WO2024034666A1 - ルテニウム錯体及びその製造方法、触媒組成物、並びに、酸化方法及び酸素含有化合物の製造方法 - Google Patents

ルテニウム錯体及びその製造方法、触媒組成物、並びに、酸化方法及び酸素含有化合物の製造方法 Download PDF

Info

Publication number
WO2024034666A1
WO2024034666A1 PCT/JP2023/029298 JP2023029298W WO2024034666A1 WO 2024034666 A1 WO2024034666 A1 WO 2024034666A1 JP 2023029298 W JP2023029298 W JP 2023029298W WO 2024034666 A1 WO2024034666 A1 WO 2024034666A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
acid
ruthenium complex
added
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/029298
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
竜也 内田
大樹 土居内
菜々子 下田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyushu University NUC
Original Assignee
Kyushu University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyushu University NUC filed Critical Kyushu University NUC
Priority to JP2024540526A priority Critical patent/JPWO2024034666A1/ja
Publication of WO2024034666A1 publication Critical patent/WO2024034666A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
    • C07C311/19—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/16—Acetic acid esters of dihydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D213/24—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 with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present disclosure relates to a ruthenium complex, a method for producing the same, a catalyst composition, an oxidation method, and a method for producing an oxygen-containing compound.
  • Carbon-hydrogen oxidation reaction is a useful reaction that can oxidize the carbon-hydrogen bond of a hydrocarbon and directly convert it into an alcohol or ketone.
  • Various catalysts using transition metals are being studied as catalysts for this reaction.
  • Patent Document 1 discloses a method for obtaining an oxygen-containing compound using a ruthenium complex and an oxidizing agent such as iodosylbenzene.
  • Patent Document 2 discloses a labeling method using a ruthenium complex and a hypervalent iodine compound.
  • Non-Patent Documents 1 and 2 disclose a C—H oxidation reaction using hydrogen peroxide (H 2 O 2 ) as an oxidizing agent using a catalyst containing a complex containing Fe or Mn as a metal ion.
  • the present disclosure provides a catalyst composition capable of oxidizing a substrate even using an oxidizing agent with weak oxidizing power, and a ruthenium complex useful as a catalyst.
  • the present disclosure provides a method for producing an oxygen-containing compound that can produce an oxygen-containing compound by oxidizing a substrate even if an oxidizing agent with weak oxidizing power is used. Furthermore, the present disclosure provides a method for producing a ruthenium complex that can produce a ruthenium complex useful as a catalyst in a simple manner.
  • a ruthenium complex according to one aspect of the present disclosure is represented by the following general formula (1).
  • R 1 is a hydrogen atom, a phenyl group, or a monovalent group in which at least one hydrogen atom of the phenyl group is substituted with an alkyl group, a hydroxy group, a phenyl group, a halogen atom, or an alkoxy group.
  • R 2 represents a hydrogen atom, a phenyl group, or an alkyl group
  • R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group.
  • L 1 represents triphenylphosphine, pyridine, imidazole, dimethyl sulfoxide, or water
  • X represents a monovalent group obtained by removing a hydrogen atom from the carboxyl group of a carboxylic acid
  • X ⁇ represents an anion of the above carboxylic acid.
  • n represents 1 or 2.
  • the ruthenium complex Since the ruthenium complex has high catalytic activity, it is useful, for example, as a catalyst for oxidizing carbon-hydrogen bonds. However, the use of the above-mentioned ruthenium complex is not limited to such a use as a catalyst.
  • a catalyst composition according to one aspect of the present disclosure includes a ruthenium complex represented by the above general formula (1). Since the ruthenium complex represented by the general formula (1) has high catalytic activity, the C—H oxidation reaction of the substrate can proceed under mild conditions. Therefore, the catalyst composition can maintain a high catalyst rotation rate (TOF) for a long period of time.
  • the ruthenium complex represented by general formula (1) may be an oxidation catalyst that oxidizes a substrate having a carbon-hydrogen bond.
  • a method for producing a ruthenium complex according to one aspect of the present disclosure includes reacting a raw material complex represented by the following general formula (2), a carboxylic acid, and a silver salt, and a ruthenium complex represented by the following general formula (1).
  • the method includes a step of obtaining a ruthenium complex.
  • R 1 is a hydrogen atom, a phenyl group, or at least one hydrogen atom of the phenyl group is substituted with an alkyl group, a hydroxy group, a phenyl group, a halogen atom, or an alkoxy group.
  • R2 represents a hydrogen atom, a phenyl group, or an alkyl group
  • R3 and R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or represents an aryl group
  • L 1 represents triphenylphosphine, pyridine, imidazole, dimethyl sulfoxide, or water
  • Y represents a halogen atom
  • Y ⁇ represents a halide ion
  • X represents a carboxyl group of a carboxylic acid.
  • X ⁇ represents an anion of the above carboxylic acid
  • n represents 1 or 2.
  • a ruthenium complex useful as a catalyst can be produced in a simple manner.
  • a catalyst composition capable of oxidizing a substrate even using an oxidizing agent with weak oxidizing power, and a ruthenium complex useful as a catalyst can be provided. It is possible to provide a method for producing an oxygen-containing compound, in which the oxygen-containing compound can be produced by oxidizing a substrate even when an oxidizing agent with weak oxidizing power is used. It is possible to provide a method for producing a ruthenium complex that is capable of producing a ruthenium complex useful as a catalyst in a simple manner.
  • FIG. 1 is a diagram showing an example of an alcohol production mechanism when a ruthenium complex is used as a catalyst.
  • FIG. 2 is a diagram showing an example of a mechanism in which a ruthenium complex coordinated with a carboxylic acid anion is activated to an oxo species by hydrogen peroxide.
  • FIG. 3 is a diagram showing the results of 1 H-NMR measurement of a ruthenium complex coordinated with a monovalent group derived from a carboxylic acid in Example 4-1.
  • FIG. 4 is a diagram showing the measurement results of a ruthenium complex coordinated with a monovalent group derived from a carboxylic acid using a time-of-flight mass spectrometer in Example 4-1.
  • FIG. 5 is a graph showing the relationship between acid dissociation constant (pKa) and conversion rate or TOF.
  • a ruthenium complex according to one embodiment is represented by the following general formula (1).
  • This ruthenium complex is useful, for example, as a catalyst for oxidizing C—H bonds in a substrate.
  • R 1 is a hydrogen atom, a phenyl group, or a monovalent group in which at least one hydrogen atom of the phenyl group is substituted with an alkyl group, a hydroxy group, a phenyl group, a halogen atom, or an alkoxy group.
  • the substituents are shown below.
  • R 1 is a phenyl group, or at least one hydrogen atom of the phenyl group is an alkyl group, a hydroxy group, a phenyl group, or a halogen atom. , or a monovalent substituent substituted with an alkoxy group.
  • R 1 is a monovalent substituent in which multiple hydrogen atoms of a phenyl group are substituted with a functional group or other atoms
  • the substituents that replace multiple hydrogen atoms in the phenyl group are mutually exclusive. They may be different or the same.
  • the alkyl group replacing at least one hydrogen atom of the phenyl group may be a methyl group, an ethyl group, or a propyl group.
  • the halogen atom substituting at least one hydrogen atom of the phenyl group may be a chlorine atom.
  • the alkoxy group substituting at least one hydrogen atom of the phenyl group may be a methoxy group, an ethoxy group, or a propoxy group.
  • R 1 is preferably a phenyl group or a 2,6-dimethylphenyl group, and is preferably a 2,6-dimethylphenyl group. It is more preferable.
  • R 2 represents a hydrogen atom, a phenyl group, or an alkyl group.
  • Alkyl groups may be methyl, ethyl or propyl groups.
  • R 2 is preferably a hydrogen atom.
  • R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group.
  • the halogen atom may be a chlorine atom or a bromine atom.
  • Alkyl groups may be methyl, ethyl or propyl groups.
  • R 3 and R 4 are preferably hydrogen atoms or halogen atoms, and more preferably hydrogen atoms.
  • X represents a monovalent group obtained by removing a hydrogen atom from the carboxyl group of a carboxylic acid.
  • the acid dissociation constant (pKa) of the carboxylic acid may be 3 or less from the viewpoint of sufficiently increasing the catalytic activity.
  • the lower limit of the acid dissociation constant (pKa) of carboxylic acid may be, for example, 0.1 or 0.3.
  • the above carboxylic acid may be a monocarboxylic acid or a dicarboxylic acid.
  • the acid dissociation constant (pKa) of the monocarboxylic acid is preferably 3 or less, more preferably 2 or less, and even more preferably 1.8 or less. This allows the catalyst to have sufficiently high activity, selectivity, and durability.
  • the monocarboxylic acid may contain halogen as a constituent element, and may contain fluorine and/or chlorine.
  • the lower limit of the acid dissociation constant (pKa) of the monocarboxylic acid may be, for example, 0.1 or 0.3.
  • the acid dissociation constant (pKa) is an index that quantitatively indicates the strength of an acid (ease of dissociating hydrogen ions). Acid dissociation constants (pKa) can be measured by neutralization titration, spectrophotometry, or capillary electrophoresis.
  • the dicarboxylic acid is preferably oxalic acid, malonic acid, maleic acid, tetrafluorophthalic acid, methylmalonic acid, cyclopropane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, or citraconic acid. , oxalic acid, malonic acid, or maleic acid. This allows the catalyst to have sufficiently high activity, selectivity, and durability.
  • X - represents a monovalent anion of the above carboxylic acid. That is, X ⁇ is an anion corresponding to the ligand X.
  • L 1 represents triphenylphosphine, pyridine, imidazole, dimethyl sulfoxide, or water. Among these, from the viewpoint of sufficiently increasing activity, selectivity, and durability as a catalyst, L 1 is preferably triphenylphosphine.
  • n represents 1 or 2.
  • the oxidation number of Ru in the above general formula (1) is, for example, +2.
  • the ruthenium complex of this embodiment functions, for example, as a catalyst that oxidizes a substrate having a carbon atom-hydrogen atom bond.
  • a substrate having the above bond can be oxidized to produce an oxygen-containing compound.
  • oxygen-containing compounds include hydroxy compounds and carbonyl compounds.
  • the ruthenium complex of general formula (1) above exhibits high catalytic activity, so even if an oxidizing agent with weak oxidizing power such as hydrogen peroxide is used, the ruthenium complex of general formula (1) can undergo C-H oxidation reaction at room temperature (for example, 10 to 30°C). can proceed.
  • the catalyst rotation rate (TOF) can be made sufficiently high. Note that the use of this ruthenium complex is not limited to oxidation catalysts, and the ruthenium complex is also useful as a reagent.
  • a catalyst composition according to one embodiment includes a ruthenium complex represented by the above general formula (1) as a catalyst.
  • the catalyst composition may be in liquid form or in solid form such as powder.
  • the catalyst composition may contain components other than the ruthenium complex (catalyst) represented by the above general formula (1).
  • Such components include silver salts, solvents or carboxylic acids.
  • Silver salts include silver fluoride, silver chloride, silver bromide, silver iodide, silver oxide and silver sulfide.
  • the silver salt preferably contains silver oxide from the viewpoint of sufficiently increasing the catalytic activity.
  • the solvent examples include 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,2-trifluoroethanol, dichloromethane, 1,1,2,2-tetrachloroethane, and acetonitrile. It will be done. From the viewpoint of sufficiently increasing the catalytic activity, the solvent preferably contains 1,1,1,3,3,3-hexafluoro-2-propanol and 2,2,2-trifluoroethanol, and 1,1 , 1,3,3,3-hexafluoro-2-propanol.
  • the carboxylic acid contained in the catalyst composition may include a carboxylic acid that becomes X coordinating with the general formula (1).
  • the carboxylic acid preferably includes a carboxylic acid used for exchanging anionic ligands when obtaining the ruthenium complex of the general formula (1) from the raw material complex. That is, examples of this carboxylic acid are as mentioned in the explanation of X in the above general formula (1).
  • the catalyst composition contains such a carboxylic acid, the C—H oxidation reaction of the substrate can be promoted.
  • the catalyst composition contains the ruthenium complex of the general formula (1) having high catalytic activity, the C--H oxidation reaction of the substrate can sufficiently proceed under mild conditions. Therefore, it can be used for a long period of time at a high catalyst rotation rate (TOF).
  • TOF catalyst rotation rate
  • a method for producing an oxygen-containing compound includes a reaction step of oxidizing a carbon-hydrogen bond of a substrate using the catalyst composition to obtain an oxygen-containing compound having a carbon-oxygen bond.
  • the substrate may be a compound containing at least one selected from the group consisting of a methine group and a methylene group.
  • the substrate may be a hydrocarbon having 5 to 30 carbon atoms, an oxygen-containing hydrocarbon, a nitrogen-containing hydrocarbon, or a sugar, in which at least one hydrogen atom may be substituted with a functional group.
  • the hydrocarbon may be a chain (linear or branched) hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon.
  • the functional group include a hydroxy group, a halogen atom, an alkoxy group, an aldehyde group, an acyl group, a carboxyl group, an allyl group, an amino group, a nitro group, an acetyl group, an oxo group, and an ester group.
  • the substrate may be a prohormone.
  • the substrate may be an alicyclic compound or a heterocyclic compound.
  • the heterocyclic compound may have one or both of nitrogen and sulfur as heteroatoms.
  • a solvent containing 1,1,1,3,3,3-hexafluoro-2-propanol and a desiccant may be used.
  • an organic solvent that does not react with the catalyst composition can be used.
  • organic solvents include 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,2-trifluoroethanol, dichloromethane, 1,1,2,2-tetrachloroethane, Examples include acetonitrile, chloroform, and 1,2-dichloroethane.
  • Desiccant agents include magnesium sulfate and sodium sulfate. Such a desiccant can absorb, for example, water produced by reduction of H 2 O 2 and allow the oxidation reaction to proceed efficiently.
  • FIG. 1 shows an example of a mechanism for producing alcohol, which is a type of hydroxy compound, from a substrate containing a tertiary carbon atom using the ruthenium complex of the above general formula (1) as an oxidation catalyst. Note that the mechanism of alcohol production is not limited to this example.
  • a ruthenium complex (LMk: L represents a ligand, M represents ruthenium, and k represents the oxidation number of ruthenium, which is 2 or 3) as a catalyst and an oxidizing agent are used. contact to form a ruthenium-oxo bond.
  • the oxidizing agent preferably includes hydrogen peroxide from the viewpoint of cost reduction, environmental protection, and improvement of atomic efficiency.
  • the oxidizing agent may include, for example, at least one selected from the group consisting of hydrogen peroxide, iodosylbenzene, cumene hydroperoxide, iodobenzene diacetate, and water.
  • the oxidizing agent may be, for example, hydrogen peroxide.
  • hydrogen peroxide contained in the oxidizing agent is preferably used in an amount of 1 to 5 mol, more preferably 1 to 3 mol, per 1 mol of substrate.
  • the ruthenium complex of the above general formula (1) is preferably used in an amount of 0.0002 to 0.02 mol, and 0.0005 to 0.005 mol, per 1 mol of substrate. It is more preferable to use portions.
  • FIG. 2 shows an example of a mechanism in which a ruthenium complex forms a ruthenium-oxo bond with hydrogen peroxide (H 2 O 2 ) in step I of FIG. 1. Note that the mechanism of formation of the ruthenium-oxo bond is not limited to this example.
  • FIG. 2A illustrates a ruthenium complex in which a monovalent group obtained by removing a hydrogen atom from a carboxyl group of a dicarboxylic acid (malonic acid) is coordinated.
  • a ruthenium complex and hydrogen peroxide come into contact, the hydrogen bond between the carboxylate and H 2 O 2 in the ruthenium complex promotes the cleavage of the O—O bond of H 2 O 2 .
  • a ruthenium-oxo bond is formed as shown in FIG. 2(B).
  • hydrogen peroxide is considered to suitably function as an oxidizing agent when the ruthenium complex has an intramolecular carboxylate. Therefore, even if H 2 O 2 has weak oxidizing power, the oxidation reaction proceeds sufficiently.
  • FIG. 2 illustrates a monovalent group obtained by removing a hydrogen atom from the carboxyl group of malonic acid, which is a dicarboxylic acid
  • the present invention is not limited thereto.
  • the ruthenium complex may be coordinated with a monovalent group obtained by removing a hydrogen atom from the carboxyl group of a carboxylic acid different from malonic acid.
  • hydrogen peroxide can be used as an oxidizing agent to smoothly form a ruthenium-oxo bond.
  • an acid may be used together with an oxidizing agent in the above step.
  • the acid it is preferable to use a carboxylic acid that produces the ligand X of general formula (1).
  • Specific examples of the carboxylic acid are as listed in the explanation of X in general formula (1).
  • the acid may be used in an amount of 0.1 to 3 mol per mol of the substrate.
  • step II of FIG. 1 a ruthenium-oxo bond and a substrate containing a tertiary carbon atom come into contact, hydrogen atoms are removed from the substrate, and a substrate radical and a ruthenium-hydroxy bond are generated.
  • R 1 , R 2 and R 3 in the substrate may be different from each other or may be the same. At least two selected from the group consisting of R 1 , R 2 and R 3 may be combined to form a ring.
  • step III of FIG. 1 the hydroxy group bonded to ruthenium bonds with the substrate radical to obtain a hydroxy compound (for example, alcohol).
  • the ruthenium complex is then used again as a catalyst.
  • This reaction allows selective hydroxylation of tertiary carbon atoms.
  • a secondary carbon atom may be hydroxylated, or a primary carbon atom may be hydroxylated.
  • Substrates may be carbonylated by a similar mechanism.
  • the generation mechanism of the oxygen-containing compound is not limited to the mechanism shown in FIG. In some examples, catalyst rotation speeds can be greater than 300 rph, greater than 400 rph, or greater than 500 rph.
  • the methylene group farthest from the functional group can be oxidized with high selectivity.
  • reaction formulas (1A) and (2A) below the 4-position carbon of pentyl benzoate and the 5-position carbon of hexyl benzoate are oxidized with high selectivity to obtain the desired product in high yield. be able to.
  • the substrate may contain a carbocyclic compound.
  • the reactivity of the reaction product obtained by oxidizing one carbon atom of the substrate is lower than the reactivity of the substrate. Therefore, as shown in reaction formula (3A) below, a product in which one carbon atom constituting the carbocyclic compound of cyclohexane is oxidized can be obtained in high yield and high selectivity.
  • the substrate may include a nitrogen-containing compound containing nitrogen as a constituent element.
  • nitrogen which is a constituent element of the nitrogen-containing compound, may be protected by protons.
  • the proton protecting agent may be perchloric acid, hydrochloric acid, chloric acid, bromic acid, sulfuric acid, nitric acid, trifluoromethanesulfonic acid, or tetrafluoroboric acid, with tetrafluoroboric acid being preferred.
  • the nitrogen-containing compound may be cyclic and may contain at least one selected from the group consisting of a nitro group and an amino group.
  • the methylene group or methine group in the primary amine can be oxidized with high selectivity to obtain the desired product in high yield. .
  • oxygen-containing compounds can be produced by oxidizing a wide variety of substrates containing methine groups or methylene groups, regardless of the type of functional group of the substrate.
  • the manufacturing method of this example includes the step (a) of manufacturing a complex mixture containing complexes represented by general formulas (2) and (3) below, and the step (a) of manufacturing a complex mixture containing complexes represented by general formulas (2) and (3) below, and a step (a) of manufacturing a complex mixture represented by general formula (2) (raw material) from the complex mixture. complex), and step (c) of coordinating a group derived from a carboxylic acid to the raw material complex.
  • R 1 is a hydrogen atom, a phenyl group, or a phenyl group in which at least one hydrogen atom is substituted with an alkyl group, a hydroxy group, a phenyl group, a halogen atom, or an alkoxy group.
  • R2 represents a hydrogen atom, a phenyl group, or an alkyl group
  • R3 and R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or represents an aryl group
  • L 1 represents triphenylphosphine, pyridine, imidazole, dimethyl sulfoxide, or water
  • Y represents a halogen atom
  • Y ⁇ represents a halide ion
  • n represents 1 or 2
  • Y ⁇ is an anion corresponding to the ligand Y.
  • Each complex (2) and (3) consists of a carboxylic acid chloride represented by the general formula (4), an amine compound represented by the general formula (5), and a bis(2) represented by the formula (6). -pyridylmethyl)amine to synthesize the ligand.
  • R 2 is the same as R 2 in general formulas (2) and (3) above.
  • Z is a halogen atom, for example a chloro group.
  • R 1 is the same as R 1 in general formulas (2) and (3) above.
  • a coordination in which two pyridine rings and Ru are arranged in a straight line or a substantially straight line with Ru in between, as shown in the above general formula (3), is referred to as a trans type.
  • a coordination in which two pyridine rings are adjacent and Ru is not arranged in a straight line is called a cis type.
  • ruthenium compound examples include ruthenium (II) chloride and a complex having dimethyl sulfoxide or triphenylphosphine as a ligand.
  • complexes include dichlorotetrakis(dimethylsulfoxide)ruthenium(II), tris(triphenylphosphine)ruthenium(II) dichloride, and the like.
  • the second step may be performed under heating under reflux using alcohol such as ethanol as a solvent. Through these first and second steps, a complex mixture containing the raw material complex is obtained.
  • a step (b) of separating the cis-type raw material complex in the complex mixture is performed.
  • This step (b) may be carried out, for example, by recrystallization or column chromatography.
  • a complex (raw material complex) represented by general formula (2) can be obtained.
  • step (c) of coordinating a monovalent group derived from a carboxylic acid to the raw material complex is performed.
  • the raw material complex obtained in step (b) is reacted with a carboxylic acid and a silver salt, thereby converting the axial ligand of the raw material complex into a monomer obtained by removing a hydrogen atom from the carboxyl group of the carboxylic acid.
  • a composition containing a ruthenium complex represented by the above general formula (1) by substitution with a valent group is obtained.
  • the silver salt is preferably used in an amount of 0.1 to 1.5 equivalents, more preferably 0.7 to 1.3 equivalents, relative to the raw material complex.
  • the acid dissociation constant (pKa) of the carboxylic acid used in step (c) may be 3 or less from the viewpoint of obtaining a ruthenium complex with sufficiently high catalytic activity.
  • the lower limit of the acid dissociation constant (pKa) of carboxylic acid may be, for example, 0.1 or 0.3.
  • the above carboxylic acid may include a monocarboxylic acid or a dicarboxylic acid.
  • the acid dissociation constant (pKa) of the monocarboxylic acid is preferably 3 or less, more preferably 2 or less, and even more preferably 1.8 or less. This allows the catalyst to have sufficiently high activity, selectivity, and durability.
  • the monocarboxylic acid may contain halogen as a constituent element, and may contain fluorine and/or chlorine.
  • the lower limit of the acid dissociation constant (pKa) of the monocarboxylic acid may be, for example, 0.1 or 0.3.
  • the dicarboxylic acid is selected from the group consisting of oxalic acid, malonic acid, maleic acid, tetrafluorophthalic acid, methylmalonic acid, cyclopropane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, and citraconic acid. It is preferable to contain at least one selected from the group consisting of oxalic acid, malonic acid, and maleic acid. This allows the catalyst to have sufficiently high activity, selectivity, and durability.
  • the silver salt preferably contains silver oxide from the viewpoint of sufficiently increasing the catalytic activity.
  • the ruthenium complex represented by the general formula (1) thus obtained is useful, for example, as a catalyst for oxidizing carbon-hydrogen bonds to obtain oxygen-containing compounds.
  • a composition containing multiple types of ruthenium complexes having different ligands X (counter anions X ⁇ ) may be obtained by using multiple types of carboxylic acids.
  • the catalyst composition containing at least one ruthenium complex obtained after the synthesis may be used as a catalyst for the C--H oxidation reaction of the substrate in a solution state, or the isolated and purified ruthenium complex of general formula (1) may be used as a catalyst for the C--H oxidation reaction of the substrate. May be used as a catalyst.
  • the above-mentioned ruthenium complex serves as a catalyst for the C--H oxidation reaction and can react the carbon-hydrogen bond of a substrate containing a methine group or a methylene group under mild conditions. In addition, it has high durability and can be used for a long period of time. Furthermore, when the above-mentioned ruthenium complex is used as an oxidation catalyst for a C--H oxidation reaction, H 2 O 2 can be used as an oxidizing agent, reducing costs and improving atomic efficiency. Moreover, compared to the case where an organic oxidizing agent is used, it is superior in terms of environmental protection.
  • R 1 is a hydrogen atom, a phenyl group, or a phenyl group in which at least one hydrogen atom is substituted with an alkyl group, a hydroxy group, a phenyl group, a halogen atom, or an alkoxy group
  • R 2 represents a hydrogen atom, a phenyl group, or an alkyl group
  • R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group.
  • n 1 or 2.
  • the carboxylic acid is oxalic acid, malonic acid, maleic acid, tetrafluorophthalic acid, methylmalonic acid, cyclopropane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, or citraconic acid.
  • the ruthenium complex according to [1].
  • a catalyst composition comprising the ruthenium complex according to any one of [1] to "3" above.
  • An oxygen-containing compound comprising the step of oxidizing a substrate having a carbon-hydrogen bond using the catalyst composition described in [4] above and an oxidizing agent to obtain an oxygen-containing compound having a carbon-oxygen bond. Production method.
  • a solvent containing 1,1,1,3,3,3-hexafluoro-2-propanol and a desiccant are used, in any one of [5] to [8] A method for producing the oxygen-containing compound described.
  • R 1 is a hydrogen atom, a phenyl group, or at least one hydrogen atom of the phenyl group is substituted with an alkyl group, a hydroxy group, a phenyl group, a halogen atom, or an alkoxy group
  • R2 represents a hydrogen atom, a phenyl group, or an alkyl group
  • R3 and R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or represents an aryl group
  • L 1 represents triphenylphosphine, pyridine, imidazole, dimethyl sulfoxide, or water
  • Y represents a halogen atom
  • Y ⁇ represents a halide ion
  • X represents a carboxyl group of a carboxylic acid.
  • X ⁇ represents an anion of the carboxylic acid
  • the carboxylic acid is selected from oxalic acid, malonic acid, maleic acid, tetrafluorophthalic acid, methylmalonic acid, cyclopropane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, and citraconic acid.
  • the mixture was cooled to 0° C. again, and 40 mL of saturated aqueous sodium hydrogen carbonate solution was added. Thereafter, the operation of blending and extracting 40 mL of dichloromethane was repeated three times.
  • the extract obtained by the three extraction operations was washed with 1N hydrochloric acid and saturated saline, sodium sulfate was added to the washing solution to remove water, and light components were distilled off using a rotary evaporator.
  • a ruthenium complex was synthesized according to the following reaction formula (1c) under heating conditions of 95° C. in the atmosphere.
  • an eggplant-shaped flask (capacity: 100 ml)
  • 901 mg (2.50 mmol) of 2-(bis(pyridin-2-ylmethyl)amino)-N-(2,6-dimethylphenyl)acetamide synthesized by the above reaction formula (1b) was placed.
  • 80 mL of ethanol, and 2.64 g (2.75 mmol) of RuCl 2 (PPh 3 ) 3 were added.
  • the reaction solution was concentrated under reduced pressure to obtain a concentrate.
  • the obtained concentrate was dissolved in 5 mL of dichloromethane, 10 mL of methanol was added, and the mixture was cooled to 0° C., and the precipitated solid was collected by filtration using a glass filter. The obtained solid was washed five times with 5 mL of methanol at 0°C, and then five times with 5 mL of hexane. The remaining solid was dissolved in 500 mL of dichloromethane and the filtrate was concentrated under reduced pressure. As a result of 1 H-NMR and single crystal X-ray structural analysis of the obtained product, it was found to be a cis-type ruthenium complex (970 mg, 1.22 mmol, yield: 48.8%) shown in reaction formula (1c). This was confirmed.
  • Example 2-2 to Example 2-34 A catalyst composition was prepared in the same manner as in Example 2-1, except that the carboxylic acids shown in Table 1 were used in place of the maleic acid used in Example 2-1 above, and the substrate was oxidized. Ta. The time for the CH oxidation reaction was 30 minutes or 1 hour. The conversion rate of the substrate and the yield of each product were calculated in the same manner as in Example 2-1. The conversion rate of the substrate, the yield of each product shown in the formulas [C7], [C3], and [C7,3] of reaction formula (2b), the ratio of each product, and TOF (rph) are shown in Table 1. Ta.
  • Example 1 The same method as Example 2-1 was used, except that a trans-ruthenium complex obtained by a known method was used instead of a cis-ruthenium complex, and pentafluorobenzoic acid was used instead of maleic acid.
  • a catalyst composition was prepared and a C--H oxidation reaction of a substrate was performed. The time for the CH oxidation reaction was 1 hour.
  • the conversion rate of the substrate and the yield of each product were calculated in the same manner as in Example 2-1.
  • Table 1 shows the conversion rate of the substrate, the yield of each product shown in formulas [C7], [C3], and [C7,3] of reaction formula (2b), and the ratio of each product.
  • ruthenium complex When a trans-type ruthenium complex was used, the oxidation reaction did not proceed. Therefore, in the following Examples, a cis-type ruthenium complex was used. Hereinafter, when it is simply referred to as a "ruthenium complex", it means a cis-type ruthenium complex.
  • Example 3-1 to Example 3-3 ⁇ Changes in catalyst performance depending on the amount of catalyst used>
  • the C-H oxidation reaction of the substrate was carried out in the following procedure, with the molar ratio of the ruthenium complex (formula (II) of reaction formula (2a)) used as a catalyst in Example 2-1 to the substrate being 0.1 mol%. Ta.
  • the CH oxidation reaction was carried out at 10° C. under air.
  • Example 3-4 to Example 3--7 Except that the carboxylic acid shown in Table 2 was used instead of the maleic acid used in Examples 3-1 to 3-3 above, and the C-H oxidation reaction time was changed as shown in Table 2.
  • the C—H oxidation reaction of the substrate was carried out in the same manner as in Examples 3-1 to 3-3.
  • the conversion rate of the substrate and the yield of each product were calculated in the same manner as in Examples 3-1 to 3-3.
  • the conversion rate of the substrate, the yield of each product shown in the formulas [C7], [C3], and [C7,3] of reaction formula (2b), the ratio of each product, and TOF (rph) are shown in Table 2.
  • Example 4-1 ⁇ Isolation and purification of ruthenium complex>
  • the reaction formula is the same as the reaction formula (2a) above.
  • 159 mg (0.200 mmol, 1.0 equivalent) of a ruthenium complex of formula (IV) shown in reaction formula (2a) and 92.9 mg (0.800 mmol, 4.0 equivalent) of maleic acid were added to a 10 mL Schlenk tube.
  • 5 mL of dichloromethane was added, and the mixture was stirred at room temperature for 5 minutes.
  • 60.3 mg (0.260 mmol, 1.3 equivalents) of silver oxide was added, and the mixture was stirred at room temperature in the dark for 1 hour. At this time, ultrasonication was performed for 1 minute every 10 minutes.
  • FIG. 3 shows the results of 1 H-NMR analysis of the isolated and purified ruthenium complex.
  • FIG. 4 shows the analysis results of time-of-flight mass spectrometry of the isolated and purified ruthenium complex. The results of these analyzes are also shown below.
  • Example 4-2 to 4-3 ⁇ Evaluation of catalytic activity of isolated and purified ruthenium complex> A catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the ruthenium complex isolated and purified in Example 4-1 above was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the C--H oxidation reaction of 4-nitrobenzoic acid ester was carried out according to the following reaction formula (2c).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the TOF of reaction formula (2c) was 138 rph.
  • the CH oxidation reaction of methylene group was carried out according to the following reaction formula (3a).
  • the C—H oxidation reaction was carried out in air at 10° C. according to the following procedure.
  • a 5 mL test tube were placed 200 mg of magnesium sulfate, 46.4 mg (400 ⁇ mol, 2.0 equivalents) of maleic acid, and 3.82 mg (4.00 ⁇ mol, 2 .0 mol%), 1000 ⁇ L of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and 38.9 ⁇ L of pentyl benzoate (38.5 mg, 200 ⁇ mol, 1.0 equivalent), Cooled to 10°C.
  • Example 6-1 ⁇ C-H oxidation reaction of nitrogen-containing compounds> A C—H oxidation reaction of a nitrogen-containing compound was carried out according to the following reaction formula (4a).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • Example 6-2 ⁇ C-H oxidation reaction of primary amine> A C—H oxidation reaction of a primary amine was carried out according to the following reaction formula (5a).
  • a catalyst composition was prepared according to the following procedure. Add 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) of reaction formula (2a) to a 5 mL Schlenk tube, and after purging the Schlenk tube with nitrogen, 1,1,1,3 , 3,3-hexafluoro-2-propanol (HFIP) (0.5 mL) was added, and the mixture was stirred at room temperature for 1 minute to obtain a catalyst composition.
  • HFIP 1,1,1,3 , 3,3-hexafluoro-2-propanol
  • the extracts obtained from the three extraction operations were combined and washed with saturated saline. After adding sodium sulfate to the obtained solution to remove water, the solvent was distilled off using a rotary evaporator.
  • the desired product glycine 6-hydroxy-6-methylheptan-2-yl (34.6 mg, yield: 85%) was obtained.
  • the TOF of reaction formula (5a) was 142 rph.
  • Example 6-3 ⁇ C-H oxidation reaction of sulfonamide> The C—H oxidation reaction of sulfonamide was carried out according to the following reaction formula (5b).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the TOF of reaction formula (5b) was 269 rph.
  • Example 6-3 ⁇ C-H oxidation reaction of imide>
  • the C—H oxidation reaction of imide was carried out according to the following reaction formula (5c).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the TOF of reaction formula (5c) was 140 rph.
  • Example 7 As a raw material complex, a ruthenium complex having C 6 H 5 (phenyl group) in place of the 2,6-dimethylphenyl group in the ruthenium complex of formula (IV) shown in reaction formula (1c) was obtained.
  • the procedure was the same as in Example 1. Synthesized with.
  • the anionic ligand of the raw material complex was exchanged using the same procedure as in Example 2-5.
  • the obtained ruthenium complex had C 6 H 5 (phenyl group) instead of the 2,6-dimethylphenyl group in the ruthenium complex used as a catalyst in Example 2-5.
  • the C—H oxidation reaction of the substrate shown in reaction formula (2b) was carried out in the same manner as in Example 2-5 except that this ruthenium complex was used as a catalyst.
  • the conversion rate of the substrate, the yield of each product shown in the formulas [C7], [C3], and [C7,3] of reaction formula (2b), the ratio of each product, and TOF (rph) are shown in Table 4. Ta. For comparison, Table 4 also shows the results of Examples 2-5.
  • the mixture obtained in the above reaction was placed in an eggplant-shaped flask, and 100 mL of ethanol and 1.58 g (1.54 mL, 31.6 mmol, 3.0 equivalent) of hydrazine monohydrate were added, and the mixture was heated under reflux for 2 hours. Stirring was performed for a period of time to obtain a reaction solution. After the reaction solution was cooled to room temperature, it was filtered to remove solid components, and light components were distilled off using a rotary evaporator.
  • Example 9 The anionic ligand was exchanged in the same manner as in Example 2-5, except that the ruthenium complex obtained in Example 8 was used as the raw material complex. In this way, a ruthenium complex was obtained in which a monovalent group obtained by removing a hydrogen atom from the carboxyl group of pentafluorobenzoic acid was coordinated in place of the chlorine atom of the axial ligand and counter anion of formula (X).
  • the C—H oxidation reaction of the substrate shown in reaction formula (2b) was carried out in the same manner as in Example 2-5 except that this ruthenium complex was used.
  • the conversion rate of the substrate, the yield of each product shown in the formulas [C7], [C3], and [C7,3] of reaction formula (2b), the ratio of each product, and TOF (rph) are shown in Table 5. .
  • Example 11 The substrate represented by reaction formula (2b) was oxidized (hydroxylated) in the same manner as in Example 2-5, except that magnesium sulfate was not used.
  • the conversion rate of the substrate, the yield of each product shown in the formulas [C7], [C3], and [C7,3] of reaction formula (2b), the ratio of each product, and TOF (rph) are shown in Table 7. Ta.
  • Table 7 also shows the results of Examples 2-5.
  • Example 12-5 to Example 12-6 A catalyst composition prepared by halving the amount of 1,1,1,3,3,3-hexafluoro-2-propanol (solvent I) used in preparing the catalyst composition, and a solvent different from solvent I Same as Example 2-5 except that 250 ⁇ L of each solvent (solvent II) was used in the C-H oxidation reaction, and the time of the C-H oxidation reaction was set as shown in Table 8. Oxidation (hydroxylation) of the substrate shown in reaction formula (2b) was performed in the following steps.
  • Example 13 ⁇ C-H oxidation reaction of 1-bromo-3,7-dimethyloctane> The C--H oxidation reaction of 1-bromo-3,7-dimethyloctane was carried out according to the following reaction formula (7).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the obtained product was analyzed by 1 H-NMR, the desired product, 7-hydroxy-3,7-dimethyloctyl bromide (32.3 mg, yield: 68%) was obtained.
  • the TOF of reaction formula (7) was 227 rph.
  • the obtained product was analyzed by 1 H-NMR, the desired product, 2,6-dimethyloctan-2,6-ol (21.0 mg, yield: 61%) was obtained.
  • the TOF of reaction formula (7) was 203 rph.
  • the obtained product was analyzed by 1 H-NMR, it was found that the desired product -(R)-3-methyl-3-hydroxypentyl benzoate (28.8 mg, yield: 58%) and benzoic acid -(R)-3-methyl-4-oxopentyl (5.2 mg, yield: 12%) was obtained.
  • the TOF of reaction formula (9) was 14 rph.
  • the obtained product was analyzed by 1 H-NMR, the desired product, 18 O-4,4-dimethyl- ⁇ -butyllactone (14.6 mg, yield: 63%) was obtained.
  • the TOF of reaction formula (10) was 105 rph.
  • Example 17 ⁇ C-H oxidation reaction of 6-methylheptan-2-yl benzoate> The C—H oxidation reaction of 4-nitrobenzoic acid ester was carried out according to the following reaction formula (11).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the obtained product was analyzed by 1 H-NMR, the desired product, 6-hydroxy-6-methylheptan-2-yl benzoate (38.6 mg, yield: 77%) was obtained.
  • the TOF of reaction formula (11) was 128 rph.
  • Example 18 ⁇ C-H oxidation reaction of 6-methylheptan-2-yl 4-cyanobenzoate> The CH oxidation reaction of 6-methylheptan-2-yl 4-cyanobenzoate was carried out according to the following reaction formula (12).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred at room temperature for 1 minute to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the obtained product was analyzed by 1 H-NMR, the desired product, 6-hydroxy-6-methylheptan-2-yl 4-cyanobenzoate (42.4 mg, yield: 77%) was obtained. It was done.
  • the TOF of reaction formula (12) was 13 rph.
  • Example 19 ⁇ C-H oxidation reaction of 6-methylheptan-2-yl (benzenesulfonic acid)> The CH oxidation reaction of 6-methylheptan-2-yl (benzenesulfonic acid) was carried out according to the following reaction formula (13).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the obtained product was analyzed by 1 H-NMR, the desired product, N-(benzenesulfonic acid) 6-methylheptan-2-yl (43.3 mg, yield: 80%) was obtained.
  • the TOF of reaction formula (13) was 133 rph.
  • Example 20 ⁇ C-H oxidation reaction of (tert-butoxycarbonyl)glycine 6-methylheptan-2-yl>
  • the C—H oxidation reaction of (tert-butoxycarbonyl)glycine 6-methylheptan-2-yl was carried out according to the following reaction formula (14).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred at room temperature for 1 minute to obtain a catalyst composition.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the TOF of reaction formula (14) was 27 rph.
  • Example 21 ⁇ C-H oxidation reaction of N-benzylglycine 6-methylheptan-2-yl> The C--H oxidation reaction of N-benzylglycine 6-methylheptan-2-yl was carried out according to the following reaction formula (15).
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the extracts obtained from the three extraction operations were combined and washed with saturated saline. After adding sodium sulfate to the obtained solution to remove water, the solvent was distilled off using a rotary evaporator.
  • the target product N-benzylglycine 6-hydroxy-6-methylheptan-2-yl (41.1 mg, yield: 70%) was obtained.
  • Ta The TOF of reaction formula (15) was 58 rph.
  • Example 24 ⁇ C-H oxidation reaction of a compound having an alicyclic structure> C—H oxidation reaction of methyl compound 3 ⁇ ,12 ⁇ -diacetoxy-5 ⁇ -cholan-24-ate of 3A in reaction formula (18) was performed.
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the obtained product was analyzed by 1 H-NMR, the desired product, a compound of formula (3V) (82.1 mg, yield: 81%) was obtained.
  • the TOF of reaction formula (18) was 135 rph.
  • Example 25 ⁇ C-H oxidation reaction of heterocyclic compound> Sulbactam-2-methylpentane ester, which is a compound of formula 3B in reaction formula (19), was subjected to a C--H oxidation reaction.
  • a catalyst composition was prepared according to the following procedure. 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) shown in reaction formula (2a) was added to a 5 mL Schlenk tube. After purging the Schlenk tube with nitrogen, 0.5 mL of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was added and stirred for 1 minute at room temperature to obtain a catalyst composition. Ta.
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the obtained product was analyzed by 1 H-NMR, the desired product, a compound of formula (3W) (53.2 mg, yield: 80%) was obtained.
  • the TOF of reaction formula (19) was 27 rph.
  • ⁇ C-H oxidation reaction of heterocyclic compound> A CH oxidation reaction of the 3C compound citaloprom in reaction formula (21) was carried out.
  • a catalyst composition was prepared according to the following procedure. Add 3.82 mg (4.00 ⁇ mol) of the isolated and purified ruthenium complex of formula (II) of reaction formula (2a) to a 5 mL Schlenk tube, and after purging the Schlenk tube with nitrogen, 1,1,1,3 , 3,3-hexafluoro-2-propanol (HFIP) (0.5 mL) was added, and the mixture was stirred at room temperature for 1 minute to obtain a catalyst composition.
  • HFIP 1,1,1,3 , 3,3-hexafluoro-2-propanol
  • the extracts obtained from the three extraction operations were combined and washed with saturated saline. After adding sodium sulfate to the obtained solution to remove water, the solvent was distilled off using a rotary evaporator.
  • the obtained product was analyzed by 1 H-NMR, it was found that the desired product was a compound of formula (3Y) (47.0 mg, yield: 69%) and a compound of formula (3Z) (12.2 mg, yield). ratio: 18%) was obtained.
  • the TOF of reaction formula (21) was 18 rph.
  • ruthenium complexes useful as catalysts are provided.
  • the present disclosure provides a method for producing an oxygen-containing compound in which the carbon-hydrogen bond of a substrate having a methine group or methylene group is oxidized using hydrogen peroxide using such a catalyst to obtain an oxygen-containing compound. is provided. Further, the present disclosure provides a method for producing a ruthenium complex that allows the production of a ruthenium complex by a simple method.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/JP2023/029298 2022-08-12 2023-08-10 ルテニウム錯体及びその製造方法、触媒組成物、並びに、酸化方法及び酸素含有化合物の製造方法 Ceased WO2024034666A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024540526A JPWO2024034666A1 (https=) 2022-08-12 2023-08-10

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022128992 2022-08-12
JP2022-128992 2022-08-12

Publications (1)

Publication Number Publication Date
WO2024034666A1 true WO2024034666A1 (ja) 2024-02-15

Family

ID=89851646

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/029298 Ceased WO2024034666A1 (ja) 2022-08-12 2023-08-10 ルテニウム錯体及びその製造方法、触媒組成物、並びに、酸化方法及び酸素含有化合物の製造方法

Country Status (2)

Country Link
JP (1) JPWO2024034666A1 (https=)
WO (1) WO2024034666A1 (https=)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021008467A (ja) * 2019-07-01 2021-01-28 国立大学法人九州大学 ルテニウム錯体及びその製造方法、触媒、並びに、酸素含有化合物の製造方法
WO2022138748A1 (ja) * 2020-12-23 2022-06-30 国立大学法人九州大学 標識方法、標識用酸化剤、ルテニウム錯体、触媒、標識化合物、及び、化合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021008467A (ja) * 2019-07-01 2021-01-28 国立大学法人九州大学 ルテニウム錯体及びその製造方法、触媒、並びに、酸素含有化合物の製造方法
WO2022138748A1 (ja) * 2020-12-23 2022-06-30 国立大学法人九州大学 標識方法、標識用酸化剤、ルテニウム錯体、触媒、標識化合物、及び、化合物

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DAIKI DOIUCHI; TATSUYA NAKAMURA; HIROKI HAYASHI; TATSUYA UCHIDA: "Non‐Heme‐Type Ruthenium Catalyzed Chemo‐ and Site‐Selective C−H Oxidation", CHEMISTRY - AN ASIAN JOURNAL, WILEY-VCH, HOBOKEN, USA, vol. 15, no. 6, 27 February 2020 (2020-02-27), Hoboken, USA, pages 762 - 765, XP072431248, ISSN: 1861-4728, DOI: 10.1002/asia.202000134 *
DOIUCHI DAIKI, UCHIDA TATSUYA: "Catalytic Highly Regioselective C–H Oxygenation Using Water as the Oxygen Source: Preparation of 17 O/ 18 O-Isotope-Labeled Compounds", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 23, no. 18, 17 September 2021 (2021-09-17), US , pages 7301 - 7305, XP055945242, ISSN: 1523-7060, DOI: 10.1021/acs.orglett.1c02812 *
MANDAL SANJAY K., QUE LAWRENCE: "Models for Amide Ligation in Nonheme Iron Enzymes", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, EASTON , US, vol. 36, no. 24, 1 November 1997 (1997-11-01), Easton , US , pages 5424 - 5425, XP093138109, ISSN: 0020-1669, DOI: 10.1021/ic970541y *

Also Published As

Publication number Publication date
JPWO2024034666A1 (https=) 2024-02-15

Similar Documents

Publication Publication Date Title
JP6011867B2 (ja) デンドリマー固定化含窒素複素環カルベン−金錯体
JPH11226417A (ja) 酸化触媒系及びそれを用いた酸化方法
WO2024034666A1 (ja) ルテニウム錯体及びその製造方法、触媒組成物、並びに、酸化方法及び酸素含有化合物の製造方法
JP2005536558A (ja) ナプロキセンのニトロオキシ誘導体の製造法
JP2021008467A (ja) ルテニウム錯体及びその製造方法、触媒、並びに、酸素含有化合物の製造方法
CN113549062A (zh) 一种金鸡纳碱衍生的大位阻手性季铵盐相转移催化剂及其合成方法
CN104774183B (zh) 一种甲酰基瑞舒伐汀钙中间体的制备方法
WO2022138748A1 (ja) 標識方法、標識用酸化剤、ルテニウム錯体、触媒、標識化合物、及び、化合物
JP4649733B2 (ja) トリフルオロメチル基含有アセトフェノン化合物の製造方法
JP5408662B2 (ja) ジスルホン酸化合物の製法、不斉マンニッヒ触媒、β−アミノカルボニル誘導体の製法及び新規なジスルホン酸塩
JP5659191B2 (ja) 複素環化合物、酸化触媒及びその使用
JP7266139B1 (ja) 芳香族ビスエーテル化合物の製造方法
JP4635251B2 (ja) 有機ビスマス化合物およびその製法
JP5552510B2 (ja) 酸化触媒及び酸化反応生成物の製造方法
JP2010202544A (ja) サリドマイド誘導体の製造方法
JPWO2008059960A1 (ja) クォータピリジン誘導体の製造方法及びその中間体
JP5762288B2 (ja) アリルアミンの製造方法
JP2024091067A (ja) 中間体化合物の製造方法、配位子の製造方法、および四級不斉炭素含有化合物の製造方法
JPH08134064A (ja) 新規クラウンチオエーテルおよびその遷移金属錯体並びにこれを用いる不斉ヒドロシリル化方法
JP4982732B2 (ja) ビナフチル誘導体およびその製造方法
JP2024166985A (ja) テルピリジン化合物の製造方法およびｃ－グリコシド化合物の製造方法
JP5552550B1 (ja) 酸化触媒及び酸化反応生成物の製造方法
JP2023020020A (ja) カルベン化合物及びその製造方法
WO2026003142A1 (en) Process
CN121698725A (zh) 一种1-丁烯-3,4-二醇的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23852628

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024540526

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23852628

Country of ref document: EP

Kind code of ref document: A1