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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
  • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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  • C07C43/00—Ethers; Compounds having groups, groups or groups
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  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
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  • C07C67/00—Preparation of carboxylic acid esters
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  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
  • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
  • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
  • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
  • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
  • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
  • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
  • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
  • B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
  • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
  • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
  • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0202—Polynuclearity
  • B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/824—Palladium

Definitions

• the present invention relates to a method for producing a polymer-immobilized palladium catalyst in which divalent palladium is used as a raw material and zero-valent palladium is immobilized on an aromatic polymer as a nano-sized cluster, and a catalyst produced by the method. And its usage.
• Non-patent Document 1 Non-patent Document 1
• Non-Patent Documents 2 to 3 immobilization of palladium on a polymer using a microcapsule method has been developed.
• palladium was immobilized as a sub-nanometer size cluster by weak coordination with the benzene ring of the styrene polymer, and showed very high catalytic activity.
• this method has been developed into a polymer-immobilized palladium catalyst with higher stability while maintaining high activity by introducing a method of cross-linking micelles (Non-Patent Documents 4-7, Patent Documents 2 and 3).
• Palladium was fixed to an aromatic polymer by ligand exchange using 0 4 valent palladium as a raw material. As a result, zero-valent palladium was present in the polymer-immobilized palladium. It exists in a fin-free state, and this is considered to contribute to the high activity as a catalyst together with the small cluster size.
• Pd Pd
• Non- Patent Documents 8 to 9 Thiols and surfactants are effective in stabilizing nanosized metal clusters, and quaternary ammonium salts are known to have the effect of dispersing metal catalysts in solution.
• quaternary ammonium salts By performing microcapsulation using a quaternary ammonium salt, even if palladium (II) acetate, which cannot be fixed by the usual microcapsule method, is used as a raw material, the aromatic polymer is zero-valent. Can be fixed (Non-patent Document 10).
• Non-patent Document 11 It has been reported that palladium acetate ( ⁇ ) is decomposed and reduced by mild heat treatment in the absence of a reducing agent to produce zero-valent palladium.
• Patent Document 1 W099 / 41259
• Patent Document 2 JP 2002-66330 A
• Patent Document 3 JP 2002-253972
• Non-patent literature l Uozumi, Y. Topics in Current Chemistry, 242, 77 (2004).
• Non-Patent Document 2 Akiyama, R. et al. Angew. Chem., Int. Ed. 40, 3469 (2001).
• Non-Patent Document 3 Akiyama, R. et al. J. Am. Chem. Soc. 125, 3412 (2003).
• Non-Patent Document 4 Kobayashi, S. et al. Chem. Commun. 2003, 449.
• Non-Patent Document 5 Okamoto, K. et al. J. Org. Chem. 69, 2871 (2004).
• Non-Patent Document 6 Okamoto, K. et al. Org. Lett. 6, 1987 (2004).
• Non-Patent Document 7 Okamoto, K. et al. J. Am. Chem. Soc. 127, 2125 (2005).
• Non-Patent Document 8 Reetz, M. T. et al. Chem. Commun. 1996, 1921.
• Non-Patent Document 9 Reetz, M. T. et al. Adv. Mater., 11, 773 (1999).
• Non-Patent Document 10 Hiroyuki Sugao et al. Abstracts of the 125th Annual Meeting of the Pharmaceutical Society of Japan 4,108 (2005)
• Non-Patent Document ll Reetz, M. T. et al. Chem. Commun. 2004, 1559.
• the present invention relates to a polymer-immobilized palladium catalyst in which an inexpensive palladium (II) compound is used as a raw material, and a nanosized noradium cluster is stably supported on an aromatic polymer. And a reaction method using the catalyst.
• Non-patent Document 11 The present inventors incorporate zero-valent palladium into an aromatic polymer by reducing palladium acetate ( ⁇ ) by heating (Non-patent Document 11) in the presence of an aromatic polymer. We examined whether it was possible.
• the divalent palladium salt and alkali metal salt are heated in a solution containing the polymer having an aromatic side chain, whereby palladium is reduced and the nanosized palladium cluster is supported on the aromatic polymer.
• the present invention has been completed.
• a polymer having an aromatic side chain, a divalent palladium salt, and an alkali metal salt are mixed in a good solvent that dissolves the polymer.
• this solution is appropriately heated above 60 ° C.
• palladium (II) is considered to have been reduced to zero valence.
• a phase-separated state is produced by gradually adding a poor solvent for the polymer to this solution, and this operation enables incorporation of zero-valent palladium as a fine cluster into the polymer.
• the present invention dissolves or disperses a crosslinkable polymer having an aromatic side chain and a crosslinkable group, a divalent palladium salt, and an alkali metal salt in a solvent that dissolves the crosslinkable polymer. Is heated to 60-200 ° C, and after cooling, a poor solvent is added to the crosslinkable polymer to form a precipitate, and a crosslinking group in the precipitate is subjected to a crosslinking reaction. It is a manufacturing method of a catalyst.
• the present invention is a polymer-immobilized palladium catalyst produced by this production method, and further, the use of this catalyst as a catalyst in the Heck reaction or the Suzuki-Kajiura coupling reaction.
• a high molecule having an aromatic side chain, a divalent palladium salt and an alkali metal salt are added at 60 ° C in a good solvent for dissolving the polymer.
• the polymer-immobilized palladium catalyst is obtained by heating to the above and then gradually adding a poor solvent for the polymer to the solution to cause phase separation.
• the polymer used in the present invention is required to have an aromatic side chain, and the molecular weight thereof is 5,000 to 300,000, preferably 20,000 to 100,000.
• the solubility in a solvent increases, and recovery, which is an advantage of a fixed catalyst, makes it difficult to reuse or phase separation may occur when a poor solvent is added.
• a polymer having a too high molecular weight is difficult to synthesize and dissolve during catalyst preparation.
• the polymer having an aromatic side chain preferably further has a crosslinking group. That is, by cross-linking the polymer-immobilized palladium obtained by the phase separation operation between the polymers, the solvent resistance is improved and the use in various solvents is possible.
• the polymer having the aromatic side chain has an aromatic group as a hydrophobic group, it becomes amphiphilic by adding a hydrophilic group, and is high when phase separation is performed by adding a poor solvent. It is possible to form molecular micelles. In many cases, the stability of the palladium cluster fixed in the polymer micelle is improved as compared with the case where the micelle is not formed. Stability can be further improved by crosslinking the polymers after forming the polymer micelles.
• Examples of the aromatic side chain include an aryl group and an aralkyl group.
• aryl group examples include those having usually 6 to 10 carbon atoms, preferably 6 carbon atoms, and specific examples include a phenyl group and a naphthyl group.
• the number of carbons defined in this specification does not include the number of carbons of the substituent that the group has.
• aralkyl group examples include those having usually 7 to 12 carbon atoms, preferably 7 to 9 carbon atoms, and specific examples include a benzyl group, a phenyl group, and a phenylpropyl group.
• the aromatic ring in the aryl group and the aralkyl group may have a substituent such as an alkyl group, an aryl group, an aralkyl group, or the like!
• the alkyl group may have a linear, branched, or cyclic alkyl group, which may be monocyclic or polycyclic, usually having 1 to 1 carbon atoms. 20, preferably 1 to 12, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl Group, n_pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl Group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptinole group, sec-heptinole group, tert-heptinole group, n-octinole group, sec-octinole group Tert
• Examples of the aryl group and aralkyl group that the aromatic ring may have include the same aryl groups and aralkyl groups as the aromatic group as described above.
• aromatic rings may have, and the substituent may be substituted with 1 to 5, preferably 1 to 2 aromatic rings in the aryl group and aralkyl group.
• a copolymer of a polymerizable monomer containing styrene is preferable as the aromatic polymer.
• crosslinking group examples include an epoxy group, a carboxyl group, an isocyanate group, a thioisocyanate group, a hydroxyl group, a primary or secondary amino group, and a thiol group.
• the crosslinking group is preferably an epoxy group, a carboxyl group, an isocyanate group, or a thioisocyanate group, and may further contain a hydroxyl group, a primary or secondary amino group, or a thiol group.
• These cross-linking groups may be protected in the polymerization of monomers, which may be used alone or in combination, as necessary, or upon reduction of palladium (II) by heating.
• crosslink between the polymers by adding a cross-linking agent having a plurality of functional groups that bind to the functional groups in the polymer after phase separation.
• a cross-linking agent having a plurality of functional groups that bind to the functional groups in the polymer after phase separation.
• examples of this include a combination of an aromatic polymer having a hydroxyl group and ethylene glycol diglycidyl ether as a crosslinking agent.
• the position of the bridging group in the polymer is not particularly limited, but is bonded to the aromatic ring, directly bonded to the main chain, or bonded to the main chain via a spacer such as a hydrocarbon group. Good.
• the number of crosslinking groups is a force depending on the molecular weight of the polymer. It is 0.2 to 20% (molar ratio) of the monomer component, preferably 1 to 5%.
• the crosslinking group is preferably a structure that is stable after the crosslinking reaction and does not inhibit the palladium catalytic reaction.
• a single crosslinking group having such a property or a combination of crosslinking groups an epoxy group alone or a combination of an epoxy group and a hydroxyl group is preferable. These are crosslinked by heating to form an ether bond. As heating conditions in this case,
• reaction time is 0.5 to 24 hours, preferably 1 to 5 hours.
• the reaction temperature is low, crosslinking is insufficient or heating for a long time is required, and when the reaction temperature is high, the polymer chain may be broken or the functional group may be decomposed.
• crosslinkable polymer a copolymer having a crosslinking group or a hydrophilic group, or a homopolymer composed of a polymer of monomers having both a hydrophobic group and a hydrophilic group may be used.
• hydrophilic group a hydroxyl group, an ether group, a carboxyl group, an amino group, and an amide group can be used. Also in this case, considering the stability of the functional group and the influence on the catalytic reaction, the most preferred hydrophilic groups are a hydroxyl group and an ether group.
• the ratio of these hydrophilic groups to hydrophobic groups is appropriately adjusted depending on the type of polymer, for example, homopolymer force copolymer force, random copolymer or block copolymer force. In the case of a copolymer, the ratio of the hydrophilic monomer to the total monomer is 3 to 50%, preferably 5 to 20%.
• the number of oxygen atoms in the monomer is 1 to 5, preferably 1 to 3.
• the bonding position of the hydrophilic group It may be bonded to the aromatic ring, directly bonded to the main chain, or bonded to the main chain via a spacer such as a hydrocarbon group, but directly to the main chain. When combined, it is easy to form polymer micelles.
• the crosslinkable polymer of the present invention may further have a hydrophobic side chain other than the aromatic side chain.
• hydrophobic side chain other than the aromatic side chain examples include an alkyl group, an alkenyl group, and an alkyl group.
• the crosslinkable polymer of the present invention may further have a hydrophilic side chain! ,.
• hydrophilic side chain a relatively short alkyl group, for example, an alkylene group having about 1 to 6 carbon atoms is bound to — ⁇ (R 1 represents —OH or a lower alkoxy group, preferably —OH).
• R 1 is the same as above, R 2 is a covalent bond or a C 1-6 alkyl o P
• a xylene group preferably a covalent bond or an alkylene group having 1 to 2 carbon atoms, R 3 and R 4 each independently represents an alkylene group having 2 to 4 carbon atoms, preferably 2; m, n and p are 1 to: an integer of L0, o represents 1 or 2.
• More preferred hydrophilic side chains include CH (OC H) OH and mono (COOC H) OH.
• the divalent palladium salt palladium acetate, palladium propionate, palladium trifluoroacetate, palladium chloride, palladium bromide, palladium iodide, palladium cyanide, palladium nitrate, palladium sulfate, palladium oxide, palladium sulfide, Or, para-dimethylacetate, or a mixture thereof, among which palladium acetate and palladium acetate are preferred, with palladium acetate and palladium nitrate being preferred.
• alkali metal acetates include nitrates or halides of lithium, sodium or potassium, lithium acetate, sodium acetate, potassium acetate and the like, but lithium acetate, sodium acetate or potassium acetate is preferred.
• Such a crosslinkable polymer, a divalent palladium salt, and an alkali metal salt are dissolved or dispersed in a solvent (good solvent) that dissolves the crosslinkable polymer, followed by heat treatment.
• a solvent good solvent
• concentration of palladium salt in a good solution is about 0.01 to 0.2M.
• concentration of alkali metal acetate in the good solution is about 0.02-0.4M.
• the conditions for this heat treatment are 60 to 200 ° C, preferably 65 to 80 ° C, 2 to 10 hours, preferably 3 to 5 hours.
• the heating temperature is 65 ° C or lower, the reduction reaction of palladium may not proceed or slow, and the immobilization of palladium (0) to the polymer will be insufficient.
• epoxide is used as the cross-linking group, reduction of palladium ( ⁇ ) at 80 ° C or higher causes insolubility due to the cross-linking reaction between high molecules, and noradium is not fixed to the high molecule as a single microcluster.
• the heating time is short, the reduction is insufficient, and when it is too long, the crosslinking reaction proceeds.
• Divalent palladium cannot be fixed by the microcapsule method. Point and catalytic power obtained by microcapsule after heat treatment Zero-valent palladium such as tetrakistriphenylphosphine palladium As a result of this heat treatment, divalent palladium is reduced to zero-valent palladium because of its catalytic activity similar to that of a catalyst fixed by the microcapsule method and the similar morphology observed by electron microscopy. (Non-Patent Document 11).
• this solution or dispersion is cooled to about room temperature, and an appropriate poor solvent is added to cause phase separation, whereby palladium is incorporated into the polymer aggregate or micelle-like aggregate.
• the method is, for example, a) dissolving in an appropriate polar good solvent and then aggregating with an appropriate polar poor solvent; b) adding an appropriate non-polar solvent after dissolving in the polar good solvent and adding palladium-supported micelles. Form aggregates, and further aggregate with a polar poor solvent, c) dissolve in a suitable nonpolar good solvent, and then aggregate with a suitable nonpolar poor solvent, d) dissolve in a nonpolar good solvent Thereafter, an appropriate polar solvent is added to form a palladium-supported micelle-like aggregate, and further aggregated with a nonpolar poor solvent.
• the hydrophobic side chain is located in the inner direction and the hydrophilic side chain is located in the outer direction of the formed micelle-like aggregate, and the method in c) and d) Then, the hydrophobic side chain is located in the outward direction of the formed micelle-like aggregate, and the hydrophilic side chain is located in the inward direction.
• the palladium ultrafine particles are supported by the interaction with the aromatic side chain in each micelle-like aggregate or polymer aggregate.
• Examples of good polar solvents include tetrahydrofuran (THF), dioxane, acetone, DMF, N-methyl-2-pyrrolidone (NMP), and dimethoxyethane (DME).
• Nonpolar good solvents include toluene, Cyclohexane, dichloromethane, black mouth form and the like can be used.
• Examples of polar poor solvents include methanol, ethanol, butanol, propyl alcohol, amyl alcohol, and jetyl ether, and nonpolar poor solvents include hexane, heptane, and octane. Further, these mixed solvents may be used as a good solvent and a poor solvent.
• the concentration of the polymer in the good solvent is about 1 to 100 mg / ml, and the amount of the palladium compound is the polymer. 0.01 to 0.5 (w / w) with respect to the good solvent and 0.2 to 10 (v / v) with respect to the good solvent.
• the addition time of the poor solvent is usually 10 minutes to 2 hours.
• the temperature at the time of phase separation is not particularly limited, but it is usually from 0 ° C to room temperature.
• the crosslinking reaction can be reacted by heating or ultraviolet irradiation depending on the type of the crosslinkable functional group.
• the crosslinking reaction is a conventionally known method for crosslinking the linear organic polymer compound to be used.
• a method using a crosslinking agent a method using a condensing agent
• a method using a radical polymerization catalyst such as a product or an azo compound
• a method in which an acid or a base is added and heated
• a method in which a dehydrating condensing agent such as carpositimide is combined with an appropriate crosslinking agent, and the like.
• a dehydrating condensing agent such as carpositimide
• the temperature at which the epoxide and the hydroxyl group are crosslinked by heating as a crosslinking group is usually 80 to 180. C, preferably 110-150. . It is.
• the reaction time for the heat crosslinking reaction is usually 0.5 to 24 hours, preferably 1 to 5 hours.
• the polymer-immobilized palladium catalyst thus obtained is considered to have a form in which palladium is supported as ultrafine particles by the interaction with the aromatic ring in the polymer. For example, it exhibits high catalytic activity for the Heck reaction and the Suzuki-Kajiura coupling reaction.
• the Heck reaction is a reaction in which a substituted olefin is synthesized by cross-coupling a halogenated aryl or a norologene vinyl with a terminal olefin in the presence of a base and using noradium (0) as a catalyst.
• the Suzuki-Kajiura coupling reaction is a cross-coupling reaction between an organic fluorine compound and a halogenated aryl or halogen butyl, aryl triflate or vinyl triflate using a noradium catalyst in the presence of a base.
• biaryl compounds, alkylaryl compounds, or substituted olefins can be produced.
• R 6 represents a hydrogen atom or an alkyl group.
• R 7 X (where R 7 is Reel group or vinyl group, X is a halogen atom or triflate group (represents (OTD))
• a biaryl compound, an alkylaryl compound, an alkenylaryl compound, or a Geny compound can be produced.
• aryl group examples include those having 6 to 10 carbon atoms, preferably 6 carbon atoms, such as a phenyl group and a naphthyl group.
• the vinyl group may have a substituent as appropriate.
• the amount of catalyst used is 0.01 to: LOmol%, preferably 0.1 to 5 mol%.
• Chlorine, bromine and iodine can be used as the halogen of the halogenated aryl or halogenated butyl, but bromine or iodine is particularly preferable.
• the reaction solvent a mixed solvent of water and an organic solvent can be used.
• organic solvent hydrocarbons such as toluene are preferable, ethers such as dimethoxyethane (DME) and tetrahydrofuran (THF), and ketones such as acetone.
• the base to be added is preferably an alkali metal carbonate or phosphate.
• the reaction temperature is 70 ° C to 150 ° C, preferably around 100 ° C.
• the reflux temperature is simple in a toluene Z water system.
• a base such as an arylphosphine ligand and an alkali metal carbonate or phosphate.
• arylphosphine ligand examples include dimethylphenol phosphine (P (CH) Ph), diphenylphosphinophlocene (dPPf), and triphenyl.
• the target compound in the post-treatment after the reaction, can be obtained by removing and collecting the polymer-immobilized catalyst by filtration, and extracting, concentrating, and purifying the filtrate.
• the recovered fixed catalyst can be reused by washing and drying.
• the reaction mixture was cooled and diluted with jetyl ether, and then the reaction was stopped by slowly adding a saturated aqueous ammonium chloride solution.
• the organic layer was separated and the aqueous layer was extracted twice with diethyl ether.
• the desiccant was filtered off and the organic layer was concentrated under reduced pressure to produce a composition obtained by silica gel column chromatography.
• the copolymer (1X200 mg), sodium acetate (21.7 mg, 0.26 mmol) and palladium nitrate (30.4 mg, 0.13 mmol) were dissolved in tetrahydrofuran (3.0 ml) at room temperature, stirred for 1 hour, and then stirred at 66 ° C for 3 hours. did.
• the mixture was allowed to cool to room temperature, hexane (20 ml) was slowly added dropwise, and the mixture was allowed to stand at room temperature for 12 hours. The supernatant was removed with decantation, washed several times with hexane, and dried at room temperature under reduced pressure for 24 hours.
• a catalyst (PIPd) was prepared in the same manner as in Example 1 except that the raw material palladium salt (II) and sodium acetate (additive) were changed, and the immobilization to the polymer was examined. The results are shown in Table 1.
• PI Pd A (0.025 mmol), odobenzene (56 ⁇ 1, 0.50 mmol), ethyl acrylate (81 ⁇ 1, 0.75 mmol) and potassium carbonate (196 mg, 1.0 mmol) were combined with N-methyl-2-pyrrolidone (NMP, 3 ml). The mixture was stirred at 120 ° C. for 1 hour and then cooled, followed by removal of hexane. The mixture was filtered through a glass filter, and the insoluble material was washed successively with tetrahydrofuran, methylene chloride, and water.
• NMP N-methyl-2-pyrrolidone
• the reaction time was extended from 1 hour to 2 hours, and the same reaction as in Example 9 was performed.
• the results are shown in Table 2.
• the yield was slightly improved (94%, Table 2).
• Example 9 The same reaction as in Example 9 was performed using PI Pd C to H instead of PI Pd A. The results are shown in Table 2. The yield of the target product, ethyl acrylate, was found to vary from 31% to quantitative (quant.) Depending on the production method of PI Pd. In any case, no leakage of palladium from the catalyst was observed It was.
• Example 9 The same reaction as in Example 9 was performed using PI Pd H instead of PI Pd A.
• the results are shown in Table 2. Although the recovery rate at the time of production of PI Pd H was low (Example 8), the yield of the reaction product when PI Pd H was used was as good as 83%.
• PI Pd A (0.0025 mmol), 2-bromotoluene (60 // g, 0.50 mmol), phenylboronic acid (9 1.4 mg, 0.75 mmol), tri (o-tolyl) phosphine (8.8 mg, 0.025 mmol) And potassium phosphate (106 mg, 0.5 mmol) were refluxed in a mixed solvent of toluene monohydrate (4/1, 5 ml) under an argon atmosphere for 4 hours.

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