Solid-supported ruthenium complex, method for producing the same, and method for producing allyl compound using the same

Abstract

To provide a solid-supported ruthenium complex useful as a catalyst for producing allyl compounds, a method for producing the same, and a method for producing an allyl compound using the same.SOLUTION: The solid-supported ruthenium complex is represented by General Formula (1), and an allyl compound is produced using the solid-supported ruthenium complex as a catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a solid-supported ruthenium complex useful as a catalyst for producing allyl compounds, a method for producing the same, and a method for producing allyl compounds using the same. [Background technology]

[0002] Allyl compounds are used in pharmaceuticals, agricultural chemicals, polymer materials, etc. Allyl halides and allyl esters are used as allylating agents to produce allyl compounds, but these methods also produce equivalent amounts of hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, or by-products such as carboxylic acid derivatives, in addition to the target allyl compounds.

[0003] The production method using an allyl alcohol compound as an allylating agent is not only low-cost but also environmentally friendly because the by-product is water. Several methods for producing allyl compounds using allyl alcohol are known, and catalysts for producing allyl compounds used in these methods have been reported (Patent Documents 1, 2, and 3). However, these require the use of homogeneous catalysts, which pose a problem of catalyst removal after the reaction. To solve this problem, a solid-supported catalyst in which a catalyst for producing allyl compounds is fixed on a support has been reported (Patent Document 4), but this has problems such as the need for high temperatures for the allylation reaction. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-212148 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-212148 [Patent Document 3] Japanese Patent Application Laid-Open No. 1992-208233 [Patent Document 4] Japanese Patent Application Laid-Open No. 2018-184376 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a catalyst for producing an allyl compound from an allyl alcohol compound in water using a heterogeneous solid-supported ruthenium complex as a catalyst, without using reactants such as an allyl halide compound that by-produces hydrogen halide, or reactants such as an allyl ester compound that by-produces a carboxylic acid derivative as a waste product, and without requiring an organic solvent or a purification operation; and a method for producing the same; and a method for producing an allyl compound using the catalyst for producing the allyl compound. [Means for solving the problem]

[0006] As a result of extensive research conducted by the present inventors to solve the above problems, they discovered that the above problems can be solved by using a solid-supported ruthenium complex as a catalyst, and thus completed the present invention.

[0007] That is, the present invention is as described in the claims, and the gist of the present disclosure is as follows. [1] General formula (1)

[0008] [ka]

[0009] (In the formula, Y 1 ,Y 2 ,Y 3 ,Y 4 and Y 5 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; Y 1 ,Y 2 ,Y 3 ,Y 4 and Y 5 At least one of R represents an alkyl group having 1 to 10 carbon atoms. 1 are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a halogen atom; R1 Adjacent groups may be bonded to each other to form a ring. The carrier represents a polymer sphere such as polystyrene, polyethylene, or polypropylene having a diameter of 10 to 320 μm and having a hydrophilic polymer chain such as a polyethylene glycol chain, a polypropylene glycol chain, a polyamide chain, a polyacrylamide chain, a polyvinyl alcohol chain, or a polyacrylic acid. Z represents -COO-, -OCO-, -CONH-, or -NHCO-. R 2 ,R 3 and R 4 each independently represents a hydrogen atom; a methyl group; or a monocyclic, polycyclic, or fused-ring aryl group having 6 to 14 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group. X - represents a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, a paratoluenesulfonate ion or a halide ion. [2]R 1 are the same or different and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group. [3] The solid-supported ruthenium complex according to the above [1] or [2], wherein the support is a polystyrene sphere having a diameter of 90 to 130 μm and having a polyethylene glycol chain as a hydrophilic polymer chain. [4] The solid-supported ruthenium complex according to any one of [1] to [3] above, wherein Z is -CONH- or -NHCO-. [5]R 5 ,R 6 and R 7 The solid-supported ruthenium complex according to any one of the above [1] to [4], wherein each independently represents a hydrogen atom, a methyl group, or a phenyl group. [6]X -The solid-supported ruthenium complex according to any one of the above [1] to [5], wherein is a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, or a paratoluenesulfonate ion. [7]Y 1 ,Y 2 ,Y 3 ,Y 4 and Y 5 The solid-supported ruthenium complex according to any one of the above [1] to [6], wherein is a methyl group. [8] The solid-supported ruthenium complex according to the above [1], wherein the general formula (1) is represented by the following formula (1-1):

[0010] [ka]

[0011] (wherein the carrier has the same meaning as above.) [9] General formula (2)

[0012] [ka]

[0013] (In the formula, Y 1 ,Y 2 ,Y 3 ,Y 4 ,Y 5 , and X - has the same meaning as above.) and a ruthenium metal salt represented by the general formula (3)

[0014] [ka]

[0015] (In the formula, R 1 ,R 2 ,R 3 ,R 4 , Z, and the support have the same meanings as above.)

[0016] [ka]

[0017] (In the formula, Y 1 ,Y 2 ,Y 3 ,Y 4 ,Y 5 ,R 1 ,R 2 ,R 3 ,R 4 ,Z,X - and the carrier has the same meaning as above.) A method for producing a solid-supported ruthenium complex represented by the formula:

[10] General formula (1)

[0018] [ka]

[0019] (In the formula, Y 1 ,Y 2 ,Y 3 ,Y 4 ,Y 5 ,R 1 ,R 2 ,R 3 ,R 4 ,Z,X - and the support has the same meaning as above.) in the presence of a solid-supported ruthenium complex represented by the general formula (5)

[0020] [ka]

[0021] (In the formula, R 5 ,R 6 ,R 7 ,R 8 and R 9each independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; a benzyl group; or a monocyclic, polycyclic, or fused-ring aryl group having 6 to 14 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group; R 5 ,R 6 ,R 7 ,R 8 and R 9 Adjacent groups may be bonded to each other to form a ring.) and an allyl alcohol compound represented by general formula (6):

[0022] [ka]

[0023] [Wherein Nu-H represents a compound represented by the general formula (8)

[0024] [ka]

[0025] (In the formula, R 10 and R 11 R each independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms; an aralkyl group having 7 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group. 10 and R 11 Adjacent groups may be bonded to each other to form a ring. 10 and R 11The residues obtained by removing a hydrogen atom from each of the above may be bonded to each other to form a ring via an oxygen atom; a nitrogen atom; a sulfur atom; a divalent amino group which may be substituted with an alkyl group having 1 to 10 carbon atoms; or a divalent amino group which may be substituted with an aryl group having 6 to 12 carbon atoms.), amines represented by the general formula (9):

[0026] [ka]

[0027] (wherein Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a fused aromatic ring, the ring constituent of which is an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the fused aromatic ring may have a substituent), a phenol represented by the general formula (10):

[0028] [ka]

[0029] (wherein Ar has the same meaning as above), thiophenols represented by the general formula (11):

[0030] [ka]

[0031] (In the formula, R 12 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group, a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a mesyl group, a paratoluenesulfonyl group, an o-nitrobenzenesulfonyl group, or a trifluoromethanesulfonyl group. 13 , R 14 , R 15 , R 16 and R 17R each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, or a cyano group. 14 , R 15 , R 16 and R 17 adjacent groups may be bonded to each other to form a ring;

[0032] [ka]

[0033] (In the formula, Ar has the same meaning as above. R 19 and R 18 each independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms; an aralkyl group having 7 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group.

[0034] [ka]

[0035] (In the formula, R 20 and R 21each independently represents an alkoxy group having 1 to 10 carbon atoms; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms; an aralkyl group having 7 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group; R 23 and R 24 The compounds represented by the general formula (7) are 1,3-dicarbonyl compounds represented by the general formula (7), wherein adjacent groups may be bonded to each other to form a ring.

[0036] [ka]

[0037] (In the formula, Nu,R 5 ,R 6 ,R 7 ,R 8 and R 9 has the same meaning as above) and / or an allyl compound represented by the general formula (7a):

[0038] [ka]

[0039] (In the formula, Nu,R 5 ,R 6 ,R 7 ,R 8 and R 9 has the same meaning as above).

[11] The method for producing an allyl compound according to the above

[10] , wherein the reaction solvent is water. [Effects of the Invention]

[0040] According to the present invention, an allyl compound can be produced from an allyl alcohol compound in water using a solid-supported ruthenium complex as a catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0041] The present invention will be described in detail below. <Solid-supported ruthenium complex> The solid-supported ruthenium complex of the present invention is a compound represented by the following general formula (1) (hereinafter also referred to as solid-supported ruthenium complex (1)).

[0042] [ka]

[0043] (In the formula, Y 1 ,Y 2 ,Y 3 ,Y 4 ,Y 5 ,R 1 ,R 2 ,R 3 ,R 4 ,Z,X - and the carrier has the same meaning as above.) The solid-supported ruthenium complex (1) of the present invention will now be described.

[0044] Y 1 ,Y 2 ,Y 3 ,Y 4 and Y 5 The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, etc. A methyl group is preferred in terms of ease of synthesis and availability.

[0045] R 1The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, etc. In terms of good yield, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, is preferred.

[0046] R 1 The haloalkyl group having 1 to 4 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, and a 2,2,3,3,4,4,4-heptafluorobutyl group.

[0047] R 1 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0048] The Two R's 1 Adjacent groups may be bonded to each other to form a ring, specifically R 1 Examples of the ring include a quinoline ring, an isoquinoline ring, a 5,6,7,8-tetrahydroquinoline ring, and a 5,6,7,8-tetrahydroisoquinoline ring, which are formed by including a pyridine ring substituted with the following:

[0049] R 1 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a trifluoromethyl group, in terms of ease of synthesis and availability.

[0050] The carrier refers to a polymer such as polystyrene, polyethylene, or polypropylene having a diameter of 10 to 320 μm and a hydrophilic polymer chain such as a polyethylene glycol chain, a polypropylene glycol chain, a polyamide chain, a polyacrylamide chain, a polyvinyl alcohol chain, or polyacrylic acid, and is preferably spherical in shape. Examples of the hydrophilic polymer chain in this carrier include a polyethylene glycol chain, a polypropylene glycol chain, a polyamide chain, a polyacrylamide chain, a polyvinyl alcohol chain, and polyacrylic acid, and a polyethylene glycol chain is preferred, with a molecular weight of 1,000 to 10,000, preferably 2,000 to 10,000.

[0051] The polymer spheres in this carrier include cross-linked polystyrene, cross-linked polyisobutylene, cross-linked polypropylene, cross-linked polyester, and cross-linked polyurethane, with cross-linked polystyrene being preferred. These are usually spherical and have a diameter of 1 μm to 1 mm, preferably 10 to 320 μm, and more preferably 90 to 130 μm.

[0052] Examples of carriers include Tentagel (registered trademark, manufactured by Rapp Polymere), NovaGel (registered trademark, manufactured by Novabiochem), NovaPEG, NovaSYN (registered trademark, manufactured by Novabiochem), PEGA, and Li-Resin. In terms of ease of synthesis, Tentagel (registered trademark, manufactured by Rapp Polymere) is preferred, as it has cross-linked polystyrene polymer spheres, polyethylene glycol chains as hydrophilic polymer chains, and a diameter of 90 to 130 μm.

[0053] Z represents an ester group (-COO- or -OCO-) or an amide group (-CONH- or -NHCO-), with the amide group being preferred in terms of high catalytic activity.

[0054] R 2 ,R 3 and R 4Examples of optionally substituted monocyclic, polycyclic, or fused-ring aryl groups having 6 to 14 carbon atoms and represented by the formula (I) include phenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, and biphenyl. The aryl group may be substituted with an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, or tert-butyl; a haloalkyl group having 1 to 4 carbon atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, or 2,2,3,3,4,4,4-heptafluorobutyl; an alkoxy group having 1 to 4 carbon atoms, such as methoxy or ethoxy; a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom; a nitro group, or a cyano group. There are no particular limitations on the position of the substituent on the aryl group. 2 ,R 3 and R 4 As the optionally substituted monocyclic, polycyclic or fused ring aryl group having 6 to 14 carbon atoms represented by the following formula, a phenyl group is preferred in terms of ease of synthesis.

[0055] R 2 ,R 3 and R 4 is preferably a hydrogen atom, a methyl group, or a phenyl group in terms of ease of synthesis and availability.

[0056] Examples of halogen atoms represented by X include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. X is preferred because of its ease of synthesis. - is preferably a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, or a paratoluenesulfonate ion, and more preferably a hexafluorophosphate ion.

[0057] Examples of the solid-supported ruthenium complex (1) of the present invention include compounds represented by the following formulas (1-1) to (1-34): Note that the solid-supported ruthenium complex of the present invention is not limited to the compounds exemplified below.

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] In terms of ease of synthesis and availability of raw materials, (1-1) is preferred. <Method for producing solid-supported ruthenium complex> Next, a method for producing the solid-supported ruthenium complex (1) of the present invention (hereinafter also referred to as Production Method 1 of the present invention) will be described. The method for producing the solid-supported ruthenium complex (1) of the present invention is not particularly limited, and it can be produced, for example, by Production Method 1 shown below.

[0065] The production method 1 of the present invention is as shown in the following reaction formula (formula 1).

[0066] [ka]

[0067] (In the formula, Y1 ,Y 2 ,Y 3 ,Y 4 ,Y 5 ,R 1 ,R 2 ,R 3 ,R 4 ,Z,X - and the carrier has the same meaning as above.) Production method 1 of the present invention is a method for producing a solid-supported ruthenium complex (1) by reacting a ruthenium metal salt represented by general formula (2) (hereinafter also referred to as ruthenium metal salt (2)) with a solid-supported 2-(allylsulfanyl)pyridine compound represented by general formula (3) (hereinafter also referred to as solid-supported 2-(allylsulfanyl)pyridine compound (3)).

[0068] The ruthenium metal salt (2) used in Production Method 1 may be a commercially available product, or may be prepared by referring to a method described in the literature (Chemical Communications, pp. 5227-5229, 2009).

[0069] The solid-supported 2-(allylsulfanyl)pyridine compound (3) used in Production Method 1 can be produced according to the following reaction formula (formula 2).

[0070] [ka]

[0071] (In the formula, R 1 ,R 2 ,R 3 ,R 4 , Z and the carrier have the same meanings as above. Z' and Z'' may be the same or different and represent an amino group, a hydroxy group, and a carboxy group. The reaction represented by reaction formula (2) is a production method in which compound (3) is obtained by forming an amide bond or an ester bond through a condensation reaction between compound (14) having a carboxy group and compound (15) having a hydroxy group or an amino group.

[0072] The reaction represented by reaction formula (2) is a production method in which compound (14) having a hydroxy group or an amino group is condensed with compound (15) having a carboxyl group to form an amide bond or an ester bond, thereby obtaining compound (3).

[0073] Examples of compound (14) in reaction formula (formula 2) include Tentagel S OH, Tentagel S NH2, Tentagel S COOH, Tentagel R OH, Tentagel R NH2, Tentagel R COOH, Tentagel HL OH, Tentagel HL NH2, Tentagel HL COOH, Tentagel MB OH, Tentagel MB NH2, Tentagel MB COOH, Aminomethyl NovaGel, NovaPEG amino resin, NovaSYN TG amino resin, NovaSYN TG carboxy resin, NovaSYN TG hydroxy resin, Amino PEGA resin, Li-Resin-Oxybenzyl Alcohol, Li-Resin-Primary Amine, Li-Resin-Primary Hydroxyl, and Li-Resin-Hydroxymethylbenzamide, which are commercially available.

[0074] The substituents Z' on the support (14) may be the same or different and represent an amino group, a hydroxy group, or a carboxy group. For convenience, the support (14) is shown with one substituent Z' substituted thereon, but one or more substituents Z' may be substituted thereon.

[0075] The 2-(arylsulfanyl)pyridine compound (15) (hereinafter also referred to as 2-(arylsulfanyl)pyridine compound (15)) in reaction formula (formula 2) may be a commercially available product, or may be prepared by referring to a method described in the literature (Bulletin de la Société Chimique de France, Vol. 130, pp. 856-878, 1993).

[0076] Reaction formula (formula 2) is a condensation reaction, and the reaction is carried out in the presence of a condensing agent.

[0077] The condensing agent used in the present invention is not particularly limited. For example, carbodiimide-based condensing agents (e.g., N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-dimethylaminopropylcarbodiimide hydrochloride, chloroformate-based condensing agents (e.g., ethyl chloroformate, isobutyl chloroformate), imidazole-based condensing agents (e.g., 1,1'-carbonyldiimidazole), phosphonium-based condensing agents (e.g., (benzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyBOP (registered trademark)), bromotripyrrolidinophosphonium hexafluorophosphate), ester (PyBrop (registered trademark)), uronium-based condensing agents (e.g., O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, 1-[bis(dimethylamino)methylene]-5-chloro-1H-benzotriazolium 3-oxide hexafluorophosphate, O-benzotriazole-N,N,N',N'-tetramethyluronium hexafluoroborate, (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate), and the like can be used.

[0078] There are no particular limitations on the type of reaction solvent that can be used in reaction formula (formula 2), as long as it does not inhibit the reaction. Examples of usable solvents include haloalkanes such as dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane; ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and tetralin; ethylene carbonate, propylene carbonate, and dimethyl carbonate. Examples of suitable solvents include carbonates such as ethyl acetate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; esters such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; amides such as N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); ureas such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); acetonitrile, and benzonitrile. One of these solvents can be used alone, or two or more can be mixed and used in any ratio. As the solvent, amides such as N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); N,N,N',N'-tetramethylurea (TMU), and N,N'-dimethylpropyleneurea (DMPU) are preferred, and N,N-dimethylformamide (DMF) is more preferred, because they provide particularly excellent reactivity to the solid-supported ruthenium complex (1).

[0079] The reaction temperature of Reaction Scheme (2) is not particularly limited. For example, the reaction can be carried out at a temperature appropriately selected within the range of -78°C to 150°C. In terms of good yield, the range of 25°C to 80°C is preferred.

[0080] The reaction time for Reaction Scheme (2) is not particularly limited. For example, the reaction can be carried out for a time appropriately selected from the range of 10 minutes to 100 hours. In terms of a good yield, the reaction time is preferably in the range of 1 hour to 48 hours.

[0081] When carrying out Reaction Scheme (2), the molar ratio of the support (14) to the 2-(allylsulfanyl)pyridine compound (15) is not particularly limited, and it is preferable to use 1 to 1.2 molar equivalents of the 2-(allylsulfanyl)pyridine compound (15) per 1 molar equivalent of the substituent Z' on the support (14) in terms of excellent yield.

[0082] The atmosphere in which the reaction formula (formula 2) is carried out is not particularly limited.

[0083] The solid-supported 2-(allylsulfanyl)pyridine compound (3) produced by reaction formula (2) can be purified by a conventional purification method selected appropriately by those skilled in the art for purifying solid-supported catalysts, such as filtration, centrifugation, and washing.

[0084] There are no particular limitations on the type of reaction solvent that can be used in Production Method 1 of the present invention, as long as it does not inhibit the reaction. Examples of usable solvents include haloalkanes such as dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane; ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and tetralin; ethylene carbonate, propylene carbonate, and dimethyl carbonate. Examples of suitable solvents include carbonates such as ethyl acetate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; esters such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; amides such as N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); ureas such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); acetonitrile, and benzonitrile. These solvents can be used alone or in combination in any ratio. Dichloromethane, 1,2-dichloroethane, or acetonitrile are preferred as solvents, as they provide a particularly excellent yield of the solid-supported ruthenium complex (1). Dichloromethane is even more preferred.

[0085] The reaction temperature in Production Method 1 of the present invention is not particularly limited. For example, the reaction can be carried out at a temperature appropriately selected within the range of -78°C to 150°C. In terms of good yield, the range of 25°C to 80°C is preferred.

[0086] The reaction time for Production Method 1 of the present invention is not particularly limited. For example, the reaction time can be appropriately selected from the range of 10 minutes to 100 hours. In terms of a good yield, the reaction time is preferably in the range of 1 hour to 48 hours.

[0087] When carrying out Production Method 1 of the present invention, the molar ratio of the ruthenium metal salt (2) to the solid-supported 2-(allylsulfanyl)pyridine compound (3) is not particularly limited, and it is preferable to use 1 to 1.2 molar equivalents of the ruthenium metal salt (2) per 1 molar equivalent of the solid-supported 2-(allylsulfanyl)pyridine (3) in terms of excellent yield.

[0088] Production method 1 of the present invention is preferably carried out in an inert gas atmosphere in view of excellent yield. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas. Nitrogen gas and argon are preferred in view of their low cost.

[0089] The solid-supported ruthenium complex (1) produced by Production Method 1 of the present invention can be purified by a purification method generally used by those skilled in the art for purifying solid-supported catalysts, such as filtration, centrifugation, and washing. <Method of producing allyl compounds> Next, a method for producing the allyl compounds represented by general formula (7) and / or general formula (7a) of the present invention (hereinafter also referred to as Production Method 2 of the present invention) will be described. Production Method 2 of the present invention is as shown in the following reaction formula (Formula 3).

[0090] [ka]

[0091] (In the formula, Y 1 ,Y 2 ,Y 3 ,Y 4 ,Y 5 ,R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,Nu,Z,X - and the carrier has the same meaning as above.) In the presence of the solid-supported ruthenium complex (1) of the present invention, an allyl alcohol compound (5) (hereinafter also referred to as allyl alcohol compound (5)) is reacted with a reaction reagent represented by general formula (6) to obtain allyl compounds represented by general formula (7) (hereinafter also referred to as allyl compounds (7)) and / or allyl compounds represented by general formula (7a) (hereinafter also referred to as allyl compounds (7a)).

[0092] The allyl alcohol compound (5) that can be used in Production Method 2 of the present invention will be explained below with reference to an example.

[0093] R 5 ,R 6 ,R 7 ,R 8 and R 9 The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group.

[0094] R 5 ,R 6 ,R 7 ,R 8 and R 9 Examples of the optionally substituted monocyclic, polycyclic, or fused-ring aryl group having 6 to 14 carbon atoms and represented by the formula (I) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. The aromatic group may be substituted with an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, or a cyano group. There are no particular limitations on the position of the substituent on the aryl group.

[0095] R 5 ,R 6 ,R 7 ,R 8 and R 9The aryl group represented by the formula (I) may be substituted with an alkyl group having 1 to 4 carbon atoms, and the alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0096] R 5 ,R 6 ,R 7 ,R 8 and R 9 The aryl group represented by the formula (I) may be substituted with a haloalkyl group having 1 to 4 carbon atoms, and the haloalkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, and a 2,2,3,3,4,4,4-heptafluorobutyl group.

[0097] R 5 ,R 6 ,R 7 ,R 8 and R 9 The aryl group represented by the formula (I) may be substituted with an alkoxy group having 1 to 4 carbon atoms, and examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and a propyloxy group.

[0098] R 5 ,R 6 ,R 7 ,R 8 and R 9 The aryl group represented by the formula (I) may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

[0099] R 5 ,R 6 ,R 7 ,R 8 and R 9 Adjacent groups may be bonded to each other to form a ring.

[0100] The allyl alcohol compound (5) used in Production Method 2 of the present invention may be a commercially available product, or may be prepared by reference to methods described in the literature (Journal of Biotechnology, Vol. 1, pp. 295-306, 1984; The Journal of Organic Chemistry, Vol. 69, pp. 1374-1377, 2004).

[0101] The reaction reagent (6) that can be used in the production method 2 of the present invention will be explained below by giving an example.

[0102] The reaction reagent (6) represented by Nu-H is

[0103] [ka]

[0104] (In the formula, R 10 and R 11 has the same meaning as above.)

[0105] [ka]

[0106] (wherein Ar has the same meaning as above),

[0107] [ka]

[0108] (wherein Ar has the same meaning as above),

[0109] [ka]

[0110] (In the formula, R 12 , R13 , R 14 , R 15 , R 16 and R 17 has the same meaning as above.)

[0111] [ka]

[0112] (In the formula, Ar, R 18 and R 19 has the same meaning as above.) or

[0113] [ka]

[0114] (In the formula, R 20 and R 21 is the same as above), and is a 1,3-dicarbonyl compound (13).

[0115] The amines (8) that can be used in Production Method 2 of the present invention will be explained below with examples.

[0116] R 10 and R 11 The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group.

[0117] R 10 and R 11 The alkenyl group having 2 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, a 3-butenyl group, and a 5-hexenyl group.

[0118] R 10 and R 11 The haloalkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.

[0119] R 10 and R 11 Examples of optionally substituted aralkyl groups having 7 to 14 carbon atoms, represented by the formula (I), include benzyl, 1-naphthylmethyl, 2-naphthylmethyl, phenylethyl, and phenylpropyl. The aralkyl group may be substituted with an alkyl group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, hexyl, heptyl, and n-octyl. The aralkyl group may also be substituted with a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom. R 10 and R 11 Examples of the optionally substituted aralkyl group having 7 to 14 carbon atoms represented by the formula (I) include a (2-fluorophenyl)methyl group, a (3-fluorophenyl)methyl group, a (4-fluorophenyl)methyl group, a 1-phenylethyl group, and a 1-phenylpropyl group.

[0120] R 10 and R 11Examples of the optionally substituted aryl group having 6 to 12 carbon atoms and represented by the formula (I) include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, etc. The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, an n-octyl group, etc. The aryl group may be substituted with a haloalkyl group having 1 to 10 carbon atoms. The haloalkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group. The aryl group may be substituted with an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and a propyloxy group. R 10 and R 11 Examples of the aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a xylyl group, a 2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-cyanophenyl group, a 3-cyanophenyl group, a 4-cyanophenyl group, a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and a 2-methyl-1-naphthyl group.

[0121] R 10 and R 11 Adjacent groups may be bonded to each other to form a ring. 10 ,R 11 The residues obtained by removing a hydrogen atom from each of the above may be bonded to each other via a divalent atom (group) to form a ring. In this case, examples of the divalent atom (group) include an oxygen atom, a nitrogen atom, a sulfur atom, a divalent amino group which may be substituted with an alkyl group having 1 to 10 carbon atoms, such as a methylamino group, an ethylamino group, a propylamino group, or a hexylamino group, and an amino group which may be substituted with an aryl group having 6 to 12 carbon atoms, such as a phenylamino group or a naphthylamino group.

[0122] The amines (8) that can be used in the production method 2 of the present invention include methylamine, ethylamine, propylamine, butylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, allylamine, diallylamine, (2,2,2-trifluoroethyl)amine, bis(2,2,2-trifluoroethyl)amine, benzylamine, dibenzylamine, aniline, (4-methylphenyl)amine, (3-methylphenyl)amine, (2-methylphenyl)amine, bis(4-methylphenyl)amine, bis(3-methylphenyl)amine, bis(2-methylphenyl)amine, (4-(tert-butyl)phenyl)amine, (3-(tert-butyl)phenyl)amine, (2-(tert-butyl)phenyl)amine, bis(4-(tert-butyl)phenyl)amine, bis(3-(tert-butyl)phenyl)amine )amine, bis(2-(tert-butyl)phenyl)amine, (4-(trifluoromethyl)phenyl)amine, (3-(trifluoromethyl)phenyl)amine, (2-(trifluoromethyl)phenyl)amine, bis(4-(trifluoromethyl)phenyl)amine, bis(3-(trifluoromethyl)phenyl)amine, bis(2-(trifluoromethyl)phenyl)amine, (4-methoxyphenyl)amine, (3-methoxyphenyl)amine, (2-methoxyphenyl)amine, bis(4-methoxyphenyl)amine, bis(3 -methoxyphenyl)amine, bis(2-methoxyphenyl)amine, (4-nitrophenyl)amine, (3-nitrophenyl)amine, (2-nitrophenyl)amine, bis(4-nitrophenyl)amine, bis(3-nitrophenyl)amine, bis(2-nitrophenyl)amine, (4-fluorophenyl)amine, (3-fluorophenyl)amine, (2-fluorophenyl)amine, bis(4-fluorophenyl)amine, bis(3-fluorophenyl)amine, bis(2-fluorophenyl)amine, (4-chlorophenyl)amine Examples of the amine include bis(4-chlorophenyl)amine, bis(3-chlorophenyl)amine, bis(2-chlorophenyl)amine, (4-cyanophenyl)amine, (3-cyanophenyl)amine, (2-cyanophenyl)amine, bis(4-cyanophenyl)amine, bis(3-cyanophenyl)amine, bis(2-cyanophenyl)amine, pyrrolidine, piperidine, piperazine, morpholine, carbazole, iminostilbene, and 1-phenylpiperazine.

[0123] Phenols (9) and thiophenols (10) that can be used in Production Method 2 of the present invention will be described below with examples.

[0124] Examples of the optionally substituted aryl group having 6 to 12 carbon atoms, represented by Ar, include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, etc. The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, an n-octyl group, etc. The aryl group may be substituted with a haloalkyl group having 1 to 10 carbon atoms, and the haloalkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group. The aryl group may be substituted with an alkoxy group having 1 to 4 carbon atoms, and examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and a propyloxy group. Examples of the aryl group having 6 to 12 carbon atoms, represented by Ar, which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a xylyl group, a 2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-cyanophenyl group, a 3-cyanophenyl group, a 4-cyanophenyl group, a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and a 2-methyl-1-naphthyl group.

[0125] Phenols (9) that can be used in Production Method 2 of the present invention include phenol, m-cresol, o-cresol, para-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, para-sec-butylphenol, 4-n-pentylphenol, 4-t-octylphenol, o-sec-butylphenol, 2,5-xylenol, 2,4-xylenol, 2,6-xylenol, 3,5-xylenol, 4-methoxyphenol, 3-methoxyphenol, 2-methoxyphenol, m-fluorophenol, o-fluorophenol, para-fluorophenol, m-chlorophenol, o-chlorophenol, para-chlorophenol, m-bromophenol, o-bromophenol, para-bromophenol, m-iodophenol, o-iodophenol, para-iodophenol, m-nitrophenol, o-nitrophenol, para-nitrophenol, m-cyanophenol, phenol, o-cyanophenol, para-cyanophenol, 4-chloro-2-nitrophenol, 4-chloro-2-methylphenol, 4-chloro-3-methylphenol, salicylaldehyde, 2,4-dichloro-6-nitrophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 2,6-dinitro-para-cresol, 4,6-dinitro-o-cresol, dinitro-o-cresol, 2,4-dinitro-6-cyclohexylphenol, 2,4-dinitrophenol, 2,6-dinitro 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-phenylphenol, 2,6-di-sec-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-pentylphenol, thymol, 2,3,4,6-tetrachlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tri-tert-butylphenol, 2,4,6-tribromophenol, 2,3,Examples include 6-trimethylphenol, 1-naphthol, 2-naphthol, 2-nitro-para-cresol, 3-nitro-para-cresol, 5-nitro-o-cresol, picric acid, 6-tert-butyl-2,4-xylenol, 2-tert-butyl-para-cresol, 6-tert-butyl-o-cresol, 4-sec-butyl-2,6-di-tert-butylphenol, butylhydroxyanisole, 2,4-di-tert-butylphenol, 2-tert-butyl-5-methylphenol, 2-tert-butyl-4-methoxyphenol, 4-(1-methylethenyl)phenol, and 3-methyl-4-nitrophenol.

[0126] Examples of the thiophenols (10) that can be used in Production Method 2 of the present invention include thiophenol, m-toluenethiol, o-toluenethiol, para-toluenethiol, 2-ethylthiophenol, 3-ethylthiophenol, 4-ethylthiophenol, 2-tert-butylthiophenol, 3-tert-butylthiophenol, 4-tert-butylthiophenol, para-sec-butylthiophenol, 4-n-pentylthiophenol, 4-t-octylthiophenol, o-sec-butylthiophenol, 2,5-xylenol, 2,4-dimethylthiophenol, 2,6-dimethylthiophenol, 3,5-dimethylthiophenol, 4-methoxythiophenol, 3-methoxythiophenol, 2-methoxythiophenol, m-fluorothiophenol, o-fluorothiophenol, para-fluorothiophenol, m-chlorothiophenol, o-chlorothiophenol, para-chlorothiophenol, m-bromothiophenol, o-bromothiophenol, para-bromothiophenol, m-iodothiophenol, o-iodothiophenol, para-iodothiophenol, m- Nitrothiophenol, o-nitrothiophenol, para-nitrothiophenol, m-cyanothiophenol, o-cyanothiophenol, para-cyanothiophenol, 4-chloro-2-nitrothiophenol, 4-chloro-2-methylthiophenol, 4-chloro-3-methylthiophenol, salicylaldehyde, 2,4-dichloro-6-nitrothiophenol, 2,4-dichlorothiophenol, 2,6-dichlorothiophenol, 2,6-dinitro-paratoluenethiol, 4,6-dinitro-o-cresol, dinitro-o-cresol, 2, 4-Dinitro-6-cyclohexylthiophenol, 2,4-dinitrothiophenol, 2,6-dinitrothiophenol, 2,6-di-tert-butyl-4-ethylthiophenol, 2,6-di-tert-butyl-4-phenylthiophenol, 2,6-di-sec-butylthiophenol, 2,6-di-tert-butyl-4-methylthiophenol, 2,4-di-tert-pentylthiophenol, 2,3,4,6-tetrachlorothiophenol, 2,4,5-trichlorothiophenol, 2,4,6-trichlorothiophenol, 2,4,Examples include 6-tri-tert-butylthiophenol, 2,4,6-tribromothiophenol, 2,3,6-trimethylthiophenol, 1-naphthalenethiol, 2-naphthalenethiol, 2-nitro-paratoluenethiol, 3-nitro-paratoluenethiol, 5-nitro-o-toluenethiol, 6-tert-butyl-2,4-dimethylthiophenol, 2-tert-butyl-paratoluenethiol, 6-tert-butyl-o-toluenethiol, 4-sec-butyl-2,6-di-tert-butylthiophenol, butylhydroxyanisole, 2,4-di-tert-butylthiophenol, 2-tert-butyl-5-methylthiophenol, 2-tert-butyl-4-methoxythiophenol, 4-(1-methylethenyl)thiophenol, and 3-methyl-4-nitrothiophenol.

[0127] The indoles (11) that can be used in Production Method 2 of the present invention will be explained below with examples.

[0128] R 12 The alkyl group having 1 to 4 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0129] R 13 , R 14 , R 15 , R 16 and R 17 The alkyl group having 1 to 4 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0130] R 13 , R 14 , R 15 , R 16 and R 17The haloalkyl group having 1 to 4 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, and a 2,2,3,3,4,4,4-heptafluorobutyl group.

[0131] R 13 , R 14 , R 15 , R 16 and R 17 Examples of the alkoxy group having 1 to 4 carbon atoms represented by the formula include a methoxy group, an ethoxy group, and a propyloxy group. R 13 , R 14 , R 15 , R 16 and R 17 Adjacent groups may be bonded to each other to form a ring.

[0132] Indoles (11) that can be used in Production Method 2 of the present invention include indole, N-methylindole, N-ethylindole, N-propylindole, N-isopropylindole, N-cyclopropylindole, N-butylindole, N-isobutylindole, N-sec-butylindole, N-tert-butylindole, N-acetylindole, N-tert-butoxycarbonylindole, N-benzoyloxycarbonylindole, N-mesylindole, N-paratoluenesulfonylindole, and N-nitroindole. N-trifluoromethanesulfonylindole, 2-methylindole, 4-methylindole, 5-methylindole, 6-methylindole, 7-methylindole, 2-ethylindole, 4-ethylindole, 5-ethylindole, 6-ethylindole, 7-ethylindole, 2-propylindole, 4-propylindole, 5-propylindole, 6-propylindole, 7-propylindole, 2-isopropylindole, 4-isopropylindole, 5-isopropylindole, 6-Isopropylindole, 7-Isopropylindole, 2-Cyclopropylindole, 4-Cyclopropylindole, 5-Cyclopropylindole, 6-Cyclopropylindole, 7-Cyclopropylindole, 2-Butylindole, 4-Butylindole, 5-Butylindole, 6-Butylindole, 7-Butylindole, 2-Isobutylindole, 4-Isobutylindole, 5-Isobutylindole, 6-Isobutylindole, 7-Isobutylindole, 2-Sec-Butylindole, 4-Sec-Butylindole indole, 5-sec-butylindole, 6-sec-butylindole, 7-sec-butylindole, 2-tert-butylindole, 4-tert-butylindole, 5-tert-butylindole, 6-tert-butylindole, 7-tert-butylindole, 2-fluoromethylindole, 4-fluoromethylindole, 5-fluoromethylindole, 6-fluoromethylindole, 7-fluoromethylindole, 2-difluoromethylindole, 4-difluoromethylindole, 5-difluoromethylindole,6-Difluoromethylindole, 7-Difluoromethylindole, 2-Trifluoromethylindole, 4-Trifluoromethylindole, 5-Trifluoromethylindole, 6-Trifluoromethylindole, 7-Trifluoromethylindole, 2-Methoxyindole, 4-Methoxyindole, 5-Methoxyindole, 6-Methoxyindole, 7-Methoxyindole, 2-Ethoxyindole, 4-Ethoxyindole, 5-Ethoxyindole, 6-Ethoxyindole, 7-Ethoxyindole, 2-Propyloxyindole, 4-Propyloxyindole, 5-Propyloxyindole, 6-Propyloxyindole, 7-Propyloxyindole, 2-Fluoroindole, 4-Fluoro Examples include ioindole, 5-fluoroindole, 6-fluoroindole, 7-fluoroindole, 2-chloroindole, 4-chloroindole, 5-chloroindole, 6-chloroindole, 7-chloroindole, 2-bromoindole, 4-bromoindole, 5-bromoindole, 6-bromoindole, 7-bromoindole, 2-iodoindole, 4-iodoindole, 5-iodoindole, 6-iodoindole, 7-iodoindole, 2-nitroindole, 4-nitroindole, 5-nitroindole, 6-nitroindole, 7-nitroindole, 2-cyanoindole, 4-cyanoindole, 5-cyanoindole, 6-cyanoindole, 7-cyanoindole, and the like.

[0133] The acetophenones (12) that can be used in Production Method 2 of the present invention will be described below with examples. R 18 and R 19 The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group.

[0134] R 18 and R 19The alkenyl group having 2 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, a 3-butenyl group, and a 5-hexenyl group.

[0135] R 18 and R 19 The haloalkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.

[0136] R 18 and R 19 Examples of the optionally substituted aralkyl group having 7 to 14 carbon atoms and represented by the formula (I) include a benzyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a phenylethyl group, a phenylpropyl group, etc. The aralkyl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, an n-octyl group, etc. The aralkyl group may be substituted with a haloalkyl group having 1 to 10 carbon atoms. The haloalkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group. The aralkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. R 18 and R 19Examples of the optionally substituted aralkyl group having 7 to 14 carbon atoms represented by the formula (I) include a (2-fluorophenyl)methyl group, a (3-fluorophenyl)methyl group, a (4-fluorophenyl)methyl group, a 1-phenylethyl group, and a 1-phenylpropyl group.

[0137] R 18 and R 19 Examples of the optionally substituted aryl group having 6 to 12 carbon atoms and represented by the formula (I) include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, etc. The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, an n-octyl group, etc. The aryl group may be substituted with a haloalkyl group having 1 to 10 carbon atoms. The haloalkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group. The aryl group may be substituted with an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and a propyloxy group. R 10 and R 11Examples of the aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a xylyl group, a 2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-cyanophenyl group, a 3-cyanophenyl group, a 4-cyanophenyl group, a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and a 2-methyl-1-naphthyl group.

[0138] R 18 and R 19 Adjacent groups may be bonded to each other to form a ring. 18 and R 19 The residues obtained by removing a hydrogen atom from each of the above may be bonded to each other via a divalent atom (group) to form a ring. In this case, examples of the divalent atom (group) include an oxygen atom, a nitrogen atom, a sulfur atom, a divalent amino group which may be substituted with an alkyl group having 1 to 10 carbon atoms, such as a methylamino group, an ethylamino group, a propylamino group, or a hexylamino group, and an amino group which may be substituted with an aryl group having 6 to 12 carbon atoms, such as a phenylamino group or a naphthylamino group.

[0139] Examples of the acetophenones (12) that can be used in the production method 2 of the present invention include acetophenone, propiophenone, butyrophenone, isobutyrophenone, cyclopropyl phenyl ketone, cyclobutyl phenyl ketone, cyclopentyl phenyl ketone, cyclohexyl phenyl ketone, cyclohexyl phenyl ketone, 2'-methylacetophenone, 3'-methylacetophenone, 4'-methylacetophenone, 2'-ethylacetophenone, 3'-ethylacetophenone, 4'-ethylacetophenone, 2' -(n-propyl)acetophenone, 3'-(n-propyl)acetophenone, 4'-(n-propyl)acetophenone, 2'-(isopropyl)acetophenone, 3'-(isopropyl)acetophenone, 4'-(isopropyl)acetophenone, 2'-(n-butyl)acetophenone, 3'-(n-butyl)acetophenone, 4'-(n-butyl)acetophenone, 2'-(tert-butyl)acetophenone, 3'-(tert-butyl)acetophenone, 4'-(tert-butyl)acetophenone, 2' -Methoxyacetophenone, 3'-methoxyacetophenone, 4'-methoxyacetophenone, 2'-ethoxyacetophenone, 3'-ethoxyacetophenone, 4'-ethoxyacetophenone, 2'-phenoxyacetophenone, 3'-phenoxyacetophenone, 4'-phenoxyacetophenone, 2'-fluoroacetophenone, 3'-fluoroacetophenone, 4'-fluoroacetophenone, 2'-chloroacetophenone, 3'-chloroacetophenone, 4'-chloroacetophenone, 2'-bromoacetophenone Examples include acetophenone, 3'-bromoacetophenone, 4'-bromoacetophenone, 2'-iodoacetophenone, 3'-iodoacetophenone, 4'-iodoacetophenone, 2'-nitroacetophenone, 3'-nitroacetophenone, 4'-nitroacetophenone, 2'-(trifluoromethyl)acetophenone, 3'-(trifluoromethyl)acetophenone, 4'-(trifluoromethyl)acetophenone, 1'-acetonaphthone, 2'-acetonaphthone, and 9-acetylanthracene.

[0140] Next, the 1,3-dicarbonyl compound (13) that can be used in Production Method 2 of the present invention will be described with examples.

[0141] R 20 and R 21 Examples of the alkoxy group having 1 to 10 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a propyloxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyl group, a neopentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a phenoxy group, and a benzyloxy group.

[0142] R 20 and R 21 The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group.

[0143] R 20 and R 21 The alkenyl group having 2 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, a 3-butenyl group, and a 5-hexenyl group.

[0144] R 20 and R 21 The haloalkyl group having 1 to 10 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.

[0145] R 20 and R 21Examples of optionally substituted aralkyl groups having 7 to 14 carbon atoms, represented by the formula (I), include benzyl, 1-naphthylmethyl, 2-naphthylmethyl, phenylethyl, and phenylpropyl. The aralkyl group may be substituted with an alkyl group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, hexyl, heptyl, and n-octyl. The aralkyl group may also be substituted with a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom. R 20 and R 21 Examples of the optionally substituted aralkyl group having 7 to 14 carbon atoms represented by the formula (I) include a (2-fluorophenyl)methyl group, a (3-fluorophenyl)methyl group, a (4-fluorophenyl)methyl group, a 1-phenylethyl group, and a 1-phenylpropyl group.

[0146] R 20 and R 21Examples of the optionally substituted aryl group having 6 to 12 carbon atoms and represented by the formula (I) include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, etc. The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a heptyl group, an n-octyl group, etc. The aryl group may be substituted with a haloalkyl group having 1 to 10 carbon atoms. The haloalkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group. The aryl group may be substituted with an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and a propyloxy group. R 20 and R 21 Examples of the aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a xylyl group, a 2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-cyanophenyl group, a 3-cyanophenyl group, a 4-cyanophenyl group, a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and a 2-methyl-1-naphthyl group.

[0147] R 20 and R 21 Adjacent groups may be bonded to each other to form a ring.

[0148] Examples of the 1,3-dicarbonyl compound (13) used in Production Method 2 of the present invention include acetylacetone, 1,5-heptanedione, 1,3-indanedione, trifluoroacetylacetone, 2,6-dimethyl-3,5-heptanedione, ethyl 2,4-dioxovalerate, 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 1,3-bis(4-methoxyphenyl)-1,3-butanedione, avobenzone, 1-(paratolyl)-1,3-butanedione, 1-(4-fluorophenyl)-1,3-butanedione, dipivaloylmethane, trimethyl Examples include ethyl acetopyruvate, 1-(2-mesitylene)-1,3-butanedione, dimedone, 1,3-cyclopentanedione, 1,3-cyclohexanedione, 1,3-cycloheptanedione, 5-methyl-1,3-cyclohexanedione, 6-methyl-2,4-heptanedione, Meldrum's acid, dimethyl malonate, diethyl malonate, dipropyl malonate, diisopropyl malonate, dibutyl malonate, di-tert-butyl malonate, di-sec-butyl malonate, tert-butylmethyl malonate, diphenyl malonate, and dibenzyl malonate.

[0149] Production Method 2 of the present invention can be carried out in the presence of a base. The base that can be used is not particularly limited, but examples include metal hydroxide salts such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; metal acetates such as potassium acetate and sodium acetate; metal phosphates such as potassium phosphate and sodium phosphate; metal fluoride salts such as sodium fluoride, potassium fluoride, and cesium fluoride; and nitrogen-containing organic bases such as triethylamine, dipropylamine, diisopropylethylamine, tetramethylethylenediamine, and pyridine. Among these, metal carbonates or nitrogen-containing organic bases are preferred in terms of good reaction yield, with sodium hydroxide or sodium hydroxide being more preferred. The amount of base is not particularly limited, but in terms of good reaction yield, the molar ratio of the base to the reaction reagent is preferably in the range of 5:1 to 1:1.

[0150] The solid-supported ruthenium complex (1) that can be used in Production Method 2 of the present invention is as described above.

[0151] The type of solvent that can be used in Production Method 2 of the present invention is not particularly limited as long as it does not inhibit the reaction. Examples of usable solvents include haloalkanes such as dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane; ethers such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and tetralin; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; esters such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; amides such as DMF, DMAc, and NMP; ureas such as TMU and DMPU; acetonitrile, benzonitrile, acetone, and water. One of these solvents can be used alone, or two or more can be mixed in any ratio. Acetonitrile, acetone, and water are preferred as solvents because they are particularly excellent in yield of allylamines, and water is more preferred because it is inexpensive, easily available, and has a low environmental impact.

[0152] The reaction temperature in Production Method 2 of the present invention is not particularly limited. For example, the reaction can be carried out at a temperature appropriately selected within the range of -78°C to 150°C. In terms of good yield, the range of 60°C to 100°C is preferred.

[0153] The reaction time for Production Method 2 of the present invention is not particularly limited. For example, the reaction time can be appropriately selected from the range of 10 minutes to 100 hours. In terms of a good yield, the reaction time is preferably in the range of 3 to 24 hours.

[0154] In the production method 2 of the present invention, it is preferable to carry out the process in an inert gas atmosphere in view of excellent yield. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas. Nitrogen gas or argon is preferred in view of low cost.

[0155] In Production Method 2 of the present invention, the molar ratio of allyl alcohol compound (5) to reaction reagent (6) is not particularly limited, and it is preferable to use 1 to 1.5 molar equivalents of reaction reagent (6) per 1 molar equivalent of allyl alcohol compound (5) in terms of excellent yield.

[0156] There is no particular limitation on the amount of solid-supported ruthenium complex (1) used in Production Method 2 of the present invention, and it is generally preferred to use 0.01 to 0.2 molar equivalents, and more preferably 0.05 to 0.1 molar equivalents, per 1 molar equivalent of the allyl alcohol compound.

[0157] In a typical embodiment of the present invention, the solid-supported ruthenium complex (1) and the allyl alcohol compound (5) are mixed in a reaction vessel, and then the reaction reagent (6) is added thereto and mixed to carry out the reaction. After the reaction is completed, the produced allyl compound can be obtained by filtering to remove the solid-supported ruthenium complex and removing water from the filtrate. [Example]

[0158] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0159] In addition, 1 H-NMR spectra were measured using a Bruker ASCEND HD (400 MHz; manufactured by BRUKER). 1 The 1 H-NMR spectrum was measured using deuterated chloroform (CDCl 3 ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard.

[0160] FT-IR spectra were measured using a JASCO FT / IR-4600 (manufactured by JASCO Corporation). Example 1: Tentagel-supported pentamethylcyclopentadienyl(2-mercaptopyridine)(allyl)ruthenium(IV) hexafluorophosphate (hereinafter referred to as solid-supported ruthenium complex (1-1))

[0161] [ka]

[0162] Tentagel (trademark, manufactured by Rapp Polymere, amino group concentration 0.26 mmol / g) (3.0 g, 0.78 mmol), 2-(2-propen-1-ylthio)-3-pyridinecarboxylic acid (170 mg, 0.86 mmol), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (250 mg, 1.3 mmol), and HOBt (40 mg, 0.26 mmol) were added to DMF (10 mL) and stirred at 25°C for 16 hours. After 12 hours, EDCI (130 mg, 0.65 mmol) was added and the mixture was stirred for 3 hours. After stirring, the resulting solid was filtered and washed (DMF, dichloromethane, acetone, acetonitrile, and water) to obtain Tentagel-supported 2-(allylsulfanyl)pyridine (3.0 g).

[0163] [ka]

[0164] Under an argon atmosphere, dichloromethane (15 mL) was added to pentamethylcyclopentadienyl tris(acetonitrile)ruthenium(II) hexafluorophosphate (430 mg, 0.43 mmol) and Tentagel-supported 2-(allylsulfanyl)pyridine (3.0 g) and the mixture was stirred at 25°C for 2 hours. After stirring, the resulting solid was filtered and washed with dichloromethane, acetone, acetonitrile, and water to obtain the desired ruthenium complex (1-1) (3.0 g). Ruthenium complex (1-1): FT-IR: 2865, 1658, 1452, 1350, 1298, 1649, 1094, 950, 837, 760, 699, 556 cm -1 . Example 2: 1-Allyl-4-phenylpiperazine

[0165] [ka]

[0166] Under an argon atmosphere, allyl alcohol (29 mg, 0.50 mmol), 1-phenylpiperazine (89 mg, 0.55 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added, and the mixture was stirred and shaken at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (1-allyl-4-phenylpiperazine) (100 mg, 99%). 1-Allyl-4-phenylpiperazine: 1 H-NMR(CDCl3)δ(ppm):7.22-7.28(m,2H),6.91-6.93(m,2H),6.82-6.86(m,1H),5.85-5.95(m,1 H),5.16-5.25(m,2H),2.60(t,J=5.0Hz,4H),3.04(dt,J=6.6,1.2Hz,2H),3.20(t,J=5.0Hz,4H). Example 3: 1-Cinnamyl-4-phenylpiperazine

[0167] [ka]

[0168] Under an argon atmosphere, 1-phenyl-2-propen-1-ol (67 mg, 0.50 mmol), 1-phenylpiperazine (89 mg, 0.55 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and stirred at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (1-cinnamyl-4-phenylpiperazine) (128 mg, 92%). 1-Cinnamyl-4-phenylpiperazine: 1H-NMR(CDCl3)δ(ppm):7.38-7.39(d,7.3Hz,2H),7.22-7.34(m,5H),6.90-6.93(m,2H),6.85(t,J=7.3H z,1H),6.55(d,J=15.8Hz,1H),6.30(dt,J=15.8,6.8Hz,1H),3.20-3.22(m,6H),2.65(t,J=5.0Hz,4H). Example 4: N-allyl-N,N-dibutylamine

[0169] [ka]

[0170] Under an argon atmosphere, allyl alcohol (29 mg, 0.50 mmol), dibutylamine (71 mg, 0.55 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and stirred at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (N-allyl-N,N-dibutylamine) (80 mg, 95%). N-Allyl-N,N-dibutylamine: 1 H-NMR(CDCl3)δ(ppm):5.81-5.91(m,1H),5.10(dq,J=17.2,1.67Hz,1H),5.08-5.11(m,1H),3.07(dt,J= 6.48,1.39Hz,2H),2.38-2.42(m,4H),1.37-1.47(m,4H),1.30(5,J=7.28Hz,4H),0.91(t,J=7.28Hz,6H). Example 5: (E)-1-phenyl-4-(3-(p-tolyl)allyl)piperazine

[0171] [ka]

[0172] Under an argon atmosphere, 1-(p-tolyl)-2-propen-1-ol (74 mg, 0.50 mmol), 1-phenylpiperazine (89 mg, 0.55 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and stirred at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound ((E)-1-phenyl-4-(3-(p-tolyl)allyl)piperazine) (120 mg, 82%). (E)-1-Phenyl-4-(3-(p-tolyl)allyl)piperazine: 1 H-NMR(CDCl3)δ(ppm):2.33(s,3H),2.66(t,J=5.0Hz.4H),3.19-3.24(m,6H),6.25(dt,J=15.8,6.8Hz,1H),6. 51(d,J=15.8Hz,1H),6.82-6.87(m,1H),6.93(dd,J=8.8,0.9Hz,2H),7.12(d,J=7.9Hz,2H),7.23-7.29(m,4H). Example 6: (E)-1-(3-(4-chlorophenyl)allyl)-4-phenylpiperazine

[0173] [ka]

[0174] Under an argon atmosphere, 1-(4-chlorophenyl)-2-propen-1-ol (84 mg, 0.50 mmol), 1-phenylpiperazine (89 mg, 0.55 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and stirred at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound ((E)-1-(3-(4-chlorophenyl)allyl)-4-phenylpiperazine) (141 mg, 90%). (E)-1-(3-(4-chlorophenyl)allyl)-4-phenylpiperazine: 1H-NMR(CDCl3)δ(ppm):2.65(t,J=5.0Hz,4H),3.19-3.23(m,6H),6.30(dt,J=15.9,7.0Hz,1H),6 .49(d,J=15.9Hz,1H),6,83-6.88(m,1H),6.91-6.95(m,2H),7.18-7.29(m,5H),7.37(brs,1H). Example 7: Naftifine

[0175] [ka]

[0176] Under an argon atmosphere, 1-phenyl-2-propen-1-ol (67 mg, 0.50 mmol), N-methyl-1-naphthylmethylamine (99 mg, 0.55 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and stirred at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (naftifine) (141 mg, 98%). 1 H-NMR(CDCl3)δ(ppm):8.34(d,J=8.5Hz,1H),7.90-7.81(m,2H),7.59-7.40(m,6H),7.35(t,J=7.5Hz,2H),7.29-7.25 (m,1H),6.62(d,J=15.8Hz,1H),6.42(dt,J=15.9,6.7Hz,1H),4.00(s,2H),3.33(dd,J=6.5,1.0Hz,2H),2.33(s,3H). Example 8: 1,3,5-trimethyl-2-(2-propen-1-yloxy)benzene

[0177] [ka]

[0178] Under an argon atmosphere, allyl alcohol (29 mg, 0.50 mmol), 2,4,6-trimethylphenol (136 mg, 0.55 mmol), potassium hydroxide (56 mg, 1.0 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and the mixture was stirred with shaking at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (1,3,5-trimethyl-2-(2-propen-1-yloxy)benzene) (12 mg, 14%). 1,3,5-Trimethyl-2-(2-propen-1-yloxy)benzene: 1 H-NMR(CDCl3)δ(ppm):6.85(s,2H),6.19-6.08(m,1H),5.45(dd,J=17.1,1.5Hz,1 H),5.28(dd,J=10.5,1.0Hz,1H),4.31(d,J=5.5Hz,2H),2.28(s,6H),2.27(s,3H). Example 9: Allyl phenyl sulfide

[0179] [ka]

[0180] Under an argon atmosphere, allyl alcohol (29 mg, 0.50 mmol), thiophenol (61 mg, 0.55 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added, and the mixture was stirred and shaken at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (allyl phenyl sulfide) (74 mg, 99%). Allyl phenyl sulfide: 1 H-NMR(CDCl3)δ(ppm):7.39-7.35(m,2H),7.33-7.28(m,2H),7.23-7.19(m,1H),5.91(ddt,J=16.9,10. 0,6.8Hz,1H),5.17(dq,J=16.9,1.4Hz,1H),5.10(dq,J=10.0,1.1Hz,1H),3.58(dt,J=6.8,1.1Hz,2H). Example 10: N-methyl-3-allylindole

[0181] [ka]

[0182] Under an argon atmosphere, allyl alcohol (29 mg, 0.50 mmol), N-methylindole (72 mg, 0.55 mmol), potassium hydroxide (56 mg, 1.0 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and the mixture was stirred with shaking at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the desired compound (N-methyl-3-allylindole) (4.2 mg, 5%). N-Methyl-3-allylindole: 1 H-NMR(CDCl3)δ(ppm):7.76(dt,J=1.5,7.0Hz,1H),7.44-7.24(m,3H),6.95(s,1H),6.23 (ddt,J=17.0,10.1,6.6Hz,1H),5.35-5.21(m,2H),3.82(s,3H),3.67(d,J=11.0Hz,2H). Example 11: 2-methyl-1-phenyl-4-penten-1-one

[0183] [ka]

[0184] Under an argon atmosphere, allyl alcohol (29 mg, 0.50 mmol), propiophenone (74 mg, 0.55 mmol), potassium hydroxide (56 mg, 1.0 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and the mixture was stirred with shaking at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (2-ethyl-1-phenyl-4-penten-1-one) (24 mg, 28%). 2-Methyl-1-phenyl-4-penten-1-one: 1H-NMR(CDCl3)δ(ppm):7.95(d,J=7.2Hz,2H),7.56(t,J=7.4Hz,1H),7.47(t,J=7.5Hz,2H),5.86-5.7(m, 1H),5.10-4.97(m,2H),3.60-3.49(m,1H),2.62-2.51(m,1H),2.26-2.13(m,1H),1.21(d,J=6.9Hz,3H). Example 12: 1,3-Diphenyl-2-(2-propen-1-yl)-1,3-propanedione

[0185] [ka]

[0186] Under an argon atmosphere, allyl alcohol (29 mg, 0.50 mmol), 1,3-diphenyl-1,3-propanedione (89 mg, 0.55 mmol), potassium hydroxide (56 mg, 1.0 mmol), solid-supported ruthenium complex (1-1) (104 mg, 0.025 mmol; ruthenium loading: 0.24 mmol / g), and water (0.50 mL) were added and the mixture was stirred and shaken at 100°C for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the target compound (1,3-diphenyl-2-(2-propen-1-yl)-1,3-propanedione) (17 mg, 13%). 1,3-Diphenyl-2-(2-propen-1-yl)-1,3-propanedione : 1 H-NMR(CDCl3)δ(ppm):.7.96(dd,J=8.0,1.5Hz,4H),7.56(tt,J=8.0,1.5Hz,2H),7.44(td,J=8.0,1.5Hz,4H),5.88(ddt,J=17 .0,10.0,7.0Hz,1H),5.31(t,J=7.0Hz,1H),5.10(dd,J=17.0,1.3Hz,1H),5.02(dd,J=10.0,1.3Hz,1H),2.88(t,J=7.0Hz,2H). [Industrial Applicability]

[0187] The present invention provides a novel complex that is easy to synthesize, has a high degree of freedom in molecular design, and is useful as a catalyst for producing allyl compounds; an indicator ligand for the complex; a catalyst for producing allyl compounds that contains the novel complex; and a method for producing allyl compounds using the catalyst without the need for a purification operation.

Claims

1. General formula (1) 【Chemistry 1】 (In the formula, Y １ , Y ２ , Y ３ , Y ４ and Y ５ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; Y １ , Y ２ , Y ３ , Y ４ and Y ５ At least one of R represents an alkyl group having 1 to 10 carbon atoms. １ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a halogen atom; R １ Adjacent groups may be bonded to each other to form a ring. The carrier represents a polymer such as polystyrene, polyethylene, or polypropylene having a hydrophilic polymer chain such as a polyethylene glycol chain, a polypropylene glycol chain, a polyamide chain, a polyacrylamide chain, a polyvinyl alcohol chain, or a polyacrylic acid. Z represents -C(O)O-, -OC(O)-, -C(O)NH-, or -NHC(O)-. R ２ , R ３ and R ４ each independently represents a hydrogen atom; a methyl group; or a monocyclic, polycyclic, or fused-ring aryl group having 6 to 14 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group. － represents a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, a paratoluenesulfonate ion or a halide ion.

2. R １ 2. The solid-supported ruthenium complex according to claim 1, wherein are the same or different and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a halogen atom.

3. 2. The solid-supported ruthenium complex according to claim 1, wherein the carrier is a polystyrene sphere having a diameter of 90 to 130 μm and having a polyethylene glycol chain as a hydrophilic polymer chain.

4. 4. The solid-supported ruthenium complex of claim 1, wherein Z is --C(O)NH-- or --NHC(O)--.

5. R ２ , R ３ and R ４ 4. The solid-supported ruthenium complex according to claim 1, wherein each of is independently a hydrogen atom, a methyl group, or a phenyl group.

6. X － 4. The solid-supported ruthenium complex according to claim 1, wherein is a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, or a paratoluenesulfonate ion.

7. Y １ , Y ２ , Y ３ , Y ４ and Y ５ 4. The solid-supported ruthenium complex according to claim 1, wherein is a methyl group.

8. 2. The solid-supported ruthenium complex according to claim 1, wherein the general formula (1) is represented by the following formula (1-1): 【Chemistry 2】 (wherein the carrier has the same meaning as above.)

9. General formula (2) 【Transformation 3】 (In the formula, Y １ , Y ２ , Y ３ , Y ４ and Y ５ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; Y １ , Y ２ , Y ３ , Y ４ and Y ５ At least one of X represents an alkyl group having 1 to 10 carbon atoms. － represents a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, a paratoluenesulfonate ion or a halide ion.) and a ruthenium metal salt represented by the general formula (3): 【Chemistry 4】 (In the formula, R １ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a halogen atom; R １ Adjacent groups may be bonded to each other to form a ring. The carrier represents a polymer sphere of polystyrene, polyethylene, polypropylene, or the like having a diameter of 10 to 320 μm and having a hydrophilic polymer chain such as a polyethylene glycol chain, a polypropylene glycol chain, a polyamide chain, a polyacrylamide chain, a polyvinyl alcohol chain, or a polyacrylic acid. Z represents —COO—, —OCO—, —CONH—, or —NHCO—. R ２ , R ３ and R ４ each independently represents a hydrogen atom; a methyl group; or a monocyclic, polycyclic, or fused-ring aryl group having 6 to 14 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group. － represents a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, a paratoluenesulfonate ion or a halide ion, and 【Transformation 5】 (In the formula, Y １ , Y ２ , Y ３ , Y ４ , Y ５ , R １ , R ２ , R ３ , R ４ , Z, X － and the carrier has the same meaning as above.) A method for producing a solid-supported ruthenium complex represented by the formula:

10. General formula (1) 【Transformation 6】 (In the formula, Y １ , Y ２ , Y ３ , Y ４ and Y ５ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; Y １ , Y ２ , Y ３ , Y ４ and Y ５ At least one of R represents an alkyl group having 1 to 10 carbon atoms. １ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a halogen atom; R １ Adjacent groups may be bonded to each other to form a ring. The carrier represents a polymer sphere of polystyrene, polyethylene, polypropylene, or the like having a diameter of 10 to 320 μm and having a hydrophilic polymer chain such as a polyethylene glycol chain, a polypropylene glycol chain, a polyamide chain, a polyacrylamide chain, a polyvinyl alcohol chain, or a polyacrylic acid. Z represents —C(O)O—, —OC(O)—, —C(O)NH—, or —NHC(O)—. R ２ , R ３ and R ４ each independently represents a hydrogen atom; a methyl group; or a monocyclic, polycyclic, or fused-ring aryl group having 6 to 14 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group. － represents a hexafluorophosphate ion, a tetrafluoroborate ion, a hexafluoroantimonate ion, a paratoluenesulfonate ion, or a halide ion, 【Transformation 7】 (In the formula, R ５ , R ６ , R ７ , R ８ and R ９ each independently represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; a benzyl group; or a monocyclic, polycyclic, or fused-ring aryl group having 6 to 14 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group; R ５ , R ６ , R ７ , R ８ and R ９ may be bonded to each other to form a ring, and an allyl alcohol compound represented by the general formula (6) 【Transformation 8】 [wherein Nu-H represents a group represented by the general formula (8) 【Chemistry 9】 (In the formula, R １０ and R １１ R each independently represents an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms; an aralkyl group having 7 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom, or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group. １０ and R １１ may be bonded to each other to form a ring. １０ and R １１ The residues obtained by removing a hydrogen atom from each of the above may be bonded to each other to form a ring via an oxygen atom; a nitrogen atom; a sulfur atom; a divalent amino group which may be substituted with an alkyl group having 1 to 10 carbon atoms; or a divalent amino group which may be substituted with an aryl group having 6 to 12 carbon atoms.), amines represented by general formula (9): 【Chemistry 10】 (wherein Ar represents a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a fused aromatic ring, the ring constituent of which is an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and the monocyclic aromatic ring, the polycyclic aromatic ring, or the fused aromatic ring may have a substituent), a phenol represented by general formula (10): 【Chemistry 11】 (wherein Ar has the same meaning as above), a thiophenol represented by the general formula (11): 【Chemistry 12】 (In the formula, R １２ R each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group, a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a methanesulfonyloxy group, a paratoluenesulfonyl group, an o-nitrobenzenesulfonyl group, or a trifluoromethanesulfonyl group. １３ , R １４ , R １５ , R １６ and R １７ R each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, or a cyano group. １４ , R １５ , R １６ and R １７ adjacent groups may be bonded to each other to form a ring; 【Chemistry 13】 (wherein Ar has the same meaning as above. R １８ and R １９ each independently represents an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms; an aralkyl group having 7 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom, or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group.), or an acetophenone represented by the general formula (13): 【Chemistry 14】 (In the formula, R ２０ and R ２１ each independently represents an alkoxy group having 1 to 10 carbon atoms; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms; an aralkyl group having 7 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom, or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a halogen atom, and a cyano group; R ２０ and R ２１ may be bonded to each other to form a ring.) represents a 1,3-dicarbonyl compound represented by general formula (7): 【Chemistry 15】 (In the formula, Nu, R ５ , R ６ , R ７ , R ８ and R ９ has the same meaning as above) and / or an allyl compound represented by the general formula (7a): 【Chemistry 16】 (In the formula, Nu, R ５ , R ６ , R ７ , R ８ and R ９ has the same meaning as above).

11. The method for producing an allyl compound according to claim 10, wherein the reaction solvent is water.

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