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WO2018135506A1 - Méthode de réduction utilisant un complexe de ruthénium - Google Patents

Méthode de réduction utilisant un complexe de ruthénium Download PDF

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Publication number
WO2018135506A1
WO2018135506A1 PCT/JP2018/001084 JP2018001084W WO2018135506A1 WO 2018135506 A1 WO2018135506 A1 WO 2018135506A1 JP 2018001084 W JP2018001084 W JP 2018001084W WO 2018135506 A1 WO2018135506 A1 WO 2018135506A1
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group
formula
substituted
ruthenium complex
unsubstituted
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PCT/JP2018/001084
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Japanese (ja)
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大岡　浩仁
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日本曹達株式会社
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Priority to JP2018563349A priority Critical patent/JP6751162B2/ja
Publication of WO2018135506A1 publication Critical patent/WO2018135506A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/68—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13—Monohydroxylic alcohols containing saturated rings
    • C07C31/133—Monohydroxylic alcohols containing saturated rings monocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C07C33/22—Benzylalcohol; phenethyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/26—Polyhydroxylic alcohols containing only six-membered aromatic rings as cyclic part

Definitions

  • the present invention relates to a reduction method using a ruthenium complex.
  • Non-Patent Document 1 discloses a ruthenium complex having a nitrogen-containing bidentate ligand represented by the formula (1), and performs structural analysis of the crystal.
  • Patent Document 1 discloses a ruthenium complex represented by the formula (2). is doing. By using the ruthenium complex, amides or lactams can be reduced to alcohols or amino alcohols, respectively.
  • Non-Patent Document 2 discloses a ruthenium complex represented by the formula (3). Using the ruthenium complex, cyclohexanone is reduced to cyclohexyl alcohol.
  • An object of the present invention is to provide a ruthenium complex that can be a reduction catalyst that can be applied to industrial production.
  • the inventor has conducted studies to achieve the above object, and as a result, has completed the present invention including the following aspects.
  • At least one selected from compounds, Formula [III] AB [III] (In the formula [III], A and B are bonded by a single bond.
  • A represents the formula [a1].
  • R 1 represents a substituent
  • p represents an integer of 0 to 3
  • * represents a bonding position with B.
  • R 2 represents a substituent
  • q represents an integer of 0 to 4
  • * represents a bonding position with B
  • B represents a substituted or unsubstituted heterocyclyl. Indicates a group.
  • At least one of the atoms adjacent to the ring atom bonded to A is a heteroatom or a carbene carbon.
  • the ruthenium complex according to the present invention is useful as a reduction catalyst.
  • the reduction catalyst according to the present invention for example, ketones, aldehydes, esters and amides can be reduced. Since the catalyst according to the present invention has high activity, the reduction reaction rate can be sufficiently improved even with a small amount of use.
  • the ruthenium complex of the present invention is a complex prepared from at least one selected from the compounds represented by the formulas [I] and [II] and the compound represented by the formula [III].
  • X 1 represents an anionic group.
  • the anionic group include CF 3 SO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ ; halogeno groups such as fluoro group, chloro group, bromo group and iodo group; hydride group; hydroxyl group; acetylacetonate and the like A substituted or unsubstituted diketonate group; a substituted or unsubstituted cyclopentadienyl group; a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, 1- Methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2 -
  • Alkenyl group methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
  • Substituted or unsubstituted alkyl group substituted or unsubstituted aryl group such as phenyl group and naphthyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i A substituted or unsubstituted alkoxy group such as -butoxy group and t-butoxy group; a substituted or unsubstituted aryloxy group such as phenoxy group and 1-naphthoxy group; a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, Substituted or unsubstituted alkyl such as i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, etc.
  • Z 1 represents a substituted or unsubstituted cyclopentadienyl group.
  • Z 1 include a cyclopentadienyl group, 1,3-diisopropylcyclopentadienyl group, tetraphenylcyclopentadienyl group, pentamethylcyclopentadienyl group and the like.
  • L 1 represents a neutral ligand.
  • the neutral ligand may be a monodentate ligand or a bidentate ligand.
  • m represents 2 or 3 when L 1 is a monodentate ligand, and represents 1 when L 1 is a bidentate ligand.
  • Examples of the “substituent” in “substituted or unsubstituted” of the groups exemplified for X 1 and Z 1 include the same groups as those in the formula [III] described later.
  • Specific examples of the compound represented by the formula [I] include chloro (1,5-cyclooctadiene) (pentamethylcyclopentadienyl) ruthenium (II), chloro (norbornadiene) (pentamethylcyclopentadienyl). ) Ruthenium (II), chloro (isoprene) (pentamethylcyclopentadienyl) ruthenium (II), and the like.
  • X 2 represents an anionic group.
  • the anionic group include CF 3 SO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ ; halogeno groups such as fluoro group, chloro group, bromo group and iodo group; hydride group; hydroxyl group; acetylacetonate and the like A substituted or unsubstituted diketonate group; a substituted or unsubstituted cyclopentadienyl group; a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, 1- Methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group,
  • Alkenyl group methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
  • Substituted or unsubstituted alkyl group substituted or unsubstituted aryl group such as phenyl group and naphthyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i A substituted or unsubstituted alkoxy group such as -butoxy group and t-butoxy group; a substituted or unsubstituted aryloxy group such as phenoxy group and 1-naphthoxy group; a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, Substituted or unsubstituted alkyl such as i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, etc.
  • Z 2 represents a substituted or unsubstituted cyclopentadienyl group.
  • Z 2 include a cyclopentadienyl group, 1,3-diisopropylcyclopentadienyl group, tetraphenylcyclopentadienyl group, pentamethylcyclopentadienyl group and the like.
  • n represents an integer of 2 to 4.
  • Examples of the “substituent” in “substituted or unsubstituted” of the groups exemplified as X 2 and Z 2 include the same groups as the substituents in the formula [III] described later.
  • A represents a structure represented by the formula [a1] or the formula [a2].
  • R 1 represents a substituent.
  • Substituents include C1-6 alkyl groups, C3-8 cycloalkyl groups, C6-10 aryl groups, 3-6 membered heterocyclyl groups, hydroxyl groups, C1-6 alkoxy groups, C6-10 aryloxy groups, carboxyl groups, Halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, amino group (group represented by NH 2 ), C1-6 alkyl-substituted amino group, C6-10 arylamino group, C1 ⁇ 7 acylamino group, C1-6 alkoxycarbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl group, C6-10 arylsulfinyl group , Heteroarylsulfiny
  • p represents an integer of 0 to 3.
  • R 2 represents a substituent.
  • Substituents include C1-6 alkyl groups, C3-8 cycloalkyl groups, C6-10 aryl groups, 3-6 membered heterocyclyl groups, hydroxyl groups, C1-6 alkoxy groups, C6-10 aryloxy groups, carboxyl groups, Halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, amino group (group represented by NH 2 ), C1-6 alkyl-substituted amino group, C6-10 arylamino group, C1 -7 acylamino group, C1-6 alkoxycarbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl group, C6-10 arylsulfinyl group , Heteroarylsulfinyl
  • q represents an integer of 0 to 4.
  • C1-6 alkyl group includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, and n-pentyl group. And n-hexyl group.
  • the “C3-8 cycloalkyl group” is a monocyclic or polycyclic alkyl group, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bicyclooctyl group. And a bicycloheptyl group.
  • “C6-10 aryl group” means a monocyclic or polycyclic aryl group.
  • a partially saturated group is included in addition to the fully unsaturated group.
  • Examples thereof include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
  • Examples of the “3- to 6-membered heterocyclyl group” include the same groups as those exemplified for B in the formula [III] described later.
  • Examples of the “C1-6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group and the like.
  • Examples of the “C6-10 aryloxy group” include a phenoxy group and a 1-naphthoxy group.
  • Examples of the “halogeno group” include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • C1-6 haloalkyl group examples include chloromethyl group, bromomethyl group, fluoromethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trichloroethyl group, 2,2,3 , 3,3-pentafluoropropyl group or 1-chlorobutyl group, 6-fluorohexyl group, 6,6,6-trifluorohexyl group and the like.
  • C6-10 haloaryl group examples include 4-chlorophenyl, 4-bromophenyl, 3,5-dichlorophenyl and the like.
  • Examples of the “C1-6 haloalkoxy group” include chloromethoxy group, bromomethoxy group, fluoromethoxy, trifluoromethoxy group and the like.
  • Examples of the “C1-6 alkyl-substituted amino group” include monoalkylamino groups such as methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-hexylamino group; dimethylamino group, diethylamino group And dialkylamino groups such as a di-n-propylamino group, a di-n-butylamino group, and an N-methyl-N-hexylamino group.
  • Examples of the “C6-10 arylamino group” include a phenylamino group and a diphenylamino group.
  • Examples of the “C1-7 acylamino group” include an acetylamino group and a diacetylamino group.
  • Examples of the “C1-6 alkoxycarbonylamino group” include a methoxycarbonylamino group and a dimethoxycarbonylamino group.
  • Examples of the “C1-6 alkylthio group” include methylthio group, ethylthio group, n-propylthio group, t-butylthio group, 1-ethylpropylthio group, n-hexylthio group and the like.
  • Examples of the “C6-10 arylthio group” include a phenylthio group and a naphthylthio group.
  • Examples of the “heteroarylthio group” include a furylthio group, a thienylthio group, a pyrrolylthio group, a pyridinylthio group, a pyrazinylthio group, and a pyridinylthio group.
  • Examples of the “C7-11 aralkylthio group” include benzylthio group, phenethylthio group, naphthylmethylthio group and the like.
  • C1-6 alkylsulfinyl group examples include methylsulfinyl group, ethylsulfinyl group, t-butylsulfinyl group and the like.
  • C6-10 arylsulfinyl group examples include a phenylsulfinyl group and a naphthylsulfinyl group.
  • heteroarylsulfinyl group examples include a furylsulfinyl group, a thienylsulfenyl group, a pyrrolylsulfenyl group, a pyridinylsulfenyl group, a pyrazinylsulfenyl group, and a pyridinylsulfenyl group.
  • C7-11 aralkylsulfinyl group include benzylsulfenyl group, phenethylsulfenyl group, naphthylmethylsulfenyl group and the like.
  • C1-6 alkylsulfonyl group examples include a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group and the like.
  • C6-10 arylsulfonyl group examples include a phenylsulfonyl group and a naphthylsulfonyl group.
  • heterocyclylsulfonyl group examples include an aziridinylsulfonyl group, an epoxysulfonyl group, a pyrrolyl sulfonyl group, a furylsulfonyl group, a thienylsulfonyl group, and the like.
  • B represents a substituted or unsubstituted heterocyclyl group.
  • at least one of the atoms adjacent to the ring atom bonded to A is a heteroatom or a carbene carbon.
  • heterocyclyl group includes 1 to 4 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as ring constituent atoms.
  • the heterocyclyl group may be monocyclic or polycyclic. In the polycyclic heterocyclyl group, if at least one ring is a hetero ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring or an aromatic ring.
  • heterocyclyl group examples include a 3-6 membered saturated heterocyclyl group, a 5-6 membered heteroaryl group, a 5-6 membered partially unsaturated heterocyclyl group, and a 9-10 membered heteroaryl group.
  • Examples of the 3- to 6-membered saturated heterocyclyl group include aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group and dioxanyl group.
  • Examples of 5-membered heteroaryl groups include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl Can do.
  • Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridanidyl group, and a triazinyl group.
  • Examples of the 5- to 6-membered partially unsaturated heterocyclyl group include 2,3-dihydropyrrolyl group, 2,3-dihydropyridinyl group, 2,3-dihydrothiazolyl group, 2,3-dihydrofuranyl group, An imidazolinyl group etc. can be mentioned.
  • the 9 to 10 membered heteroaryl group is a bicyclic heterocyclyl group having a benzene ring, and examples thereof include an indolyl group, a quinolinyl group, a benzimidazolyl group, a benzofuranyl group, and a benzothiazolinyl group.
  • Examples of the substituent for the heterocyclyl group include a C1-6 alkyl group, a C3-8 cycloalkyl group, a C6-10 aryl group, a 3-6 membered heterocyclyl group, a hydroxyl group, a C1-6 alkoxy group, a C6-10 aryloxy group, Carboxyl group, halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, amino group (group represented by NH 2 ), C1-6 alkyl-substituted amino group, C6-10 arylamino Group, C1-7 acylamino group, C1-6 alkoxycarbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl group, C6-10 Arylsulfinyl group, heteroarylsulf
  • R 1 and R a each independently represent a substituent
  • p represents an integer of 0 to 3
  • p1 represents an integer of 0 to 4.
  • Substituents in R 1, R a may be mentioned the same as R 1 in the formula [a1].
  • R 1 and R b each independently represent a substituent
  • p represents an integer of 0 to 3
  • p2 represents an integer of 0 to 3.
  • Substituents in R 1, R b may be exemplified the same as R 1 in the formula [a1].
  • R 1 and R c each independently represents a substituent
  • p represents an integer of 0 to 3
  • p3 represents an integer of 0 to 3.
  • Substituents in R 1, R c may be mentioned the same as R 1 in the formula [a1].
  • R 1 and R d each independently represent a substituent
  • R 3 represents a C1-6 alkyl group
  • p represents an integer of 0 to 3
  • p4 represents 0 to 4 represents any integer.
  • Substituents in R 1, R d may include the same ones as R 1 in the formula [a1].
  • R 1 and R e each independently represents a substituent
  • R 4 represents a C1-6 alkyl group
  • p represents an integer of 0 to 3
  • p5 represents 0 to 4 represents any integer.
  • Substituents in R 1, R e may be mentioned the same as R 1 in the formula [a1].
  • R 2 and R f each independently represent a substituent
  • q represents an integer of 0 to 4
  • p6 represents an integer of 0 to 4.
  • Substituent in R 2, R f may be mentioned the same as R 2 in the formula [a2].
  • R 2 and R g each independently represent a substituent
  • q represents an integer of 0 to 4
  • p7 represents an integer of 0 to 2.
  • Examples of the substituent for R 2 and R g include the same as R 2 in formula [a2].
  • R 2 and R h each independently represent a substituent
  • q represents an integer of 0 to 4
  • p8 represents an integer of 0 to 4.
  • R 2, R h definitive substituent group include the same as R 2 in the formula [a2].
  • the ruthenium complex of the present invention is obtained by mixing and reacting at least one selected from the compounds represented by the formula [I] and the formula [II] with the compound represented by the formula [III] in an organic solvent. Can be prepared.
  • organic solvent used in the reaction examples include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane and hexane; dichloromethane, chloroform, trichloromethane, carbon tetrachloride, and 1,2-dichloroethane.
  • Halogen ethers such as; ethers such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane, 1,4-dioxane; alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, and benzyl alcohol N, N-dimethylformamide (DMF), N, N-dimethylacetamide, 1,3-dimethylimidazolidine, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, hexamethylphosphoric triamide (HMPT) Amides; acetonitrile, nitriles such as benzonitrile; and the like dimethyl sulfoxide (DMSO). These solvents can be used alone or in admixture of two or more.
  • ethers such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane, 1,
  • the amount of solvent used is preferably 1 to 100 ml, more preferably 5 to 30 ml, with respect to 1 g of the reactant.
  • the temperature during the reaction is usually room temperature to the boiling point of the reaction solvent, preferably 25 to 100 ° C.
  • the reaction time varies depending on the reaction scale, but is usually 0.1 to 48 hours, preferably 0.1 to 18 hours.
  • the solution containing the ruthenium complex may be used as it is as a catalyst for the reduction reaction, or the ruthenium complex is isolated from the solution containing the ruthenium complex by a known method and used as the catalyst for the reduction reaction, etc. May be used.
  • the amount of the compound represented by the formula [III] is preferably 0.5 to 5 mol, more preferably 1.0 to 1 mol with respect to 1 mol of the compound represented by the formula [I] and the formula [II]. 1.5 moles.
  • the method of the present invention uses a ruthenium complex prepared from at least one selected from a compound represented by the formula [I] and a compound represented by the formula [II] and a compound represented by the formula [III].
  • ketones, aldehydes, esters and amides are reduced in the presence of a hydrogen donor and a base.
  • Examples of the hydrogen donor include hydrogen gas, isopropanol, formic acid, formate, and the like. These can be used alone or in combination of two or more. Of these, hydrogen gas is preferred.
  • Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide, ammonia, C3-30
  • bases such as organic amines. These can be used alone or in combination of two or more.
  • Specific examples of the C3-30 organic amines include triethylamine, tributylamine, diisopropylethylamine, isopropyldimethylamine, trimethylamine, n-trioctylamine, iso-trioctylamine, 1,8-diazabicyclo [5.4.0].
  • the amount of the base to be used is not particularly limited, but is an amount that is 1 mol or more with respect to 1 mol of the ruthenium complex.
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
  • aldehydes examples include formaldehyde, acetaldehyde, and benzaldehyde.
  • esters examples include methyl benzoate, ethyl benzoate, isopropyl benzoate, methyl 3-phenylpropionate, methyl cyclopropanecarboxylate, and phthalide.
  • amides examples include N-methylacetanilide and 1-phenyl-2-pyrrolidone.
  • solvent used for the reduction reaction water; alcohol solvents such as methanol, ethanol, 2-propanol, tert-butyl alcohol, trifluoroethanol, hexafluoroisopropanol; aromatic solvents such as toluene and xylene; diethyl ether, tetrahydrofuran Ether solvents such as 2-methyltetrahydrofuran; halogen solvents such as dichloromethane and chloroform can be used.
  • alcohol solvents such as methanol, ethanol, 2-propanol, tert-butyl alcohol, trifluoroethanol, hexafluoroisopropanol
  • aromatic solvents such as toluene and xylene
  • diethyl ether, tetrahydrofuran Ether solvents such as 2-methyltetrahydrofuran
  • halogen solvents such as dichloromethane and chloroform
  • the amount of the ruthenium complex used is such that ruthenium in the complex is preferably 0.001 to 100 mmol, more preferably 0.06 to 20 mmol, relative to 1 mol of the substrate.
  • the amount of the hydrogen donor to be used is preferably 1 mol or more, more preferably 2 mol or more, further preferably 10 mol or more, still more preferably 20 mol or more with respect to 1 mol of the functional group to be reduced in the substrate. It is.
  • the temperature during the reduction reaction can be selected from the range of preferably ⁇ 20 to 150 ° C., more preferably 0 to 100 ° C.
  • the time for the reduction reaction varies depending on the amount of catalyst used, but is preferably 0.1 to 100 hours, more preferably 0.1 to 10 hours.
  • the product can be separated and purified by general operations such as distillation, extraction, chromatography, and recrystallization.
  • Example 1 (Hydrogenation of acetophenone) To a glass autoclave were added 5 mg (0.01 mmol) of ruthenium complex 1 and 11 mg (0.1 mmol) of potassium t-butoxide, and the atmosphere was replaced with argon. 1.20 g (10 mmol) of acetophenone was dissolved in 5 ml of isopropanol, degassed, and then purged with argon. The acetophenone solution was transferred to an autoclave and stirred at room temperature for 1 hour under a hydrogen atmosphere of 0.9 MPa. After releasing the residual pressure, GC analysis (FID) was performed. 1-phenylethane-1-ol was obtained at a relative area ratio of 98.9%.
  • FID GC analysis
  • Example 2 (Hydrogenation of acetophenone) The hydrogenation reaction of acetophenone was performed in the same manner as in Example 1 except that the ruthenium complex 4 was used instead of the ruthenium complex 1. 1-Phenylethane-1-ol was obtained at a relative area ratio of 99.6%.
  • Example 3 (Hydrogenation of acetophenone) The hydrogenation reaction of acetophenone was performed in the same manner as in Example 1 except that the ruthenium complex 5 was used instead of the ruthenium complex 1. 1-phenylethane-1-ol was obtained at a relative area ratio of 96.3%.
  • Example 4 (Hydrogenation of acetophenone) The hydrogenation reaction of acetophenone was performed in the same manner as in Example 1 except that the ruthenium complex 6 was used instead of the ruthenium complex 1. 1-Phenylethane-1-ol was obtained at a relative area ratio of 99.7%.
  • Example 5 (Hydrogenation of acetophenone) The hydrogenation reaction of acetophenone was carried out in the same manner as in Example 1 except that ruthenium complex 3 was used instead of ruthenium complex 1. 1-phenylethane-1-ol was obtained at a relative area ratio of 98.6%.
  • Example 6 (hydrogenation of methyl benzoate) After adding 5 mg (0.01 mmol) of ruthenium complex 1 to the metal autoclave, the reaction system was purged with argon. 2.72 g (20 mmol) of methyl benzoate was dissolved in 7.5 ml of tetrahydrofuran, degassed, and purged with argon. The ester solution was transferred to the autoclave followed by the addition of 1 ml of 1M potassium t-butoxide / tetrahydrofuran solution. The mixture was stirred at 80 ° C. for 3 hours under a hydrogen atmosphere of 5 MPa. After cooling, HPLC analysis was performed.
  • Benzyl alcohol was produced with a relative area ratio of 95.6% (quantitative analysis yield 92.4%).
  • methyl benzoate was present in a relative area ratio of 1.7% and benzyl benzoate was present in a relative area ratio of 0.3%.
  • Example 7 (hydrogenation of methyl benzoate) A hydrogenation reaction of methyl benzoate was carried out in the same manner as in Example 6 except that ruthenium complex 3 was used instead of ruthenium complex 1. Benzyl alcohol was produced with a relative area ratio of 77.1%. In addition, methyl benzoate was present in a relative area ratio of 15.4% and benzyl benzoate was present in a relative area ratio of 5.7%.
  • Comparative Example 1 (hydrogenation of methyl benzoate) A hydrogenation reaction of methyl benzoate was performed in the same manner as in Example 6 except that ruthenium complex A was used instead of ruthenium complex 1. Benzyl alcohol was produced with a relative area ratio of 39.7%. In addition, methyl benzoate was present at a relative area ratio of 54.0% and benzyl benzoate was present at a relative area ratio of 4.5%.
  • Example 8 (hydrogenation of phthalide)
  • a metal autoclave 2.68 g (20 mmol) of phthalide and 4 mg (0.01 mmol) of ruthenium complex 2 were added and substituted with argon.
  • 10 ml of degassed tetrahydrofuran 1 ml (5 mol%) of a potassium t-butoxide / tetrahydrofuran solution (1M)
  • the reaction solution was neutralized with acetic acid and concentrated by silica gel column chromatography to obtain 2.47 g (yield 89%) of 1,2-benzenedimethanol.
  • Example 9 (phthalide hydrogenation)
  • a metal autoclave 2.68 g (20 mmol) of phthalide and 4 mg (0.01 mmol) of ruthenium complex 3 were placed and substituted with argon. Thereto were added 10 ml of degassed tetrahydrofuran and 1 ml (5 mol%) of a potassium t-butoxide / tetrahydrofuran solution (1M), and the mixture was stirred at 80 ° C. for 5 hours in a 5 MPa hydrogen atmosphere. After cooling, the reaction mixture was neutralized with acetic acid and concentrated by silica gel column chromatography to obtain 2.30 g of 1,2-benzenedimethanol (yield 83%).
  • Example 10 (hydrogenation of phthalides) A metal autoclave was charged with 2.68 g (20 mmol) of phthalide and 5 mg (0.01 mmol) of ruthenium complex 1 and substituted with argon. Thereto were added 10 ml of degassed tetrahydrofuran and 1 ml (5 mol%) of a potassium t-butoxide / tetrahydrofuran solution (1M), and the mixture was stirred at 80 ° C. for 5 hours in a 5 MPa hydrogen atmosphere. After cooling, the reaction solution was neutralized with acetic acid and concentrated by silica gel column chromatography to obtain 2.47 g (yield 89%) of 1,2-benzenedimethanol.
  • Example 11 (hydrogenation of isopropyl benzoate) 5 mg (0.01 mmol) of ruthenium complex 1 was added to the metal autoclave, and the atmosphere was replaced with argon. 3.28 g (20 mmol) of isopropyl benzoate was dissolved in 7.5 ml of tetrahydrofuran, degassed, and purged with argon. The ester solution was transferred to an autoclave followed by the addition of 1 ml of 1M potassium t-butoxide / tetrahydrofuran solution. The mixture was stirred at 80 ° C. for 1.5 hours under a hydrogen atmosphere of 5 MPa. After cooling, the reaction solution was sampled and subjected to HPLC analysis (UV wavelength: 210 nm) to obtain benzyl alcohol with a relative area ratio of 91.2% (quantitative analysis yield: 87.8%).
  • HPLC analysis UV wavelength: 210 nm
  • Example 12 (Hydrogenation of methyl 3-phenylpropionate) 5 mg (0.01 mmol) of ruthenium complex 1 was placed in a metal autoclave and purged with argon. In a Schlenk tube, 1.64 g (10 mmol) of methyl 3-phenylpropionate was added to 10 ml of tetrahydrofuran, deaerated, and purged with argon. The ester solution was transferred to an autoclave, and then 0.5 ml (5 mol%) of potassium t-butoxide / tetrahydrofuran solution (1M) was added. The mixture was stirred at 80 ° C. for 5 hours under a hydrogen atmosphere of 5 MPa. After cooling and neutralizing with acetic acid, the reaction solution was concentrated. Purification by silica gel column chromatography gave 1.15 g (yield 84%) of 3-phenylpropanol.
  • Example 13 (hydrogenation of methyl cyclopropanecarboxylate) 5 mg (0.01 mmol) of ruthenium complex 1 was added to the metal autoclave, and the atmosphere was replaced with argon. 1.00 g (10 mmol) of methyl cyclopropanecarboxylate was dissolved in 10 ml of tetrahydrofuran, degassed, and purged with argon. The ester solution was transferred to an autoclave, followed by the addition of 0.5 ml of 1M potassium t-butoxide / tetrahydrofuran solution. The mixture was stirred at 80 ° C. for 5 hours under a hydrogen atmosphere of 5 MPa.
  • reaction solution was sampled and subjected to GC analysis (FID) to obtain cyclopropylmethanol with a relative area ratio of 80.1%.
  • FID GC analysis
  • Example 14 (Hydrogenation of 1-phenyl-2-pyrrolidone) A metal autoclave was charged with 5 mg (0.01 mmol) of ruthenium complex 1 and purged with argon. In a Schlenk tube, 1.61 g (10 mmol) of 1-phenyl-2-pyrrolidone was added to 10 ml of tetrahydrofuran, deaerated, and purged with argon. The lactam solution was transferred to the autoclave, and then 0.5 ml (5 mol%) of potassium t-butoxide / tetrahydrofuran solution (1M) was added. The mixture was stirred at 80 ° C. for 5 hours under a hydrogen atmosphere of 5 MPa.
  • Example 15 (Hydrogenation of methyl benzoate) A hydrogenation reaction of methyl benzoate was carried out in the same manner as in Example 6 except that ruthenium complex 7 was used instead of ruthenium complex 1. Benzyl alcohol was produced with a relative area ratio of 80%. In addition, methyl benzoate was present in a relative area ratio of 7.7% and benzyl benzoate was present in a relative area ratio of 5.6%.
  • Example 16 (hydrogenation of methyl benzoate) A hydrogenation reaction of methyl benzoate was carried out in the same manner as in Example 6 except that ruthenium complex 8 was used instead of ruthenium complex 1. Benzyl alcohol was produced with a relative area ratio of 63.9%. In addition, methyl benzoate was present in a relative area ratio of 21.9% and benzyl benzoate was present in a relative area ratio of 12.2%.

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Abstract

Le but de la présente invention est de fournir un complexe de ruthénium qui peut servir de catalyseur de réduction qui est applicable à une production industrielle. Selon la présente invention, des cétones, des aldéhydes, des esters ou des amides sont réduits, en présence d'un donneur d'hydrogène et d'une base, à l'aide d'un complexe de ruthénium qui est préparé à partir d'au moins un composé choisi parmi les composés représentés par la formule (I) Ru(X1)(L1)m(Z1) (dans la formule (I), X1 représente un groupe anionique ; Z1 représente un groupe cyclopentadiényle substitué ou non substitué ; L1 représente un ligand neutre ; et m représente un nombre entier de 1 à 3) et des composés représentés par la formule (II) [Ru(X2)(Z2)]n (dans la formule (II), X2 représente un groupe anionique ; Z2 représente un groupe cyclopentadiényle substitué ou non substitué ; et n représente un nombre entier de 2 à 4), et un composé représenté par la formule (III) A-B (dans la formule (III), A représente un groupe représenté par la formule (a1) ou similaire ; et B représente un groupe hétérocyclyle substitué ou non substitué, à condition qu'au moins un atome adjacent à un atome d'anneau lié à A dans le groupe hétérocyclyle substitué ou non substitué soit un hétéroatome ou un atome de carbone de carbène).
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CN113264504A (zh) * 2021-06-08 2021-08-17 西安交通大学 生物质高效制氢催化体系循环利用的方法
WO2023228980A1 (fr) * 2022-05-25 2023-11-30 ダイキン工業株式会社 Procédé de production d'un composé contenant un groupe fluoropolyéther

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112209916A (zh) * 2020-10-23 2021-01-12 河北师范大学 一种钌配合物、制备方法和催化用途
CN112209916B (zh) * 2020-10-23 2021-06-01 河北师范大学 一种钌配合物、制备方法和催化用途
CN113264504A (zh) * 2021-06-08 2021-08-17 西安交通大学 生物质高效制氢催化体系循环利用的方法
CN113264504B (zh) * 2021-06-08 2024-02-06 西咸新区青氢华屹能源科技有限公司 生物质高效制氢催化体系循环利用的方法
WO2023228980A1 (fr) * 2022-05-25 2023-11-30 ダイキン工業株式会社 Procédé de production d'un composé contenant un groupe fluoropolyéther
JP2023174585A (ja) * 2022-05-25 2023-12-07 ダイキン工業株式会社 フルオロポリエーテル基含有化合物の製造方法
JP7421154B2 (ja) 2022-05-25 2024-01-24 ダイキン工業株式会社 フルオロポリエーテル基含有化合物の製造方法

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