen atom, OR₃₈[R₃₈Is C_1-20Alkyl, polyhalo C_1-20Alkyl, C_2-20Alkynyl (preferably acetylenyl), C_2-20Alkenyl (preferably vinyl), optionally 1-5 halogen atoms or C_1-6Phenyl substituted with an alkyl group, and phenyl substituted C_1-6Selected from alkyl], SR₃₉, OC (= O) R₃₉, OP (= O) R₃₉, OP (= O) (OR₃₉)₂, OP (= O) OR₃₉, ON (R₃₉)₂, And SC (= S) N (R)₃₉)₂Selected from the group consisting of, where R₃₉Is aryl or C_1-20Alkyl or N (R)₃₉)₂2 Rs if groups are present₃₉The groups together form a 5, 6 or 7-membered heterocycle (according to the definition of heteroaryl above), and --R₃₅, R₃₆And R₃₇Independently, hydrogen atom, halogen atom, C_1-20Alkyl (preferably C_1-6Alkyl), C_3-8Cycloalkyl, C (= O) R₄₀(R₄₀Is C_1-20Alkyl, C_1-20(Selected from the group consisting of alkoxy, aryloxy or heteroaryloxy), C (= O) NR₄₁R₄₂(In the formula, R₄₁And R₄₂Are independent of each other, hydrogen atom and C_1-20Selected from the group consisting of alkyl or R₄₁And R₄₂Together the carbon atoms form 2-5 alkylene groups), COCl, OH, CN, C_2-20Alkenyl (preferably vinyl), C_2-20Alkynyl, oxylanyl, glycidyl, aryl, heteroaryl, arylalkyl, and aryl substituted C_2-20Selected from the group consisting of alkenyl.

In these polymerization initiators, X₁Is preferably bromine, which results in high reaction rate and low polymer polydispersity.

Alkyl, cycloalkyl or alkyl-substituted aryl groups are R₃₅, R₃₆And R₃₇When selected as one of the alkyl groups, the X is further described above.₁It may be substituted with a group. That is, the polymerization initiator can function as a raw material molecule for a branched or star (co) polymer. One example of such a polymerization initiator is 2,2-bis (halomethyl) -1,3-dihalopropane [eg, 2,2-bis (chloromethyl) -1,3-dichloropropane or 2,2. -Bis (bromomethyl) -1,3-dibromopropane], a preferred example of which is R₃₅, R₃₆And R₃₇One of them, each independently further X₁C which may be substituted with a group_1-6This is the case when the phenyl is substituted with 1 to 5 alkyl substituents [eg, α, α'-dibromoxylene, hexax (α-chloromethyl or α-bromomethyl) benzene]. Preferred polymerization initiators are 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, and 2-halo-C._1-6C of carboxylic acid (2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.)_1-6Alkylating esters are included.

Any transition metal component that can participate in the oxidation-reduction cycle of the polymerization initiator and the inert polymer chain but does not form a direct carbon-metal bond with the polymer chain, such as ruthenium, osmium, iron, molybdenum. , Tungsten, titanium, renium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, nickel, and cobalt are suitable for use in the present embodiment of the present invention.

In the seventh embodiment of the present invention, the catalytic metal carbene component of the present invention is an anionic ligand R.₂However, preferably a halogen atom, C_1-6Alkoxy, sulfate, phosphate, hydrogenophosphate, triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), cyano, tetrafluoroborate, and C._1-6It is selected from the group consisting of carboxylates.

As is well known to those skilled in the art, such a catalytic component having an anionic ligand such as tetrafluoroborate can be appropriately used as an anionic ligand R.₂The metal carbene component having a halogen atom is reacted with a metal compound having another anion capable of extracting and replacing the halogen atom (for example, silver tetrafluoroborate), thereby forming a cationic alkylidene complex. It can be preferably prepared by the ligand exchange. It was surprisingly found that such a cationic alkylidene complex exhibits better catalytic activity than the corresponding metal carbene complex coordinated to the halogen ligand.

In this feature of the invention, the amounts and relative ratios of the polymerization initiator and the transition metal carbene compound are useful for carrying out ATRP. The molar ratio of the transition metal carbene compound to the polymerization initiator is 0.0001: 1 to 10: 1, preferably 0.1: 1 to 5: 1, more preferably 0.3: 1 to 2: 1, and most preferably 0.9: 1. ~ 1.1: 1.

The ATRP of the present invention may be carried out in the absence of a solvent, i.e. in chunks. However, when solvents are used, suitable solvents include ethers, cyclic ethers, alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, acetonitrile, dimethylformamides and mixtures thereof, and supercritical solvents (eg CO).₂) Is included. ATRP can also be carried out according to known suspension, emulsification, or precipitation methods.

Suitable ethers include diethyl ether, ethyl propyl ether, dipropyl ether, methyl t-butyl ether, di-t-butyl ether, glyme (dimethoxyethane), diglime (diethylene glycol dimethyl ether) and the like. Suitable cyclic ethers include tetrahydrofuran and dioxane. Suitable alkanes include pentane, hexane, cyclohexane, octane and dodecane. Suitable aromatic hydrocarbons include benzene, toluene, o-xylene, m-xylene, p-xylene and cumene. It should be confirmed that the selected halogenated hydrocarbons do not function as polymerization initiators under reaction conditions, but suitable halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, and 1 ~. Benzene substituted with 6 fluorine / chlorine atoms is included.

ATRP can be carried out in the gas phase (eg, by passing a gaseous monomer through the bed of the catalytic system) in a sealed container or autoclave. The (co) polymerization can be carried out at a temperature of about 0 ° C to 160 ° C, preferably about 60 ° C to 120 ° C. Typically, the reaction time is 30 minutes to 48 hours, more preferably 1 to 24 hours. The (co) polymerization can be carried out at a pressure of about 0.1 to 100 atm, preferably 1 to 10 atm.

According to another embodiment, ATRP is such that an emulsion or suspension of a (co) copolymer is formed in an emulsion or suspension in a suspension medium for suspending the monomer. The method can also be carried out using the metal carbene complex of the present invention in combination with a surfactant. The suspension medium is usually an inorganic liquid, preferably water. In this embodiment of the invention, the weight ratio of the organic layer to the suspension medium is usually 1: 100 to 100: 1, preferably 1:10 to 10: 1. If desired, the suspension medium may be a buffer solution. Preferably, the surfactant is selected to control the stability of the emulsion, i.e. to form a stable emulsion.

To carry out polymerization in a heterogeneous medium (in a suspension medium, i.e. water or CO₂Medium, if the monomer / polymer is insoluble or slightly soluble), the metal catalyst component must be at least partially soluble in the monomer / polymer. That is, a ligand that matches the above conditions, such as a ligand containing a long alkyl chain that increases the solubility of the catalyst in the hydrophobic monomer to be polymerized, is appropriately selected. Only if good and controlled ATRP polymerization can be achieved in the water-mediated system of this embodiment. From the above description of the ligands coordinated to the metal M in the catalytically active metal carbene complex of the present invention, those skilled in the art can make appropriate selections.

An important factor in the preparation of a stable emulsion of this embodiment is to stabilize the suspension / emulsion of the initial monomer and the growing polymer particles and prevent unwanted coagulation / aggregation of the particles. Therefore, a surfactant is used. However, in order to carry out ATRP in an emulsion, care must be taken to select a detergent that does not interfere with the end of the catalyst or inert chain. Suitable surfactants include nonionic, anionic and cationic surfactants, with cationic and nonionic surfactants being preferred in non-buffered solutions. Particularly preferred nonionic surfactants include polyethylene glycol, polyoxyethylene oleyl ether, and polyoxyethylene sorbitan monoalkyl. A preferred cationic surfactant is dodecyltrimethylammonium bromide. Regardless of the surfactant used, efficient stirring is preferred to obtain a good dispersion or latex.

Surfactants are typically about 0.01 to 50% by weight based on the total weight of all components introduced into the polymerization reactor, namely suspension mediums, monomers, surfactants and catalyst systems. Present in concentration.

High solubility in suspension media is not a requirement for polymerization initiators, as evidenced by the use of poorly water soluble ethyl 2-bromoisobutyrate to initiate emulsion polymerization. The order of addition of the polymerization initiator and the other reaction components may be arbitrary, but when the initiator is added to the reaction mixture before emulsification, a stable latex is usually obtained. Suitable polymerization initiators are as described above in the solvent embodiment in the ATRP method. The polymerization initiator can also be a macromolecule containing an atom or group capable of radical transfer. Typical types of such macromolecules may be water-soluble or amphipathic, may be incorporated into the polymer particles after initiation of the reaction, and may be grown by the hydrophilic segment of the macroinitiator. The particles inside may be stabilized.

(Co) After the polymerization step is completed, the formed polymer is subjected to a known operation method, for example, precipitation in a suitable solvent, filtration of the precipitated polymer, and then washing and drying of the filtered polymer. Isolate. Precipitation typically uses either a suitable alkane or cycloalkane solvent, such as pentane, hexane, heptane, cyclohexane or mineral oil, or an alcohol (eg, methanol, ethanol or isopropanol), or a suitable solvent. It can be carried out using a mixture of.

The precipitated (co) polymer can be filtered by gravity or by vacuum filtration and may use, for example, a Buchner funnel and an aspirator. The polymer can then be washed with the solvent used to precipitate the polymer, if desired. The steps of precipitation, filtration and washing may be repeated if desired. After isolation, the (co) polymer may be dried by aspirating air from the (co) polymer by vacuum. The dried (co) polymer can then be analyzed and / or characterized by, for example, size exclusion chromatography or NMR spectral analysis.

The (co) polymers produced by the catalytic process of the present invention are generally useful as molding materials (eg, polystyrene) and as barrier or surface materials (eg, polymethylmethacrylate). However, typically, having more uniform properties than polymers produced by conventional radical polymerization is most suitable for special applications.

For example, a block copolymer of polystyrene (PSt) and polyacrylate (PA) (eg, Pst-PA-PSt) is a useful thermoplastic elastomer. Polymethylmethacrylate / acrylate 3-block copolymers (eg PMMA-PA-PMMA) are useful, fully acrylic thermoplastic elastomers. Styrene, (meth) acrylate, and / or acrylonitrile homopolymers and copolymers are useful plastics, elastomers, and adhesives. Blocks or random copolymers of styrene and (meth) acrylate or acrylonitrile are useful thermoplastic elastomers with high solvent resistance. Further, the block copolymer produced by the present invention in which blocks alternate between polar monomers and non-polar monomers is used to produce a highly uniform polymer blend. Is a useful amphipathic surfactant or dispersant. Star-shaped (co) copolymers, such as styrene-butadiene star-shaped copolymers, are useful impact-resistant copolymers.

The (co) polymers produced by the catalytic method of the present invention generally have a number average molecular weight of about 1,000 to 1,000,000, preferably 5,000 to 250,000, more preferably 10,000 to 200,000. Its structure can include block, multi-block, star-shaped, gradient, random, hyperbranched, grafted, comb-shaped, and dendritic copolymers due to the high flexibility of living radical polymerization. Each of these various copolymers will be described later.

Since ATRP is a living polymerization method, it can actually be started and stopped at will. In addition, the polymer product contains the functional groups X required to initiate further polymerization.₁keeping. Thus, in one embodiment, once the first monomer is consumed in the initial polymerization step, then the second monomer is added and on the growing polymer chain in the second polymerization step. A second block can be formed in. Multi-block copolymers can be prepared by performing additional polymerization with the same or different monomers. Moreover, since ATRP is a radical polymerization, these blocks can be prepared in essentially any order.

The (co) polymer produced by the catalytic method of the present invention has an extremely low dispersity, and the ratio Mw / Mn of its weight average molecular weight to the number average molecular weight is generally about 1.1 to 1.9, preferably about 1.1 to 1.9. It is 1.2 to 1.8.

The living (co) polymer chain is X as a terminal group or, in one embodiment, as a substituent in a monomeric unit of the polymer chain.₁Since they retain fragments of polymerization initiators containing, they can be considered terminal-functional or intra-chain functional (co) polymers. Thus, such (co) polymers are used for further reactions, including cross-linking, chain extension (eg, to form long-chain polyamides, polyurethanes and / or polyesters), reactive injection molding, etc. Can be converted to a (co) polymer having the same functional groups (eg, halogens can be converted to hydroxyl or amino groups by known methods, and nitriles or carboxylic acid esters can be converted to known methods. Can be hydrolyzed to carboxylic acid).

The pentacoordinated metal complex of the present invention is also useful for addition polymerization of one or more α-olefins having 2 to 12 carbon atoms in combination with one or more dienes having 4 to 20 carbon atoms, if desired. Is. More preferably, the catalytically active 5-coordinated metal complex for such a reaction is such that the polydentate ligand provides a 5-membered ring structure with the metal, such as a complex having the general formula (IB). ..

Also, preferably, the complex is a catalyst for the addition polymerization of one or more α-olefins having 2 to 12 carbon atoms in combination with one or more dienes having 4 to 20 carbon atoms, if desired. A system with the following elements: (A) A complex having the general formula (IB), (B) A compound having the ability to convert its imine component (moiety) into a metallic amine structure by reacting with compound (A), and (C) A compound having the ability to form an ion pair by reacting with compound (A), Used in catalytic systems containing.

Suitable Ingredients (B) for this purpose include organic aluminum compounds, in particular tri-n-alkylaluminum (eg, triethylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, tri). -n-butylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum), and its branched chain analogs; dialkylaluminum hydride, trialkenyl Aluminum, alkylaluminum alkoxide, dialkylaluminum alkoxide, dialkylaluminum aryloxide, dialkylaluminum halide) are included.

Suitable components (C) for this purpose include Lewis acids (preferably boron trifluoride and triarylboron), ionic compounds (eg, carbonium, oxonium, ammonium, phosphonium, ferrosenium, etc.), borane compounds. (For example, decavorane) and salts thereof, metal carboranes, and heteropoly compounds (eg, phosphomolybdic acid, silicomolybdic acid, phosphomolybdovanadic acid, etc.) are included.

The catalyst system described above is well defined for continuous or batch polymerization of α-olefins at moderate temperatures ranging from about 40 ° C to about 80 ° C under atmospheric pressure and with high productivity. -Defined) Efficient in obtaining polymers.

If desired, the transition metal catalyst can be removed from the polymerization medium by adding a commercially available ion exchange resin, as is well known in the art. However, as described below, it is also desirable to modify the catalyst to a dendrimer material in order to facilitate removal by ultrafiltration.

In order to facilitate the use of the pentacoordinated metal carbene compounds of the invention in heterogeneous catalytic reactions, the invention is further particularly suitable for covalent bonding to carriers having one of the general formulas (IA) and (IB). Derivatives of the compound, provided that R'and / or R'' are of the following formula:

<chemistry num="6"><img file="JP5100728B2_D0006.tif" /></chemistry>

(During the ceremony, --R₂₀Is C_1-6Alkylene, arylene, heteroarylen, and C_3-8A free radical selected from the group consisting of cycloalkylenes, which radical is optionally C._1-20Alkyl, C_2-20Alkenyl, C_2-20Alkyne, C_1-20Carboxylate, C_1-20Alkoxy, C_2-20Alkenyloxy, C_2-20Alkynyloxy, C_2-20Alkoxycarbonyl, C_1-20Alkylsulfonyl, C_1-20Alkyl sulfinyl, C_1-20One or more substituents independently selected from the group consisting of alkylthio, aryloxy, and aryl, respectively.₂₄Replaced by; --D is oxygen, sulfur, silicon, arylene, methylene, CHR₂₄, C (R)₂₄)₂, NH, NR₂₄, And PR₂₄A divalent atom or radical selected from the group consisting of; --R₂₁, R₂₂And R₂₃Are independent hydrogen atoms, halogen atoms, and R₂₄Selected from the group consisting of; --n is an integer from 1 to 20; (However, R₂₁, R₂₂And R₂₃At least one of_1-20Alkoxy, C_2-20Alkenyloxy, C_2-20Alkynyloxy, C_2-20Alkoxycarbonyl, C_1-20Alkylsulfonyl, C_1-20Alkyne sulfinyl, C_1-20(Selected from the group consisting of alkylthio and aryloxy) With respect to the derivative which has been replaced or substituted with a group having.

The most preferred of the above groups are derivatives in which R'is replaced or substituted with a 3- (triethoxysilyl) propyl group. Alternatively, suitable derivatives include molded organic siloxane copolymer products as disclosed in EP-A-484,755.

In another embodiment, the invention comprises the product of (a) a covalent bond between a derivative as defined above and (b) a carrier containing one or more inorganic oxides or organic polymer substances. It relates to a supported catalyst for use in a heterogeneous catalytic reaction. Preferably, the inorganic carrier is selected from silica, aluminosilica, zirconia, natural and synthetic zeolites, and mixtures thereof, or the organic polymer carrier has a C aromatic ring._1-6Alkyl, C_3-8A polystyrene resin or derivative thereof substituted with one or more groups selected from cycloalkyl, aryl, and heteroaryl. More detailed examples of suitable carriers are as described above.

As mentioned above, for the purpose of more easily removing the catalytic component from the reaction medium, the invention also presents directly or indirectly via spacer molecules, by its N and / or Z atoms, and / or R. When , R or R carries a functional group, the functional group confuses the core molecule with the carrier present in the carrier-type catalyst embodiment of the present invention. A five-coordination metal complex having any of the above-mentioned general formulas (IA), (IB), (IIA), and (IIB), and general formulas (IIIA) and (IIIB), each of which is bound to (not). ), A dendrimer substance containing two or more compounds selected from a tetracoordinated metal complex having any of).

The core molecule is not rigorous for this feature of the invention, due to its reactivity with the metal carbene compound of interest, or with the spacer molecule if it is present in the dendrimer material. It is only limited.

For example, the core molecule Aryl, polyaryl, heteropolyaryl, alkyl, cycloalkyl, and heterocyclic cycloalkyl groups, and --Formula A (R)₂₀)_nX_3-n[R₂₀Is C_1-6Alkylene, arylene, heteroarylen, and C_3-8A free radical selected from the group consisting of cycloalkylenes, which radical is optionally C._1-20Alkyl, C_2-20Alkenyl, C_2-20Alkyne, C_1-20Carboxylate, C_1-20Alkoxy, C_2-20Alkenyloxy, C_2-20Alkynyloxy, C_2-20Alkoxycarbonyl, C_1-20Archisulfonyl, C_1-20Arkis Rufinil, C_1-20One or more substituents independently selected from the group consisting of alkylthio, aryloxy, and aryl, respectively.₂₄Substituted with; A is a Group IIIA element (preferably boron or aluminum) or nitrogen in the periodic table. ]; Or the formula G (R₂₀)_nX_4-n[G is a Group IVA element (preferably carbon, silicon or tin). ]; Or formula J (R₂₀)_nX_5-n[J is a Group VA element other than nitrogen (ie, preferably phosphorus, arsenic or antimony). ]; Or formula E (R₂₀)_nX_2-n[E is a Group VIA element (preferably oxygen or sulfur). ] (In these equations, X is hydrogen or halogen), and --Organic or inorganic transition metal compounds (eg, titanium tetrachloride, vanadium trichloride, zirconium tetrachloride, C) from any of the metals IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB in the periodic table._1-6Alkyl titanate, vanadate, zirconate, etc.), Selected from the group consisting of.

When the spacer molecule is used in the formation of the dendrimer material of the present invention, the spacer molecule is limited only by the reactivity with both the core molecule and the metal carbene compound. For example, this is the general formula R₂₀-(CH₂)-D (R)₂₀, N and D are defined as described above for derivatives suitable for covalent attachment to the carrier. ) Can have.

The dendrimer substance of the present invention is produced by reacting two or more of the above-mentioned 5- or 4-coordinated metal complexes with a core molecule (for example, the above-mentioned one) using a method known in the art. can do.

As described above, the dendrimer substance of the present invention can be used as a catalyst for converting a first olefin into at least one second olefin or an oligomer or polymer of a linear olefin. The catalyst is suitable for removal from the reaction mixture by ultrafiltration.

Furthermore, the present invention provides a one-step method for synthesizing a 1-hetero-2,4-cyclopentadiene compound from a heterodiallyl compound. In one specific embodiment of this method, the heterodiallyl compound is in which one metal is 5-coordinated to one or more of a carbene ligand, a polydentate ligand and another ligand. The other metal is contacted with a dimetal complex that is 4-coordinated to one or more of the neutral ligands and one or more of the anionic ligands. Surprisingly, this method not only results in ring-closing metathesis to dihydropyrrole compounds (dihydrofuran or dihydrothiophene compounds, respectively, depending on the heterodiallyl compound of origin), but also 1-hetero by isomerization and dehydrogenation of the latter. It results in a -2,4-cyclopentadiene compound.

The dimetal complexes that can be used are, for example, as shown in the general formulas (IVA) and (IVB) of FIG. 3 [M, Z, R', R'', R''', R.₃And R₄Is defined as described above for equations (IA) and (IB), M'is a metal defined as described above for M (M and M'are the same or different), and X₁, X₂And X₃Is R₂Is an anionic ligand defined with respect to, as well as L is R₁₆Is a neutral electron donor as defined above. ].

The 1-hetero-2,4-cyclopentadiene compounds that can be produced in one step of this method are selected from the group consisting of pyrrole, furan, thiophene, and derivatives thereof. When the heteroatom is nitrogen, the presence of substituents on the heteroatom does not prevent unexpected reactions from occurring. In particular, certain new pyrrole derivatives, such as dialkyl1H-pyrrole-1-ylmethylphosphonate, where the alkyl group has 1 to 4 carbon atoms, are new in this way, where the alkyl group has 1 to 4 carbon atoms. It can be produced from dialkyldialylaminomethylphosphonate as described in Examples below.

More broadly, the present invention relates to novel 1-hetero-2,4-cyclopentadiene compounds obtained by the above methods.

<p> The present invention will be further described with reference to the following series of examples, but it should be understood that this only describes various embodiments thereof without limiting the scope of the invention. ..</p><p> First, a general procedure for the preparation of a ruthenium compound having the general formula (IA) of the present invention with y = 2 will be described with reference to FIG. First, a Schiff base ligand having the formula (I) [not to be confused with the above formulas (IA) and (IB)] is described by the following formula: R'''C (OH) = C (R'') CHO Aldehyde (preferably salicylaldehyde), the formula H₂It is prepared and purified using a method known in the art by condensing it with a primary amine having NR'at reflux temperature in an organic solvent (eg, tetrahydrofuran). After cooling, the viscous yellow oily condensation product is purified by silica gel chromatography to give the desired salicylaldimine ligand of formula (I). In the second step, a Schiff base-substituted ruthenium complex having the formula (II) [not to be confused with the above formulas (IIA) and (IIB)] was subjected to a metal alkoxide (not to be confused with the above formulas (IIA) and (IIB)] using a method known in the art. Preferably tarthenium alkoxide) is added to the organic solution of the ligand of formula (I), then the resulting solid is filtered under an inert atmosphere to quantitatively obtain the corresponding ruthenium salt. And purify.</p><p> Then, an organic solution of the thallium salt was added at room temperature [RuCl.₂(p-cumene)]₂Was reacted with the organic solution of. After filtering the tarium chloride by-product and evaporating the solvent, the residue was crystallized, washed and dried to give a Schiff base ruthenium complex of formula (II) with the appearance of a reddish brown solid.</p><p> Prior to performing the third step, t- has formula (III), where "mes" is an abbreviation for 2,4,6-trimethylphenyl [not to be confused with formulas (IIA) and (IIB) above]. The organic solution of the butoxyrylated compound is added to the organic solution of potassium t-butoxide at room temperature to the organic solution of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazolium tetrafluoroborate. Then, it is prepared by filtering the potassium tetrafluoroborate by-product in an inert atmosphere.</p><p> A mixture of an organic solution of the complex of formula (II) and an organic solution of the t-butoxylation compound having formula (III) was heated at 70-80 ° C for 1 hour. After evaporating the solvent, the solid residue was washed, recrystallized and dried under vacuum to give a pure Schiff base substituted ruthenium complex of formula (IV) as a brown microcrystalline solid.</p><p> For a pure Schiff base-substituted arenilidene complex having formula (V), an organic solution of the complex having formula (IV) is added to an organic solution of diphenylpropargyl alcohol, the mixture is stirred for 17 hours at room temperature and the solvent is placed under vacuum. It is obtained as a dark brown microcrystalline solid in four steps of evaporation and then recrystallization of the remaining solid residue.</p><p> According to another synthetic route, the Schiff base substituted indenylidene complex having formula (VI) is prepared by adding an organic solution of the ruthenium complex having formula (II) to the organic solution of diphenylpropargyl alcohol and stirring the mixture at room temperature for 17 hours. The solvent is vaporized under vacuum and then the remaining solid remnants are recrystallized to give a reddish brown microcrystalline solid. Then, the Schiff base-substituted ruthenium complex having the formula (VII) is prepared by first adding an organic solution of the t-butoxylation compound having the formula (III) to the organic solution of the Schiff base-substituted indenylidene complex having the formula (VI), and mixing the mixture. Is prepared by stirring at 70-80 ° C for 1 hour. After removing the solvent, the solid residue is washed, recrystallized and then dried under vacuum to give a pure compound of formula (VII) as a reddish brown microcrystalline solid.</p><p> Second, a general procedure for the preparation of a ruthenium compound having the general formula (IC) of the present invention with y = 2 will be described with reference to FIG. First, a Schiff base ligand having the formula (I) and a thallium salt thereof are prepared as described above. Separately, the dichlorodicyclohexylphosphinidene ruthenium complex can be found in the solvent [RuCl.₂(p-cumene)]₂Is prepared by reacting with both dicyclohexylphosphine and substituted acetylene at 70 ° C. The resulting solution of dark brown polycrystalline solid is then reacted with the Schiff base thallium salt prepared above.</p><p> The various synthetic pathways shown in Attached Figures 1 and 2 have been described herein with respect to ruthenium complexes, but those skilled in the art may, for example, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, Corresponding complexes of other transition metals such as manganese, rhodium, vanadium, zinc, gold, silver, nickel, and cobalt have also been made with reference to the above description and [RuCl.₂(p-cumene)]₂It is possible to produce each metal complex corresponding to the above and its analogs as raw materials.</p><p>[Example 1]-Preparation of Schiff base ligands of equations (Ia) to (If)- A Schiff base ligand having the formulas (Ia) to (If), in which R and R'have the meaning shown in the lower end of FIG. 1 attached, Me is methyl, and iPr is isopropyl, was prepared as follows. Purified. Condensation of salicylaldehyde with an aliphatic primary amine (ie, R'is an aliphatic or alicyclic radical) is stirred at reflux temperature for 2 hours in tetrahydrofuran (hereinafter referred to as THF). I went by. After cooling to room temperature, the viscous yellow oily condensate was purified by silica gel chromatography to yield the desired salicylaldimine ligands of formulas (Ia) and (Ib) in yields of 95% and 93%, respectively. I got it in.</p><p> Condensation of salicylaldehyde with the aromatic primary amine was also performed by stirring at 80 ° C. for 2 hours in ethanol. Cooling to 0 ° C. precipitated a yellow solid from the reaction mixture. The solid was filtered, washed with cold ethanol and then dried under vacuum to give the desired salicylaldimine ligand of formula (Ic)-(If) in 90% to 93% yield. .. These ligands can be stored in desiccators for several months without causing physicochemical changes.</p><p> Compounds (Ia ~ d) are subjected to proton nuclear magnetic resonance (hereinafter referred to as NMR) spectral analysis (CDCl at 25 ° C).₃The characteristics were determined by (intermediate implementation) and infrared spectrum analysis (IR), and the results of these analyzes are as follows.</p><p> Compound (Ia): Yellow liquid;¹H-NMR (CDCl₃) δ 12.96 (s, 1H), 8.75 (s, 1H), 7.50 (d, 1H), 7.15 (d, 1H), 7.27 (t, 1H), 6.78 (t, 1H) and 3.30 (d, 3H) ;¹³C-NMR (CDCl₃) δ 166.4, 161.7, 137.0, 133.8, 120.8, 119.9, 118.4 and 45.9; IR (cm)^-1) 3325 (ν_OH, br), 3061 (ν_CH, w), 2976 (ν)_{HC = N}, w), 2845-2910 (ν)_CH3, br), 1623 (ν)_{C = N}, s), 1573 (ν_{C = C (Ph)}, w), 1525 (ν)_{C = C (Ph)}, w), 1497 (ν)_{C = C (Ph)}, w), 1465 (ν)_{C = C (Ph)}, W) and 1125 (ν)_CO, br).</p><p> Compound (Ib): Yellow liquid;¹H-NMR (CDCl₃) δ 13.18 (s, 1H), 8.98 (s, 1H), 8.10 (d, 1H), 8.03 (d, 1H), 7.67 (d, 1H) and 3.41 (d, 3H);¹³C-NMR (CDCl₃) δ 168.2, 164.3, 143.4, 137.9, 134.7, 123.1, 120.8 and 49.4; IR (cm)^-1) 3329 (ν_OH, br), 3067 (ν_CH, w), 2986 (ν)_{HC = N}, w), 2840-2912 (ν)_CH3, br), 1618 (ν)_{C = N}, s), 1570 (ν_NO2, s), 1546 (ν_{C = C (Ph)}, w), 1524 (ν)_{C = C (Ph)}, w), 1492 (ν)_{C = C (Ph)}, w), 1465 (ν)_{C = C (Ph)}, w), 1329 (ν)_NO2, S) and 1133 (ν)_co, br).</p><p> Compound (Ic): Yellow solid;¹H-NMR (CDCl₃) δ 12.85 (s, 1H), 8.32 (s, 1H), 7.45 (d, J = 7.0 Hz, 1H), 7.30 (t, J = 7.1 Hz, 1H), 7.03 (s, 2H), 6.99 (t) , J = 7.3 Hz, 1H), 6.84 (d, J = 6.9 Hz, 1H) and 2.21 (s, 6H);¹³C-NMR (CDCl₃) δ 164.0, 160.9, 138.0, 132.4, 130.1, 129.8, 127.6, 127.1, 117.6, 117.3, 116.4 and 18.2; IR (cm)^-1) 3342 (ν_OH, br), 3065 (ν_CH, w), 3031 (ν)_CH, w), 2850-2925 (ν)_CH3, br), 1620 (ν)_{C = N}, S), 1569 (ν_{C = C (Ph)}, w), 1523 (ν)_{C = C (Ph)}, w), 1491 (ν)_{C = C (Ph)}, w), 1467 (ν)_{C = C (Ph)}, W) and 1093 (ν)_CO, br).</p><p> Compound (Id): Yellow solid;¹H-NMR (CDCl₃) δ 13.93 (s, 1H), 8.43 (s, 1H), 8.33 (d, J = 3 Hz, 1H), 8.29 (d, J = 9 Hz, 1H), 7.26 (s, 2H), 7.12 (d , J = 9 Hz, 1H) and 2.18 (s, 6H);¹³C-NMR (CDCl₃) δ 166.2, 165.3, 145.5, 139.9, 131.2, 130.2, 128.7, 128.5, 118.5, 118.0, 117.4 and 18.1; IR (cm)^-1) 3337 (ν_OH, br), 3068 (ν_CH, w), 3036 (ν)_CH, w), 2848-2922 (ν)_CH3, br), 1626 (ν)_{C = N}, s), 1567 (ν_NO2, s), 1548 (ν_{C = C (Ph)}, w), 1527 (ν)_{C = C (Ph)}, w), 1494 (ν)_{C = C (Ph)}, w), 1467 (ν)_{C = C (Ph)}, w), 1334 (ν)_NO2, S) and 1096 (ν)_CO, br).</p><p>[Example 2]-Preparation of Schiff base-substituted ruthenium complex of formulas (II.a) to (II.f)- A Schiff base-substituted ruthenium complex having formulas (II.a) to (II.f) shown in the attached figure was prepared in two steps and purified as follows. In the first step, a solution of thallium ethoxydo in THF (5 ml) is added dropwise to a solution of the appropriate Schiff bases of formulas (Ia)-(If) in THF (10 ml) prepared according to Example 1 at room temperature. Added. Immediately after the addition, a pale yellow solid was formed. The reaction mixture was then stirred at 20 ° C. for 2 hours. Filtration of the solid under an argon atmosphere gave the corresponding salicylaldimintalium salt in quantitative yield. It was used immediately in the next step without further purification.</p><p> In a solution of the salicylic aldimint thallium salt in THF (5 ml), [RuCl in THF (5 ml)₂(p-cumene)]₂The solution was added and the reaction mixture was then stirred for 6 hours at room temperature (20 ° C). Thallium chloride by-products were filtered off. After evaporating the solvent, the residue was dissolved in the smallest amount of toluene and cooled to 0 ° C. Next, the obtained crystals were washed with cold toluene (3 × 10 ml) and dried to obtain Schiff base ruthenium complexes of the formulas (II.a) to (II.f) as reddish brown solids.</p><p>[Example 3]-Preparation of Schiff base-substituted ruthenium complex of formulas (IV.a) to (IV.f)- 1 equivalent of a solution of potassium t-butoxide in THF (5 ml), a solution of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazolium tetrafluoroborate in THF (10 ml) After stirring the reaction mixture at room temperature (20 ° C) for 5 minutes, the potassium tetrafluoroborate by-product was filtered off in an inert atmosphere to quantify the t-butoxylation compound having formula (III). It was formed in the target yield. After evaporating the solvent, compound (III) was dissolved in toluene (10 ml) and used immediately in the next step without further purification. After adding 1 equivalent of a solution in toluene (10 ml) of a suitable Schiff base-substituted ruthenium complex having one of formulas (II.a)-(II.f) prepared according to Example 2, the reaction mixture is vigorously stirred. While heating at 70-80 ° C for 1 hour. After evaporation of the solvent, the solid residue was washed with hexane (3 x 10 ml) and recrystallized from the toluene / pentane mixture at 0 ° C. It was then dried under vacuum to form pure Schiff base-substituted ruthenium complexes of formula (IV.a)-(IV.f) as brown polycrystalline solids in yields ranging from 90% to 95%. ..</p><p>[Example 4]-Preparation of Schiff base-substituted ruthenium complex of formulas (Va) to (Vf)- A Schiff base-substituted arenilidene compound having formulas (Va)-(Vf) is a toluene (toluene) of a suitable Schiff-base-substituted ruthenium complex having one of formulas (IV.a)-(IV.f) prepared according to Example 3. The solution in 15 ml) was added to 1.2 equivalents of the solution of commercially available diphenylpropargyl alcohol in toluene (5 ml) and then the reaction mixture was stirred at room temperature (20 ° C) for 17 hours. Toluene is evaporated under vacuum and the remaining solid residue is recrystallized from the dichloromethane / hexane mixture, washed with hexane (3 x 10 ml) and dark brown crystallites in yields ranging from 80-90%. The desired compound was obtained as a sex solid.</p><p>[Example 5]-Preparation of Schiff base-substituted ruthenium complex of formulas (VI.a) to (VI.f)- The Schiff base-substituted toluene compounds of formulas (VI.a)-(VI.f) are suitable Schiff-base-substituted toluene complexes having one of the formulas (II.a)-(II.f) prepared according to Example 2. To a solution in toluene (15 ml) of is added to 1.2 equivalents of a solution of commercially available diphenylpropargyl alcohol in toluene (5 ml), then obtained by stirring the reaction mixture at room temperature (20 ° C) for 17 hours. It was. Evaporate toluene under vacuum and recrystallize the remaining solid residue from the dichloromethane / hexane mixture and wash with hexane (3 x 10 ml) to give a reddish-brown microcrystalline solid in yields greater than 70%. The desired compound was obtained.</p><p>[Example 6]-Preparation of Schiff base-substituted ruthenium complex of formulas (VII.a) to (VII.f)- Formula (III) prepared as in Example 3 in solution in toluene (10 ml) of a suitable Schiff base-substituted ruthenium complex having one of formulas (VI.a)-(VI.f) prepared according to Example 5. ) Was added in 1 equivalent of a solution in toluene (10 ml) of the t-butoxylation compound. The reaction mixture was then vigorously stirred at 70-80 ° C for 1 hour. After evaporating the solvent, the solid residue was washed with hexane (3 x 10 ml) and recrystallized from the dichloromethane / hexane mixture. Then, it was dried under vacuum to obtain a pure compound of the formulas (VII.a) to (VII.f) as a reddish brown microcrystalline solid in a quantitative yield.</p><p>[Example 7]-Ring-opening metathesis polymerization- Ring-opening metathesis polymerization of various cyclic olefins was carried out in 1 ml of toluene as a solvent, and 0.005 mmol of the Schiff base-substituted arenilidene compound having the formula (Va) prepared in Example 4 was used as a catalyst. Table 1 below shows the names of olefin monomers, olefin / catalyst molar ratios, polymerization temperature T (shown in ° C), and polymerization time t (in minutes), and the polymerization yield at time t. It shows the rate.</p><p><tables num="1"><img file="JP5100728B2_D0007.tif" /></tables></p><p>[Example 8]-Ring-closing metathesis reaction- Ring-closing metathesis reactions of various diene were carried out in 1 ml of deuterated benzene as a solvent (however, deuterated methanol was used as a solvent only in the case of diallylamine hydrochloride), and the following was used at that time.</p><p>--As a catalyst, the Schiff base-substituted arenilidene compound having the formula (Va) prepared in Example 4 0.005 mmol, and --Diene / catalyst molar ratio 100.</p><p> Table 2 below shows the names of the dienes used, the reaction temperature T (in ° C), the reaction time t (in minutes), the reaction yield at time t (in%), and the resulting product. The name is also shown.</p><p><tables num="2"><img file="JP5100728B2_D0008.tif" /></tables></p><p>[Example 9]-Atomic transition radical polymerization- Atomic transfer radical polymerization of various olefins was carried out in 1 ml of toluene at the temperatures shown below (indicated by ° C) for 8 hours using the following.</p><p>--As a catalyst, Schiff base-substituted arenilidene ruthenium complex 0.0116 mmol having the formula (Va) prepared in Example 4, --As polymerization initiators, ethyl-2-methyl-2-bromopyropionate (when the monomer is methacrylate), methyl-2-bromopropionate (when the monomer is acrylate), 1-bromocyano Etan (if the monomer is acrylonitrile), or (1-bromoethyl) benzene (if the monomer is styrene), -[Catalyst] / [Polymerization initiator] / [Monomer] molar ratio 1: 2: 800.</p><p> Table 3 below shows the names of the olefins used, the polymerization temperature, and the polymerization yield (in%).</p><p><tables num="3"><img file="JP5100728B2_D0009.tif" /></tables></p><p>[Example 10]-Atomic transfer radical polymerization in water- Atomic transfer radical polymerization of various olefins in water as a solvent --As a catalyst, a Schiff base-substituted arenilidene compound having the formula (Va) prepared in Example 4 previously treated with 1 equivalent of silver tetrafluoroborate 0.0116 mmol [more specifically, the above amount of the compound (Va). Toluene 1 ml and 0.2 M in toluene AgBF₄It was added to 56 μl of solution and then stirred for 20 minutes until AgCl turbidity was observed, resulting in a cationic ruthenium complex in which the chloride ligand was removed and replaced with toluene. ], --The same polymerization initiator and the same as those already described in Example 9 and -[Catalyst] / [Polymerization initiator] / [Monomer] molar ratio 1: 2: 800, Was used for 8 hours at the temperatures shown in Table 4 below. The catalyst and polymerization initiator were dissolved in toluene to give a toluene: water volume ratio of 1: 1. Table 4 below shows the names of the olefins used, the polymerization temperature, and the polymerization yield (in%).</p><p><tables num="4"><img file="JP5100728B2_D0010.tif" /></tables></p><p>[Example 11]-Atomic transfer radical (co) polymerization of vinyl monomer- Atomic transfer radical polymerization and copolymerization of various vinyl monomers were carried out using:</p><p>--The same polymerization initiator and the same as those used in Example 9 and --As a catalyst, it was previously disclosed as an olefin metathesis catalyst in Organometallics (1998) 17: 3460 by Chang et al.</p><p><chemistry num="7"><img file="JP5100728B2_D0011.tif" /></chemistry></p><p>(In the formula, Cy indicates cyclohexyl, Ph indicates phenyl, Me indicates methyl, iPr indicates isopropyl) Ruthenium carbene complex (Aa) ~ (Af) having.</p><p> A typical procedure for this purpose is as follows. That is, the polymerization was carried out in a sealed glass vial under an argon atmosphere. 0.0117 mmol of catalyst was placed in a glass test tube (degassed by 3 vacuum-nitrogen cycles) capped with a 3-way stopcock containing a magnetic stir bar. Next, by adding a monomer and a polymerization initiator, the molar ratio of [catalyst] / [polymerization initiator] / [monomer] was set to 1/2/800. All liquids were handled with a dry syringe under an argon atmosphere. The reaction mixture was then heated at a reaction temperature of 85 ° C [for (meth) acrylate] or 110 ° C (for styrene) for 17 hours. After cooling, it was diluted in THF and poured into 50 ml of n-heptane [for (meth) acrylate] or 50 ml of methanol (for styrene) with vigorous stirring. The precipitated polymer was then filtered and dried under vacuum overnight.</p><p> Table 5 below shows the polymerization yields of the monomers and catalytic ruthenium complexes used as a function.</p><p><tables num="5"><img file="JP5100728B2_D0012.tif" /></tables></p><p> Table 6 shows the single weights formed from methyl acrylate (first number), styrene (second number), or methyl methacrylate (third number) using the ruthenium carbene complexes (Ac)-(Af), respectively. The weight average molecular weight Mw, number average molecular weight Mn, and dispersity (PDI) of the coalescence are shown.</p><p><tables num="6"><img file="JP5100728B2_D0013.tif" /></tables></p><p>[Example 12]-Atomic transfer radical (co) polymerization of vinyl monomer in the presence of cationic ruthenium complex- Atomic transfer radical polymerization and copolymerization of various vinyl monomers was carried out in solvent S using:</p><p>--The same polymerization initiator and the same one used in Example 9 and --The scheme shown in FIG. 11 by treating the ruthenium carbene complex of Example 11 having the appropriate formulas (Aa) to (Af) with a salt in the presence of solvent S according to the scheme described later as a catalyst. Cationic ruthenium carbene complex (Ba) ~ (Bf) [Tos is an abbreviation for tosylate (p-toluenesulfonate), and Tf is an abbreviation for triflate (trifluoromethanesulfonate). ].</p><p> When toluene was used as the solvent, the monomer / toluene ratio was reduced to 1/1 (volume / volume) by dissolving the monomer, polymerization initiator and catalyst in a small amount of toluene. For suspension polymerization in a water / toluene mixture, the monomer / toluene ratio is obtained by dissolving the monomer, polymerization initiator and catalyst in a small amount of toluene and then dissolving the distilled water in an organic solution. Was set to 1 / 3.5 (capacity / capacity), and the ratio of water / organic layer was set to 1/1 (capacity / capacity). No dispersion aid or surfactant (particle stabilizer) was added to the polymerization medium.</p><p> To investigate the effect of counterions on catalytic activity, three different salts (silver tetrafluoroborate, silver p-toluenesulfonate, and trimethylsilyl triflate) were used from the complexes (Aa)-(Af). Chloride was extracted.</p><p> Table 7 below shows the monomers and solvents used, and the respective cationic catalytic ruthenium complexes of methyl acrylate (first number), styrene (second number) or methyl methacrylate (third number). The polymerization yield as a function is shown.</p><p><tables num="7"><img file="JP5100728B2_D0014.tif" /></tables></p><p> Table 8 below shows homopolymers formed from methyl acrylate (first number), styrene (second number) or methyl methacrylate (third number) using the cationic ruthenium carbene complex (Bb). Weight average molecular weight Mw, number average molecular weight Mn, and dispersity (PDI) are shown.</p><p><tables num="8"><img file="JP5100728B2_D0015.tif" /></tables></p><p>[Example 13]-Atomic transfer radical addition of vinyl olefin- Atomic transfer radical addition of carbon tetrachloride to various vinyl olefins was carried out in an organic solvent using a Schiff base-substituted arenilidene compound having the formula (Va) prepared in Example 4 as a catalyst. The catalyst (0.03 mmol) was dissolved in toluene (1 ml) and then added through a diaphragm to a solution of vinyl monomer (9 mmol) and carbon tetrachloride (13 mmol) in toluene (3 ml). The reaction mixture was then heated at 65 ° C. for 17 hours. Table 9 below shows the names of the vinyl monomers tested and the yields (% representation) of the chlorinated saturated addition products obtained.</p><p><tables num="9"><img file="JP5100728B2_D0016.tif" /></tables></p><p>[Example 14]-Preparation of dichlorologi (tricyclohexylphosphine) vinylidene ruthenium complex- [RuCl in toluene (17 ml)₂(p-cumene)]₂Tricyclohexylphosphine (0.617 g, 2.2 mmol) and phenylacetylene C in a suspension of (306 mg, 0.5 mmol), respectively.₆H₅CCH (0.102 g, 1 mmol) was added. The mixture was slowly heated to 70 ° C and stirred for 24 hours. The mixture was concentrated to about 4 ml by inhalation and excretion of volatiles. By adding 10 ml of acetone and cooling to 78 ° C., a dark brown microcrystalline solid was precipitated, which was filtered and vacuum dried. This solid was obtained in 85% yield, but proton NMR spectrum analysis (CDCl)₃(Implemented at 30 ° C), Cl₂Ru {= C = CHC₆H₅} (PCy₃)₂The characteristics were determined and the following data were obtained. δ 7.16-7.08, 6.97-6.88 (both m, 5H, phenyl), 4.65 (t, J_PH= 3.3 Hz, 1H), 2.83-2.71, 2.26-2.12, 1.77-1.45, 1.28-1.01 (each m, C₆H₁₁)。 </p><p> Using the same procedure, Cl₂Ru {= C = CHt-C₄H₉} (P (cyclohexyl)₃)₂Was prepared, but here a molar excess of tetrabutyl acetylene was used and the reaction mixture was maintained at 40 ° C for the first 4 hours. The ruthenium complex was obtained in 69% yield, but proton NMR spectrum analysis (CDCl).₃The characteristics were determined by (conducted at 30 ° C), and the following data were obtained. δ 2.81 (t, J_PH= 3.0 Hz, 1H), 2.65-2.51, 2.14-1.99, 1.86-1.53, 1.33-1.12 (each m, 66H, C₆H₁₁) And 1.01 (s, 9H).</p><p>[Example 15]-Preparation of Schiff base vinylidene ruthenium complex- In a solution of the dichlorodicyclohexylphosphine vinylidene ruthenium complex (3 mmol) obtained in Example 14 in THF (5 ml) in THF (10 ml) of the salicyl aldimintalium salt obtained at the end of the first step of Example 2. Solution was added. The reaction mixture was stirred at 20 ° C. for 4 hours and the thallium chloride formed was filtered and separated. The solid residue was recrystallized from pentane at -70 ° C to give the Schiff base vinylidene ruthenium complex having formula (IC).</p><p> By this method, four different complexes were produced. The complex identified as 4a in FIG. 2 (ie, R₁Is a hydrogen atom and R₂Is phenyl) is recovered as a brown solid in 81% yield and proton NMR spectrum analysis (C).₆D₆The characteristics were determined by (conducted at 25 ° C), and the following data were obtained. δ 8.20 (d, J = 5.2 Hz, 1H), 7.38 (d, J = 7.0 Hz, 1H), 7.30 (t, J = 7.2 Hz, 1H), 7.22-7.14, 6.99-6.94, 6.89-6.79 (each) m, 5H), 7.13 (s, 2H), 7.06 (t, J = 7 Hz, 1H), 4.36 (t, J = 4.2 Hz), 2.14 (s, 3H), 1.61-1.31 (m, 20H), 1.27 (d, J = 6 Hz, 3H) and 1.19 (m, 10H).</p><p> The complex identified as 4b in Figure 2 (ie, R₁Is nitro and R₂Is phenyl) is recovered as a dark brown solid in 80% yield and proton NMR spectrum analysis (C).₆D₆The characteristics were determined by (conducted at 25 ° C), and the following data were obtained. δ 8.24 (d, J = 2.5 Hz, 1H), 8.08 (dd, J = 9 Hz, 2.4 Hz, 1H), 7.94 (d, J = 5.6 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H) ), 7.29 (d, J = 9.8 Hz, 1H), 7.16 (s, 2H), 7.13-7.07 (oH), 7.02-6.96 (pH), 6.89-6.80 (mH) (each m, 5H), 4.25 ( t, J = 5 Hz), 2.44 (q, J = 11 Hz, 3H), 2.34 (s, 3H), 1.70-1.63 (bs, 20H), 1.54 (d, J = 12Hz, 3H) and 1.36-1.08 (bs, 20H).</p><p> The complex identified as 5a in Figure 2 (ie, R₁Is a hydrogen atom and R₂Is t-butyl), recovered as a dark brown solid in 78% yield and proton NMR spectral analysis (C).₆D₆The characteristics were determined by (conducted at 25 ° C), and the following data were obtained. δ 8.28 (d, J = 2.7 Hz, 1H), 7.42 (d, J = 7.2 Hz, 1H), 7.23 (t, J = 7.0 Hz, 1H), 7.06 (m, 3H), 6.74 (d, J = 6.7 Hz, 1H), 2.83 (t, J = 3 Hz), 1.78-1.50 (m, 23H), 1.26-1.15 (m, 10H) and 1.08 (s, 9H).</p><p> The complex identified as 5b in Figure 2 (ie, R₁Is nitro and R₂Is t-butyl), recovered as a brown solid in 70% yield and proton NMR spectrum analysis (C).₆D₆The characteristics were determined by (conducted at 25 ° C), and the following data were obtained. δ 8.30 (d, J = 2.9 Hz, 1H), 7.6 (dd, J = 9, 2.3 Hz, 1H), 7.37 (d, J = 5 Hz, 1H), 7.13 (s, 2H), 6.99 (d, J = 9.8 Hz, 1H), 3.06 (t, J = 4 Hz), 2.50 (q, J = 12 Hz, 3H), 2.38 (s, 3H), 1.88-1.75 (bs, 20H), 1.60 (d, J = 12.5 Hz, 3H), 1.34-25 (m, 10H) and 1.07 (s, 9H).</p><p>[Example 16]-Ring-opening metathesis polymerization of cyclic olefins- Ring-opening metathesis polymerization of cyclic olefins identified by formulas 6-17 and reference numbers of the schemes described below was performed according to the following procedure.</p><p><chemistry num="8"><img file="JP5100728B2_D0017.tif" /></chemistry></p><p> CH monomer 6 [ie, norbornene] (7.5 mmol)₂Cl₂CH of Schiff base vinylidene ruthenium complex (7.5 μmol) dissolved in (2.0 ml) and prepared in a container according to Example 15.₂Cl₂It was added and mixed with the solution in (2 ml). The container was flushed with argon and maintained at a constant temperature of 80 ° C in an oil bath. After 2 hours, the mixture became extremely viscous and could no longer be agitated. The mixture is transferred to a beaker and CH containing 2,6-di-t-butyl-4-methylphenol (0.4 mmol) as an oxidation inhibitor and ethyl vinyl ether (4 mmol) as a polymerization inhibitor.₂Cl₂Treated with (10 ml). The obtained solution was stirred for 1 hour, filtered through a silica gel column, and then precipitated in vigorously stirred methanol. The resulting white viscous polymer was filtered, washed with methanol and dried under vacuum.</p><p> For the other cyclic olefins, the experimental method was the same, but the amount of monomer used was changed to 6 mmol (monomer 7 to 16) or 1.87 mmol (monomer 17).</p><p> In Table 10 below, the experimental numbers (first column) are followed by the Schiff base vinylidene ruthenium complex used as a catalyst (using the same identification number as in Example 15), and the monomer reference numbers 6 to 17 (parentheses). Monomer / catalyst molar ratio followed by), polymerization temperature, time, and yield, as well as number average molecular weight Mn and dispersity Mw / measured by gel permeation chromatography using polystyrene standard material. Indicates Mn.</p><p><tables num="10-1"><img file="JP5100728B2_D0018.tif" /></tables></p><p><tables num="10-2"><img file="JP5100728B2_D0019.tif" /></tables></p><p><tables num="10-3"><img file="JP5100728B2_D0020.tif" /></tables></p><p><tables num="10-4"><img file="JP5100728B2_D0021.tif" /></tables></p><p>d: The molecular weight could not be measured because the polymer was insoluble.</p><p>[Example 17]-Ring-closing metathesis reaction- Ring-closing metathesis reactions of various diene were performed according to the following procedure. In a 10 ml Schlenk test tube, 0.095 mmol of diene, 13.2 μl (0.095 mmol) of mesitylene, and 50 μl of the Schiff base vinylidene ruthenium complex prepared according to Example 15 were added to 1 ml of dehydrogenated benzene, then 70 or 85 with stirring. Heated to ° C (as listed in Table 11 below). The ethylene formed was removed under vacuum at 10 minute intervals. After 2 hours, the solution was cooled to 20 ° C and poured into an NMR test tube. Product yield depends on the integral of allylic protons¹Measure by 1 H-NMR. The formation of cyclic isomers, oligomers or telomeres was excluded by GC-MS analysis of the reaction mixture. The reaction product was identified by purification of the reaction mixture concentrated by flash column chromatography on a silica gel column (hexane / ethyl acetate = 6: 1, Rf = 0.3).</p><p> Table 11 below sequentially shows, for each experiment, the reaction temperature T (° C representation, column 1), followed by the structure of the diene used, the structure of the product obtained, the reaction time (indicated by time), and The reaction yields are shown for each of the Schiff base vinylidene ruthenium complexes used as catalysts (using the same identification numbers as in Example 15).</p><p><tables num="11"><img file="JP5100728B2_D0022.tif" /></tables></p><p>[Example 18]-Preparation of a catalyst in which a Schiff base-containing ruthenium complex is anchored in a mesoporous crystalline molecular sieve. All reactions and operations were performed in an argon atmosphere by using the conventional Schlenk test tube method. Argon gas is P₂O₅Dryed through (Aldrich, 97%).¹The H-NMR spectrum (500 MHz) was recorded on a Bruker AM spectroanalyzer. Chemical shifts were expressed in ppm and TMS was used as a control compound.</p><p> For solid phase NMR spectra, use the Bruker DSX-300 spectrophotometer.¹300.18MHz for 1 H-NMR,¹³75.49MHz for C-NMR,³¹121.51MHz for P-NMR, and²⁹In the case of Si-NMR, it was obtained by operating at 59.595 MHz. The spectra were recorded under MAS conditions using a conventional 4 mm probe head that provides spin frequencies up to 12 KHz.</p><p> Uniform catalyst anchoring was confirmed by a Raman spectrophotometer Bruker Equinox 55 with the FRA106 module. The load of the heterogeneous hybrid catalyst was measured by a Varian Liberty ICP / MS spectrophotometer and an ARL9400 SequentialXRF spectrophotometer. The XRD spectrum was recorded with a Siemens diffractometer D5000. Elemental analysis was performed on the Carlo Erba EA1110 instrument.</p><p> BET analysis was performed on a Gemini micrometric 2360 surface area analyzer with a Flow prep060 deaerator. The sample was dried overnight at 423 ° K, cooled to room temperature and then adsorbed. Due to the possibility of air oxidation, special attention was required with the substance imparted with functionality, so the transfer to the balance and the deaeration of the system were rapid. The nitrogen isotherm curve was recorded at 77 ° K. The specific surface area was calculated from the straight part of the BET plot (P / P).₀=0.05~0.3)。 </p><p> After calcination, mesoporous crystalline molecular sieve MCM-41, XRD, N₂The characteristics were determined by adsorption and Raman spectrophotometric analysis. MCM-41 was dried at 423 ° K overnight under vacuum to thermally desorb physically adsorbed water from the silica surface.</p><p> Two pathways shown in FIG. 7 were tested for the synthesis of solid-supported catalysts 5 and 11, respectively.</p><p> In the first embodiment, the Schiff base ruthenium complex 10 shown in FIG. 7 was prepared by route 2 and its characteristics were determined as follows. That is, 2 mmol of salicylaldehyde 1 was dissolved in 15 ml of THF. With stirring, 2 mmol 4-bromo-2,6-dimethylaniline 6 was added, then the reaction mixture was stirred at reflux temperature for 2 hours. The resulting salicylaldimin product precipitated when cooled to 0 ° C to form a solid yellow product. The solid was filtered, washed and dried under vacuum to give the desired salicylargimine ligand 7 in excellent yield (95%).</p><p> A solution of thallium ethoxydo 2 mmol in THF (5 ml) was added dropwise to a solution of Schiff base ligand 7 (2 mmol) in THF 15 ml at room temperature. Immediately after the addition, a pale yellow solid formed and the reaction mixture was stirred at room temperature for 2 hours. The quantitatively formed salt 8 was immediately used in the next step without further purification. To a suspension of 2 mmol of Mg powder in THF (10 ml), 2 mmol of bromopropyltrimethoxysilane was added dropwise, then the mixture was stirred at room temperature for 3 hours to quantitatively convert to salt 8 at room temperature. The mixture was stirred for 6 hours to obtain a spacer-modified Schiff base ligand 9 as a green-yellow solid.</p><p> In a solution of thallium ethoxylated salt 9, the catalyst in 10 ml of THF [RuCl₂(PCy₃)₂A solution of = CHPh] 2 mmol was added. The reaction mixture was stirred for 4 hours at room temperature. After evaporating the solvent, the residue was dissolved in the smallest amount of benzene and cooled to 0 ° C. Thallium chloride was filtered and separated. The desired complex was then washed with cold benzene (3 times with 10 ml) to evaporate the filtrate. The solid residue was recrystallized from pentane (-70 ° C) to obtain Schiff base-modified complex 10 as a green-brown solid, and the characteristics were determined as follows.</p><p> - ¹H-NMR (CDCl₃) δ (ppm) 19.41 (d, 1H), 8.18 (d, 1H), 7.96 (d, 1H), 7.91 (d, 2H), 6.93 (d, 1H), 7.53 (t, 1H), 7.31 (t) , 1H), 7.20 (t, 2H), 7.03 (t, 1H), 7.00 (s, 1H), 6.95 (s, 1H), 3.71 (m, 6H), 2.44 (q, 3H), 2.29 (s, 3H), 1.77 (d, 3H), 1.69 (t, 2H), 1.17-1.67 (m, 30H), 1.15 (m, 4H), 1.11 (t, 9H); --- ³¹P-NMR (CDCl₃) δ (ppm) 58.19; --Elemental analysis value (%): RuC₄₉H₇₃PO₄Calculated values for NClSi (935.61): C 63.90, H 7.86, N 1.50; Measured values: C 62.97, H 7.73, N 1.53.</p><p> Next, 2 mmol of Schiff base-modified complex 10 was dissolved in 15 ml of THF. The solution was quantitatively transferred to 3 g of MCM-41, which was dried overnight at 150 ° C.</p><p> After refluxing in THF for 24 hours, the heterogeneous catalyst 11 was filtered under a nitrogen atmosphere and then thoroughly washed with THF and toluene until the filtrate became colorless. Then, it was dried under vacuum to obtain a heterogeneous catalyst 11 as a green powder.</p><p> In the second embodiment, the Schiff base-modified complex 4 was produced by the route 1 shown in FIG. 7, and its characteristics were determined as follows.</p><p> - ¹H-NMR (CDCl₃) δ (ppm) 19.92 (d, 1H), 8.95 (d, 1H), 7.55 (t, 1H), 7.02-7.35 (br m, 7H), 6.83 (t, 1H), 3.89 (m, 6H), 3.57 (q, 3H), 1.86 (t, 2H), 1.25-1.81 (m, 30H), 1.21 (m, 4H), 1.17 (t, 9H); --- ³¹P-NMR (CDCl₃) δ (ppm) 58.70; --Elemental analysis value (%): RuC₄₁H₆₅PO₄Calculated values for NClSi (831.46): C 59.22, H 7.88, N 1.68; Measured values: C 58.71, H 8.54, N 1.60.</p><p> Next, the heterogeneous catalyst 5 was prepared from the Schiff base-modified complex 4 in the same manner as in the case of the catalyst 11.</p><p> Next, both heterogeneous catalysts 5 and 11 were further characterized, and their structures were subjected to X-ray diffraction, nitrogen adsorption analysis, Raman spectroscopy, X-ray fluorescence, and solid-state NMR analysis to obtain the raw material MCM-41 material. Compared. The results are shown below.</p><p> The XRD measurement results confirmed that the synthesized mesoporous carrier had an MCM-41 structure. Calcinated MCM-41 shows extremely strong peaks at 3.733 nm (100) d-spacing and three weak peaks at 2.544 nm (110), 2.010 nm (200), and 1.240 nm (210). Shown in. These four peaks are a₀= 4.310nm (a₀= 2d₁₀₀Matches the hexagonal unit cell of / 3).</p><p> For heterogeneous catalyst 5, d100 spacing and a₀Are 3.611 nm and 4.170 nm, respectively. In the case of catalyst 11, the values are 3.714 nm and 4.289 nm, respectively. Since the XRD pattern of the heterogeneous catalyst is essentially the same as that of the original MCM-41, it was confirmed that the structure of the long-range order of the carrier was preserved.</p><p> N₂The data obtained from adsorption measurements and XRD analysis are summarized below.</p><p><tables num="12"><img file="JP5100728B2_D0023.tif" /></tables></p><p>a: N₂BET surface area (BET surface area = Bruner-Emmett-Teller surface area) obtained from the desorption branch of the adsorption isotherm curve. b: Pore capacity obtained from the Barrett-Joyner-Halenda equation. c: Mesopore (intermediate pore) diameter was obtained from the PSD curve (PSD curve = pore diameter distribution curve). d: wall thickness = a₀-APD (APD = average pore size).</p><p> The surface area, pore capacity and pore size of the catalyst were as expected for mesoporous materials. Furthermore, measurements of porosity of both MCM-41 and heterogeneous catalysts showed a type IV IUPAC adsorption-desorption isothermal curve. As mentioned above, the BET surface area and pore capacity of the heterogeneous catalyst were reduced by about 60% when compared to MCM-41. All these results indicate that the internal pores of MCM-41 are occupied by the catalytic complex and that the contactability and structure of the intermediate pores are maintained after modification.</p><p> Raman spectroscopy was performed to confirm the formation of covalent bonds between the Tris (alkoxy) silyl functionalizing homogeneous complexes (4 and 10 respectively) and the MCM-41 surface. Here, only the anchoring process of giving the heterogeneous catalyst 5 will be discussed. A comparison of the Raman spectra of MCM-41 (Figure A below) and spacer-modified MCM-41 (Figure B below) clearly shows the overlap of spacer vibrations on the MCM-41 baseline. Comparison of the Raman spectra of MCM-41 and heterogeneous catalyst 5 (Figure D below) reveals grafting of homogeneous species 4.</p><p> By comparing the Raman spectra of the spacer-modified homogeneous catalyst 4 (Fig. C below) and the catalyst 5, any questions regarding the chemical bonding of the homogeneous catalyst are eliminated. It is revealed that each peak of the spectrum of the homogeneous catalyst 4 is also present in the spectrum of the heterogeneous catalyst 5. The slight shift of some peaks in Figure D when compared to Figure C indicates changes in the chemical environment of the various functional groups resulting from the chemical bonding of the catalyst to the carrier. In conclusion, both Raman and BET data confirm the desired covalent anchorage.</p><p><tables num="13"><img file="JP5100728B2_D0024.tif" /></tables></p><p>Figure: Raman spectra of MCM-41 (A), MCM-41 + spacer (B), spacer-modified homogeneous catalyst 4 (C), and heterogeneous catalyst system 5 (D).</p><p> XRF measurements reveal the loading of 0.1069 mmol Ru complex / g heterogeneous catalyst 5 and 0.054 mmol Ru complex / g heterogeneous catalyst 11.</p><p> The structures of heterogeneous catalysts 5 and 11 were also investigated by solid state NMR. In the case of MCM-41, the proton spectrum only reveals the presence of silanol groups or water. MCM-41²⁹In Si CP MAS NMR, three peaks of 90ppm, 100ppm, and 110ppm were observed. Each of these values is Si (OH)₂(OSi)₂, Si (OH) (OSi)₃, And Si (OSi)₄Can be attributed to. The proton spectra of MCM-41 + aminopropyltriethoxysilane and MCM-41 + bromopropyltriethoxysilane are -CH.₂And -CH₃It only reveals the existence of the group. A small signal near 0 ppm is the spacer molecule SiCH.₂Can be attributed to.</p><p> However, of these samples¹³The C CP MAS NMR spectrum reveals some interesting features. For MCM-41 + aminopropyltriethoxysilane, the two peaks of 50ppm and 70ppm are -OCH, respectively.₂-And-CH₂It can be attributed to the N- configuration. For MCM-41 + bromopropyltriethoxysilane, the two peaks of 50ppm and 36ppm are -OCH, respectively.₂-And-CH₂It can be attributed to the molecular configuration of Br-. A signal near 50 ppm observed as a broad, undegraded peak indicates that grafting is not complete.</p><p> For MCM-41 + aminopropyltriethoxysilane,²⁹The Si CP MAS NMR spectrum shows (SiO) at -58.34 ppm.₃Si^*(SiO) at C-species and -106.98 ppm₂(OEt) Si^*It clearly shows the existence of C-species. For MCM-41 + bromopropyltriethoxysilane, these signals are observed at -59.69 ppm and -106.0 ppm, respectively. For both samples, (SiO)₂(OH) Si^*The presence of the C-signal is degraded. For MCM-41 + aminopropyltriethoxysilane and MCM-41 + bromopropyltriethoxysilane, these signals are observed at -43.26 ppm and -43.98 ppm, respectively. The presence of Si-OH species is confirmed by the proton spectra of the two samples showing a small signal at 1.8 ppm.</p><p> The proton spectrum of the heterogeneous hybrid catalyst only reveals the presence of aromatic and aliphatic protons as broad, undecomposed peaks. Small peaks of imine protons in catalysts 5 and 11 are revealed at 8.96 ppm and 8.18 ppm, respectively. Heterogeneous catalyst¹³The C CP MAS NMR spectrum reveals the carbon of the -C = N-bond at 166.1 ppm and 164.2 ppm of complexes 5 and 11, respectively.</p><p> Again, the spectrum reveals aromatic and aliphatic carbon atoms. At around 5.24ppm, at 4.91ppm respectively, -CH of catalysts 5 and 11₃And-SiCH₂-Peak overlap is observed. Heterogeneous catalyst²⁹The Si CP MAS NMR spectrum is (SiO)₃Si^*C-, (SiO)₂(OEt) Si^*C-, and (SiO)₂(OH) Si^*It also reveals the existence of C-species. Heterogeneous catalyst³¹The P CP-MAS NMR spectra show P (cyclohexyl) at 58.73 ppm and 58.23 ppm for heterogeneous catalysts 5 and 11, respectively.₃Reveals the existence of. From this, we conclude that the anchoring of the homogeneous catalyst over the MCM-41 via spacer molecules is caused by two or three covalent bonds.</p><p>[Example 19]-Ring-opening metathesis polymerization with a heterogeneous catalyst- Ring-opening metathesis polymerization of various olefins in the solvent was performed using both heterogeneous catalysts 5 and 11 of Example 18. Cyclooctene and norbornene derivatives were purchased from Aldrich and CaH under nitrogen before use.₂Distilled from. A commercial grade solvent was dried, deoxidized under a suitable desiccant under a nitrogen atmosphere for 24 hours, distilled and then used.</p><p> In a typical ROMP experiment, 0.005 mmol of the catalyst suspension in toluene was transferred to a 15 ml container and then the monomer in toluene / dichloromethane was added (2000 eq for norbornene, 200 eq for cyclooctene). 800 equivalents, and 800 equivalents for norbornene derivatives). The reaction mixture was continuously stirred at 35 ° C. for 6 hours. To inactivate the catalyst, 2.5 ml of ethyl vinyl ether / 2,6-di-t-butyl-methylphenol (BHT) solution was added and the solution was stirred until complete inactivation occurred. The solution was poured into 50 ml of methanol (containing 0.1% BHT) to precipitate the polymer and filtered.</p><p> CHCl polymer₃The catalyst was filtered by dissolving in. Then CHCl until high viscosity₃Was removed from the polymer solution under vacuum, and then 100 ml of methanol was added to precipitate the polymer. The white polymer was then filtered and dried under vacuum overnight. Gel permeation chromatography (CHCl) using polystyrene standard material to determine the number average molecular weight and weight average molecular weight (Mn and Mw) and dispersity (Mw / Mn) of the polymer.₃, 25 ° C). The GPC equipment used was Waters' Maxima 820 system with a PL gel column. The DSC measurement was performed by the TA instrument DSC-TGA (SDT2960) while using the thermomechanical analyzer (TMA2940). The yield [%] of the formed polymer is shown in Table 12 below.</p><p><tables num="14"><img file="JP5100728B2_D0025.tif" /></tables></p><p> In addition, the data summarized in Table 13 show that the solvent used is very critical to the properties of the resulting polymer. This is independent of the catalyst used, as the lower the dispersity and the higher the efficiency of the polymerization initiator, the more controlled the polymerization proceeds by using dichloromethane instead of toluene. is there.</p><p><tables num="15"><img file="JP5100728B2_D0026.tif" /></tables></p><p>[Example 20]-Ring-closing metathesis polymerization in the presence of a heterogeneous catalyst- The reaction was carried out on a laboratory table in air by measuring 5 mol% of the catalyst in a dry 10 ml container and suspending the solid in 2 ml of benzene. A solution of a suitable diene substrate (0.1 mmol) in benzene (2 ml) was added with internal standard dodecane. The reaction mixture was stirred at the appropriate temperature shown in Table 14 below for the appropriate time. Product formation and diene loss are monitored by gas chromatography (GC) and through the integration of allylic methylene peaks.¹It was confirmed in a reproducibility test by 1 H-NMR spectrum analysis (the solvent was benzene deuterated, and the internal standard was 1,3,5-mesitylene). Also, GC analysis of the reaction mixture excluded the formation of cycloisomers, oligomers or telomeres.</p><p> Table 14 summarizes the results obtained using several representative substrates, where the effects of reaction temperature and reaction time on the activity of catalysts 5 and 11 of Example 18 were examined. The catalyst system 11 showed higher efficiency than the system 5, regardless of the temperature and reaction time used. 1,7-Octadiene, diallyl ether, and diethyldialyl malonate proceeded smoothly in both catalyst systems at 55 ° C for only 4 hours, due to the conversion of tri and tetra-substituted malonate derivatives. Needs harsher conditions. It is also clear that the reaction temperature is a decisive factor in achieving good catalytic performance. Importantly, the post-treatment of the ring closure reaction product simply consists of filtration of the catalyst and evaporation of the solvent under vacuum.</p><p><tables num="16"><img file="JP5100728B2_D0027.tif" /></tables></p><p>[Example 21]-Atomic transfer radical polymerization in the presence of heterogeneous catalyst- All reagents and solvents were dried, distilled and stored under nitrogen at -20 ° C by conventional methods. In a typical ATRP experiment, 0.0117 mmol of the heterogeneous catalyst 11 produced in Example 18 was degassed by a glass tube (three vacuum-nitrogen cycles) capped with a three-way stopcock containing a magnetic stir bar. I put it in (keep). Next, styrene (as a monomer) and 1-bromomethylbenzene (as a polymerization initiator) so that the molar ratio [catalyst] / [polymerization initiator] / [monomer] is 1: 2: 800. Was added. All liquids were handled under argon using a dry syringe.</p><p> The reaction mixture was heated at 110 ° C. for 17 hours, cooled, diluted in THF, poured into 50 ml of methanol with vigorous stirring, and then the precipitated polystyrene was suction filtered. Finally, the polymer is CHCl₃The catalyst was filtered off by dissolving in. Then CHCl until high viscosity₃Was removed from the polymer solution under vacuum, then the polymer was precipitated by adding 100 ml of methanol, filtered off, dried under vacuum for 15 minutes for analysis. The yield of the polymer was 73%, the molecular weight (Mn) was 39,000, and the dispersity (Mw / Mn) was 1.62.</p><p> In order to confirm the living characteristics of the ATRP reaction, the present inventors conducted the following kinetic experiments. That is, the conversion of the monomer and the number average molecular weight (Mn) were tracked as a function of time, and the dependence of the molecular weight and the degree of dispersion on the conversion of the monomer was shown in FIG. The linear dependence observed for Mn is consistent with a controlled process with a certain number of growth chains. Furthermore, a significant decrease in dispersity during polymerization (reaching a value of 1.62 at a conversion of 73%) indicates that the radicals have a long lifetime. In addition, the first-order kinetic plot (Fig. 9) shows a linear time dependence, indicating that the polymerization termination reaction was almost completely eliminated. Therefore, the present inventors have concluded that the polymerization proceeds in a controlled manner, which enables the synthesis of polystyrene having a predetermined molecular weight and a narrow dispersity.</p><p>[Example 22]-Addition of color in the presence of heterogeneous catalyst- All reagents and solvents were dried, distilled and stored under nitrogen at -20 ° C by conventional methods. The reaction was carried out on a laboratory table in air by weighing 0.01 mmol of catalyst 5 or 11 of Example 18 in a dry 10 ml container and suspending the solid in 2 ml of toluene. Next, alkene (3 mmol) in toluene (1 ml), CCl₄A solution of (4.33 mmol) and dodecane (0.083 ml) was added and the reaction mixture was heated at the appropriate reaction temperature shown in Table 15 for 17 hours. The yield of the obtained product was determined by GC analysis of the reaction mixture using dodecane as an internal standard, and is shown in Table 15 below.</p><p><tables num="17"><img file="JP5100728B2_D0028.tif" /></tables></p><p>[Example 23]-Vinylation reaction in the presence of heterogeneous catalyst- In a typical vinylization experiment, 4.4 mmol of carboxylic acid (formic acid or acetic acid), 4.4 mmol of alkyne (phenylacetylene or 1,7-octadine), and 0.04 mmol of catalyst 5 or 11 of Example 18 are contained in 3 ml of toluene. Transferred to a 15 ml glass container. The reaction mixture was then heated at 100 ° C. for 4 hours in an inert atmosphere. Total yield is ν of phenylacetylene or 1,7-octadine_CCThe decrease in intensity was followed and measured by Raman spectroscopic analysis using a calibration curve. The conformation of the resulting product was measured by GC / MS using various fragmentations of the isomers. GC / MS measurements excluded the formation of products other than those reported below.</p><p> The results of these vinylization experiments are summarized in Table 16 [M stands for Markovnikov]. When 1,7-octadine was used as the substrate, the addition of both carboxylic acids corresponds to the regioselective and stereoselective anti-Markovnikov addition of the acid to the triple bond, regardless of the catalytic system used. (E) -Selective formation of alkane-1-enyl ester occurred. However, the total yield depends on the catalyst used and the type of carboxylic acid. In addition to the formation of the (E) -alkane-1-enyl ester, low proportions of the (Z) -alkane-1-enyl ester, Markovnikov adduct and di-substituted enol ester were also obtained. When phenylacetylene was used as the alkyne, the total yield was clearly higher than that of 1,7-octadine. The latter induced completely different selectivity in the vinylization process, i.e. the heterogeneous catalyst resulted in a high level of reactivity for the formation of Markovnikov adducts.</p><p><tables num="18"><img file="JP5100728B2_D0029.tif" /></tables></p><p>[Example 24]-Preparation of Schiff base-modified homodimetal ruthenium complex- This synthesis proceeded according to the scheme shown in FIG. A Schiff base-substituted ruthenium complex having the formula (2.af) was prepared and purified in two steps as follows. In the first step, a solution of thallium ethoxydo in THF (5 ml) was added dropwise to a solution of the appropriate Schiff base of formula (1.af) in THF (10 ml) prepared according to Example 1 at room temperature. .. Immediately after the addition was complete, a pale yellow solid was formed, then the reaction mixture was stirred at 20 ° C. for 2 hours. The solid was filtered under an argon atmosphere and each salicylaldimintalium salt obtained in quantitative yield was immediately used in the next step without further purification.</p><p> In the second step, the solution of the salicylic aldimint thallium salt in THF (5 ml) is mixed with the formula [RuCl] in THF (5 ml).₂(PCy₃)₂= CHC₆H₅] A solution of the catalyst was added. The reaction mixture was stirred at room temperature for 4 hours. After evaporating the solvent, the residue was dissolved in the smallest amount of benzene and cooled to 0 ° C. Thallium chloride was filtered off. After evaporation of the solvent, the residue was recrystallized from pentane (-70 ° C) to give each Schiff base substituted ruthenium complex (2.af) as a brown solid in good yield.</p><p> Next, in a 1 mmol benzene solution (25 ml) of the Schiff base-substituted ruthenium complex (2.af), the formula [RuCl₂(p-cumene)]₂A benzene solution (25 ml) of the dimer complex (1 mmol) having the above was added. The solution was stirred at room temperature for 4 hours, during which time a solid precipitate formed from the solution. The solid was filtered under an inert atmosphere to isolate it, washed with benzene (3 times at 30 m) and [(p-cumene) RuCl.₂P (cyclohexyl)₃] By-products and unreacted raw materials, if any, were removed. After recrystallization from the chlorobenzene / pentane mixture and then further washing with 10 ml (twice) of pentane to remove residual chlorobenzene, the product is dried under vacuum and the two metal Schiff bases in the yields shown below. A substituted ruthenium complex 3.af was obtained. The complex was further characterized by nuclear magnetic resonance (NMR) and infrared spectral analysis (IR). The analysis results are as follows.</p><p> 2-Metal Ruthenium Complex 3.a: 0.419g (63%) as an orange-green powder.¹H-NMR (CDCl₃) δ 19.97 (d, 1H), 9.03 (d, 1H), 7.64 (t, 1H), 7.09-7.44 (br m, 7H), 7.01 (t, 1H), 5.58 (d, 1H), 5.46 (d , 1H), 5.29 (d, 1H), 5.15 (d, 1H), 3.31 (d, 3H), 2.92 (septet, 1H), 2.19 (s, 3H), 1.35 (d, 3H) and 1.32 (d, 3H). IR (cm)^-1) 3060 (ν_CH, w), 3054 (ν)_CH, w), 2838-2901 (ν)_CH3, br), 2806 (ν_CH2, w), 1617 (ν)_{C = N}, s), 1605 (ν_{C = C (Ph)}, w), 1583 (ν)_{c = c (ph)}, w), 1506 (ν)_{C = C (Ph)}, w), 1455 (ν)_{C = C (Ph)}, w), 1449 (ν)_CH2, w), 1382 (skel._iPr, m), 1361 (skel._iPr, m), 1106 (ν_Ru-O-Ph, w), 1003 (ν)_skel.PCy3, w), 773 (γ_CH, w), 564 (ν)_Ru-O-Ph, w), 544 (ν)_Ru-o-Ph, w), 512 (ν)_Ru-Cl, W) and 440 (ν)_Ru-N, w). Elemental analysis value (%): Ru₂C₂₅H₂₈ONCl₃Calculated values at (666.96): C 45.02, H 4.23, N 2.10; Measured values: C 45.10, H 4.25, N 2.11.</p><p> 2-Metal Ruthenium Complex 3.b: 0.476g (67%) as an orange-green powder.¹H-NMR (CDCl₃) δ 20.02 (d, 1H), 9.08 (d, 1H), 8.34 (d, 1H), 8.19 (d, 1H), 7.53 (d, 2H), 7.45 (t, 1H), 7.38 (t, 2H) , 7.16 (d, 1H), 5.64 (d, 1H), 5.52 (d, 1H), 5.33 (d, 1H), 5.19 (d, 1H), 3.36 (d, 3H), 2.96 (septet, 1H), 2.21 (s, 3H), 1.40 (d, 3H) and 1.37 (d, 3H). IR (cm)^-1) 3054 (ν_CH, w), 3047 (ν)_CH, w), 2835-2898 (ν)_CH3, br), 2802 (ν)_CH2, w), 1615 (ν)_{C = N}, s), 1600 (ν_{c = c (ph)}, w), 1577 (ν)_{C = C (Ph)}, w), 1550 (ν)_NO2, s), 1500 (ν_{C = C (Ph)}, w), 1447 (ν)_{C = C (Ph)}, w), 1441 (ν)_CH2, w), 1382 (skel._iPr, m), 1363 (skel._iPr, m), 1332 (ν_NO2, S), 1098 (ν_Ru-O-Ph, w), 997 (ν)_skel.PCy3, w), 768 (γ_CH, w), 558 (ν)_Ru-O-Ph, w), 540 (ν)_Ru-O-Ph, w), 503 (ν)_Ru-Cl, W) and 437 (ν)_Ru-N, w). Elemental analysis value (%): Ru₂C₂₅H₂₇O₃N₂Cl₃Calculated values at (711.94): C 42.17, H 3.82, N 3.93; Measured values: C 42.24, H 3.84, N 3.91.</p><p> Two-metal ruthenium complex 3.c: 0.511 g (61%) as an orange powder.¹H-NMR (CDCl₃) δ 19.48 (d, 1H), 8.21 (d, 1H), 8.12 (d, 1H), 8.06 (d, 2H), 7.72 (t, 1H), 7.44 (t, 2H), 7.38 (t, 1H) , 7.12 (t, 1H), 7.09 (s, 1H), 7.06 (d, 1H), 7.02 (s, 1H), 5.45 (d, 1H), 5.30 (d, 1H), 5.17 (d, 1H), 5.06 (d, 1H), 2.84 (septet, 1H), 2.06 (s, 3H), 2.03 (s, 3H), 1.89 (d, 3H), 1.28 (d, 3H) and 1.24 (d, 3H). IR (cm)^-1) 3052 (ν_CH, w), 3038 (ν)_CH, w), 2848-2968 (ν)_CH3, br), 1601 (ν_{C = N}, S), 1579 (ν_{C = C (Ph)}, w), 1523 (ν)_{C = C (Ph)}, w), 1466 (ν)_{C = C (Ph)}, w), 1443 (ν)_{C = C (Ph)}, w), 1385 (skel._iPr, m), 1367 (skel._iPr, m), 1062 (ν_Ru-O-Ph, w), 1003 (ν)_Skel.PCy3, w), 801 (γ_CH, w), 784 (γ_CH, w), 692 (ν)_C-Br, s), 666 (ν_Ru-N, w), 554 (ν)_Ru-O-Ph, w), 527 (ν)_Ru-O-Ph, W) and 492 (ν)_Ru-Cl, w). Elemental analysis value (%): Ru₂C₃₂H₃₃ONCl₃Calculated for Br (835.97): C 45.97, H 3.98, N 1.68; Measured: C 46.03, H 4.01, N 1.65.</p><p> Two-metal ruthenium complex 3.d: 0.602 g (68%) as a dark orange powder.¹H-NMR (CDCl₃) δ 19.50 (d, 1H), 8.36 (d, 1H), 8.31 (d, 1H), 8.10 (d, 2H), 7.76 (t, 1H), 7.71 (d, 1H), 7.43 (t, 2H) , 7.15 (d, 1H), 7.11 (s, 1H), 7.07 (s, 1H), 5.49 (d, 1H), 5.36 (d, 1H), 5.21 (d, 1H), 5.11 (d, 1H), 2.86 (septet, 1H), 2.09 (s, 3H), 2.06 (s, 3H), 1.96 (d, 3H), 1.31 (d, 3H) and 1.29 (d, 3H). IR (cm)^-1) 3045 (ν_CH, w), 3031 (ν)_CH, w), 2844-2963 (ν)_CH3, br), 1597 (ν_{C = N}, s), 1576 (ν_{C = C (Ph)}, w), 1541 (ν)_NO2, s), 1517 (ν_{C = C (Ph)}, w), 1458 (ν)_{C = C (Ph)}, w), 1440 (ν)_{C = C (Ph)}, w), 1389 (skel._iPr, m), 1369 (skel._iPr, m), 1322 (ν)_NO2, S), 1044 (ν_Ru-O-Ph, w), 995 (ν)_skel.PCy3, w), 793 (γ_CH, w), 779 (γ)_CH, w), 683 (ν)_C-Br, S), 659 (ν_Ru-N, w), 541 (ν)_Ru-O-Ph, w), 514 (ν)_Ru-O-Ph, W) and 482 (ν)_Ru-Cl, w). Elemental analysis value (%): Ru₂C₃₂H₃₂O₃N₂Cl₃Calculated values for Br (880.95): C 43.63, H 3.66, N 3.18; Measured values: C 43.71, H 3.70, N 3.17.</p><p> 2-Metal Ruthenium Complex 3.e: 0.597g (73%) as a yellow-green powder.¹H-NMR (CDCl₃) δ 19.71 (d, 1H), 8.12 (d, 1H), 7.96 (d, 2H), 7.55 (t, 1H), 7.11-7.44 (br m, 8H), 6.66 (t, 1H), 5.42 (d) , 1H), 5.27 (d, 1H), 5.12 (d, 1H), 5.01 (d, 1H), 3.41 (septet, 1H), 2.81 (septet, 1H), 2.25 (septet, 1H), 2.01 (s, 3H), 1.67 (d, 3H), 1.29 (d, 3H), 1.26 (d, 3H), 1.21 (d, 3H) and 0.82 (dd, 6H). IR (cm)^-1) 3059 (ν_CH, w), 3040 (ν)_CH, w), 2857-2961 (ν)_CH3, br), 1607 (ν_{C = N}, s), 1586 (ν_{C = C (Ph)}, w), 1527 (ν)_{C = C (Ph)}, w), 1469 (ν)_{C = C (Ph)}, w), 1445 (ν)_{C = C (Ph)}, w), 1383 (skel._iPr, m), 1364 (skel._iPr, m), 1070 (ν_Ru-O-Ph, w), 1009 (ν)_skel.PCy3, w), 806 (γ_CH, w), 794 (γ)_CH, w), 688 (ν)_Ru-N, w), 564 (ν)_Ru-O-Ph, w), 537 (ν)_Ru-O-Ph, W) and 508 (ν)_Ru-Cl, w). Elemental analysis value (%): Ru₂C₃₆H₄₂ONCl₃Calculated values in (813.18): C 53.17, H 5.21, N 1.72; Measured values: C 53.23, H 5.24, N 1.74.</p><p> 2 Metal Ruthenium Complex 3.f: 0.587g (68%) as orange powder.¹H-NMR (CDCl₃) δ 19.81 (d, 1H), 8.32 (d, 1H), 8.22 (d, 1H), 8.16 (d, 1H), 7.34-7.98 (br m, 8H), 7.06 (d, 1H), 5.39 (d) , 1H), 5.25 (d, 1H), 5.08 (d, 1H), 4.97 (d, 1H), 3.51 (septet, 1H), 2.77 (septet, 1H), 2.32 (septet, 1H), 1.98 (s, 3H), 1.74 (d, 3H), 1.34 (d, 3H), 1.20 (d, 3H), 1.16 (d, 3H) and 0.88 (dd, 6H). IR (cm)^-1) 3054 (ν_CH, w), 3037 (ν)_CH, w), 2850-2965 (ν)_CH3, br), 1602 (ν)_{C = N}, s), 1582 (ν_{C = C (Ph)}, w), 1550 (ν)_NO2, s), 1528 (ν_{C = C (Ph)}, w), 1464 (ν)_{C = C (Ph)}, w), 1444 (ν)_{C = C (Ph)}, w), 1387 (skel._iPr, m), 1366 (skel._iPr, m), 1331 (ν_NO2, s), 1100 (ν_Ru-O-Ph, w), 1057 (ν)_skel.PCy3, w), 798 (γ)_CH, w), 785 (γ_CH, w), 678 (ν)_Ru-N, w), 557 (ν)_Ru-O-ph, w), 529 (ν)_Ru-O-Ph, W) and 496 (ν)_Ru-Cl, w). Elemental analysis value (%): Ru₂C₃₆H₄₁O₃N₂Cl₃Calculated values in (858.16): C 50.38, H 4.82, N 3.26; Measured values: C 50.44, H 4.85, N 3.25.</p><p>[Example 25]-Preparation of diethyldialylaminomethylphosphonate- 0.60 g (2.9 mmol) of diethylallylaminoethylphosphonate was dissolved in 50 ml of dry diethyl ether, then 1.17 g (11.6 mmol) of triethylamine was added. After stirring at room temperature for 15 minutes, 1.40 g of allyl bromide was added dropwise. The mixture was refluxed for 4 days. Add 50 ml of water to the mixture, then 50 ml CH₂Extracted 3 times with Cl. Combine the organic layers and EDTA₄Dry on top. DDL₄The resulting product is further purified by high vacuum distillation and under low pressure of 0.1 mbar, 0.6 g (2.4 mmol, 84) of diethyl diallyl aminomethylphosphonate having a boiling point of 65 ° C. % Yield) was obtained. This product was further characterized by the following spectrum.</p><p> - ¹H-NMR (270 MHz, CDCL₃): Shift 1.32 (3H, t, J = 7, 1 Hz, O-CH₂-C<u style="single">H</u>₃), 1.33 (3H, t, J = 6.9 Hz, O-CH₂-C<u style="single">H</u>₃), 2.87 (2H, d, J_PH= 10.9 Hz, N-CH₂-P), 3.25 (4H, d, J = 6.27 Hz, 2x NC<u style="single">H</u>₂-CH = CH₂), 4.14 (4H, m, 2x, OC<u style="single">H</u>₂-CH₃), 5.19 (4H, m, 2x N-CH₂-CH = C<u style="single">H</u>₂) And 5.83 (2H, m, 2x, N-CH₂-C<u style="single">H</u>= CH₂); - ¹³C-NMR (68 MHz, CDCl₃): Shift 16.50 (d, J_pc= 4.8 Hz, 2x O-CH₂-<u style="single">C</u>H₃), 48.19 (d, J_PC= 163.6 Hz, N-<u style="single">C</u>H₂-P), 58.09 (d, J_PC= 7.3 Hz, 2x N-<u style="single">C</u>H₂-CH = CH₂), 61.90 (d, J_PC= 3.6 Hz, 2x O-<u style="single">C</u>H₂-CH₃), 118.17 (d, J_PC= 2.5 Hz, 2x N-CH₂-CH =<u style="single">C</u>H₂) And 135.04 (2x N-CH)₂-<u style="single">C</u>H = CH₂); - ³¹P-NMR (109 MHz, CDCl₃) δ: 26.01; --Infrared analysis: Light absorption band 1260 cm^-1(P = O) and 1643 cm^-1(C = C); --Mass spectrum analysis: 247 (M)⁺, 3), 232 (M⁺-15.7), 206 (30), 110 (M⁺-PO (OEt)₂, 100), 81 (14), 68 (21) and 41 (26).</p><p>[Example 26]-Preparation of diethyl1H-pyrrole-1-ylmethylphosphonate- 0.1 g (0.41 mmol) of diethyldiallylaminomethylphosphonate prepared in Example 25 was dissolved in 2 ml of chlorobenzene, and then 0.014 g (0.02 mmol) of the dimetallic ruthenium complex 3.e prepared in Example 24 was added. The mixture was then stirred at 60 ° C. for 16 hours. After evaporation of chlorobenzene, the catalyst was removed by column chromatography to obtain 0.04 g (0.18 mmol, yield 45%) of diethyl1H-pyrrole-1-ylmethylphosphonate. The product was further characterized by the following spectrum.</p><p> - ¹H-NMR (270 MHz, CDCl₃) δ: 1.27 (6H, t, J = 6.9 Hz, 2x O-CH₂-C<u style="single">H</u>₃), 3.97-4.05 (4H, m, 2x OC<u style="single">H</u>₂-CH₃), 4.26 (2H, d, J_PH= 9.6 Hz, N-CH₂-P), 6.17 (2H, s, 2x N-CH = C<u style="single">H</u>), 6.72 (2H, s, 2x NC<u style="single">H</u>= CH); --- ¹³C-NMR (68 MHz, CDCl₃) δ: 18.07 (d, J_PC= 6.1 Hz, 2x O-CH₂-<u style="single">C</u>H₃), 47.50 (d, J_PC= 157.5 Hz, N-CH₂-P), 64.48 (d, J_PC= 6.1 Hz, 2x O-<u style="single">C</u>H₂-CH₃), 110.69 (2x N-CH =<u style="single">C</u>H), 123.54 (2x N-<u style="single">C</u>H = CH); --- ³¹P-NMR (109 MHz, CDCl₃) δ: 19.72; --Infrared analysis: Light absorption band 1244 cm^-1(P = O) and 1496 cm^-1(C = C); --Mass spectrum analysis: 217 (M⁺, 57), 202 (M⁺-15.17), 174 (13), 107 (29), 80 (M⁺-PO (OEt)₂, 100) and 53 (14).</p><p>[Example 27]-Preparation of diallyl glycine methyl ester- 1.5 g (11.9 mmol) of glycine methyl ester hydrochloride was added to 100 ml of dry THF, followed by 3.61 g (35.8 mmol) of triethylamine. After stirring at room temperature for 15 minutes, 4.33 g (35.8 mmol) of allyl bromide was added dropwise, then the mixture was refluxed for 16 hours. 100 ml of 2N hydrochloric acid was added and then extracted with 100 ml of diethyl ether. The aqueous phase, after acid extraction, K₂CO₃Alkalined with, then CH₂Cl₂Extracted in (3 times with 100 ml). EDTA the organic layer₄After drying above and evaporating the solvent, the product was further purified by column chromatography to give 0.78 g (5.75 mmol, 49% yield) of diallyl glycine methyl ester with 100% selectivity. The product was further characterized by the following spectrum.</p><p> - ¹H-NMR (270 MHz, CDCL₃) δ: 3.24 (4H, d, J = 6.6 HZ, 2x NC<u style="single">H</u>₂-CH = CH₂), 3.32 (2H, s, NC<u style="single">H</u>₂-COOMe), 3.69 (3H, s, COOCH)₃), 5.13-5.24 (4H, m, 2x CH₂-CH = C<u style="single">H</u>₂), 5.86 (2H, ddt, J = 17.2 Hz, J = 10.2 Hz en J = 6.6 Hz, CH-C<u style="single">H</u>= CH₂); - ¹³C-NMR (68 MHz, CDCl₃) δ: 51.39 (N-<u style="single">C</u>H₂-COOMe), 53.71 (COO)<u style="single">C</u>H₃), 57.27 (2x N-<u style="single">C</u>H₂-CH = CH₂), 118.20 (2X CH₂-CH =<u style="single">C</u>H₂), 135.42 (2x CH₂-<u style="single">C</u>H = CH₂) And 171.75 (<u style="single">C</u>OOMe); --Infrared analysis: Light absorption band 1643 cm^-1(CH = CH₂) And 1741 cm^-1(C = O); --Mass spectrum analysis: 169 (M)⁺ -41.25), 110 (M⁺-COOMe, 100) and 41 (CH₂= CH-CH₂+, 28)。 </p><p>[Example 28]-Preparation of methyl-1H-pyrrole-1-ylacetate- 0.22 g (1.3 mmol) of diallyl glycine methyl ester prepared in Example 27 was dissolved in 3 ml of chlorobenzene, and then 0.046 g (0.064 mmol) of the dimetalruthenium complex 3.e prepared in Example 24 was added. The mixture was stirred at 65 ° C for 16 hours. After evaporation of chlorobenzene, the catalyst was removed by column chromatography to give 0.05 g (0.36 mmol, 28% yield) of methyl 1H-pyrrole-1-yl acetate with 100% selectivity. The product was further characterized by the following spectrum.</p><p> - ¹H-NMR (270 MHz, CDCL₃) δ: 3.76 (3H, s, COOC)<u style="single">H</u>₃), 4.56 (2H, s, NC<u style="single">H</u>₂-COOMe), 6.21 (2H, T, J = 1.98 Hz, 2x N-CH = C<u style="single">H</u>) And 6.67 (2H, t, J = 1.98 Hz, 2x NC<u style="single">H</u>= CH); --- ¹³C-NMR (68 MHz, CDCl₃) δ: 50.68 (N-<u style="single">C</u>H₂-COOMe), 52.51 (COOCH)₃), 109.09 (2x N-CH =<u style="single">C</u>H), 121.74 (2x N-CH = CH) and 169.22 (<u style="single">C</u>OOMe); --Infrared analysis: Light absorption band 1745 cm^-1(C = O); --Mass spectrum analysis: 139 (M⁺, 63) and 80 (M⁺-PO (OEt)₂, 100)。 </p>