Polycyclic compound, method for reducing organic compound, and method for coupling organic compound

Abstract

Provided are: a polycyclic compound applicable to a reduction reaction and a coupling reaction of an organic compound using visible light as an energy source; and a polycyclic compound applicable to a fluorescent material. A polycyclic compound according to the present invention is represented by formula (1a) or formula (1b). In formula (1a) or formula (1b), R1a-R11a and R1b-R9b each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group having 1-20 carbon atoms and optionally having a hetero atom, a hydrocarbon oxy group having 1-20 carbon atoms, a monoalkylamino group having 1-20 carbon atoms, a dialkylamino group having 2-21 carbon atoms, an ester group, or a cyano group, and Xa - and Xb - each represent a counter anion.

Description

Polycyclic compounds, reduction method of organic compounds, and coupling method of organic compounds

[0001] The present invention relates to a polycyclic compound, a method for reducing an organic compound, and a method for coupling an organic compound. This application claims priority based on Japanese Patent Application No. 2023-217785, filed on December 25, 2023, the contents of which are incorporated herein by reference.

[0002] Photocatalysts are used in reduction reactions and coupling reactions of organic compounds such as carbonyl compounds. Known photocatalysts include iridium-based catalysts and ruthenium-based catalysts (see, for example, Non-Patent Document 1).

[0003] David W. C. MacMillan, et al., “Chem. Rev.”, 2013, Volume 113, No. 7, p. 5322-5363

[0004] Conventional photocatalysts have limitations in reducing reactions and coupling reactions under mild conditions, such as when visible light is used as an energy source. Therefore, conventional photocatalysts are not suitable for reducing reactions and coupling reactions of organic compounds using visible light as an energy source. The present invention aims to provide novel compounds that are applicable to reducing reactions and coupling reactions of organic compounds using visible light as an energy source. Another object of the present invention is to provide novel compounds that are applicable to fluorescent materials.

[0005] The present invention has the following aspects: [1] A polycyclic compound represented by formula (1a) or formula (1b).

[0006]

[0007] In formula (1a), R １ａ ~R １１ａ are each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbonoxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group; ａ － is the counteranion.

[0008]

[0009] In formula (1b), R １ｂ ~R ９ｂ are each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbonoxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group; ｂ － is the counteranion.

[0010] [2] R in formula (1a) １ａ ~R ４ａ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and R ６ａ is a hydrogen atom, a hydroxy group, a hydrocarbonoxy group having 1 to 20 carbon atoms, or a dialkylamino group having 2 to 21 carbon atoms, and R ５ａ , R ７ａ , R ８ａ ~R １１ａ are each a hydrogen atom, and R in formula (1b) １ｂ ~R ４ｂ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and R ６ｂ is a hydrogen atom, a hydroxy group, a hydrocarbonoxy group having 1 to 20 carbon atoms, or a dialkylamino group having 2 to 21 carbon atoms, and R ５ｂ , R ７ｂ , R ８ｂ ~R ９ｂ [3] A polycyclic compound of [1], wherein R in formula (1a) is a hydrogen atom. １ａ ~R ４ａ are each independently an alkyl group or an aralkyl group having 1 to 20 carbon atoms which may contain a heteroatom, and R in formula (1b) １ｂ ~R ４ｂ [4] The polycyclic compound of [2], wherein R in formula (1a) is an alkyl group or an aralkyl group having 1 to 20 carbon atoms, which may contain a heteroatom. １ａ ~R ４ａ are each independently an alkyl group having 1 to 10 carbon atoms and not containing a heteroatom, and R in formula (1b) １ｂ ~R ４ｂare each independently an alkyl group having 1 to 10 carbon atoms and not containing a heteroatom. [5] A polycyclic compound according to any one of [1] to [4], which is a photocatalyst. [6] A polycyclic compound according to any one of [1] to [4], which is a fluorescent material. [7] A method for reducing an organic compound using a polycyclic compound according to any one of [1] to [4]. [8] A method for coupling organic compounds using a polycyclic compound according to any one of [1] to [4].

[0011] According to the present invention, it is possible to provide a polycyclic compound that can be applied to reduction reactions and coupling reactions of organic compounds using visible light as an energy source, and also to provide a polycyclic compound that can be applied to fluorescent materials.

[0012] 1 shows an ultraviolet-visible absorption spectrum of the compound (1a-1) obtained in Example A1. 1 shows a fluorescence spectrum of the compound (1a-1) obtained in Example A1.

[0013] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and can be practiced with various modifications within the scope of the gist thereof. In this specification, a numerical range expressed as "to" means a numerical range that includes the numerical values ​​before and after "to" as the lower and upper limits. For example, A to B is synonymous with A or more and B or less. In this specification, a methyl group is also represented as "Me", an ethyl group is also represented as "Et", an n-butyl group is also represented as "Bu", and an acetyl group is also represented as "Ac".

[0014] [Polycyclic Compound] The polycyclic compound of the present invention is a cationic polycyclic compound having a heteroatom represented by formula (1a) or formula (1b). In the present invention, the polycyclic compound represented by formula (1a) is also referred to as "compound (1a)," and the polycyclic compound represented by formula (1a) is also referred to as "compound (1b)." Compound (1a) and compound (1b) are also collectively referred to as "compound (1)."

[0015]

[0016] In formula (1a), R １ａ ~R １１ａare each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbonoxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group; ａ － is the counteranion.

[0017]

[0018] In formula (1b), R １ｂ ~R ９ｂ are each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbonoxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group; ｂ － is the counteranion.

[0019] In formula (1a), R １ａ ~R １１ａ are each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbonoxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group. １ｂ ~R ９ｂ are each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbonoxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group.

[0020] R １ａ ~R １１ａ , and R １ｂ ~R ９ｂThe number of carbon atoms in the hydrocarbon group in the formula (I) is 1 to 20, preferably 1 to 16, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 2 to 8, and particularly preferably 2 to 5. Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group, with an alkyl group and an aryl group being preferred, and an alkyl group being more preferred. The hydrocarbon group may have a substituent. Examples of the substituent include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a cyano group, a hydroxy group, an amino group, an amide group, a halogen atom, and a phenyl group. The number of carbon atoms in the hydrocarbon group mentioned above includes the number of carbon atoms in the substituent. The alkyl group may be linear, branched, or cyclic. Examples of alkyl groups include linear or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl. Examples of aryl groups include phenyl, tolyl, and xylyl. Examples of aralkyl groups include alkyl groups in which one hydrogen atom is substituted with an aryl group, such as benzyl and phenethyl.

[0021] The hydrocarbon group may contain a heteroatom. The heteroatom is preferably contained between carbon atoms. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0022] The hydrocarbon group is preferably an alkyl group containing no heteroatoms. The number of carbon atoms in the alkyl group is preferably 1 to 16, more preferably 1 to 12, even more preferably 1 to 10, still more preferably 1 to 8, particularly preferably 2 to 8, and particularly preferably 2 to 5.

[0023] R １ａ ~R １１ａ , and R １ｂ ~R ９ｂ The number of carbon atoms in the hydrocarbonoxy group in the formula (I) is 1 to 20, preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 5. Examples of hydrocarbonoxy groups include alkoxy groups, alkenyloxy groups, and aryloxy groups, with alkoxy groups being preferred. The alkyl group bonded to the oxygen atom in the alkoxy group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a cyano group, a hydroxy group, an amino group, an amide group, a halogen atom, and a phenyl group. The number of carbon atoms in the alkoxy group mentioned above includes the number of carbon atoms in the substituent. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a cyclohexyloxy group. Preferred are methoxy, ethoxy, propoxy, and butoxy groups, with methoxy and ethoxy groups being more preferred, and methoxy being even more preferred. These groups may have a substituent. Examples of the alkenyloxy group include a vinyloxy group, an isopropenyloxy group, and an allyloxy group, with an allyloxy group being preferred. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

[0024] R １ａ ~R １１ａ , and R １ｂ ~R ９ｂThe number of carbon atoms in the monoalkylamino group is 1 to 20, preferably 1 to 10, and more preferably 1 to 4. The alkyl group in the monoalkylamino group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include those exemplified above in the description of the alkoxy group. The number of carbon atoms in the monoalkylamino group mentioned above includes the number of carbon atoms in the substituent. Examples of the monoalkylamino group include a methylamino group, an ethylamino group, and a butylamino group. A methylamino group or an ethylamino group is preferred, and a methylamino group is more preferred.

[0025] R １ａ ~R １１ａ , and R １ｂ ~R ９ｂ The number of carbon atoms in the dialkylamino group is 2 to 21, preferably 2 to 12, and more preferably 2 to 8. The number of carbon atoms in the dialkylamino group refers to the total number of all carbon atoms contained in the dialkylamino group. The alkyl groups in the dialkylamino group may be linear, branched, or cyclic. Furthermore, two alkyl groups substituting the amino groups of the dialkylamino group may be bonded to each other directly or via a nitrogen atom that may be substituted with an oxygen atom, a sulfur atom, or an alkyl group having 1 to 6 carbon atoms to form a ring. The alkyl group may have a substituent. Examples of the substituent include those exemplified above in the description of the alkoxy group. The number of carbon atoms in the dialkylamino group mentioned above includes the number of carbon atoms of the substituent. The two alkyl groups and the substituents on the alkyl groups may be the same or different. Examples of the dialkylamino group include a dimethylamino group, a methylethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a piperidinyl group, a pyrrolidinyl group, a morpholinyl group, and a piperazinyl group. Of these, a dimethylamino group, a methylethylamino group, a diethylamino group, a dipropylamino group, and a dibutylamino group are preferred, a dimethylamino group, a methylethylamino group, and a diethylamino group are more preferred, a dimethylamino group and a diethylamino group are still more preferred, and a dimethylamino group is particularly preferred.

[0026] R １ａ ~R １１ａ , and R １ｂ ~R ９ｂ The ester group in the above refers to a functional group in which the aforementioned hydrocarbon group is bonded via an ester bond. The number of carbon atoms in the ester group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. The number of carbon atoms in the ester group includes the number of carbon atoms in the hydrocarbon group bonded via the ester bond and the number of carbon atoms in the substituent on the hydrocarbon group.

[0027] R in formula (1a) １ａ ~R ４ａ and R in formula (1b) １ｂ ~R ４ｂ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, an alkyl group or aralkyl group having 1 to 20 carbon atoms which may contain a heteroatom, an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom, an alkyl group having 1 to 20 carbon atoms which does not contain a heteroatom, an alkyl group or aralkyl group having 1 to 10 carbon atoms which may contain a heteroatom, an alkyl group having 1 to 10 carbon atoms which may contain a heteroatom, an alkyl group having 1 to 10 carbon atoms which may contain a heteroatom, an alkyl group or aralkyl group having 2 to 8 carbon atoms which may contain a heteroatom, an alkyl group having 2 to 8 carbon atoms which may contain a heteroatom, an alkyl group having 2 to 8 carbon atoms which may contain a heteroatom, an alkyl group having 2 to 8 carbon atoms which does not contain a heteroatom, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, or an n-heptyl group. R in formula (1a) may also be an alkyl group having 2 to 5 carbon atoms which does not contain a heteroatom. １ａ ~R ４ａ may be the same or different. From the viewpoint of ease of production, it is preferable that they are the same. １ｂ ~R ４ｂ may be the same or different. From the viewpoint of ease of production, it is preferable that they are the same.

[0028] R in formula (1a) ５ａ and R７ａ and R in formula (1b) ５ｂ and R ７ｂ is preferably a hydrogen atom. ５ａ and R ７ａ may be the same or different. From the viewpoint of ease of production, it is preferable that they are the same. ５ｂ and R ７ｂ may be the same or different. From the viewpoint of ease of production, it is preferable that they are the same.

[0029] R in formula (1a) ６ａ and R in formula (1b) ６ｂ are each independently preferably a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, or a dialkylamino group having 2 to 21 carbon atoms, more preferably a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms, and even more preferably a hydrogen atom, a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, a dimethylamino group, a diethylamino group, a dipropylamino group, or a dibutylamino group. The alkyl group in the alkoxy group and the dialkylamino group may have a substituent, and when it has a substituent, a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a hydroxy group, a methoxy group, or an ethoxy group is preferred, and a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, or a butoxycarbonyl group is more preferred. R in formula (1a) ６ａ and R in formula (1b) ６ｂ may each independently be a hydrogen atom, a hydroxy group, a methoxy group, a dimethylamino group, a 3-methoxycarbonylpropyloxy group, or a 3-carboxypropyloxy group.

[0030] R in formula (1a) ８ａ ~R １１ａ and R in formula (1b) ８ｂ and R ９ｂ is preferably a hydrogen atom. ８ａ ~R １１ａmay be the same or different. From the viewpoint of ease of production, it is preferable that they are the same. ８ｂ and R ９ｂ may be the same or different. From the viewpoint of ease of production, it is preferable that they are the same.

[0031] In formula (1a), X ａ － is a counter anion. In formula (1b), X ｂ － is a counter anion. Examples of the counter anion include Cl － ,Br － , I － , ClO ４ － , B.F. ４ － , P.F. ６ － , C.H. ３ COO － , C.F. ３ SO ３ － , C.H. ３ SO ３ － , p-CH ３ C ６ H ４ SO ３ － , F － , SbF ６ － and Cl － , B.F. ４ － , C.H. ３ COO － , C.F. ３ SO ３ － is preferred.

[0032] Compound (1a) includes, but is not limited to, compounds represented by formulas (1a-1) to (1a-12). Compound (1b) includes, but is not limited to, compounds represented by formulas (1b-1) to (1b-12).

[0033]

[0034]

[0035] Compound (1a) can be produced, for example, as follows: Compound (2a) of the following formula is reacted with compound (31a) of the following formula and compound (32a) of the following formula in a solvent in the presence of a catalyst and an oxidizing agent to obtain compound (1a).

[0036]

[0037] Compound (2a) may be synthesized by a known method, or a commercially available product may be used. Compound (31a) and compound (32a) may each be synthesized by a known method, or a commercially available product may be used. Compound (31a) and compound (32a) may be the same compound or different compounds.

[0038] The reaction ratio of compound (2a) with compound (31a) and compound (32a) is preferably 1 to 5 equivalents, more preferably 1 to 3 equivalents, and even more preferably 2.5 equivalents, of the total of compound (31a) and compound (32a) relative to compound (2a). When compound (31a) and compound (32a) are different compounds, the amount of compound (32a) relative to compound (31a) is preferably 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents, and even more preferably 1 equivalent.

[0039] Examples of the catalyst include dichloro(pentamethylcyclopentadienyl)rhodium(III) (dimer) ([Rh(Cp*)Cl ２ ] ２ ), diacetoxy(pentamethylcyclopentadienyl)rhodium(III) (Rh(Cp*)(OAc) ２ The catalyst may be used alone or in any combination of two or more kinds in any ratio. The ratio of the catalyst to the compound (2a) is preferably 0.01 to 0.05 equivalents, more preferably 0.02 to 0.04 equivalents, and even more preferably 0.03 equivalents.

[0040] Examples of oxidizing agents include silver acetate (AgOAc) and copper acetate (Cu(OAc) ２ ), hydrogen peroxide (H ２ O ２The oxidizing agent may be used alone or in any combination of two or more kinds in any ratio. The ratio of the oxidizing agent to compound (2a) is preferably 2 to 10 equivalents, more preferably 3 to 6 equivalents, and even more preferably 4 equivalents.

[0041] Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol, etc.; saturated aliphatic hydrocarbon solvents such as hexane, etc.; ether solvents such as tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, methyl t-butyl ether, etc.; aromatic hydrocarbon solvents such as toluene, xylene, etc.; nitrile solvents such as acetonitrile, benzonitrile, etc. The solvent may be used alone or in any combination and ratio.

[0042] The reaction conditions can be appropriately set depending on the chemical and / or physical properties of the substrate. The reaction temperature is preferably 40 to 110°C, more preferably 80 to 90°C. The reaction time is preferably 12 to 72 hours, more preferably 15 to 24 hours. The reaction of compound (2a) with compound (31a) and compound (32a) is preferably carried out under a nitrogen atmosphere.

[0043] When silver acetate is used as an oxidizing agent, for example, X in formula (1a) ａ － is CH ３ COO － Compound (1a) represented by the formula: X is obtained by adding a chloride such as sodium chloride, potassium chloride, magnesium chloride, or calcium chloride to a reaction solution containing the reaction product compound (1a). ａ － is Cl － The compound (1a) is obtained. The exchange of the counter anion can be carried out in a similar manner. The same applies to the production of the compound (1b).

[0044] Compound (1b) can be produced, for example, as follows: Compound (2b) of the following formula is reacted with compound (31b) of the following formula and compound (32b) of the following formula in a solvent in the presence of a catalyst and an oxidizing agent to obtain compound (1b).

[0045]

[0046] Compound (2b) may be synthesized by a known method, or a commercially available product may be used. Compound (31b) and compound (32b) may each be synthesized by a known method, or a commercially available product may be used. Compound (31b) and compound (32b) may be the same compound or different compounds.

[0047] The reaction ratio of compound (2b) with compound (31b) and compound (32b) is preferably 1 to 5 equivalents, more preferably 1 to 3 equivalents, and even more preferably 2.5 equivalents, of the total of compound (31b) and compound (32b) relative to compound (2b). When compound (31b) and compound (32b) are different compounds, the reaction ratio of compound (32b) relative to compound (31b) is preferably 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents, and even more preferably 1 equivalent.

[0048] The catalyst, oxidizing agent, and solvent, and their ratios, are the same as those used in producing compound (1a). The reaction temperature and reaction time are the same as those used in producing compound (1a). The reaction of compound (2b) with compound (31b) and compound (32b) is preferably carried out under a nitrogen atmosphere.

[0049] The polycyclic compounds of the present invention described above can absorb ultraviolet and visible light, can utilize the absorbed light as an energy source, and have high oxidizing and reducing powers, making them ideal as photocatalysts. In other words, the polycyclic compounds of the present invention can also be considered cationic organic photocatalysts. The polycyclic compounds of the present invention can be used as photocatalysts for various reactions, but are suitable as photocatalysts for reduction reactions and coupling reactions of organic compounds. In particular, the polycyclic compounds of the present invention can utilize visible light as an energy source, making them ideal as photocatalysts applicable to reduction reactions and coupling reactions of organic compounds using visible light as an energy source. Furthermore, the polycyclic compounds of the present invention are soluble in water and organic solvents, so reduction reactions, coupling reactions, etc. can be carried out in water, organic solvents, or mixed solvents of water and organic solvents. Reduction reactions and coupling reactions using the polycyclic compounds of the present invention will be described later.

[0050] The polycyclic compound of the present invention is capable of emitting absorbed light again as light, and is therefore suitable as a fluorescent material, specifically as a fluorescent material for organic EL devices, wavelength conversion films, fluorescent paints, etc.

[0051] [Reduction Method] The reduction method of an organic compound of the present invention (hereinafter also referred to as "reduction reaction") is a method of reducing an organic compound in the presence of the polycyclic compound of the present invention described above. Examples of organic compounds suitable for the reduction method of the present invention include compounds having a carbonyl group (hereinafter also referred to as "carbonyl compounds", including ester compounds, aldehyde compounds, ketone compounds, and carboxylic acid compounds) and imine compounds. The reduction method of the present invention is suitable as a reduction method for reducing carbonyl compounds, and more suitable as a reduction method for reducing ester compounds. Furthermore, the reduction method of the present invention is suitable as a reduction method for reducing aromatic carbonyl compounds, and more suitable as a reduction method for reducing aromatic ester compounds.

[0052] In the reduction method of the present invention, the concentration of the organic compound in 100% by mass of the reaction solution is preferably 0.001 to 10% by mass, more preferably 0.001 to 1% by mass, and even more preferably 0.01 to 0.1% by mass. The proportion of the polycyclic compound relative to the organic compound is preferably 0.001 to 0.2 equivalents, more preferably 0.005 to 0.1 equivalents, and even more preferably 0.01 to 0.05 equivalents.

[0053] As described above, the polycyclic compound of the present invention can absorb ultraviolet and visible light and can utilize the absorbed light as an energy source. Therefore, the reduction reaction of the organic compound is preferably carried out while irradiating with ultraviolet or visible light, and more preferably while irradiating with visible light. Visible light is light having a wavelength of 380 to 780 nm. Examples of visible light include light with wavelengths corresponding to colors such as blue, green, yellow, and red. In particular, light having a wavelength of 380 to 500 nm, so-called blue light, is preferred from the viewpoint of versatility. The irradiation dose (cumulative light amount) of visible light is 1,000 to 100,000 J / cm. ２ is preferred, and 3500 to 50,000 J / cm ２ More preferably, 7000 to 30000 J / cm ２ The output of visible light may be set so that the irradiation amount falls within the above range, and although it differs depending on the size of the device and the irradiation range, it is preferably 1 to 1000 W, more preferably 5 to 500 W, and even more preferably 10 to 100 W.

[0054] The reduction reaction is usually carried out in the presence of a reducing agent. The reducing agent is not particularly limited, but examples thereof include oxalic acid, ammonium oxalate, sodium oxalate, sodium ascorbate, triethylamine, tributylamine, triethanolamine, and diisopropylethylamine. The reducing agent may be used alone or in any combination of two or more kinds in any ratio.

[0055] However, because oxalic acid, ammonium oxalate, and sodium oxalate (hereinafter collectively referred to as "oxalic acid (salt)") are difficult to oxidize, conventional photocatalysts have difficulty extracting electrons from oxalic acid (salt). Even if electrons can be extracted, transferring the extracted electrons to an organic compound is difficult. Therefore, oxalic acid (salt) is unsuitable as a reducing agent in reduction reactions using conventional photocatalysts. However, the polycyclic compound of the present invention has high oxidizing power and high reducing power, so it can easily extract electrons from oxalic acid (salt) and further transfer the extracted electrons to an organic compound. Therefore, the present invention makes it possible to suitably use oxalic acid (salt) as a reducing agent. Since oxalic acid (salt) is oxidized to carbon dioxide, even if it remains in the reaction system, it is unlikely to inhibit the reduction reaction. Furthermore, because oxalic acid (salt) is soluble in water and inexpensively available, the reduction reaction can be carried out in water at low cost.

[0056] The proportion of the reducing agent is preferably 1 to 10 equivalents, more preferably 1 to 6 equivalents, and even more preferably 2 to 4 equivalents, relative to the organic compound.

[0057] The reduction reaction is carried out in a solvent. Examples of the solvent include water; dimethyl sulfoxide; nitrile solvents such as acetonitrile and benzonitrile; alcohol solvents such as methanol, ethanol, and propanol; saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as dimethylformamide and dimethylacetamide. The solvent may be used alone or in any combination of two or more kinds in any ratio.

[0058] The reaction conditions can be appropriately set depending on the chemical and / or physical properties of the substrate. The reaction temperature for the reduction reaction is preferably 0 to 100° C., more preferably 25 to 50° C. The reaction time for the reduction reaction is preferably 1 to 48 hours, more preferably 2 to 24 hours.

[0059] The reduction method of an organic compound of the present invention described above uses the polycyclic compound of the present invention as a photocatalyst, so that visible light can be used as an energy source and the reduction reaction can be carried out under mild conditions. Moreover, with the present invention, oxalic acid (salt) can be suitably used as a reducing agent. In addition, since the polycyclic compound of the present invention is soluble in water as well as organic solvents, water can be used as a reaction solvent.

[0060] [Coupling Method] The organic compound coupling method of the present invention (hereinafter also referred to as "coupling reaction") is a method of coupling organic compounds (hereinafter one will be referred to as "organic compound (I)" and the other will be referred to as "organic compound (II)") in the presence of the polycyclic compound of the present invention described above. Examples of organic compound (I) and organic compound (II) suitable for the coupling method of the present invention include carbonyl compounds, imine compounds, halides, nitrile compounds, nitro compounds, hydroxy compounds, and unsaturated aliphatic hydrocarbons. Organic compound (I) and organic compound (II) may be the same compound or different compounds. That is, the organic compound coupling reaction of the present invention may be a homocoupling reaction or a cross-coupling reaction.

[0061] At least one of the organic compound (I) and the organic compound (II) is preferably a carbonyl compound, and more preferably an ester compound. That is, the coupling method of the present invention is suitable as a coupling method for coupling a carbonyl compound with an organic compound, particularly as a coupling method for coupling an ester compound with an organic compound.

[0062] Preferred combinations of organic compound (I) and organic compound (II) include, for example, a combination of two carbonyl compounds, a combination of a carbonyl compound and a halide, a combination of a carbonyl compound and an unsaturated aliphatic hydrocarbon, and a combination of two halides. Examples of coupling reactions include the following (i) to (iv):

[0063] (i): A reductive coupling reaction between an ester compound represented by formula (12) and a carbonyl compound represented by formula (13)

[0064]

[0065] (ii): A coupling reaction between an ester compound represented by formula (12) and a halide represented by formula (14)

[0066]

[0067] (iii): A coupling reaction between an ester compound represented by formula (12) and an alkene represented by formula (15)

[0068]

[0069] (iv): Coupling reaction between halides represented by formula (16) and formula (17)

[0070]

[0071] In the coupling reaction scheme shown above, R ３６ and R ３７ R each independently represents a hydrocarbon group, an alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group, a hydroxy group, or a hydrogen atom. ３８ and R ３９ R each independently represents a hydrocarbon group, an alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group, a hydroxy group, or a hydrogen atom. ４０ is a hydrocarbon group, and X ２ is a bromine atom, a chlorine atom, or an iodine atom. ４１ ~R ４４ R are each independently a hydrocarbon group, an alkoxy group, an amino group, or a hydrogen atom. ４５ and R ４６ are each independently a hydrocarbon group, and X ３ and X ４ are each independently a bromine atom, a chlorine atom, or an iodine atom. ４５ and R ４６are each independently preferably an aryl group. Here, examples of the hydrocarbon group, alkoxy group, monoalkylamino group and dialkylamino group include the hydrocarbon groups, alkoxy groups, monoalkylamino groups and dialkylamino groups exemplified above in the description of the polycyclic compound, respectively.

[0072] In the coupling method of the present invention, the total concentration of organic compound (I) and organic compound (II) in a 100% by mass reaction solution is preferably 0.002 to 20% by mass, more preferably 0.002 to 2% by mass, and even more preferably 0.02 to 0.2% by mass. The reaction ratio of organic compound (I) to organic compound (II) is preferably 1 to 100 equivalents of organic compound (II) relative to organic compound (I), more preferably 1 to 50 equivalents, and even more preferably 1 to 10 equivalents. Note that when the coupling reaction is, for example, any of (i) to (iii) above, the ester compound may be organic compound (I) or organic compound (II), but is preferably organic compound (I).

[0073] The proportion of the polycyclic compound is preferably 0.001 to 0.2 equivalents, more preferably 0.005 to 0.1 equivalents, and even more preferably 0.01 to 0.05 equivalents, relative to the organic compound (I).

[0074] As described above, since the polycyclic compound of the present invention can absorb ultraviolet and visible light and can utilize the absorbed light as an energy source, the coupling reaction of the organic compound is preferably carried out while irradiating with ultraviolet or visible light, more preferably while irradiating with visible light. The visible light, its irradiation dose, and output are the same as those in the reduction reaction of the organic compound described above.

[0075] The coupling reaction is usually carried out in the presence of a reducing agent. Examples of the reducing agent include those exemplified above in the description of the reduction reaction of the organic compound. As mentioned above, in the present invention, oxalic acid (salt) can be suitably used as the reducing agent. The proportion of the reducing agent relative to the organic compound (I) is preferably 1 to 20 equivalents, more preferably 1 to 12 equivalents, and even more preferably 2 to 8 equivalents.

[0076] The coupling reaction is carried out in a solvent, such as those exemplified above in the description of the reduction reaction of the organic compound.

[0077] The reaction conditions can be appropriately set depending on the chemical and / or physical properties of the substrate. The reaction temperature for the coupling reaction is preferably 0 to 100° C., more preferably 25 to 50° C. The reaction time for the coupling reaction is preferably 1 to 48 hours, more preferably 12 to 24 hours.

[0078] The organic compound coupling method of the present invention described above uses the polycyclic compound of the present invention as a photocatalyst, so visible light can be used as an energy source, and the coupling reaction can be carried out under mild conditions. Moreover, with the present invention, oxalic acid (salt) can be suitably used as a reducing agent. In addition, since the polycyclic compound of the present invention is soluble in water as well as organic solvents, water can be used as a reaction solvent.

[0079] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0080] Example A1 Synthesis of Compound (1a-1)

[0081]

[0082] 589 mg of compound (2a-1) and 645 mg of compound (3a-1) were placed in a reaction vessel, and 20 mL of methanol was added to dissolve them, and then [Rh(Cp*)Cl ２ ] ２ To the reaction mixture, 62 mg of sodium chloride and 2,790 mg of silver acetate were added. Next, the atmosphere inside the reaction vessel was replaced with nitrogen, and the mixture was stirred at 80°C for 16 hours under a nitrogen atmosphere. After cooling, a saturated aqueous sodium chloride solution and dichloromethane were added, and the target substance was extracted from the aqueous layer with dichloromethane. The obtained organic layers were combined and dried to recover a solid. The recovered solid was purified by column chromatography and dried to obtain compound (1a-1) as a yellow solid in an amount of 620 mg and a yield of 45%.

[0083] The physicochemical data of the obtained compound (1a-1) are shown below.１ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 7.87 (t, J = 8.0 Hz, 1H), 7.36 (d, J = 8.4 Hz, 2H), 5.23 (s, 4H), 2.82 (q, J = 8.0Hz, 4H), 2.72 (q, J=8.0Hz, 4H), 1.34 (t, J=8.0Hz, 6H), 1.21 (t, J=8.0Hz, 6H). １３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 148.1, 140.1, 137.3, 136.5, 121.3, 117.0, 116.5, 48.8, 22.1, 20.2, 13.5, 13.1. HRMS (ESI+): Calcd for C ２１ H ２７ N ２ , [M-Cl] ＋ 307.2169, Found m / z 307.2177. IR (ATR): 2973 (m), 1665 (s), 1603 (s), 1580 (s), 1168 (s) cm －１ .

[0084] The ultraviolet-visible absorption spectrum of compound (1a-1) was measured using an ultraviolet-visible spectrophotometer (Agilent Technologies, product name "Agilent 8453"). The results are shown in Figure 1. In addition, the fluorescence spectrum of compound (1a-1) was measured at an excitation wavelength of 350 nm using a fluorescence spectrophotometer (JASCO Corporation, product name "FP-8350"). The results are shown in Figure 2.

[0085] Example A2 Synthesis of compound (1a-2)

[0086]

[0087] 10.0 mg of compound (1a-1) obtained in Example A1 and 8.5 mg of silver tetrafluoroborate (AgBF4) were placed in a reaction vessel, the reaction vessel was purged with nitrogen, 0.9 mL of dichloromethane was added to dissolve them, and the mixture was stirred at room temperature for 2 hours. The reaction product was then filtered, and the filtrate was dried to obtain compound (1a-2) in a yield of 9.8 mg and 85% as a yellow solid.

[0088] The physicochemical data of the obtained compound (1a-2) are shown below. １ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 7.88 (t, J = 8.2 Hz, 1H), 7.37 (d, J = 7.8 Hz, 2H), 5.02 (s, 4H), 2.79, (q, J =7.5Hz, 4H), 2.73 (q, J = 7.3Hz, 4H), 1.33 (t, J = 7.8Hz, 6H), 1.22 (t, J = 7.5Hz, 6H). １３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 148.4, 140.1, 137.5, 136.7, 121.6, 117.3, 116.6, 48.4, 22.2, 20.4, 13.5, 13.3. １９ F-NMR (373 MHz, solvent: CDCl ３ ): δ (ppm) = -155.1 (trifluoromethylbenzene was used as the internal standard: δ = -63.7). HRMS (ESI+): Calcd for C ２１ H ２７ N ２ , ([M] ＋ ) 307.2169, Found m / z 307.2175. IR (ATR): 2973 (m), 1666 (s), 1604 (s), 1581 (s), 1052 (s) cm －１ .

[0089] Example A3 Synthesis of compound (1a-3)

[0090]

[0091] 9.9 mg of compound (1a-1) obtained in Example A1 and 7.5 mg of silver acetate (CHCOOAg) were placed in a reaction vessel, the reaction vessel was purged with nitrogen, 0.9 mL of dichloromethane was added to dissolve them, and the mixture was stirred at room temperature for 2 hours. The reaction product was then filtered, and the filtrate was dried to obtain compound (1a-3) in a weight of 10.2 mg and a yield of 96% as a brown solid.

[0092] The physicochemical data of the obtained compound (1a-3) are shown below. １H-NMR (400 MHz, solvent: methanol-d4): δ (ppm) = 7.97 (t, J = 8.2 Hz, 1H), 7.53 (d, J = 8.2 Hz, 2H), 4.79 (s, 4H), 2. 84 (q, J=7.6Hz, 4H), 2.83 (q, J=7.5Hz, 4H), 1.89 (s, 3H), 1.34 (t, J=7.5Hz, 6H), 1.25 (t, J=7.5Hz, 6H). １３ C-NMR (101 MHz, solvent: methanol-d4): δ (ppm) = 180.1, 150.1, 141.4, 138.6, 137.8, 122.4, 118.4, 117.8, 49.1, 24.1, 22.7, 21.0, 13.6, 13.5. HRMS (ESI+): Calculated for C ２１ H ２７ N ２ , ([M] ＋ ) 307.2169, Found m / z 307.2178. IR (ATR): 2968 (m), 1667 (s), 1605 (s), 1580 (s) cm －１ .

[0093] Example A4 Synthesis of compound (1a-4)

[0094] 34.5 mg of the compound (1a-1) obtained in Example A1 and silver trifluoromethanesulfonate (AgSO ３ CF ３ The reaction vessel was purged with nitrogen, and 1.3 mL of dichloromethane was added to dissolve the components, followed by stirring at room temperature for 4 hours. The reaction product was then filtered, and the filtrate was dried to obtain compound (1a-4) in an amount of 45.7 mg (yield: 99%) as a yellow solid.

[0095] The physicochemical data of the obtained compound (1a-4) are shown below. １ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 7.88 (t, J = 8.0 Hz, 1H), 7.38 (d, J = 8.0 Hz, 2H), 4.95 (s, 4H), 2.77 (q, J = 7.6Hz, 4H), 2.73 (q, J=8.0Hz, 4H), 1.32 (t, J=8.0Hz, 6H), 1.22 (t, J=8.0Hz, 6H). １３C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 148.2, 139.9, 137.3, 136.6, 121.5, 117.2, 116.4, 48.2, 22.0, 20.2, 13.3, 13.1. １９ F-NMR (373 MHz, solvent: CDCl ３ ): δ (ppm) = 79.4 (trifluoromethylbenzene was used as the internal standard: δ = -63.7). HRMS (ESI+): Calcd for C ２１ H ２７ N ２ , [M-OTf] ＋ 307.2169, Found m / z 307.2173. IR (ATR): 2979 (m), 1667 (s), 1606 (s), 1583 (s), 1262 (s) cm －１ .

[0096] Example A5 Synthesis of compound (1a-5)

[0097]

[0098] Compound (1a-5) was obtained as a yellow solid in an amount of 50 mg and a yield of 5%, in the same manner as in Example 1A, except that compound (2a-1) was changed to 2-(4-methoxyphenyl)-2-imidazoline.

[0099] The physicochemical data of the obtained compound (1a-5) are shown below. １ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 6.81 (s, 2H), 5.16 (s, 4H), 4.00 (s, 3H), 2.80 (q, J = 7.7Hz, 4H ), 2.68 (q, J=7.6Hz, 4H), 1.32 (t, J=7.5Hz, 6H), 1.21 (t, J=7.7Hz, 6H). 　１３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 166.6, 147.0, 140.7, 139.2, 120.4, 111.4, 102.9, 55.8, 48.6, 22.2, 20.2, 13.5, 12.9. HRMS (ESI+): Calcd for C ２２ H ２９ N ２, ([M] ＋ ) 337.22744, Found m / z 337.22822. IR (ATR): 2969 (M), 1667 (S), 1602 (S), 1577 (S), 1397 (s), 1216 (s), 1047 (s) cm －１ .

[0100] Example A6 Synthesis of compound (1a-6)

[0101] 975 mg of compound (2a-2) and 994 mg of compound (3a-1) were placed in a reaction vessel, and 30 mL of methanol was added to dissolve them, followed by addition of [Rh(Cp*)Cl ２ ] ２ To the reaction mixture, 92 mg of sodium chloride and 4,210 mg of silver acetate were added. Next, the atmosphere inside the reaction vessel was replaced with nitrogen, and the mixture was stirred at 80°C for 20 hours under a nitrogen atmosphere. After cooling, a saturated aqueous sodium chloride solution and dichloromethane were added, and the target substance was extracted from the aqueous layer with dichloromethane. The resulting organic layers were combined and dried to recover a solid, which was then purified by column chromatography. Thereafter, reprecipitation was carried out using acetonitrile and toluene, and the precipitate was recovered and dried to obtain compound (1a-6) as a yellow solid in an amount of 127 mg and a yield of 6%.

[0102] The physicochemical data of the obtained compound (1a-6) are shown below. １ H-NMR (400 MHz, solvent: CD ３ OD): δ (ppm) = 6.85 (s, 2H), 4.70 (s, 4H), 2.79 (q, J = 7.3Hz, 4H), 2. 73 (q, J=7.8Hz, 4H), 1.31 (t, J=7.8Hz, 6H), 1.22 (t, J=7.8Hz, 6H). １３ C-NMR (101 MHz, solvent: CD ３ OD): δ (ppm) = 167.0, 148.7, 141.6, 140.8, 121.2, 111.7, 105.7, 22.7, 21.1, 13.5, 13.4. HRMS (ESI+): Calcd for C ２１ H ２７ N ２ O, [M-Cl] ＋323.2118, Found m / z 323.2122. IR (ATR): 3579 (br), 3436 (br), 3200-2400 (br), 1668 (s), 1574 (vs), 1409 (s) cm －１ .

[0103] Example A7 Synthesis of compound (1a-7)

[0104]

[0105] Compound (1a-7) was obtained as an ochre solid in a yield of 33 mg and 4%, in the same manner as in Example 1A, except that compound (2a-1) was changed to 2-(4-dimethylaminophenyl)-2-imidazoline.

[0106] The physicochemical data of the obtained compound (1a-7) are shown below. １ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 6.47 (s, 2H), 5.05 (s, 4H), 3.20 (s, 6H), 2.75 (q, J = 7.6Hz, 4H ), 2.65 (q, J=7.5Hz, 4H), 1.30 (t, J=7.6Hz, 6H), 1.20 (t, J=7.6Hz, 6H). １３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 155.7, 146.4, 139.9, 137.9, 119.5, 107.7, 99.8, 48.2, 40.5, 22.1, 20.1, 13.5, 12.8. HRMS (ESI+): Calcd for C ２２ H ２９ N ２ , ([M] ＋ ) 350.25907, Found m / z 350.25800. IR (ATR): 2969 (m), 1668 (s), 1579 (s), 1420 (s) cm －１ .

[0107] Example A8 Synthesis of compound (1a-8)

[0108]

[0109] Compound (1a-8) was obtained as a pale yellow solid in a yield of 94 mg and a yield of 34%, in the same manner as in Example 1A, except that compound (2a-1) was changed to 2-(4-(3-methoxycarbonylpropyloxy)phenyl)-2-imidazoline.

[0110] The physicochemical data of the obtained compound (1a-8) are shown below. １ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 6.79 (s, 2H), 5.18 (s, 4H), 4.21 (t, J = 6.2Hz, 2H), 3.73 (s, 3H), 2.79 (q, J = 7.6Hz, 4H), 2.67 (q, J = 7 .5Hz, 4H), 2.60 (t, J=7.1Hz, 2H), 2.21 (tt, J=6.9, 6.9Hz, 2H), 1.32 (t, J=7.8Hz, 6H), 1.20 (t, J=7.6Hz, 6H). １３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 173.4, 165.8, 147.0, 140.6, 139.2, 120.4, 111.4, 103.3, 67.3, 51.7, 48.6, 30.1, 24.3, 22.2, 20.2, 13.4, 12.9. HRMS (ESI+): Calcd for C ２６ H ３５ N ２ O ３ , ([M] ＋ ) 423.26422, Found m / z 423.26377. IR (ATR): 2968 (m), 1723 (s), 1670 (s), 1201 (s) cm －１ .

[0111] Example A9 Synthesis of compound (1a-9)

[0112]

[0113] To 39 mg of compound (1a-8) obtained in Example A8, 2 mL of water and 19 mg of lithium hydroxide (LiOH) were added, and the mixture was stirred at 50°C for 25 hours and then concentrated under reduced pressure to obtain a solid. The obtained solid was purified by column chromatography to obtain compound (1a-9) as a pale yellow solid in an amount of 35 mg and a yield of 93%.

[0114] The physicochemical data of the obtained compound (1a-9) are shown below. １ H-NMR (400MHz, solvent: methanol-d4): δ (ppm) = 6.96 (s, 2H), 4.75 (s, 4H), 4.26 (t, J = 6.4Hz, 2H), 2.83-2.74 (m , 8H), 2.51 (t, J=7.4Hz, 2H), 2.14 (tt, J=6.9, 6.9Hz, 2H), 1.32 (t, J=7.6Hz, 6H), 1.23 (t, J=7.6Hz, 6H). １３ C-NMR (101 MHz, solvent: methanol-d4): δ (ppm) = 177.7, 167.5, 148.8, 142.0, 140.6, 121.6, 112.5, 104.6, 69.0, 48.9, 31.8, 25.8, 22.8, 21.0, 13.5, 13.4. HRMS (ESI+): Calculated for C ２５ H ３３ N ２ O ３ , ([M] ＋ ) 409.24857, Found m / z 409.24730. IR (ATR): 3540-2600 (br), 2925 (m), 1667 (s), 1577 (s), 1173 (s) cm －１ .

[0115] Example A10 Synthesis of compound (1a-10)

[0116] 176 mg of compound (2a-1) and 336 mg of compound (3a-2) were placed in a reaction vessel, and 6 mL of methanol was added to dissolve them, followed by addition of [Rh(Cp*)Cl ２ ] ２ To the reaction mixture, 18 mg of sodium chloride and 842 mg of silver acetate were added. Next, the atmosphere inside the reaction vessel was replaced with nitrogen, and the mixture was stirred at 80°C for 16 hours under a nitrogen atmosphere. After cooling, a saturated aqueous sodium chloride solution and dichloromethane were added, and the target substance was extracted from the aqueous layer with dichloromethane. The obtained organic layers were combined and dried to recover a solid. The recovered solid was purified by column chromatography and dried to obtain compound (1a-10) as a yellow solid in an amount of 112 mg and a yield of 21%.

[0117] The physicochemical data of the obtained compound (1a-10) are shown below.１ H-NMR (396 MHz, solvent: CDCl ３ ): δ (ppm) = 7.85 (t, J = 8.2Hz, 1H), 7.32 (d, J = 8.2Hz, 2H), 5.20 (s, 4H), 2.75 (t, J=8.6Hz, 4H), 2.65 (t, J=8.2Hz, 4H), 1.67-1.49 (m, 16H), 1.02-0.98 (m, 12H). １３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 148.2, 139.4, 137.6, 136.6, 120.5, 117.2, 116.5, 49.1, 31.3, 30.7, 28.7, 27.0, 23.1, 22.9, 14.0, 13.9. HRMS (ESI+): Calcd for C ２９ H ４３ N ２ , [M-Cl] ＋ 419.3421, Found m / z 419.3430. IR (ATR): 2957 (m), 2870 (m), 1667 (m), 1604 (s), 1581 (m) cm －１ .

[0118] Example A11 Synthesis of Compound (1a-11)

[0119]

[0120] In addition, C in the formula ５ H １１ represents n-pentyl.

[0121] Compound (1a-11) was obtained as a yellow solid in an amount of 334 mg and a yield of 15%, in the same manner as in Example 1A, except that compound (3a-1) was changed to dodec-6-yne.

[0122] The physicochemical data of the obtained compound (1a-11) are shown below. １ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 7.83 (t, J = 8.0 Hz, 1H), 7.30 (d, J = 8.0 Hz, 2H), 5.17 (s, 4H), 2.73 (t, J = 8.0Hz, 4H), 2.63 (t, J = 7.6Hz, 4H), 1.66-1.34 (m, 24H), 0.93 (t, J = 7.2Hz, 12H).１３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 148.2, 139.5, 137.6, 136.6, 120.5, 117.2, 116.5, 49.1, 32.2, 31.9, 29.1, 29.0, 28.4, 27.3, 22.6, 22.5, 14.2, 14.1. HRMS (ESI+): Calcd for C ３３ H ５１ N ２ , ([M] ＋ ) 475.4047, Found m / z 475.4048. IR (ATR): 2955 (m), 1667 (s), 1580 (m) cm －１ .

[0123] Example A12 Synthesis of compound (1b-1)

[0124]

[0125] Compound (1b-1) was obtained as a yellow solid in an amount of 85 mg and a yield of 7%, in the same manner as in Example 1A, except that compound (2a-1) was changed to 2-phenyl-2-imidazole.

[0126] The physicochemical data of the obtained compound (1b-1) are shown below. １ H-NMR (400 MHz, solvent: CDCl ３ ): δ (ppm) = 9.47 (s, 2H), 8.30 (dd, J = 8.2, 7.8Hz, 1H), 8.16 (d, J = 8.2Hz, 2H), 3.49 (q , J=7.6Hz, 4H), 3.20 (q, J=7.6Hz, 4H), 1.51 (t, J=7.6Hz, 6H), 1.41 (t, J=7.6Hz, 6H). １３ C-NMR (101 MHz, solvent: CDCl ３ ): δ (ppm) = 136.1, 133.1, 131.7, 130.7, 126.5, 120.4, 118.2, 113.2, 22.1, 21.0, 14.2, 12.7. HRMS (ESI+): Calcd for C ２１ H ２５ N ２ , ([M] ＋) 305.20123, Found m / z 305.20184. IR (ATR): 2970 (m), 1686 (m), 1569 (s), 1052 (s) cm －１ .

[0127] Comparative Example A1 Synthesis of Compound (C-1) Compound (C-1) of the following formula was synthesized by the method described in Org. Lett., 2017, Vol. 19, No. 9, p. 1702.

[0128]

[0129] Comparative Example A2 Synthesis of Compound (C-2) Compound (C-2) of the following formula was synthesized by the method described in Org. Biomol. Chem., 2015, Vol. 13, No. 2, p. 447.

[0130]

[0131] Comparative Example A3 Compound (C-3) Compound (C-3) of the following formula was prepared using a compound manufactured by Aldrich under the trade name "Ru(bpz) ３ ][PF ６ ] ２ " was used.

[0132]

[0133] Comparative Example A4 Synthesis of Compound (C-4) Compound (C-4) of the following formula was synthesized by the method described in Chem. Sci., 2018, Vol. 9, No. 36, p. 7230.

[0134]

[0135] Example 1

[0136]

[0137] 27.7 mg of compound (4-1) as an ester compound, 2.10 mg of compound (1a-1) as a photocatalyst, and 114 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 40°C for 12 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, acetone was added, the solid was removed by filtration, and the filtrate was dried to obtain compound (P-1).

[0138] The yield of the obtained compound (P-1) was determined by GC measurement. The results are shown in Table 1. The GC measurement is as follows: (GC Measurement) Apparatus: Agilent Technologies, Inc., product name "Agilent 6850". Column: Agilent Technologies, Inc., product name "HP-5MS". Column length: 30 m. Injection volume: 1 μL. Vaporizer temperature: 250°C. Column oven temperature: After holding at 40°C for 1 minute, the temperature was increased from 40°C to 300°C at a rate of 30°C / min. Then, the temperature was held at 300°C for 15 minutes. Carrier gas: Helium.

[0139] Example 2 The ester compound was reduced in the same manner as in Example 1, except that 2.71 mg of compound (1a-4) was used as the photocatalyst, to obtain compound (P-1). The yield is shown in Table 1.

[0140] Example 2a An ester compound was reduced in the same manner as in Example 1, except that 2.2 mg of compound (1a-5) was used as the photocatalyst, to obtain compound (P-1) in a yield of 59%.

[0141] Comparative Example 1 An attempt was made to reduce an ester compound in the same manner as in Example 1, except that 2.08 mg of compound (C-1) was used as the photocatalyst, but reduction was unsuccessful and compound (P-1) was not obtained.

[0142] Comparative Example 2 The ester compound was reduced in the same manner as in Example 1, except that 5.50 mg of compound (C-2) was used as the photocatalyst, to obtain compound (P-1). The yield is shown in Table 1.

[0143] Comparative Example 3 An attempt was made to reduce the ester compound in the same manner as in Example 1, except that 5.11 mg of compound (C-3) was used as the photocatalyst, but reduction was unsuccessful and compound (P-1) was not obtained.

[0144] Comparative Example 4 An attempt was made to reduce the ester compound in the same manner as in Example 1, except that 4.67 mg of compound (C-4) was used as the photocatalyst, but reduction was unsuccessful and compound (P-1) was not obtained.

[0145]

[0146] As is clear from the results of Table 1 and Example 2a, the polycyclic compounds of the present invention were able to reduce ester compounds to alcohols in high yields using visible light as an energy source. On the other hand, compound (C-1) used in Comparative Example 1 did not have the function of a photocatalyst that uses visible light as an energy source, and was unable to reduce the ester compounds. Compounds (C-2) to (C-4) used in Comparative Examples 2 to 4, although common photocatalysts, were unable to reduce the ester compounds, or even if they were able to partially reduce them, the yield was very poor.

[0147] Example 3

[0148]

[0149] 38.2 mg of compound (4-2) as an ester compound, 2.04 mg of compound (1a-1) as a photocatalyst, and 62.7 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 40°C for 3 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, acetone was added, and the solid was removed by filtration. The filtrate was purified by column chromatography and dried to obtain the following compound (P-2). The yield of the obtained compound (P-2) was determined by NMR measurement. The results are shown in Table 2.

[0150] Example 4

[0151]

[0152] 43.4 mg of compound (4-3) as an ester compound, 2.09 mg of compound (1a-1) as a photocatalyst, and 114 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 50°C for 8 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and dichloromethane were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain compound (P-3) below. The yield of the obtained compound (P-3) was determined by NMR measurement. The results are shown in Table 2.

[0153] Example 5

[0154]

[0155] 44.3 mg of compound (4-4) as an ester compound, 2.11 mg of compound (1a-1) as a photocatalyst, and 113 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 50°C for 12 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and ethyl acetate were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain the following compound (P-4). The yield of the obtained compound (P-4) was determined by NMR measurement. The results are shown in Table 2.

[0156] Example 6

[0157]

[0158] 32.2 mg of compound (4-5) as an ester compound, 2.04 mg of compound (1a-1) as a photocatalyst, and 114 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 50°C for 12 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and ethyl acetate were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain compound (P-5) below. The yield of the obtained compound (P-5) was determined by NMR measurement. The results are shown in Table 2.

[0159] Example 7

[0160]

[0161] 39.0 mg of compound (4-6) as an ester compound, 2.07 mg of compound (1a-1) as a photocatalyst, and 62.5 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 40°C for 2 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and ethyl acetate were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain compound (P-6) below. The yield of the obtained compound (P-6) was determined by NMR measurement. The results are shown in Table 2.

[0162] As is clear from Table 2, the polycyclic compounds of the present invention were able to reduce ester compounds to alcohols in high yields using visible light as an energy source.

[0163] Example 8

[0164]

[0165] 28.1 mg of compound (12-1) as an ester compound (organic compound (I)), 112 mg of compound (13-1) as a carbonyl compound (organic compound (II)), 3.40 mg of compound (1a-1) as a photocatalyst, and 84.6 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 40°C for 24 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and ethyl acetate were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain the following compound (P-7). The yield of the obtained compound (P-7) was determined by NMR measurement. The results are shown in Table 3.

[0166] Example 9

[0167]

[0168] 28.3 mg of compound (12-1) as an ester compound (organic compound (I)), 3.41 mg of compound (1a-1) as a photocatalyst, and 84.9 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.1 mL of water and 2.1 mL of compound (13-2) as a carbonyl compound (organic compound (II)) were added. The mixture was then stirred at 40°C for 24 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and ethyl acetate were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain the following compound (P-8). The yield of the obtained compound (P-8) was determined by NMR measurement. The results are shown in Table 3.

[0169] Example 10

[0170]

[0171] 26.7 mg of compound (12-1) as an ester compound (organic compound (I)), 149 mg of compound (13-3) as a carbonyl compound (organic compound (II)), 3.36 mg of compound (1a-1) as a photocatalyst, and 85.0 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 40°C for 24 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and ethyl acetate were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain the following compound (P-9). The yield of the obtained compound (P-9) was determined by NMR measurement. The results are shown in Table 3.

[0172] Example 11

[0173]

[0174] 44.3 mg of compound (12-2) as an ester compound (organic compound (I)), 151 mg of compound (13-3) as a carbonyl compound (organic compound (II)), 3.35 mg of compound (1a-1) as a photocatalyst, and 285 mg of ammonium oxalate as a reducing agent were placed in a reaction vessel, and 1.6 mL of water and 1.6 mL of acetonitrile were added. The mixture was then stirred at 50°C for 24 hours while irradiating with blue light (Kessil, product name "A160WE Tuna Blue", output 40 W, wavelength 462 nm). After cooling, a saturated aqueous sodium chloride solution and ethyl acetate were added, and the organic layer was extracted. The extracted organic layer was purified by column chromatography and dried to obtain the following compound (P-10). The yield of the obtained compound (P-10) was determined by NMR measurement. The results are shown in Table 3.

[0175] As is clear from Table 3, the polycyclic compound of the present invention can couple an ester compound with a carbonyl compound other than an ester compound using visible light as an energy source, and the desired coupling product can be produced in high yield.

[0176] The polycyclic compound of the present invention has high oxidizing and reducing power and can utilize visible light as an energy source, and is therefore suitable as a photocatalyst used in, for example, reduction reactions and coupling reactions. Moreover, the polycyclic compound of the present invention is also suitable as a fluorescent material for, for example, organic EL devices, wavelength conversion films, fluorescent paints, etc.

Claims

1. A polycyclic compound represented by formula (1a) or formula (1b). In formula (1a), R １ａ ~R １１ａ are each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon oxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group, and X ａ － is a counter anion. In formula (1b), R １ｂ ~R ９ｂ are each independently a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon oxy group having 1 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 21 carbon atoms, an ester group, or a cyano group, and X ｂ － is a counter anion.

2. R in formula (1a) １ａ ~R ４ａ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and R ６ａ is a hydrogen atom, a hydroxy group, a hydrocarbon oxy group having 1 to 20 carbon atoms, or a dialkylamino group having 2 to 21 carbon atoms, and R ５ａ , R ７ａ , R ８ａ ~R １１ａ are each a hydrogen atom, and R in formula (1b) １ｂ ~R ４ｂ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and R ６ｂ is a hydrogen atom, a hydroxy group, a hydrocarbon oxy group having 1 to 20 carbon atoms, or a dialkylamino group having 2 to 21 carbon atoms, and R ５ｂ , R ７ｂ , R ８ｂ ~R ９ｂ are each a hydrogen atom, The polycyclic compound according to claim 1.

3. R in formula (1a) １ａ ~R ４ａ is each independently an alkyl group or aralkyl group having 1 to 20 carbon atoms which may contain a hetero atom, and R in formula (1b) １ｂ ~R ４ｂ is each independently an alkyl group or aralkyl group having 1 to 20 carbon atoms which may contain a hetero atom, the polycyclic compound according to claim 2.

4. R in formula (1a) １ａ to R ４ａ is each independently an alkyl group having 1 to 10 carbon atoms and containing no hetero atom, and R in formula (1b) １ｂ to R ４ｂ is each independently an alkyl group having 1 to 10 carbon atoms and containing no hetero atom, the polycyclic compound according to claim 3.

5. The polycyclic compound according to any one of claims 1 to 4, which is a photocatalyst.

6. The polycyclic compound according to any one of claims 1 to 4, which is a fluorescent material.

7. A method for reducing an organic compound using the polycyclic compound according to any one of claims 1 to 4.

8. A method for coupling organic compounds using the polycyclic compound according to any one of claims 1 to 4.

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