Metal complexes for use in metathesis

The present invention relates to metal chains useful as catalytic components in olefin transfer reactions, atomic or group transfer radical polymerization or addition reactions and vinylization reactions. The present invention also relates to the use of α-olefins, preferably with respect to the substituent class of the metal chain, which have high activity at moderate temperatures, and optionally as components of the catalytic system for the polymerization of conjugated diene. The present invention also relates to obtaining a polymer having an extremely narrow molecular weight distribution by living polymerization. The present invention also relates to a method for producing the metal chain and a novel intermediate involved in such a method. The present invention also relates to certain derivatives of the metal chain that are suitable for covalent attachment to a carrier, the covalent product of which 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 dendrimer materials containing metal chains attached to core molecules that are catalysts 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 transfer.

The olefin transition is an important step in the reaction between the first olefin and the first transition metal alkylene chain to form the unstable intermediate metallocyclobutane ring, which is then followed by the second olefin and the second. It is a catalytic process including conversion to a metal cyclolidene chain of the above according to the following formula (1). Because this type of reaction is reversible and competitive with each other, the overall result is highly dependent on their respective rates and, if volatile or insoluble product formation occurs, the movement of equilibrium. are doing.

<chemistry num="1"><img file="JP2005515260A_D0001.tif" /></chemistry>

Several non-limiting examples of monoolefin or diolefin transfer reactions are shown in the following equations (2) to (5). Removal of products such as etylidene in formula (2) from the system dramatically changes the process and / or rate of the desired rearrangement reaction, which is the reaction of ethylene with the alkylidene strand to methylene (M = CH).₂) It forms a strand, because it is the most reactive and least stable of the alkylidene strands.

<chemistry num="2"><img file="JP2005515260A_D0002.tif" /></chemistry>

The potential advantage of the present invention over the coupling (Equation 2) is the cross-coupling between two different terminal olefins. Coupling reactions involving diene result in linear and cyclic dimers, oligomers and ultimately linear or cyclic polymers (Equation 3). The latter reaction is commonly referred to as the non-dry diene transition (hereafter referred to as ADMET), which is favorable in very high concentrations or in bulk, whereas cyclization is favorable at low concentrations. is there. When the intramolecular coupling of diene occurs to produce a cyclic alkene, the official residence is called a ring closure transition (hereinafter referred to as RCM) (Equation 4). It is possible that the cyclic olefin is ring-opened and becomes an oligomer or a polymer (ring-opening transfer polymerization represented by the formula 5 (hereinafter referred to as ROMP)). If the alkylidene catalyst reacts more rapidly with cyclic olefins (eg norbornene or cyclobutane) than with carbon-carbon double bonds in the growing polymer chain, "living ring-opening transition polymerization" occurs, i.e., the polymerization reaction. Almost no outage occurs during or after.

The majority of well-defined single-component metal carbene chains have been prepared and utilized in the olefin transition. One major development in the olefin transition was the discovery of ruthenium and osmium carbene chains by Grubbs et al. US Pat. No. 5,977,393 discloses a Schiff base for such compounds, which is useful as an olefin transfer catalyst and reacts with metal-neutral electron donors such as reel phosphine or tri (cyclo) alkyl phosphine. And is coordinated by an anionic ligand. While such catalysts have advanced thermal stability, they maintain transfer activity even in polar protic solvents. They can also cyclize diallylamine hydrochloride to dihydropyrrole hydrochloride. The problems to be solved with respect to Grubbs carbene chains are (i) improving catalyst stability (ie delaying degradation) as well as improving transfer activity, and (ii) using such catalysts. This extends the range of achievable organic products, eg, the ability to close the highly substituted diene into tri- and tetra-substituted olefins.

Living polymerization systems, on the other hand, have been reported for anionic and cationic polymerization, but their industrial application is limited due to the need for high purity monomers and solvents, reaction initiators and anhydrous conditions. It was. 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 carried out in the presence of water. However, the free radical polymerization method often forms a polymer having a miscontrolled molecular weight and high polydispersity. Therefore, the combination of living polymerization and radical polymerization is extremely convenient, and (1) the transfer pathway of an atom or group, and (2) the atom (or group) transfer of US Pat. No. 5,763,548 involving radical intermediates. It is achieved by the radical polymerization method (hereinafter referred to as ATRP). In this type of living polymerization, chain breaking reactions such as transition and termination are substantially absent, and various parameters of the large molecular structure such as molecular weight, molecular weight distribution and terminal functional groups can be controlled. It also allows the preparation of various copolymers, such as block and star copolymers. Living / controlled radical polymerization requires low steady-state concentrations of radicals in equilibrium with various inert species. It can use new polymerization initiation systems based on the reversible formation of growing radicals in redox reactions between various transition metal furniture and polymerization initiators such as alkyl halides or haloalkyl esters. ATRP is based on the dynamic equilibrium between the Amplifying radical and the Inactive Species, established through reversible transition metal-catalyzed cleavage of the covalent bond between carbon and halogen in the Inactive Species. .. Polymerization systems utilizing this concept have been developed using, for example, chains 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, which is based on the following scheme:

<chemistry num="3"><img file="JP2005515260A_D0003.tif" /></chemistry>

It consists of the addition of polyhalogenated alkanes via olefins 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 Kharash reaction.

Experiments have shown that the efficiency of ruthenium alkenidene chains in olefin transfer reactions is inversely proportional to their activity in ATRP and ATRA, i.e., they show the lowest activity in ATRP and ATRA, which is the most efficient for olefin transfer reactions. There is. Therefore, there is a need in the art for catalytic components capable of exhibiting high efficiencies in both olefin transfer reactions and ATRP and ATRA. Furthermore, there is a need in the art for catalytic components capable of initiating olefin transfer reactions under extremely mild conditions, such as at room temperature. Finally, catalytic components capable of initiating the vinylization reaction with high efficiency are also needed in the art.

Furthermore, the currently available synthetic pathways for obtaining the catalyst of US Pat. No. 5,977,393 proceed through the conversion of ruthenium bisphosphan carbene, thus having equal or even better performance properties, 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.

Copolymers of poly-α-olefins such as polyethylene, polypropylene and ethylene with propylene and / or butane-1-ene are extremely widespread in various fields such as all types of extrusions, coextrusions and mold moldings. in use. The need for poly-α-olefins with various physical properties is increasing. Furthermore, in order to improve the productivity, it is also an important requirement to increase the yield of polyolefin per amount of catalyst and to maintain the catalytic activity over the period of continuous production. WO02 / 02649 reacts with (A) a transition metal compound having a bidentate ligand containing an imine structural moiety, preferably a transition metal in which the transition metal is titanium, zirconium or hafnium, and (B-1) compound (A). Disclosed is an olefin polymerization catalyst system containing a compound having a reducing ability capable of converting an imine structure portion into a metal amine structure, and a compound (B-2) that reacts with the compound (A) to form an ion pair. However, WO 02/02649 does not describe a transition metal compound in which the metal is coordinated to a carbene ligand. Regarding the description of WO02 / 02649, there is still a need to improve the olefin polymerization activity and its maintenance in the art.

All of the above needs constitute various objectives to be achieved by the present invention.

<p> In the present invention, the modified olefin transfer catalyst is pK by modifying a Schiff base derivative of ruthenium and osmium of the prior art, or a corresponding derivative of another transition metal._aBy giving a limiting steric hindrance group of at least 15 as a ligand and / or by giving a carbene ligand to form 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 by giving. Conveniently, modified Schiff base derivatives of such ruthenium, osmium and other transition metals may be produced directly from cheaper and more readily available raw materials than prior art catalysts. The present invention also presents such modified Schiff base derivatives of ruthenium, osmium and other transition metals as efficient olefin transfer catalysts, as well as ATRP or ATRA and vinylization reactions such as enol-ester synthesis. 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. 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 also ATRP or ATRA and vinylization reactions such as enol-ester synthesis, etc. It may be used in catalyzing or initiating a radical reaction of an atom (or group) transition. Furthermore, the present invention includes novel intermediates used in methods for preparing novel catalytically active modified Schiff base derivatives. Yet another feature of the invention includes supported catalysts for use in heterogeneous catalytic reactions involving catalytically active Schiff base derivatives and carriers suitable to support them. In particular, the present invention further chemically modifies a metal chain of Schiff bases to form a porous inorganic solid (eg, amorphous or similar grade material, crystalline molecular sieve or modified layered material, eg inorganic oxide) or Provided are a derivative suitable for covalent bonding to a carrier such as an organic polymer resin. Another feature of the present invention is that two or more catalytically active Schiff base derivatives are bound to the core molecule in order to successfully remove the catalyst from the reaction mixture by ultrafiltration. Includes limmer material. Finally, another finding of the invention is that the particular dimetal shift base of the transition metal terminates the reaction with a dihydropyrrole, dihydrofuran or dihydrothiophene compound, unlike the corresponding monometal shift base catalyst. The point is that it can catalyze the direct one-step synthesis of pyrrole, furan and thiophene compounds from diallyl compounds. Yet another finding of the present invention is that certain metal compounds may be used as components of the catalytic system for the polymerization of α-olefins and conjugated diene, which have high activity at moderate temperatures.</p><p> (Definition) As used herein, the term chain or coordinating compound refers to a metal (acceptor) and several neutral molecules or ionic compounds 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 with a donor). A ligand having one or more atoms having a lone pair of electrons is called a polydentate ligand.</p><p> In this specification, C_1-6The term alkyl means the monovalent group of a linear or branched saturated hydrocarbon having 1 to 6 carbon atoms, such as methyl, ethyl, prople, 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 related group having 2 to 6 carbon atoms and the like.</p><p> In this specification, C_1-6The term alkylene is defined above as C_1-6It means a divalent hydrocarbon group corresponding to alkyl.</p><p> In this specification, C_3-10The term cycloalkyl means a monocyclic aliphatic group having 3 to 8 carbon atoms, such as cyclopropyl, cyclooctyl, etc., or C having 7 to 10 carbon atoms._7-10Polycyclic aliphatic groups such as norbornyl or adamantyl.</p><p> In this specification, C_3-10The term cycloalkylene is defined above as C_3-10It means a divalent hydrocarbon group corresponding to cycloalkyl.</p><p> As used herein, the term aryl refers to mono- or polyaromatic monovalent groups such as phenyl, benzyl, naphthyl, anthracenyl, adamantyl, phenanthrasyl, fluoranthenyl, chrysenyl, pyrenyl, biphenylyl, pisenyl, etc. Yes, for example condensed benzo-C_5-8Includes cycloalkyl groups such as indanyl, 1,2,3,4-tetrahydronaphthalenyl, fluorenyl and the like.</p><p> As used herein, the term heteroaryl means a mono- or poly heteroaromatic monovalent group containing one or more heteroatoms independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus. And, for example, pyridyl, pyrazinyl, pyrimidinyl, pyridadinyl, triazinyl, triazolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, pyrrolyl, frilly, thienyl, indrill, indazolyl, benzofuryl, benzothienyl, quinolyl, quinazolinyl, quinoxalinyl, carbazolinyl Phenothiazinyl, xanthenyl, prynyl, benzothienyl, naphthothenyl, thiantrenyl, pyranyl, isobenzofuranyl, chromenyl, phenoxathinyl, indridinyl, quinolinyl, isoquinolyl, phthalazinyl, naphthyldinyl, cinnolinyl, pteridinyl, carborinyl, acridinyl, perimidinyl. Lorinyl, phenazinyl, phenothiazinyl, imidazolinyl, imidazolidinyl, pyrazolinyl, pyrazoridinyl, pyrrolinyl, pyrrolidinyl and the like, and all possible isomer forms thereof.</p><p> In this specification, C_1-6The term alkoxy refers to C bonded to an oxygen atom._1-6It means an alkyl group and includes, for example, methoxy, ethoxy, propoxy, butoxy, etc .; C_2-6Alkoxy means a related group having 2 to 6 carbon atoms and the like.</p><p> As used herein, the term halogen means an atom selected from the group consisting of fluorine, chlorine, bromine and iodine.</p><p> In this specification, C_1-20The term alkyl is C_1-6Includes alkyl (as defined above) and its higher analogs with 7-20 carbon atoms such as heptyl, ethylhexyl, octyl, nonyl, decyl, dodecyl, octadecyl and the like.</p><p> In the present specification, 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.</p><p> In this specification, C_2-20The term alkenyl is defined as a straight or branched hydrocarbon group 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 in addition, C._4-20Cycloalkenyl, a cyclic hydrocarbon group containing one or more double bonds and 4 to 20 carbon atoms, such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclooctadienyl, cyclopentadienyl, cycloocta Includes trienyl, norbornadienyl, indenyl and the like.</p><p> In this specification, C_2-20The term alkynyl is defined as a straight or branched hydrocarbon group containing one or more triple bonds and having 2 to 20 carbon atoms, such as acetylenyl, 2-propynyl, 3-butynyl, 2-butynyl. , 2-Pentynyl, 3-Pentynyl, 3-Methyl-2-butynyl, 3-Hexenyl, 2-Hexenyl and the like and all possible isomers of these.</p><p> In this specification, C_1-20The term alkoxy refers to C having 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.</p><p> 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.</p><p> As used herein, the term "constraint steric hindrance" refers to a group or ligand whose movement is restricted, usually a branched or substituted group or ligand, i.e., its movement. A group that causes measurable molecular strain (angular strain or bond elongation) due to X-ray diffraction, depending on the size of the group.</p><p> As used herein, the term "enantiomer" has an optical purity of at least 80%, preferably at least 90%, and more preferably at least 98% (as measured by standard methods in the art). Means an independently optically active form of each of the compounds of the invention.</p><p> As used herein, the term "solvent" refers to protic and aprotic solvents and non-polar solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters. Refers to the association of the metal chains of the present invention with a solvent molecule selected from the group consisting of, ketones, amides and water.</p>

(Detailed Description of the Invention) In its broadest interpretation, the invention includes one or more carbene ligands, polydentate ligands and other ligands, and at least one of the other ligands. Is pK_aWith respect to a pentacoordinated metal chain, its salt, its solvate or its enantiomer, which is a restricted steric hindrance ligand having at least 15. This five-coordinated metal chain is a one-metal chain or a two-metal chain, and one metal is five-coordinated to one or more neutral ligands and one or more anionic ligands. It may be a rank and the other may be a 4-coordinate. 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 strand of the invention may contain two other ligands or may be a tridentate ligand, in which case. The metal chain contains one other ligand.

Preferably, the metal in the pentacoordinated metal chain of the present invention 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. More preferably, the metal consists of ruthenium, osmium, iron, molybdenum, tungsten, titanium, renium, copper, chromium, manganese, palladium, platinum, rhodium, vanadium, zinc, cadmium, mercury, gold, silver, nickel and cobalt. Selected from the group.

Preferably, the polydentate ligand of the pentacoordinated metal chain of the present invention comprises 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. Cumrenylidene ligands such as butane-1,2,3-trienylidene, penta-1,2,3,4-tetranylidene and the like.

In one feature that is particularly useful when the strands are used in the presence of an organic solvent, one of the other ligands present in the pentacoordinated metal strand of the present invention is an anionic ligand. Yes, the meaning of the term anionic ligand is conventional in the art and is preferably consistent with the definition of US Pat. No. 5,977,393. In another feature that is particularly useful when the strands are used in the presence of water, one of the other ligands 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 and aryl sulfonates in which the alkyl group may be substituted with one or more halogen atoms. Suitable solvents for coordinating with metals in such cationic species are protonic solvents, polar aproton solvents and non-polar solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols. , Estel, ketone, amide, water or selected from the group.

More typically, pK, which is a central feature of the metal chains of the present invention._aThe restricted steric-damaging ligand with at least 15 is a derivative in which one or more of the hydrogen atoms is a nonionic prophosphatran superbase or imidazol-2-iriden, dihydroimidazol-2-iriden, oxazole-2. -Ilidene, Thiazole-5-Ilidene, Thiazole-2-Ilidene, Bis (imidazolin-2-iriden), Bis (imidazolidine-2-iriden), Pyrrolilidene, Pyrazolilidene, Dihydropyrrolilidene, Pyrrolidinilidene and benzo-condensations thereof It is substituted with a limiting steric hindrance group of N-heterocyclic carbene selected from the group consisting of derivatives.

The present invention further comprises (i) a polydentate ligand and one or more other ligands, at least one of the other ligands being pK._aA tetracoordinated metal chain that is a restricted steric disorder ligand with at least 15 is selected from the group consisting of (ii) alkynyl compounds, diazo compounds and dialkynyl compounds, where the reactants are carbenes to metals. Provided is a method for producing a 5-coordinated metal chain body disclosed above, which comprises a step of producing a 5-coordinated 1-metal chain body by reacting with a substance capable of giving a ligand. The present invention also provides another method for producing a pentacoordinated metal chain, which includes the following steps:-(i) polydentate ligand, and pK._aA tetracoordinated metal chain containing at least one other ligand other than the carbene ligand and other than the restricted steric hindrance ligand in which is (ii) an alkynyl compound, a diazo compound and a dialkynyl. A first step of producing a 5-coordinated 1-metal chain by reacting with a reactant selected from the group consisting of compounds, wherein the reactant can provide a carbene ligand for a metal, and , Then-the 5-coordinated 1-metal chain obtained in the first step, pK_aSpecies containing restricted steric hindrance groups with at least 15 and pK_aSecond step of reacting under conditions that allow the species containing the restricted steric hindrance group of at least 15 to coordinate to the metal instead of one of the other ligands other than the carbene ligand. , Including.

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

When the five-coordinated metal strand of the present invention is a two-metal strand 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 resulting 5-coordinated 1-metal chain with a 2-metal chain in which each metal is 4-coordinated. Such a reactive tetra-coordinated 2-metal chain is, for example, [RuCl.₂(p-cumene)]₂Alternatively, it may have a dimer structure such as an analog thereof. Alternatively, the reactive tetracoordinated dimetal chain may be formed in situ by contacting the terpenen with a trichloride of ruthenium, rhodium or cobalt. The reactive 4-coordinated 2-metal chain may be the same as or different from the metal of the 5-coordinated metal chain.

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 a particular embodiment, the 5-coordinated metal chain used in the first step of the above general method is a 5-coordinated 1 containing one anionic ligand by containing one anionic ligand. The step of providing the metal chain and further extracting the anionic ligand from the 5-coordinated 1-metal chain by reacting the 5-coordinated 1-metal chain in the presence of a salt and a solvent. To form a 5-coordinated 1-metal chain, which is a cationic species associated with an anion, in which the metal coordinates with respect to the solvent.

In another embodiment, the invention is a tetracoordinated 1 metal chain comprising a polydentate ligand and one or more other ligands, at least one of the other ligands. Is pK_aProvided is the above-mentioned strand which is a restricted steric hindrance ligand having a value of at least 15. Surprisingly, such a 4-coordinated 1-metal chain is not only useful as an intermediate for producing a catalytic component, but also has catalytic activity itself in ROMP, ATRP, ATRA and vinylization reactions. There is.

More specifically, the present invention is a pentacoordinated metal chain selected from metal chains having one of the general formulas (IA) and (IB) shown in FIG. 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, renium, copper. , Chromium, manganese, rhodium, ruthenium, zinc, gold, silver, nickel and cobalt;-Z is oxygen, sulfur, selenium, NR'''', PR'''', AsR'' Selected from the group consisting of'' and SbR'''';-R'', R'''' and R'''' are hydrogen and C, respectively._1-6Alkyl, C_3-10Cycloalkyl, 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 to form an aryl or heteroaryl group, each of which (if not hydrogen) , In some cases 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_3-10Substituent R independently selected from the group consisting of cycloalkylsilyl, alkylammonium and arylammonium₅Substituted by 1 or more, preferably 1 to 3;-R'is similar to R'', R'''and R'''' when contained in compounds having the general formula (IA). 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 ;- R₁Is pK_aIs a restricted steric hindrance group with at least 15 ;- R₂Is an anionic ligand;-R₃And R₄Are hydrogen 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 group selected from the group consisting of alkylammoniums and arylammoniums;-R'and R₃And R₄One is interconnected to form a bidentate ligand; -R'''and R'''' are interconnected and hetero selected from the group consisting of nitrogen, phosphorus, arsenic and antimony. Forming an aliphatic ring system containing atoms;-R₃And R₄Together form a condensed aromatic ring system, and-y are M and R₃And R₄Sp between the carbon atoms carrying₂It indicates the number of carbon atoms and provides those which are integers 0-3, their salts, solvates and enantiomers.

In the above definition of the compounds of the invention, the group R₁Due to the ability to give restricted steric hindrance, and its pK_aOnly limited by value, the latter is what is traditionally defined and measured in the art. R like this₁Non-limiting examples of groups include the following high pK in which one or more hydrogen atoms are substituted with a group that causes restricted steric hindrance._aIncludes derivatives of groups. --Imidazole-2-iriden (pK)_a= 24),-Dihydroimidazol-2-ylidene (pK)_aIs higher than 24),-Oxazole-2-Ilidene, -Thiazole-5-Ilidene, -Thiazole-2-Ilidene, -Pyrrolilidene (pK)_a= 17.5),-Pyrazolilidene, -Dihydropyrrolilidene, -Pyrroliridinilidene (pK)_a= 44),-bis (imidazolin-2-iriden) and bis (imidazolidine-2-iriden), -benzo-condensed derivatives such as indolilidene (pK)_a= 16), and-Nonionic prophosphatran superbases, such as those described in US Pat. No. 5,698,737, preferably trime dustpan triazaprophosphatran P (CH) known as Verkade superbases.₃NCH₂CH₂)₃N.

The limiting steric hindrance group is, for example, a branched chain or a substituted R'group, such as a t-butyl group, a substituted C._3-10Cycloalkyl group, C_1-6Aryl groups with one or more alkyl substituents (eg 2,4,6-trimethylphenyl (mesyl), 2,6-dimethylphenyl, 2,4,6-triisopropylphenyl or 2,6-diisopropylphenyl) or C_1-6A heteroaryl group having one or more alkyl substituents (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 R₃Located between the group-carrying carbon atoms, the synthetic pathways for each of these species of compounds differ with respect to the manufacturing process, as described below in the specification. That is, unsaturated carbon chains such as arenilidene or cumlenilidene (eg butane-1,2,3-trienylidene, penta-1,2,3,4-tetraenylidene, etc.) may be present in the carbene ligand. For simplification of the manufacturing route, the 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 condensed aromatic ring system with formula (IV) in FIG.

In the above definition of compounds of the invention having formula (IA), the group R'is preferably selected from methyl, phenyl and substituted phenyl (eg, dimethylbromophenyl or diisopropylphenyl). In the case of the 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 preferably from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium and rhenium, especially if the compounds are intended for use in olefin transfer reactions. Be selected.

The present invention is also the first method for the production of a 5-coordinated metal chain having one of the formulas (IA) and (IB), the 4-coordinate having one of the general formulas (IIA) or (IIB). Coordinate metal chains, but in the formula 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, but R in formula₁Is defined as described above, and Y is reacted with a leaving group to form an intermediate having the general formula (IIIA) or (IIIB) of FIG. The following substances:-Formula R₃R₄R₇Alkynyl compounds with COCH, but R₃And R₄Is defined above for the general formulas (IA) and (IB), and R₇Is hydrogen, hydroxyl and R₃Selected from the group consisting of (when y = 2),-Equation N₂CR₃R₄Diazo compounds with, but R₃And R₄Is defined above (if y is 0),-Equation R₃Alkynyl compounds with CCH, but R₃Is defined as described above (if y is 1), and-Equation R₂₁CCCCR₂₂Dialkynyl compounds with, but R₂₁And R₂₂Provide methods comprising reacting with a reactant selected from the group consisting of one independently selected from hydrogen and trialkylsilyl (if y is 3), respectively.

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 hydrogen, C_1-6Alkoxy (eg t-butoxy), PR₃And NR₃, But R₃Is selected from the group consisting of those defined as described above. 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, and R₇Is a compound in which is hydroxy. If y is 3, then a suitable dialkynyl compound is butaziin or tetramethylsilylbutadiine.

The present invention is also a second method for the preparation of a pentacoordinated metal chain having one of the general formulas (IA) and (IB), in the first step, the general formula (IIA) shown in FIG. ) Or (IIB), but M, Z, R, R', R'', R''', R'''' and R in the formula₂Is defined above for equations (IA) and (IB), and R₆Is a leaving group, the following substances:-Equation R₃R₄R₇Alkynyl compounds with COCH, but R₃And R₄Is defined above for equations (IA) and (IB), and R₇Is hydrogen, hydroxyl and R₃Selected from the group consisting of (when y = 2),-Equation N₂CR₃R₄Diazo compounds with, but R₃And R₄Is defined as above (if y is 0),-Equation R₃Alkynyl compounds with CCH, but R₃Is defined as above (if y is 1), and-Equation R₂₁CCCCR₂₂Dialkynyl compounds with, but R₂₁And R₂₂Is independently selected from hydrogen and trialkylsilyl (when y is 3), reacts with a reactant selected from the group consisting of, and in the second step, further in the first step. The reaction product of₁Compound with Y, but R in formula₁Is defined as described above, and Y provides the above method including reacting with a leaving group. In this second method, a suitable example of the leaving group Y 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), which group is optionally C._1-6It is substituted with one or more alkyl groups. A suitable example of such a group is methylpropylphenyl, where the methyl and isopropyl substituents of the phenyl group are in the para position.

The present invention also comprises a tetracoordinated metal chain having one of the general formulas (IIIA) or (IIIB) shown in FIG. 4, where -M is 4, 5, 6, 7, 8, 9, in the periodic table. Transition metals selected from the group consisting of groups 10, 11 and 12, preferably ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, cobalt and A metal selected from nickel;-Z is selected from the group consisting of oxygen, sulfur, selenium, NR'''', PR'''', AsR'''' and SbR'''';-R '', R'''' and R'''' are hydrogen and C, respectively._1-6Alkyl, C_3-8Selected from the group consisting of cycloalkyl, aryl and heteroaryl, or R and R together to form an aryl or heteroaryl group, each of which optionally has a halogen atom, C_1-6Alkyl, C_1-6Substituent R independently selected from the group consisting of alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium and arylammonium₅Substituted by 1 or more, preferably 1 to 3;-R'is similar to R'', R'''and R'''' when contained in compounds having the general formula (IIIA). 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 ;- R₁Is pK_aIs a restricted steric hindrance group with at least 15 ;- R₂Provides the above-mentioned strands, salts thereof, solvates and enantiomers which are anionic ligands.

The present invention also comprises a tetracoordinated metal chain having one of the general formulas (IIA) or (IIB) shown in FIG. 4, where -M is 4, 5, 6, 7, 8, 9, in the periodic table. Transition metals selected from the group consisting of groups 10, 11 and 12, preferably ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, cobalt and A metal selected from nickel;-Z is selected from the group consisting of oxygen, sulfur, selenium, NR'''', PR'''', AsR'''' and SbR'''';-R '', R'''' and R'''' are hydrogen and C, respectively._1-6Alkyl, C_3-8Selected from the group consisting of cycloalkyl, aryl and heteroaryl, or R and R together to form an aryl or heteroaryl group, each of which optionally has a halogen atom, C._1-6Alkyl, C_1-6Substituent R independently selected from the group consisting of alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium and arylammonium₅Substituted with one or more, preferably 1-3, or R and R together to form an aryl or heteroaryl group, which groups are bromine, iodine, C._2-6Substituent R selected from the group consisting of alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, alkylammonium and arylammonium₅1 or halogen atom, C_1-6Alkyl, C_1-6Alkoxy, aryl, alkyl sulfonate, aryl sulfonate, alkyl phosphonate, aryl phosphonate, C_1-6Alkyl-C_1-6Alkoxysilyl, C_1-6Substituent R independently selected from the group consisting of alkyl-aryloxysilyl, alkylammonium and arylammonium₅Substituted by two or more;-R'is defined similarly to R'', R'''and R'''' when contained in compounds having the general formula (IIA), or is generally C if contained in a compound of formula (IIB)_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 ;- R₂Is an anionic ligand;-R₆Are aromatic and unsaturated alicyclics, preferably aryl and C_4-20A cycloalkenyl (eg, cyclooctadienyl, norbornadienyl, cyclopentadienyl and cyclooctatrienyl) group, the group of which is C._1-6Provided are the above chain, a salt thereof, a solvate thereof and an enantiomer thereof, which are optionally substituted with one or more alkyl groups.

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 there.

Intermediates with formula (IIA) are first described as hydroxyaldehydes with the following general formula: R'''C (OH) = C (R'') CHO, such as salicylaldehyde (if Z is oxygen) or the corresponding thio. Aldehydes (when Z is sulfur), aminoaldehydes (when Z is NR''''), phosphinaldehydes (when Z is PR''''), arcinoaldehydes (when Z is AsR'''') (If) or stibinoaldehyde (if Z is SbR''''), but the hydroxy, thio, amino, phosphino, arcino or stibino group at the β position with respect to the aldehyde group, the primary aliphatic or Condensing with an aromatic amine and then reacting the resulting aldehyde with an alkoxide of, for example, any of the Group IA, IIA or IIIA metals of the periodic table (eg sodium, potassium, magnesium or tallium). Converting to flame, then converting the salt to, for example, [RuCl₂(p-cumene)]₂It may be prepared by a method similar to a well-known method including reacting with a metal chain 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, then o-hydroxyaniline (when Z is oxygen (, amino), in order to obtain the desired 5-membered chelate ligand. Thiol (if Z is sulfur), diamine (if Z is NR''''), aminophosphine (if Z is PR''''), aminoarcin (if Z is AsR'''') or Aminostibin (if Z is SbR''''), but condensing with an amino alcohol such as a hydroxy, thio, diamino, phosphino, arcino or stybino group at the β position with respect to the first amino group, The resulting amidino is then converted to its salt, and then the salt is reacted with a metal chain having an unstable ligand in a manner similar to that shown for compound (IA) above. May be prepared.

The present invention also includes the following components: (a) a catalytically active pentacoordinated metal chain as defined above, and (b) a carrier suitable for supporting the catalytically active pentacoordinated metal chain (a). Provided are supported catalysts for use in heterogeneous catalytic reactions, including support amounts of.

In such supported catalysts, the carrier is a porous inorganic solid (including silica, zirconia, aluminosilica), such as amorphous or similar grade materials, crystalline molecular sieves and modified layered materials, such as. It may be selected from the group consisting of one or more inorganic oxides and organic polymer resins such as polystyrene resins and derivatives thereof.

The porous inorganic solid that may be used with the catalyst of the present invention has an open microstructure that allows molecules to contact the relatively large surface area of the catalyst and these substances that enhance sorption activity. These porous materials can be classified into three broad categories using the details of their microstructure on which the classification is based. These categories are amorphous or similar grade 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 their pore size. Variations, the presence or absence of X-ray diffraction patterns, the details of such patterns, and their microstructures are manifested as differences in the appearance of the material when examined by transmission electron microscopy and electron diffraction. Amorphous or similar grade 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 similar grade transition alumina used as solid acid catalysts and petroleum refining catalyst supports. The term "amorphous" refers herein to substances that do not have a long range order, because almost all substances have some degree of order, at least on a local scale. , May be somewhat misleading. Another term used to describe these substances is "X-ray neutrality". The microstructure 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 between the particles. It arises from the voids.

Similar grade materials such as transition alumina also have a broad distribution of porosity, but with a well-defined X-ray diffraction pattern that is usually more than a few 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)). Since there is no long-range order that controls the pore size of any material, the variety of pore sizes is typically extremely high. The pore size of these materials belongs to a region called a mesoporous range including pores in the range of, for example, about 15 to about 200 angstroms.

In stark contrast to these, structurally misdefined 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 smaller. They are connected to each other by 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 are rejected, and these materials are known as "molecular sieves" and take advantage of these properties. It is used in many types of methods. Both natural and synthetic such molecular sieves contain a wide range of cation-containing crystalline silicates. These silicates are SiO₄And the oxides of Group IIIB elements of the Periodic Table, eg AlO₄Can be described as a three-dimensional skeleton of the rigidity of, in which the tetrahedrons are cross-bonded by sharing an oxygen atom, which allows all IIIB elements such as aluminum and IVB elements such as silicon to be cross-bonded. The ratio of atoms to oxygen atoms is 1: 2. The electron valence of tetrahedrons containing Group IIIB elements, such as aluminum, is balanced by encapsulation in the crystals of cations, such as alkali metal or alkaline earth metal cations. This is shown when the ratio of Group IIIB elements, such as aluminum, to various cations, such as Ca, Sr, Na, K or Li, is equal to 1. One type of cation may 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 appropriate cation selection. 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. 3,832,449) 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, No. 409). The latter is also its synthesis from a crystalline molecular sieve composition of a substance called PSH-3 and a reaction mixture of hexamethyleneimine, an organic compound that acts as a directing substance for the synthesis of stratified MCM-56. Is described. Similar compositions with different structural elements are described in European Patent Application No. 293,032. Hexamethyleneimine is also a crystalline molecular sieve MCM-22 in US Pat. No. 4,954,325; MCM-35 in US Pat. No. 4,981,663; MCM-49 in US Pat. No. 5,236,575; and ZSM-12 in US Pat. No. 5,021,141. Described for use in synthesis. The molecular sieve composition SSZ-25 is described in US Pat. No. 4,826,667 and European Patent Application No. 231,860, the zeolite being 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, silicoaluminum phosphate SAPO-5, SAPO-37, SAPO-40, A molecular sieve material selected from the group consisting of MCM-9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5 and mesoporous crystal MCM-41 is suitable for inclusion in the supported catalysts of the present invention. Described in 667 and European Patent Application No. 231,860, 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, silicoaluminum phosphate SAPO-5, SAPO-37, SAPO-40, A molecular sieve material selected from the group consisting of MCM-9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5 and mesoporous crystal MCM-41 is suitable for inclusion in the supported catalysts of the present invention. Described in 667 and European Patent Application No. 231,860, 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, silicoaluminum phosphate SAPO-5, SAPO-37, SAPO-40, A molecular sieve material selected from the group consisting of MCM-9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5 and mesoporous crystal MCM-41 is suitable for inclusion in the supported catalysts of the present invention.

A material with a high level of porosity can be obtained by pillaring a particular stratified material, including a layer that can be isolated with a swelling agent. An example of such a stratified material is clay. Such clays are swollen with water, which separates the viscous layer with water molecules. Other stratified materials cannot swell with water, but can be swelled with certain organic swelling agents such as amines and quaternary ammonium compounds. Examples of such non-water-swelling stratified materials are described in US Pat. No. 4,859,648, which includes stratified silicates, magadites, kenites, trititanates and perovskites. Another example of a non-water-swellable stratified material is one that can be swollen with a particular organic swelling agent, including the void-containing titanometallate material described in US Pat. No. 4,831,006. Once the stratified material swells, the material is struts between the isolated layers by intervening thermostable materials such as silica. U.S. Pat. Nos. 4,831,006 and 4,859,648 described above describe methods for strutting the described non-water-swellable stratified material, with reference to the definition of strut and strut material. Incorporated into the specification. Other patents describing struts and strut products of stratified material include US Pat. Nos. 4,216,188; 4,248,739; 4,176,090; and 4,367,163, and European Patent Application No. 205, 711 is included. The X-ray diffraction pattern of the strut stratified material varies depending on the extent to which swelling and strut formation usually destroy well-ordered stratified microstructures. The microstructure regularity in some strut stratified 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 strut material. Will be done. 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 strut stratified materials is narrower than that of amorphous and similar grade materials, but broader than that of crystalline skeleton materials.

The present invention also includes those within the broad tolerances mentioned above or one of the general formulas (IA) and (IB), preferably one in which the metal M is selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten and ruthenium. Use of a 5-coordinated metal chain having or a supported catalyst containing the above-mentioned simple substance as a catalyst component in a reaction selected from the group consisting of a transfer reaction, an atomic transfer radical reaction, an addition polymerization reaction and a vinylization reaction. I will provide a.

In the first embodiment, the reaction is to convert the first olefin to at least one second olefin (different from the first olefin) or to a linear olefin oligomer or polymer or cyclic olefin. Transfer reaction. That is, the present invention comprises a transfer reaction comprising 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 by a suitable carrier. Regarding how to do it. The high levels of rearrangement activity of the metal carbene compounds of the invention dictate these compounds and catalyze the rearrangement reactions between all types of olefins. Examples of reactions made possible by the metal carben compounds of the present invention include, for example, ring-opening transfer polymerization of cyclic olefins, ring-closing transition of acyclic diene, cross-transfer reaction involving at least one acyclic or cyclic olefin, and It is a depolymerization of an olefin polymer. In particular, the catalyst of the present invention can catalyze a ring-sized cyclic olefin of at least 3 atoms. Examples of cyclic olefins that may be used in such transition reactions are norbornene and its functional derivatives (eg, as described in Examples below), cyclobutene, norbornadiene, cyclopentene, dicyclopentadiene, cycloheptane, cyclooctane, 7. Includes -oxanorbornene, 7-oxanorbornadiene, cyclooctadiene and cyclododecene.

The transfer reaction of the present invention may be carried out by dissolving the catalytic amount of the metal carben catalyst in the solvent in an inert atmosphere, and optionally adding the cyclic olefin dissolved in the solvent to the carben solution with stirring. Solvents that may be used to carry out the transfer reaction include all types of organic solvents that are inert under polymerization conditions, such as protic and aprotic and non-polar solvents, as well as aqueous solvents. More typical examples are aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, esters, ketones, amides, water and mixtures thereof, and supercritical solvents such as carbon dioxide (reactions). Is performed under supercritical conditions). 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 transfer polymerization reaction depends on the solvent selected and the molecular weight of the resulting polymer. The reaction temperature can typically vary from about 0 ° C to about 100 ° C, preferably 20 ° C to 50 ° C. The reaction time is about 1 to about 600 minutes. The molar ratio of catalysts to olefins is not exact, from about 1: 100 to about 1: 1,000,000, preferably 1: 100 to about 1: 300,000, and more preferably 1: 200 to 1:10, It is in the range of 000. An antioxidant and / or a polymerization terminator (or chain transfer agent) may be added to the reaction mixture before the formed polymer solidifies, or optionally when the desired molecular weight of the polymer has been achieved. The examples of polymerization inhibitors used are not rigorous for the present invention, except that the polymerization inhibitors react with the catalytic carbene metal compounds (IA) or (IB) under predominant temperature conditions and are inert. That is, another carbene metal compound that cannot further proceed with the reaction must be produced. Suitable examples of such polymerization inhibitors include vinyl compounds such as phenylvinyl sulfide, ethyl vinyl ether, vinyl acetate and N-vinylpyrrolidone.

In particular, the (IA) and (IB) pentacoordinated metal chains of the present invention are stable in the presence of various functional groups, so that they can catalyze a wide variety of olefins under a wide variety of process conditions. You may use it. In particular, the first olefin compound to be converted in the transition reaction is a functional atom or group, such as hydroxyl, thiol (mercapto), ketone, aldehyde, ester (carboxylate), thioester, cyano, cyanate, epoxy, silyl. , Cyriloxy, Silanyl, Syroxazanyl, Boronato, Boryl, Stanyl, Disulfide, Carbonate, Imine, Carboxyl, Amine, Amide, Carboxyl, Isocyanate, Thiolisocyanate, 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_1-20It may contain one or more selected from the group consisting of alkylsulfanilic, arylsulfinyl, sulfonamides and sulphonates (preferably paratoluenesulfonates, methanesulphonates or trifluoromethanesulphonates). The functional atom or group of the first olefin may be either a substituent portion of the first olefin or a carbon chain portion of the first olefin compound.

The high level of transfer activity of the pentacoordinated metal chains of the present invention also provides acyclic dienes such as diallyl compounds (diallyl ethers, diallylthioethers, dialkylphthalates, diallyl net compounds such as diallylamines, diallylaminophosphonates, diallyl glycine esters). Etc.), 1,7-octadiene, substituted 1,6-heptadiene, etc., when catalyzing ring-closing transitions in the presence or absence of a solvent at a relatively low temperature (about 20 ° C to 80 ° C). It is considered useful. In the case of the diallyl compounds described above, the reaction proceeds unexpectedly further and may give a pyrrolyl compound, a furanyl compound or a thiophenyl compound, that is, a dehydrogenated compound, except that the pentacoordinated metal chain used is one. It is a two-metal chain in which the metal is 5-coordinated and the other is 4-coordinated.

The pentacoordinated metal chains of the present invention are also telechelic polymers, i.e. one reactive end group which is a useful material for chain extension steps, block copolymer synthesis, reactive injection molding, and polymer network formation. It may also be used for the preparation of macromolecules having the above. An example is hydroxyl telechelic polybutadiene, which may 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 polymer via ring-opening polymerization are well known in the art, in which acyclic olefins are used to regulate the molecular weight of the telechelic polymer produced. Acts as a chain transfer agent. When an α, ω-2 functional olefin is used as a chain transfer agent, a bifunctional telechelic polymer can be actually synthesized.

In summary, the rearrangement reaction method of the present invention can be carried out such that the first olefin compound is an acyclic monoolefin. For example, the method for olefin coupling by cross-transfer is the present invention in the presence of a first acyclic olefin or a functionalized olefin, eg, a second olefin or a functionalized olefin described above. Includes the step of contacting the metal carbene compound of. More preferably, the cross-rearrangement reaction is of formula R.₈CH = CHR₁₀Monoolefin with and formula R₉CH = CHR₁₁A mixture of monoolefins with, but R₈, R₉, R₁₀And R₁₁Independently carries one or more of the above-mentioned functional atoms or groups, in some cases C_1-20The one selected from the alkyl groups, the formula R₈CH = CHR₉Monoolefin with and formula R₁₁CH = CHR₁₀Can be for conversion to a mixture of monoolefins having.

Alternatively, the first olefin compound is a diolefin or a cyclic monoolefin having a ring size of at least 3 carbon atoms, and the transfer reaction is preferably a diolefin or an oligomer of a linear olefin from a cyclic olefin or a linear olefin. It is carried out under suitable conditions for conversion to a polymer. When the first olefin Kagobutsuga is a diolefin, the transfer reaction is also carried out under conditions suitable for converting the diolefin into a mixture of a cyclic olefin and an aliphatic alpha olefin.

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

<chemistry num="4"><img file="JP2005515260A_D0004.tif" /></chemistry>

Selected from olefins with the following formula:

<chemistry num="5"><img file="JP2005515260A_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, and c is selected from 0 and 1. , M and p allow the hydrocarbon chain of formula (V) to contain 10-18 carbon atoms, and r and t are in the hydrocarbon chains of two non-identical olefins of formula (IV). The total number of carbon atoms is 12-40, where X, X'and X'' are hydrogen, halogen, methyl, acetyl, -CHO and -OR.₁₂Selected independently from, where R₁₂Hydrogen and Tetrahydropyranyl, Tetrahydrofuranyl, t-Butyl, Trityl, ethoxyethyl and SiR₁₃R₁₄R₁₅Selected from the alcohol protecting groups selected from the group consisting of, where R₁₃, R₁₄And R₁₅Are independent C_1-6It is selected from alkyl and aryl groups.

The unsaturated bioactive compound having formula (V) is a pheromone or pheromone precursor, pesticide or pesticide precursor, pharmaceutically active compound or pharmaceutical intermediate, fragrance or fragrance precursor. As a few examples of the unsaturated bioactive compounds, 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 commercially available pheromone useful in pest control, especially given its effectiveness in disrupting the mating and reproductive cycles of targeted insect species. is there. It can be conveniently made from 1,5,9-tetradecatorien, the latter from cyclooctadiene and 1-hexene according to the present invention.

When carrying out the rearrangement reaction of the present invention, the reaction proceeds very rapidly in most cases, but for certain olefins, further in order to improve the reaction rate and / or the yield of the rearrangement reaction. , It is convenient to contact the first olefin compound and optionally the second olefin compound with an organic or inorganic acid or an aluminum, titanium or boron-based Lewis acid well known in the art.

Conversely, as described in some of the examples below, norbornene in ring-opening transfer polymerization (ROMP) reactions using the catalysts of the present invention is such that the control of polymerization becomes a problem in the absence of appropriate means. And for monomers such as substituted norbornene, the process may proceed in a very rapid manner. This kind of problem is after mixing the liquid olefin monomer and the catalyst, injecting, casting or injecting into the mold, and removing the molded part from the mold when the polymerization is complete (ie curing the product). It is likely to occur during molding of thermosetting polymers that are post-cured if necessary, as in the case of reactive injection molding (RIM). The ability to control the reaction rate, i.e. the pot life of the reaction mixture, becomes more important in the casting of larger parts. The use of the catalysts of the present invention, the extension of pot life, and / or the control of the rate of the transfer polymerization reaction can be carried out in various ways, such as increasing the ratio of catalyst / olefin and / or reacting with a polymerization retarder. This may be done in addition to the mixture or the like. In addition, it also states: (a) the above-mentioned transition catalyst (which is optionally supported) with an olefin and a first temperature in the reactor in which the transition catalyst is substantially inert (inert). In the first step of contacting in, and (b) the temperature of the reactor is set to a second temperature exceeding the first temperature at which the catalyst is activated (for example, overheating the reactor). It can be achieved by an advanced embodiment including the above steps.

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 should be cooler than room temperature, eg about 0 ° C. It may be appropriate to cool to. The second temperature is preferably about 40 ° C and may be up to about 90 ° C.

As will be described by Examples described later, the ring-opening transfer 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 molecular weight (number average) in the range of about 1.2 to 3.5, preferably about 1.3 to about 2.5. Polymers such as polynorbornene and functional derivatives thereof having well-controlled properties such as polydispersity index (Mw / Mn) are easily achieved.

When the ring-opening transfer 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, composition aids such as antistatic agents, antioxidants, ceramics, etc. It may occur in the presence of light stabilizers, plasticizers, dyes, contents, fillers, reinforcing fibers, lubricants, adhesion promoters, viscosity enhancers, and demolding agents.

Further of the metal carben compounds of the invention having one of the general formulas (IA) and (IB), wherein the metal M is preferably selected from the group consisting of ruthenium, osmium, iron, molybdenum, tungsten, titanium and ruthenium. Another use is as a catalyst for the radical addition reaction of polyhalogenated alkenes to olefins. 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 such as styrene or vinyltoluene, α, β-ethylenically unsaturated acid esters, such as C._1-10Alkylate acrylate and methacrylate, acrylonitrile and the like.

The present invention may also be on a carrier, as disclosed above, for atomic or group transfer radical polymerization of radical (co) polymerizable monomers, or as a catalytic component of a catalytic system for ATRA or vinylation reactions. A 5-coordinated metal chain supported by the above, or a 5-coordinated metal compound having one of the general formulas (IC) and (ID) shown in FIG. 4 or a cationic species thereof (in some cases, an anionic ligand is extracted). In some cases combined with the support of the carrier, where:-M, Z, R', R'', R''', R'''', R₂, R₃, R₄And y are defined above for equations (IA) and (IB), -R₁₆With respect to the use of those that are neutral electron donors.

Restricted steric hindrance groups R for compounds (IA) and (IB)₁Unlike compounds (IC) and (IC) neutral electron donating groups R₁₆Is less than about 15 pK_aHave. R₁₆A good example of is the expression RR₁₇R₁₈R₁₉Phosphine, but R₁₇, R₁₈And R₁₉Are independent 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) and functionalized phosphine, arsine, stilbene, allen, heteroallene, etc. Compounds (IC) and (ID) are less effective than compounds (IA) and (IB) in catalysis of olefin transfer reactions, but they are efficient in catalysis of AATRP, ATRA and vinylization reactions. I know.

Some of the compounds having one of the general formulas (IC) and (ID), especially those with y of 0 and M of ruthenium or osmium, are well known in the art and are well known in the art as transfer catalysts in US Pat. No. 5,977,393. It is described in the issue. Y is 1 to 3 or y is 0 but M is selected from the group consisting of iron, molybdenum, tungsten, titanium, ruthenium, 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 any of the methods described herein as second and third embodiments of the invention. In that case, in the raw material of the process of the corresponding method, R₁And R₁₆Simply replace.

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 ~ 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 mol / l ~ 1 mol / l). Therefore, it is desirable to adjust the respective amounts of the catalyst 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, radicals from non-catalytic species). 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 become uncontrollable. On the other hand, when the concentration of the Inactive Species is greater than 1 mol / l, the molecular weight of the reactive organism tends to be under-reduced, resulting in oligomeric properties not greater than about 10 monomeric units. Approximately 10 in a lump^-2A polymer having a molar / l inert chain concentration of about 100,000 g / mol is given.

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, stellate, graft, comb, superbranched and dendritic (co) polymers.

More typically, a monomer suitable for living radical polymerization according to the seventh embodiment of the present invention is of formula R.₃₁R₃₂C = CR₃₃R₃₄Including the ones in the formula,-R₃₁And R₃₂Are independent of each other hydrogen, halogen, CN, CF₃, C_1-20Alkyl (preferably C_1-6Alkyl), α, β-unsaturated C_2-20Alkyl (preferably acetylenyl), α, β-unsaturated C_2-20Alkenyl (preferably vinyl), but optionally (preferably at the α-position) halogen, C_3-8Cycloalkyl, phenyl, however, selected from the group consisting of those carrying 1 to 5 substituents, and those substituted with;-R₃₃And R₃₄Are independently hydrogen, halogen (preferably fluorine or chlorine), C_1-6Alkyl and COOR₃₅(R in the formula₃₅Is hydrogen, alkali metal or C_1-6Selected from the group consisting of (selected from alkyl); and-R₃₁, R₃₂, R₃₃And R₃₄At least two of them are hydrogen or halogen.

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

Other preferred monomers are:-C_1-20Alcoholic (meth) acrylic acid ester,-acrylonitrile,-C_1-20Alcoholic cyanoacrylic acid ester,-C_1-6Didehydromatonate diesters of alcohols, -vinyl ketones in which the α-carbon atom of the alkyl group does not carry a hydrogen atom, and-possibly C on the vinyl moiety (preferably the α-carbon atom)._1-6Styrene carrying 1 to 5 substituents on an alkyl group and a phenyl ring, where 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_1-6Includes those selected from the group consisting of acyl-protected hydroxy, cyano and phenyl.

In the seventh embodiment of the present invention, the catalytic component of the present invention is more dependent because the ATRP catalytic system is based on the reversible formation of growing radicals in the redox reaction between the metal component and the polymerization initiator. It is preferably used in combination with a polymerization initiator having an atom or group capable of radical transfer.

A suitable polymerization initiator is formula R₃₅R₃₆R₃₇CX₁Including those with, in the formula,-X₁Is halogen, 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_1-6(Selected from alkyl), SR₃₉, OC (= O) R₃₉, OP (= O) R₃₉, OP (= O) (OR₃₉)₂, OP (= O) OR₃₉, ON (R₃₉)₂And 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 R₃₇Are independent of hydrogen, halogen, and C_1-20Alkyl (preferably C_1-6Alkyl), C_3-8Cycloalkyl, C (= O) R₄₀(However, R₄₀Is C_1-20Alkyl, C_1-20(Selected from the group consisting of alkoxy, aryloxy or heteroaryloxy), C (= O) NR₄₁R₄₂(R in the formula₄₁And R₄₂Are independent of each other hydrogen and C_1-20Selected from the group consisting of alkyl or R₄₁And R₄₂Together form an alkylene group with 2-5 carbon atoms), 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 group may be further substituted with the X1 group described above. That is, the polymerization initiator can function as a raw material molecule for a branched chain or star-shaped (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), and a preferred example 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'-dibromoxylenehexakis (α-chloro- 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.)_1-6Alkyl 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, such as rhenium, rhodium, iron, molybdenum, tungsten. , Titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, nickel and cobalt are suitable for use in the present embodiments 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.₂Is preferably halogen, 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 known to those skilled in the art, such catalytic components having an anionic ligand such as tetrafluoroborate are optionally anionic ligand R.₂The metal carbene component having a halogen is reacted with a metal compound having another anion capable of extracting and replacing a halogen atom, for example, silver tetrafluoroborate, thereby forming a cationic alkylidene chain. It may be prepared by exchanging the position. It was surprisingly discovered that such cationic alkylidene chains exhibit better catalytic activity than the corresponding metal carbene chains coordinated to halogen ligands.

In this feature of the invention, the amounts and relative ratios of the polymerization initiator and the transition metal carbene compound are effective 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 to 0.9. 1.1: 1.

The ATRP of the present invention may be carried out in the absence of a solvent, i.e. in chunks. However, if 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 may 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 noted that the selected halogenated hydrocarbons do not act as polymerization initiators under reaction conditions, but suitable halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane and fluorine atom / chlorine. Includes benzene substituted with 1 to 6 atoms.

ATRP may be carried out in the gas phase (eg, by passing a gaseous monomer through the catalytic bed) in a sealed container or autoclave. (Co) Polymerization may 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 may be carried out at a pressure of about 0.1 to 100 atm, preferably 1 to 10 atm.

According to another embodiment, ATRP is in an emulsion or suspension in a suspension medium for suspending the monomer, and the emulsion or suspension of the (co) polymer is formed. The method may be carried out using the metal carbene chain of the present invention in combination with a surfactant. The suspension medium is usually an inorganic liquid, preferably water. In this embodiment of the present 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 unnecessary or only 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 chain of the present invention, those skilled in the art will be able to make appropriate selections.

An important factor in the preparation of a stable emulsion of this embodiment is to stabilize the initial monomer suspension / emulsion and the growing polymer particles and to prevent unwanted aggregation / condensation of the particles. Is to use a surfactant. However, care must be taken to select a catalyst or a detergent that does not buffer the end of the chain if it is inert in order to carry out ATRP in the emulsion. 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 usually present in concentrations of about 0.01-50% by weight based on the total weight of all components introduced into the polymerization reactor, namely suspension mediums, monomers, surfactants and catalyst systems. ..

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 conversion order of the polymerization initiator and other reaction components may be arbitrary, but when the inhibitor is added to the reaction mixture before emulsification, a stable latex is usually obtained. Suitable polymerization initiators are as described above in the solvent embodiments in the ATRP step. 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 rather amphipathic, and may be incorporated into the polymer particles after initiation of the reaction, and by the hydrophilic segment of the macropolymerization initiator. The growing particles may be stabilized.

(Co) After the polymerization step is completed, the formed polymer is isolated by a known operation method, for example, precipitation in a suitable solvent, filtration of the precipitated polymer, and then washing and drying of the collected polymer. To do. Precipitation typically uses a suitable alkane or cycloalkane solvent such as pentane, hexane, heptane, cyclohexane or mineral oil, or a mixture of alcohols such as methanol, ethanol or isopropanol or a suitable solvent. It can be carried out. 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 drawing air through the (co) polymer in a 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 barriers or surface materials (eg polymethylmethacrylate). However, it is typically most suitable for special applications to have more uniform properties than polymers produced by conventional radical polymerization. For example, block copolymers of polystyrene (PSt) and polyacrylates (PA), such as 3-block copolymers of Pst-PA-PSt, are useful thermoplastic elastomers. Polymethylmethacrylate / acrylate 3-block copolymers (eg PMMA-PA-PMMA) are useful and fully acrylic thermoplastic elastomers, homopolymers and copolymers of styrene, (meth) acrylate and / or acrylonitrile. Are useful plastic elastomers and adhesives. Blocks or random copolymers of styrene and (meth) acrylate or acrylonitrile are useful thermoplastic elastomers with high solvent resistance. Furthermore, block copolymers in which blocks alternate between polar monomers and non-polar monomers produced according to the invention are useful for producing highly homogeneous polymer blends. Amphiphilic surfactant or dispersant. Star-shaped (co) polymers, such as styrene-butadiene star-shaped copolymers, are useful high-impact copolymers.

The (co) polymers produced by the catalytic process of the present invention typically have a number average molecular weight of about 1,000 to 1,000,000, preferably 5,000 to 250,000, and more preferably 10,000 to 200,000. The structure may include blocks, multi-blocks, stellate, gradient, random, hyperbranched chains, grafts, "comb-like" 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 process, it can actually be started and stopped at will. Furthermore, the polymer product has the functional groups X required to initiate further polymerization.₁Holds. That is, in one embodiment, once the first monomer is consumed in the initial polymerization step, the second monomer is then added and the growing polymer chain in the second polymerization step. A second block can be formed on top. A multi-block copolymer can be prepared by further polymerization with the same or different monomers. Furthermore, since ATRP is radical polymerization, these blocks can be prepared in essentially any order.

The (co) polymer produced by the catalytic process of the present invention has an extremely low polydispersity index, that is, its weight average molecular weight to number average molecular weight ratio Mw / Mn is typically about 1.1 to 1.9. , Preferably 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.₁They may be considered terminal-functional or intrachain-functional (co) polymers because they retain fragments of the polymerization initiators that contain. That is, such (co) polymers have other functionalities for further reactions, including cross-bonding, chain extension (eg to form long-chain polyamides, polyurethanes and / or polyesters), reactive injection molding, etc. Group-bearing (co) polymer 2 may be converted (eg, halogens can be converted to hydroxy or amino by known methods, and nitriles or carboxylic acid esters may be hydrolyzed to carboxylic acids by known methods). ..

The pentacoordinated metal chain of the present invention is useful in addition polymerization of one or more dienes having 4 to 20 carbon atoms and one or more α-olefins having 2 to 12 carbon atoms in some cases combined. More preferably, the catalytically active 5-coordinated metal chain for such a reaction is such that the polydentate ligand provides a 5-membered ring structure with the metal, such as a chain having the general formula (IB). .. Further, preferably, the chain is a catalyst system 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 in some cases. , The following elements: (A) a chain having the general formula (IB), (B) a compound capable of converting its imine moiety into a metal amine structure by reacting with compound (A), and (C) compound. It is used in the above catalytic system containing a compound having the ability to form an ion pair by reacting with (A).

Suitable Ingredients (B) for this purpose include organic aluminum compounds, especially 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 branch chain analogs; dialkylaluminum hydride, trialkenylaluminum, alkylaluminum alkoxide, dialkyl Aluminum alkoxides, dialkylaluminum aryloxides, dialkylaluminum halides) 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 (eg, ferrosenium, etc.). Decabolan) and salts thereof, metal carborane and heteropoly compounds such as phosphomolybdic acid, silicomolybdic acid, phosphomolybdovanadic acid and the like are included.

The above-mentioned catalyst system is a polymer clarified with high productivity when polymerizing α-olefins continuously or in a batch manner at a moderate temperature in the range of about 40 ° C to about 80 ° C under atmospheric pressure. Is efficient in obtaining.

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 later, it may be desirable to modify the catalyst to a dendrimer material in order to facilitate removal by ultrafiltration.

To facilitate the use of the pentacoordinated metal carben 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). It is a derivative of the compound, but R'and / or R'' is the following formula:

<chemistry num="6"><img file="JP2005515260A_D0006.tif" /></chemistry>

(In the formula, -R₂₀Is C_1-6Alkylene, arylene, heteroarylen and C_3-8A group selected from the group consisting of cycloalkylenes, which may be C._1-20Alkyl, C_2-20Alkenyl, C_2-20Alkyne, C_1-20Carboxylate, C_1-20Alkoxy, C_2-20Substituent R each independently selected from the group consisting of alkylthio, aryloxy and aryl₂₄Substituted by one or more;-D is oxygen, sulfur, silicon, arylene, methylene, CHR₂₄, C (R)₂₄)₂, NH, NR₂₄And PR₂₄A divalent atom or group selected from the group consisting of;-R₂₁, R₂₂And R₂₃Are independent of hydrogen, halogen 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_1-20With respect to the above derivatives which have been replaced or substituted with a group having (selected from the group consisting of alkylthio and aryloxy).

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 shaped organic siloxane co-condensation products such as those disclosed in EP-A-484,755.

In another embodiment, the invention is heterogeneous, comprising the product of a covalent bond between (a) a derivative as defined above and (b) a carrier containing one or more inorganic oxides or an organic polymer substance. With respect to supported catalysts for use in catalytic reactions. 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_3-10A polystyrene resin or derivative thereof substituted with one or more groups selected from cycloalkyl, aryl and heteroaryl. More detailed examples of suitable carriers are already mentioned 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. If a', R'' or R''' carries a functional group, the functional group should not be confused with the core molecule, which is present in the supported catalyst embodiments of the present invention. ), Which of the five-coordinated metal chains having any of the above-mentioned general formulas (IA), (IB), (IIA), and (IIB) and the general formulas (IIIA) and (IIIB), each of which is bound to). Provided is a dendrimer substance containing two or more compounds selected from a tetracoordinated metal chain having any of them.

The core molecule is not exact for this feature of the invention and is limited by its reactivity with the metal carbene compound of interest or with the spacer molecule if present in the dendrimer material. Only. For example, the core molecule has the following elements: -aryl, polyaryl, C_1-20Alkyl, cycloalkyl and heterocyclic cycloalkyl groups, and-Formula A (R)₂₀)_nX_3-n, But here R₂₀Is C_1-6Alkylene, arylene, heteroarylen and C_3-8A group selected from the group consisting of cycloalkylenes, which may be 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_1-20Substituent R each independently selected from the group consisting of alkylthio, aryloxy and aryl₂₄Substituted by one or more; A is a Group IIIA element (preferably boron or aluminum) or nitrogen in the Periodic Table, or formula G (R)₂₀)_nX_4-nHowever, G is an element of Group IVA (preferably carbon, silicon or tin), or the formula J (R).₂₀)_nX_5-n, Where J is a Group VA element other than nitrogen (ie preferably phosphorus, arsenic or antimony); or formula E (R)₂₀)_nX_2-n, Where E is a Group VIA element (preferably oxygen or sulfur); where X is hydrogen or halogen in the formula, and-IIB, IIIB, IVB, of the Periodic Table. Transitional metal compounds of any of the VB, VIB, VIIB and VIIIB metals, such as titanium tetrachloride, vanadium trichloride, zirconium tetrachloride, C._1-6It is selected from the group consisting of alkyl titanates, vanadates, zirconates and the like.

When the spacer molecule is used in the construction 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 may have, and here R₂₀, N and D are defined as described above for derivatives suitable for covalent attachment to the carrier.

The dendrimer substance of the present invention may be produced by reacting two or more kinds of 5- or 4-coordinated metal chains as described above with a core molecule (for example, those described above) using a method known in the art.

That is, the dendrimer material of the present invention may be used as a catalyst for transferring a first olefin to at least one second olefin, or to an oligomer or polymer of a linear olefin, and the catalyst is limited. It is suitable for removal from the reaction mixture by ultrafiltration. In one typical embodiment of the method, the heterodiaryl compound has one metal in the 5-coordination with one or more carben ligands, polydentate ligands and one or more other ligands. The other metal is contacted with two or more metal chains that are tetracoordinated to one or more neutral ligands and one or more anionic ligands. Surprisingly, this method not only results in a closed ring transition to the dihydropyrrole compound (dihydrofuran or dihydrothiophene compound, respectively, depending on the heterodiallyl compound of origin), but also 1-hetero-2 by isomerization and dehydration of the latter It results in a 4-cyclopentadiene compound. The two metal chains that may be used are, for example, as shown in the general formulas (IVA) and (IVB) of FIG. 3, where M, Z, R, R', R'', R''', R₃And 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 R₂As mentioned above, and L is R₁₆Is a natural electron donor as defined above.

The 1-hetero-2,4-cyclopentadiene compound which may be produced in one step of the present invention is selected from the group consisting of pyrrole, furan, thiophene and derivatives. When the heteroatom is nitrogen, the presence of substituents on it does not prevent unpredictable reactions from occurring. In particular, certain new pyrrole derivatives, such as dialkyl 1H-pyrrole-1-ylmethylphosphonates in which the alkyl group has 1 to 4 carbon atoms, are new in such a manner in which the alkyl group has 1 to 4 carbon atoms. It may be prepared from dialkyldialylaminomethylphosphonate as described in Examples below.

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

The present invention will be further described by 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.

First, a general procedure for preparing a ruthenium compound having the general formula (IA) of the present invention with y = 2 will be described with reference to FIG. First, the Schiff base ligand having the formula (I) which should not be confused with the above formulas (IA) and (IB) is described by the following formula: R'''C (OH) = C (R'') CHO. The aldehyde having, preferably salicylaldehyde, is represented by the formula H.₂It is prepared and purified using methods known in the art by condensing 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 chain having a formula (II) that should not be confused with the above formulas (IIA) and (IIB) is a metal alkoxide, preferably a thallium ethoxydo, in the formula (I). Prepared and purified using methods known in the art by adding to the organic solution of the ligand and then filtering the resulting solid under an inert atmosphere to quantitatively obtain the relevant thallium salt. To do. Next, add an organic solution of the salt at room temperature [RuCl.₂(p-cumene)]₂Was reacted with the organic solution of. After filtering the thallium chloride by-product and evaporating the solvent, the residue was crystallized, washed and dried to give a Schiff base ruthenium chain of formula (II) having the appearance of a reddish brown solid.

Prior to performing the third step, t-butoxylization having formula (III), where "mes" is an abbreviation for 2,4,6-trimethylphenyl and should not be confused with formulas (IIA) and (IIB) above. The 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 inert. Prepared by filtering the potassium tetrafluoroborate by-product in an atmosphere. A mixture of an organic solution of the strand 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 chain of formula (IV) as a brown microcrystalline solid. For a pure Schiff base-substituted arenilidene chain having formula (V), an organic solution of the chain 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 vacuumed. It is obtained as a dark brown microcrystalline solid in four steps by evaporating down and then recrystallizing the remaining solid residue.

According to another synthetic route, the Schiff base-substituted indenylidene chain having formula (VI) adds an organic solution of ruthenium chain having formula (II) to an organic solution of diphenylpropargyl alcohol, and the mixture is stirred at room temperature for 17 hours. Then, the solvent is vaporized under vacuum, and then the remaining solid residue is recrystallized to obtain a reddish-brown microcrystalline solid. Next, the Schiff base-substituted ruthenium chain 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 chain having the formula (VI). , And 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.

Second, a general procedure for preparing 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, dichlorodicyclohexylphosphinidene ruthenium chain is added to the solvent [RuCl.₂(p-cumene)]₂Is prepared by reacting with both dicyclohexylphosphine and substituted acetylene at 70 ° C. Next, the obtained dark brown microcrystalline solid solution is reacted with the Schiff base thallium salt prepared above.

Although the various synthetic pathways shown in Attached Figures 1 and 2 have been described herein for ruthenium chains, those skilled in the art have described other transition metals such as osmium, iron, molybdenum, tungsten, titanium, rhenium, copper and chromium. Corresponding chains of manganese, rhodium, vanadium, zinc, gold, silver, nickel and cobalt also make use of the above description, and [RuCl.₂(p-cumene)]₂It is possible to produce each metal chain corresponding to the above and its analogs as raw materials.

<u style="single">Example 1-Preparation of Schiff base ligands of equations (Ia) to (If)</u> Schiff base ligands having formulas (Ia) to (If), in which R and R'have the meanings shown at the lower end of the attached figure and Me is methyl and iPr is isopropyl, were prepared and purified as follows. Condensation of salicylaldehyde with a primary aliphatic amine (ie, R'is an aliphatic or alicyclic group) was carried out by stirring in tetrahydrofuran (hereinafter referred to as THF) at a reflux temperature for 2 hours. 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)-(If) in 95% and 93% yields, respectively. Obtained. Condensation of salicylaldehyde with aromatic primary amine was also performed by stirring in ethanol at 80 ° C for 2 hours. A yellow solid precipitated from the reaction mixture by cooling to 0 ° C. The solid was filtered, washed with cold ethanol and then dried under vacuum to give the desired salicylaldimine ligand of formulas (Ia)-(If) in 90% -93% yield. These ligands can be stored for several months in a desiccator without causing physicochemical changes.

Compounds (Ia ~ d) are proton nuclear magnetic resonance (hereinafter referred to as NMR) spectral analysis (CDCl at 25 ° C).₃Characterized by (mid-implementation) and infrared spectrum analysis (IR), the results of these analyzes are as follows.

<tables num="1"><img file="JP2005515260A_D0007.tif" /></tables>

<u style="single">Example 2-Preparation of Schiff base-substituted ruthenium chains of formulas (II.a) to (II.f)</u> Schiff base-substituted ruthenium chains having formulas (II.a) to (II.f) shown in the attached figure were 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 addition, a pale yellow solid formed and the reaction mixture was stirred at 20 ° C. for 2 hours. Filtration of the solid under an argon atmosphere gave the corresponding salicylaldimintalium salt in quantitative yield, which was used immediately in the next step without further purification.

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 (3x10 ml) and dried to obtain Schiff base ruthenium chains of formulas (II.a) to (II.f) as reddish brown solids.

<u style="single">Example 3-Preparation of Schiff base-substituted ruthenium chains of formulas (IV.a) to (IV.f)</u> 1 equivalent of a solution of potassium t-butoxide in THF (5 ml) to a solution of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazolium tetrafluoroborate in THF (10 ml) After addition, the reaction mixture was stirred at room temperature (20 ° C) for 5 minutes, then the potassium tetrafluoroborate by-product was filtered off in an inert atmosphere to quantify the t-butoxylation compound of formula (III). Formed in yield. After evaporating the solvent, compound (III) was dissolved in toluene (10 ml) and used immediately in the next step without further purification. Add 1 equivalent of a suitable Schiff base-substituted ruthenium chain solution having one of formulas (II.a)-(II.f) prepared according to Example 2 in toluene (10 ml), followed by vigorous stirring. The reaction mixture was heated to 70-80 ° C for 1 hour. After evaporation of the solvent, the solid residue was washed with hexane (3x10 ml) and recrystallized from the toluene / pentane mixture at 0 ° C. It was then dried under vacuum to form pure Schiff base-substituted ruthenium chains of formula (IV.a)-(IV.f) as brown polycrystalline solids in yields ranging from 90% to 95%.

<u style="single">Example 4-Preparation of Schiff base-substituted ruthenium chains of formulas (Va) to (Vf)</u> Schiff base substitutions having formulas (Va) to (Vf) A suitable Schiff base substitution having one of formulas (IV.a) to (IV.f) prepared according to Example 3 in toluene (15 ml). A solution of the ruthenium chain was added to 1.2 eq of a 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 and washed with hexane (3x10 ml) to give the desired dark brown polycrystalline solid in yields in the range 80-90%. Compound was obtained.

<u style="single">Example 5-Preparation of Schiff base-substituted ruthenium chains of formulas (VI.a)-(VI.f)</u> The Schiff base-substituted indenylidene compounds of formulas (VI.a)-(VI.f) are suitable having one of formulas (II.a)-(II.f) prepared according to Example 2 in toluene (15 ml). A solution of Schiff base-substituted ruthenium chains was added to 1.2 eq of a 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. Evaporate toluene under vacuum and recrystallize the remaining solid residue from the dichloromethane / hexane mixture and wash with hexane (3x10 ml) to obtain the desired compound as a reddish-brown microcrystalline solid in yields greater than 70%. Obtained.

<u style="single">Example 6-Preparation of Schiff base-substituted ruthenium chains of formulas (VII.a) to (VII.f)</u> Example 3 in toluene (10 ml) in a solution of a suitable Schiff base-substituted ruthenium chain having one of formulas (VI.a)-(VI.f) prepared according to Example 5 in toluene (10 ml). One equivalent of a solution of the t-butoxylation compound having formula (III) prepared as described above was added. 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 (3x10 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.

<u style="single">Example 7-Ring-opening transition polymerization</u> Ring-opening transfer polymerization of various cyclic olefins was carried out in 1 ml of toluene as a solvent, and 0.005 mol of a 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 the olefin monomers, the molar ratio of olefins / catalysts, the polymerization temperature T (in ° C) and the polymerization time t (in minutes), and further shows the polymerization yield at time t. Shown.

<tables num="2"><img file="JP2005515260A_D0008.tif" /></tables>

<u style="single">Example 8-Ring closure rearrangement reaction</u> The ring-closure transition reaction of various diene was 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. --Schiff base-substituted arenilidene compound 0.005 mmol having the formula (Va) prepared in Example 4 as a catalyst, and-diene / catalyst molar ratio 100. Name of diene used in Table 2 below, reaction temperature T (°) (C display), reaction time t (minute display), reaction yield (% display) at time t, and the name of the obtained product are also shown.

<tables num="3"><img file="JP2005515260A_D0009.tif" /></tables>

<u style="single">Example 9-Atomic Transfer Radical Polymerization</u> Atomic transfer radical polymerization of various olefins was carried out in 1 ml of toluene for 8 hours at the temperatures shown below (indicated by ° C) using: --As a catalyst, Schiff base-substituted acrylonitrile having the formula (Va) prepared in Example 4 0.0116 mol of strands at room temperature, -As a polymerization initiator, ethyl-2-methyl-2-bromopyropionate (monomer) Is methacrylate), methyl-2-bromopropionate (when the monomer is acrylate), 1-bromocyanoethane (when the monomer is acrylonitrile) or (1-bromoethyl) benzene (when the monomer is acrylate) (For styrene),-[Catalyst] / [Initiator] / [Polymer] molar ratio 1: 2: 800. Table 3 below shows the name of the olefin used, the polymerization temperature and the polymerization yield (% display). ) Is shown.

<tables num="4"><img file="JP2005515260A_D0010.tif" /></tables>

<u style="single">Example 10-Atomic Transfer Radical Polymerization</u> Schiff-based substituted arenilidene having formula (Va) prepared in Example 4 pretreated with 1 equivalent of silver tetrafluoroborate as a catalyst in water using atomic transfer radical polymerization of various olefins as a solvent. 0.0116 mol of compound (more specifically, the above amount of compound (Va) in 1 ml of toluene and 0.2 M of AgBF in toluene.₄Add to 56 μl of solution and then stir for 20 minutes until AgCl turbidity is observed, which results in a cationic ruthenium chain in which the chloride ligand has been extracted and replaced with toluene), and-. The following table, using the same polymerization initiators already described in Example 9 and- [catalyst] / [polymerization initiator] / [monomer] molar ratio 1: 2: 800. It was carried out at the temperature shown in the above for 8 hours. 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%).

<tables num="5"><img file="JP2005515260A_D0011.tif" /></tables>

<u style="single">Example 11-Atomic transition radical (co) polymerization of vinyl monomer</u> Atomic transfer radical polymerization and copolymerization of various vinyl monomers were carried out using: --A polymerization initiator similar to that used in Example 9, and-as a catalyst, previously disclosed as an olefin transfer catalyst by Organometallics (1998) 17: 3460, such as Chang et al.

<chemistry num="7"><img file="JP2005515260A_D0012.tif" /></chemistry>

(In the formula, Cy indicates cyclohexyl, Ph indicates phenyl, Me indicates methyl, iPr indicates isopropyl), and ruthenium carbene chains (Aa) to (Af).

A typical procedure for this purpose is as follows, i.e., 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 (evacuated by 3 vacuum-nitrogen cycles) capped with a 3-way stopcock containing a magnetic stir bar. Next, the molar ratio of [catalyst] / [polymerization initiator] / [monomer] was adjusted to 1/2/800 by adding a monomer and a polymerization initiator. All liquids were handled using 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 methanol (for styrene) with vigorous stirring. The precipitated polymer was then filtered and dried under vacuum overnight.

Table 5 below shows the polymerization yields of the monomers and catalytic ruthenium chains used as a function.

<tables num="6"><img file="JP2005515260A_D0013.tif" /></tables>

Table 6 shows homopolymers formed from methyl acrylate (Fig. 1), styrene (Fig. 2) or methyl methacrylate (Fig. 3) using ruthenium carbene chains (Ac) to (Af), respectively. Weight average molecular weight Mw, number average molecular weight Mn and polydispersity index (PDI) are shown.

<tables num="7"><img file="JP2005515260A_D0014.tif" /></tables>

<u style="single">Example 12-Atomic transition radical (co) polymerization of vinyl monomer in the presence of cationic ruthenium chain</u> Atomic transfer radical polymerization and copolymerization of various vinyl monomers were carried out in solvent S using: --The same polymerization initiator and catalyst used in Example 9, Tos is an abbreviation for tosylate (p-toluenesulfonate) and Tf is an abbreviation for triflate (trifluoromethanesulfonate), which will be described later. Cationic ruthenium carbene chains obtained according to the scheme shown in FIG. 11 by treating the ruthenium carbene complex of Example 11 having the appropriate formulas (Aa)-(Af) with salts in the presence of solvent S according to the scheme. (Ba) ~ (Bf).

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 1 by dissolving the monomer, polymerization initiator and catalyst in a small amount of toluene and then in distilled water in an organic solution. It was set to /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.

Chloride from chains (Aa) to (Af) using three different salts (silver tetrafluoroborate, silver p-toluenesulfonate and trimethylsilyl triflate) to investigate the effect of counterions on catalytic activity. Was extracted.

Table 7 below shows the functions of the monomer, solvent and methyl acrylate (Fig. 1), styrene (Fig. 2) or methyl methacrylate (Fig. 3), respectively, of the cationic catalytic ruthenium chain used. The polymerization yield as is shown.

<tables num="8"><img file="JP2005515260A_D0015.tif" /></tables>

Table 8 below shows a homopolymer formed from methyl acrylate (Fig. 1), styrene (Fig. 2) or methyl methacrylate (Fig. 3) using a cationic ruthenium carbene chain (Bb). Weight average molecular weight Mw, number average molecular weight Mn and polydispersity index (PDI) are shown.

<tables num="9"><img file="JP2005515260A_D0016.tif" /></tables>

<u style="single">Example 13-Atomic transition radical addition of vinyl olefin</u> 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 to the graduates of vinyl monomer (9 mmol) and carbon tetrachloride (13 mmol) in toluene (3 ml) through septum. The reaction mixture was then heated to 65 ° C for 17 hours. Table 9 below shows the names of the vinyl monomers tested and the yields (%) of the resulting chlorinated saturated addition products.

<tables num="10"><img file="JP2005515260A_D0017.tif" /></tables>

<u style="single">Example 14-Preparation of dichlorologi (tricyclohexylphosphine) vinylidene ruthenium chain</u> [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 pumping the volatiles. The dark brown microcrystalline solid precipitated by adding 10 ml of acetone and cooling to 78 ° C. was filtered and dried under vacuum. The solid obtained in 85% yield was proton NMR spectral analysis (CDCl).₃(Implemented at 30 ° C above) by Cl₂Ru {= C = CHC₆H₅} (PCy₃)₂Was characterized and the following data were obtained.

<tables num="11"><img file="JP2005515260A_D0018.tif" /></tables>

Cl using the same operation method₂Ru {= 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 chain obtained in 69% yield was obtained by proton NMR spectrum analysis (CDCl).₃Characterized by (conducted at 30 ° C above), the following data were obtained.

<tables num="12"><img file="JP2005515260A_D0019.tif" /></tables>

<u style="single">Example 15-Preparation of Schiff Base Vinylidene Ruthenium Chains</u> THF (10 ml) of the satityl aldimint thallium salt obtained at the end of the first step of Example 2 in a solution of the dichlorodicyclohexylphosphine vinylidene ruthenium chain (3 mmol) obtained in Example 14 in THF (5 ml). The solution in was added. The reaction mixture was stirred for 4 hours at 20 ° C. 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 chain having formula (IC).

Four different strands were produced by this method. The strand identified as 4a in FIG. 2, ie R is hydrogen and R₃The phenyl is recovered as a brown solid with a yield of 81%, and proton NMR spectrum analysis (C)₆D₆Characterized by (conducted at 25 ° C above), the following data were obtained.

<tables num="13"><img file="JP2005515260A_D0020.tif" /></tables>

The strand identified as 4b in Figure 2, ie R is nitro and R₃The phenyl is recovered as a dark brown solid with a yield of 80%, and proton NMR spectrum analysis (C)₆D₆Characterized by (conducted at 25 ° C above), the following data were obtained.

<tables num="14"><img file="JP2005515260A_D0021.tif" /></tables>

The strand identified as 5a in FIG. 2, ie R is hydrogen and R₃Is t-butyl, recovered as a dark brown solid with a yield of 78%, and proton NMR spectrum analysis (C).₆D₆Characterized by (conducted at 25 ° C above), the following data were obtained.

<tables num="15"><img file="JP2005515260A_D0022.tif" /></tables>

The strand identified as 5b in Figure 2, ie R is nitro and R₃Is t-butyl, recovered as a brown solid in 70% yield, and proton NMR spectrum analysis (C).₆D₆Characterized by (conducted at 25 ° C above), the following data were obtained.

<tables num="16"><img file="JP2005515260A_D0023.tif" /></tables>

<u style="single">Example 16-Ring-opening transition polymerization of cyclic olefin</u> Ring-opening transfer polymerization of cyclic olefins identified by formulas 6 to 17 and reference numbers of the schemes described below was carried out according to the following procedure.

<chemistry num="8"><img file="JP2005515260A_D0024.tif" /></chemistry>

CH monomer 6, ie norbornene (7.5 mmol)₂Cl₂Dissolve in (2.0 ml) and CH in container₂Cl₂It was added to and mixed with a solution of PVC postponed vinylidene ruthenium chain (7.5 μmol) prepared according to Example 15 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, which became extremely viscous and could no longer be agitated, was transferred to a beaker as an antioxidant 2,6-di-t-butyl-4-methylphenol (0.4 mmol)) and as a polymerization inhibitor. CH containing ethyl vinyl ether (4 mmol)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 obtained viscous polymer of the tooth feces h group was filtered, washed with methanol, and dried under vacuum.

For the other cyclic olefins, the experimental method was the same, but the amount of monomer used was changed to 6 mmol (monomer 7-16) or 1.87 mmol (monomer 17).

In Table 10 below, the experimental numbers (first column) are followed by the Schiff base vinylidene ruthenium chain used as a catalyst (using the same identification number as in Example 15), and the monomer reference numbers 6 to 17 (parentheses). The molar ratio of monomer / catalyst follows), polymerization temperature, time and yield, both measured by gel permeation chromatography using polystyrene standard material, number average molecular weight Mn and polydisperse Mw / Indicates Mn.

<tables num="17"><img file="JP2005515260A_D0025.tif" /></tables>

<tables num="18"><img file="JP2005515260A_D0026.tif" /></tables>

<tables num="19"><img file="JP2005515260A_D0027.tif" /></tables>

<u style="single">Example 17-Ring closure rearrangement reaction</u> Ring closure reactions of various diene were carried out according to the following procedure. In a 10 ml Schlenck test tube, 0.095 mmol of diene, 13.2 μl (0.095 mmol) of mesitylene and 50 μl of the Schiff base vinylidene ruthenium chain prepared according to Example 15 were added to 1 ml of deuterated benzene and at 70 or 85 ° C. Heated with stirring (as described 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 incorporation of allylic protons¹Measure by 1 H-NMR. The formation of cyclic isomers, oligomers or telomeres was distinguished by GC-MS analysis of the reaction mixture. Reactive organisms were 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).

Table 11 below sequentially shows, for each experiment, the reaction temperature T (° C, first column) followed by the structure of the diene used, the structure of the product obtained, the reaction time (in terms of time) and the reaction yield. The rate is shown for each of the Schiff base vinylidene ruthenium chains used as a catalyst (using the same identification numbers as in Example 15).

<tables num="20"><img file="JP2005515260A_D0028.tif" /></tables>

<u style="single">Example 18-Schiff base-containing ruthenium chain in mesoporous crystalline molecular sieve</u><u style="single">Preparation of catalysts moored by the body</u> All reactions and operations were performed in an argon atmosphere using the conventional Schlenck test tube method. Argon gas is P₂O₅Dryed through (Aldrich, 97%).¹The H-NMR spectrum (500 MHz) was recorded on a Brooker AM spectroanalyzer. Chemical shifts were expressed in ppm and TMS was used as a control compound. For solid phase NMR spectra, use the Bruker DSX-300 spectrophotometer.¹300.18MHz for 1 H-NMR,¹³75.49MHz for C-NMR,³¹121.51MHz and for P-NMR²⁹In 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 with spin frequencies up to 12 KHz. Uniform catalyst mooring 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 Sequential XRF spectrophotometer. The XRD spectrum was recorded with a Siemens diffractometer D5000. Elemental analysis was performed on the Carlo Erba EA1110 instrument. BET analysis was performed on a Gemini micrometric 2360 surface area analyzer with a Flow prep060 deaerator. The sample was dried at 423 ° K overnight, cooled to room temperature and then adsorbed. Special attention was required with the functionalized material due to the possibility of air oxidation, so the transfer to the balance and deaeration of the system were rapid. The nitrogen isotherm curve was recorded at 77 ° C. The specific surface area was determined from the straight part of the BET plot.

After carbonization, mesoporous crystalline molecular sieve MCM-41 was characterized by XRD, N2 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.

Two pathways shown in FIG. 7 were tested for the synthesis of solid support catalysts 5 and 11, respectively.

In the first embodiment, the Schiff base ruthenium chain 10 shown in FIG. 7 was prepared by route 2 and characterized as follows. That is, 2 mmol of salicylaldehyde 1 was dissolved in 15 ml of THF. With stirring, 2 mmol of 4-bromo-2,6-dimethylaniline 6 was added and the reaction mixture was stirred at reflux temperature for 2 hours. The resulting salicylaldimin product precipitated when cooled to 0 ° C, forming a solid yellow product. The solid was filtered, washed and dried under vacuum to give the desired salicylargimine ligand 7 in excellent yield (95%). A solution of 2 mmol of thallium ethoxydo in THF (5 ml) was added dropwise to a solution of Schiff base ligand 7 (2 mmol) in 15 ml of THF. 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) was added dropwise 2 mmol of bromopropyltrimethoxysilane, then the mixture was stirred at room temperature for 3 hours, quantitatively converted to salt 8 and at room temperature. Stirring for 6 hours gave a spacer-modified Schiff base ligand 9 as a green-yellow solid.

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 strands were then washed with cold benzene (10 ml 3 times) and the filtrate was evaporated. The Schiff base-modified chain 10 obtained as a green-brown solid by recrystallizing the solid residue from pentane (-70 ° C) was characterized as follows.

<tables num="21"><img file="JP2005515260A_D0029.tif" /></tables>

--Elemental analysis value: RuC₄₉H₇₃PO₄Calculated values for NClSi (935.61): C63.90, H7.86, N1.50; Measured values: C62.97, H7.73, N1.53.

Next, 2 mmol of Schiff base-modified chain 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.

After refluxing in THF for 24 hours, the heterogeneous catalyst 11 was filtered under a nitrogen atmosphere and washed thoroughly 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.

In the second embodiment, Schiff base-modified strand 4 was produced by route 1 shown in FIG. 7 and characterized as follows.

<tables num="22"><img file="JP2005515260A_D0030.tif" /></tables>

--Elemental analysis value: RuC₄₁H₆₅PO₄Calculated values for NClSi (831.46): C59.22, H7.88, N1.68; Measured values: C58.71, H8.54, N1.60.

Next, the heterogeneous catalyst 5 was prepared from the Schiff base-modified chain 4 in the same manner as in the case of the catalyst 11.

Both heterogeneous catalysts 5 and 11 were then further characterized and their structures compared to the raw material MCM-41 material by X-ray diffraction, nitrogen adsorption analysis, Raman spectroscopy, X-ray fluorescence and solid state NMR analysis. The results are shown below.

The XRD measurement results confirmed that the synthesized mesoporous support had an MCM-41 structure. The calcined MCM-41 showed extremely strong peaks at 3.733 nm (100) d-spacing, and also showed three weak peaks at 2.544 nm (110), 2.010 nm (200) and 1.240 nm (210). .. These four peaks are a₀= 4.310nm (a₀= 2d₁₀₀/ 3) Fits hexagonal unit cells. For heterogeneous catalyst 5, d100 spacing and a₀Will be 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 similar to that of Pristine MCM-41, it was confirmed that the structure of the long-range order of the support is preserved.

The data obtained from N2 adsorption measurement and XRD analysis are summarized below.

<tables num="23"><img file="JP2005515260A_D0031.tif" /></tables>

^aBET surface area (BET surface area = Brunauer-Emmett-Teller surface area) obtained from the desorption branch of the N2 adsorption isotherm curve.^bPore capacity obtained from the Barrett-Joyner-Halenda equation.^cThe mesoporous diameter was obtained from the PSD curve (PSD curve = pore size distribution curve).^dWall pressure = a0-APD (APD = average pore size).

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 catalytic chains and that the mesoporous pores are maintained for ease of contact and structure after modification.

Raman spectroscopy was performed to confirm the formation of covalent bonds between the Tris (alkoxy) silyl functionalized homogeneous chains (4 and 10 respectively) and the MCM-41 surface. Only the mooring step of giving the heterogeneous catalyst 5 is discussed here. 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. A comparison of the Raman spectra of MCM-41 and heterogeneous catalyst 5 (Figure D below) reveals uniform species 4 grafting. By comparing the Raman spectra of the spacer-modified homogeneous catalyst 4 (Fig. C below) and the catalyst 5, any question regarding the chemical bonding of the homogeneous catalyst is 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 mooring.

<tables num="24"><img file="JP2005515260A_D0032.tif" /></tables>

Figure: 0.1069 mmol Ru chain / according to Raman spectrum XRF measurements of MCM-41 (A), MCM-41 + spacer (B), spacer modified homogeneous catalyst 4 (C) and heterogeneous catalyst system 5 (D). The loading of g heterogeneous catalyst 5 and 0.054 mmol Ru chain / g heterogeneous catalyst 11 is revealed.

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 SiC PMAS NMR, three peaks of 90ppm, 100ppm and 110ppm were observed. Each of these values is Si (OH)₂(OSi)₂, Si (OH) (OSi)₃And Si (OSi)₄Can be attributed to. The proton spectra of MCM-41 + aminopropyltriethoxysilane and MCM-41 + bromopropyltriethoxysilane are -CH₂And -CH₃It only reveals the existence of the group. Small signals near 0 ppm are the spacer molecule SiCH₂Can be attributed to. However, of these samples¹³The C CP MAS NMR spectrum reveals some interesting features. For MCM-41 + aminopropyltriethoxysilane, the two peaks at 50ppm and 70ppm are -OCH, respectively.₂-And-CH₂It can be attributed to the N- configuration. For MCM-41 + blotting also propyltriethoxysilane, 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. For MCM-41 + aminopropyltriethoxysilane,²⁹Si CP MAS NMR spectrum is (SiO) at -58.34 ppm₃Si^*(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.

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 chains 5 and 11, respectively. Again, the spectrum reveals aromatic and aliphatic carbon atoms. At around 5.24ppm and 4.91ppm, -CH of catalysts 5 and 11₃And-SiCH₂-Peak overlap is observed. Heterogeneous catalyst²⁹The Si CP MAS NMR spectrum is also (SiO)₃Si^*C-, (SiO)₂(OEt) Si^*C- and (SiO)₂(OH) Si^*It reveals the existence of C-species. Heterogeneous catalyst³¹P 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 mooring of the homogeneous catalyst with the spacer molecule on MCM-41 is caused by two or three covalent bonds.

<u style="single">Example 19-Ring-opening transition polymerization with a heterogeneous catalyst</u> Ring-opening transfer polymerization of various olefins in the solvent was performed using both heterogeneous catalysts 5 and 11 of Example 18. Purchased 100 million Ichikuro and norbornene derivatives from Aldrich and CaH under nitrogen₂Used after distilling from. A commercial grade solvent was dried, deoxidized on a suitable desiccant under a nitrogen atmosphere for 24 hours, distilled and then used. 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 and norbornene). Derivative is 800 equivalents). 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. CHCl polymer₃The catalyst was filtered by dissolving in. CHCl until the next 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 dried on filter paper overnight under vacuum. Gel permeation chromatography (CHCl) with polystyrene standard for number and weight average molecular weight (Mn and Mw) and polydispersity (Mw / Mn) of polymers₃, 25 ° C). The GPC equipment used was Waters' Maxima 820 system with a PL gel column. DSC measurements were performed with the TA instrument DSC-TGA (SDT2960) using a thermomechanical analyzer (TMA2940). The yield [%] of the formed polymer is shown in Table 12 below.

<tables num="25"><img file="JP2005515260A_D0033.tif" /></tables>

Furthermore, the data summarized in Table 13 clearly show that the solvent used determines the properties of the resulting polymer. This is irrelevant to the catalyst used, as it indicates that the lower the polydispersity and the higher the efficiency of the polymerization initiator, the more controlled the polymerization proceeds by using dichloromethane instead of toluene.

<tables num="26"><img file="JP2005515260A_D0034.tif" /></tables>

<u style="single">Example 20-Ring-closure transition polymerization in the presence of heterogeneous catalyst</u> The reaction was carried out on a bench top 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 the peak of allylic methylene is integrated via integration.¹It was confirmed in the reproducibility test by 1 H-NMR spectrum analysis (the solvent was benzene deuterated and the internal standard was 1,3,5-mesitylene). GC analysis of the reaction mixture also distinguished the formation of cycloisomers, oligomers or telomeres.

Table 14 summarizes the results obtained using some representative substrates, and here we examined the effects of reaction temperature and reaction time on the activities of catalysts 5 and 11 of Example 18. 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, but for conversion of tri and tetra-substituted malonate derivatives, More extreme conditions are needed. It is also clear that the reaction temperature is a decisive factor in achieving good catalytic performance. The important point is that the post-treatment of the ring closure reaction product simply consists of filtration of the catalyst and evaporation of the solvent under vacuum.

<tables num="27"><img file="JP2005515260A_D0035.tif" /></tables>

<u style="single">Example 21-Atomic transfer radical polymerization in the presence of heterogeneous catalyst</u> 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 is degassed by a glass tube capped with a 3-way stopcock containing a magnetic stir bar (3 vacuum-nitrogen cycles). I put it in (put). Next, styrene (as a monomer) and 1-bromomethylbenzene (as a polymerization initiator) are added so that the molar ratio [catalyst] / [polymerization initiator] / [monomer] is 1: 2: 800. did. All liquids were handled under argon using a dry syringe. 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. CHCl until the next 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 polydispersity index (Mw / Mn) was 1.62.

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 traced as a function of time, and the dependence of the molecular weight and the polydispersity on the conversion of the monomer is 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 polydispersity during polymerization (reaching a value of 1.62 at 73% conversion) indicates that the radicals have a long lifetime. Furthermore, 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 concluded that the polymerization proceeded in a controlled manner, which enabled the synthesis of polystyrene having a predetermined molecular weight and narrow polydispersity.

<u style="single">Example 22-Kharash addition in the presence of heterogeneous catalyst</u> All reagents and solvents were dried, distilled and stored under nitrogen at -20 ° C by conventional methods. The reaction was carried out on a benchtop 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 5 below.

<tables num="28"><img file="JP2005515260A_D0036.tif" /></tables>

<u style="single">Example 23-Vinylation reaction in the presence of heterogeneous catalyst</u> 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 5 or 110.04 mmol of catalyst of Example 18 in 15 ml volumes containing 3 ml of toluene. Transferred to a glass container. The reaction mixture was then heated at 100 ° C. for 4 hours in an inert atmosphere. Total yield is V 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 monomer. GC / MS measurements differentiated the formation of products other than those reported below.

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 (E) -alkane-1-enyl ester, low proportions of (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.

<tables num="29"><img file="JP2005515260A_D0037.tif" /></tables>

<u style="single">Example 24-Preparation of Schiff base-modified homodimetal ruthenium chain</u> This synthesis proceeded according to the scheme shown in FIG. A Schiff base-substituted ruthenium chain 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 in THF (10 ml) of the appropriate Schiff base of formula (2.af) prepared according to Example 1 at room temperature. .. Immediately after the addition was complete, a pale yellow solid formed and the reaction mixture was stirred at 20 ° C. for 2 hours. The solid was filtered under an argon atmosphere and the corresponding salicyl aldimintalium salt obtained in quantitative yield was immediately used in the next step without further purification.

In the second step, the solution of the salicyl 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 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 off. After evaporation of the solvent, the residue was recrystallized from pentane (-70 ° C) to give the corresponding Schiff base substituted ruthenium chain (2.af) as a brown solid in good yield.

Next, the formula [RuCl] was added to a 1 mmol benzene solution (25 ml) of Schiff base-substituted ruthenium chain (2.af).₂(p-cumene)]₂A benzene solution (25 ml) of a dimer chain (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. This solid was filtered under an inert atmosphere to isolate it, washed with benzene (30 ml 3 times) and [(p-cumene) RuCl.₂P (cyclohexyl)₃] By-products and unreacted raw materials, if any, were removed. After removing residual chlorobenzene by recrystallization from the chlorobenzene / pentane mixture and further washing with 10 ml (twice) of pentane, the product was dried under vacuum and replaced with two metal Schiff bases in the yields shown below. A ruthenium chain 3.af was obtained. The strands were further characterized by nuclear magnetic resonance (NMR) and infrared spectral analysis (IR), and the analysis results were as follows.

2 Metal Ruthenium Chain 3.a: 0.419g (63%) as an orange-green powder.

<tables num="30"><img file="JP2005515260A_D0038.tif" /></tables>

Elemental analysis value (%): Ru₂C₂₅H₂₈ONCl₃Calculated values at (666.96): C45.02, H4.23, N2.10; Measured values: C45.10, H4.25, N2.11.

2 Metal Ruthenium Chain 3.b: 0.476g (67%) as orange-green powder.

<tables num="31"><img file="JP2005515260A_D0039.tif" /></tables>

Elemental analysis value (%): Ru₂C₂₅H₂₇O₃N₂Cl₃Calculated values at (711.94): C42.17, H3.82, N3.93; Measured values: C42.24, H3.84, N3.91.

2 Metal Ruthenium Chain 3.c: 0.511g (61%) as orange powder.

<tables num="32"><img file="JP2005515260A_D0040.tif" /></tables>

Elemental analysis value (%): Ru₂C₃₂H₃₃ONCl₃Br (835.97) calculated values: C45.97, H3.98, N1.68; measured values: C46.03, H4.01, N1.65.

2 Metal Ruthenium Chain 3.d: 0.602g (68%) as dark orange powder.

<tables num="33"><img file="JP2005515260A_D0041.tif" /></tables>

Elemental analysis value (%): Ru₂C₃₂H₃₂O₃N₂Cl₃Br (880.95) calculated values: C43.63, H3.66, N3.18; measured values: C43.71, H3.70, N3.17.

2 Metal Ruthenium Chain 3.e: 0.597g (73%) as a yellow-green powder.

<tables num="34"><img file="JP2005515260A_D0042.tif" /></tables>

Elemental analysis value (%): Ru₂C₃₆H₄₂ONCl₃Calculated values in (813.18): C53.17, H5.21, N1.72; Measured values: C53.23, H5.24, N1.74.

2 Metal Ruthenium Chain 3.f: 0.587g (68%) as orange powder.

<tables num="35"><img file="JP2005515260A_D0043.tif" /></tables>

Elemental analysis value (%): Ru₂C₃₆H₄₁O₃N₂Cl₃Calculated values in (858.16): C50.38, H4.82, N3.26; Measured values: C50.44, H4.85, N3.25.

<u style="single">Example 25-Preparation of diethyldiallylaminomethylphosphonate</u> 0.60 g (2.9 mmol) of diethylallylaminoethylphosphonate was dissolved in 50 ml of dry diethyl ether, and 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. 50 ml of water was added to the mixture and then 250 ml of CH2Cl was added 3 times. Combine organic layers and DEV₄Dry on top. DDL₄The resulting product was further purified by high vacuum distillation and 0.6 g (2.4 mmol, 84%) of diethyldialylaminomethylphosphonate having a boiling point of 65 ° C under a low pressure of 0.1 mbar. Yield) was obtained. This product was further characterized by the following spectrum.

<tables num="36"><img file="JP2005515260A_D0044.tif" /></tables>

--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).

<u style="single">Example 26-Preparation of diethyl1H-pyrrole-1-ylmethylphosphonate</u> 0.1 g (0.41 mmol) of diethyldiallylaminomethylphosphonate prepared in Example 25 was dissolved in 2 ml of chlorobenzene, and then 3.e 0.014 g (0.02 mmol) of the dimetal ruthenium chain prepared in Example 24 was added. The mixture was then stirred at 60 ° C. for 16 hours. The catalyst was removed after evaporation of chlorobenzene by column chromatography to obtain 0.04 g (0.18 mmol, yield 45%) of diethyl1H-pyrrole-1-ylmethylphosphonate. This product was further characterized by the following spectrum.

<tables num="37"><img file="JP2005515260A_D0045.tif" /></tables>

--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).

<u style="single">Example 27-Preparation of diallyl glycine methyl ester</u> 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 and the mixture was refluxed for 16 hours. 100 ml of 2N hydrochloric acid was added and then benefited with 100 ml of diethyl ether. K after acid extraction of the aqueous phase₂CO₃Alkaline with, and CH₂Cl₂Extracted with (100 ml 3 times). EDTA the organic layer₄After drying over 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. This product was further characterized by the following spectrum.

<tables num="38"><img file="JP2005515260A_D0046.tif" /></tables>

--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)。

<u style="single">Example 28 Preparation of Methyl-1H-Pyrrole-1-ylacetate</u> 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 dimetal ruthenium chain 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. This product was further characterized by the following spectrum.

<tables num="39"><img file="JP2005515260A_D0047.tif" /></tables>

--Infrared analysis: Light absorption band 1745 cm^-1(C = O). --Mass spectrum analysis: 139 (M)⁺, 63) and 80 (M⁺-PO (OEt)₂、100)。

<figref num="1">A synthetic route for producing a ruthenium catalytic compound having the general formula (IA) according to the embodiment of the present invention is shown.</figref><figref num="2">A synthetic route for producing a ruthenium catalytic compound having the general formula (IC) according to another embodiment of the present invention is shown.</figref><figref num="3">1 General formulas (IA) and (IB) of metal chains, 2 General formulas (IVA) and (IVB) of metal chains of the present invention, and their groups 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">The formulas (IIA), (IIB), (IIIA) and (IIIB) of the one-metal intermediate chain and the general formulas (IC) and (ID) of the other one-metal chain of the present invention are shown.</figref><figref num="5">The formulas (IIIC) and (IIID) of the monometal intermediate chain of the present invention are shown.</figref><figref num="6">It is a schematic diagram which shows the mooring of the derivative of 1 metal chain of this invention to a mesoporous crystalline molecular sieve.</figref><figref num="7">Two alternative synthetic routes for producing derivatives of the single metal chains of the invention that are covalently attached to a carrier are shown.</figref><figref num="8">We show advances in molecular weight and polydispersity of polystyrene produced by atomic transfer radical polymerization in the presence of heterogeneous catalysts of the present invention as a function of time or conversion.</figref><figref num="9">We show advances in molecular weight and polydispersity of polystyrene produced by atomic transfer radical polymerization in the presence of heterogeneous catalysts of the present invention as a function of time or conversion.</figref><figref num="10">It is a schematic diagram which shows the synthetic route for producing the two metal chains of this invention.</figref><figref num="11">It is a schematic diagram which shows the preparation of the cation species of the ruthenium 1 metal chain of this invention.</figref>