Compound and method for producing the same, fluorescent labeling agent, method for labeling a substance, and organic fluorescent material

Abstract

To provide a compound that can be used as an organic fluorescent dye and a method for producing the same.SOLUTION: A compound represented by a formula (1) is provided. [In the formula (1), R1 and R2 independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a substituted amino group. R3, R4, R5, and R6 independently represent a hydrogen atom, an alkyl group, or an aryl group. Two selected from a group consisting of R3, R4, R5, and R6 may bond to each other and form a ring along with a carbon atom which each bonds, where the pairs of R3, R4, R5, and R6 may be the same or different from each other].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound and a method for producing the same, a fluorescent labeling agent, a method for labeling a substance, and an organic fluorescent material. [Background technology]

[0002] Analysis, imaging, and sensing technologies utilizing fluorescent materials have become indispensable in a wide range of research fields, from basic to applied. Among the many fluorescent materials, organic fluorescent dyes have become extremely useful because their molecular structure can be freely tuned from the perspectives of luminescence properties, biocompatibility, etc. For example, non-patent documents 1 to 3 report organic fluorescent dyes with various molecular structures. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] M.Shimizu, Y.Takeda, M.Higashi, T.Hiyama, Angew.Chem., Int.Ed.2009,48,3653-3656. [Non-patent document 2] M.Shimizu,Chem.Rec.2021,21,1-18. [Non-patent document 3] J. Kim, JHOh, D. Kim, Org. Biomol. Chem. 2021, 19, 933-946. Summary of the Invention [Problem to be solved by the invention]

[0004] A main object of the present invention is to provide a novel compound that can be used as an organic fluorescent dye and a method for producing the same. [Means for solving the problem]

[0005] The present invention provides a compound according to [1], a method for producing the compound according to [2], a fluorescent labeling agent according to [3], a method for labeling a substance according to [4], and an organic fluorescent material according to [5].

[0006] [1] A compound represented by the following formula (1): [ka] [In formula (1), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a substituted amino group. R 3 , R 4 , R 5 , and R 6 R each independently represents a hydrogen atom, an alkyl group, or an aryl group. 3 , R 4 , R 5 , and R 6 Two of the R groups may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. 3 , R 4 , R 5 , and R 6 may be the same or different from each other. [2] A method for producing the compound according to [1], comprising a step of subjecting a mixed solution containing a compound represented by the following formula (2) and a compound represented by the following formula (3) to an electrolytic reaction: [ka] [In formula (2), R 1 and R 2 has the same meaning as above.] [ka] [In formula (3), R 3 , R 4 , R 5 , and R6 has the same meaning as above.] [3] A fluorescent labeling agent comprising the compound according to [1]. [4] A method for labeling a substance, comprising the step of binding the compound according to [1] to the substance. [5] An organic fluorescent material comprising the compound according to [1]. [Effects of the Invention]

[0007] The present invention provides novel compounds that can be used as organic fluorescent dyes and methods for producing the same. Furthermore, such compounds exhibit fluorescence in a variety of solvents. Some embodiments of the compounds exhibit emission wavelengths exceeding 500 nm. Furthermore, the present invention provides fluorescent labeling agents, methods for labeling substances, and organic fluorescent materials that use such compounds. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0009] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in one stage may be replaced with the upper or lower limit of a numerical range in another stage. Furthermore, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in an example.

[0010] In this specification, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more within the range that meets the conditions. When multiple substances corresponding to each component are present, the content of each component means the total amount of the multiple substances unless otherwise specified.

[0011] [Common term] Hereinafter, terms commonly used in this specification have the following meanings unless otherwise specified.

[0012] The "halogen atom" includes, for example, a fluorine atom, a chlorine atom, and a bromine atom.

[0013] The "alkyl group" may be any of a linear alkyl group, a branched alkyl group, or a cyclic alkyl group (cycloalkyl group). The linear alkyl group usually has 1 to 20 carbon atoms, and may have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. The branched alkyl group usually has 3 to 20 carbon atoms, and may have 3 to 10, 3 to 6, or 3 to 4 carbon atoms. The cyclic alkyl group usually has 3 to 20 carbon atoms, and may have 3 to 10 or 3 to 6 carbon atoms. The alkyl group may have a substituent. The number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent.

[0014] Examples of the straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, and an n-hexadecyl group.

[0015] Examples of branched alkyl groups include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, and a 2-decyltetradecyl group.

[0016] Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and an adamantyl group.

[0017] Examples of the substituted alkyl group include a methoxyethyl group, a benzyl group, a trifluoromethyl group, a perfluorohexyl group, and a chloromethyl group.

[0018] The "alkoxy group" may be any of a linear alkoxy group, a branched alkoxy group, or a cyclic alkoxy group (cycloalkoxy group). The linear alkoxy group usually has 1 to 20 carbon atoms, and may have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. The branched alkoxy group usually has 3 to 20 carbon atoms, and may have 3 to 10, 3 to 6, or 3 to 4 carbon atoms. The cyclic alkoxy group usually has 3 to 20 carbon atoms, and may have 3 to 10 or 3 to 6 carbon atoms. The alkoxy group may have a substituent. The number of carbon atoms of the alkoxy group does not include the number of carbon atoms of the substituent.

[0019] Examples of the alkoxy group include linear alkoxy groups such as a methoxy group, an ethoxy group, an n-propyloxy group, an n-butyloxy group, an n-hexyloxy group, an n-octyloxy group, an n-dodecyloxy group, and an n-hexadecyloxy group; branched alkoxy groups such as an isopropyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a 2-ethylhexyloxy group, a 3,7-dimethyloctyloxy group, a 2-hexyldecyloxy group, a 2-octyldodecyloxy group, and a 2-decyltetradecyloxy group; and cyclic alkoxy groups such as a cyclopentyloxy group and a cyclohexyloxy group.

[0020] An "aryl group" is a group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the aromatic hydrocarbon is usually 6 to 60, and may be 6 to 20 or 6 to 10. The aryl group may have a substituent. Note that the number of carbon atoms in the aryl group does not include the number of carbon atoms in the substituent.

[0021] Aromatic hydrocarbons include compounds in which two or more members selected from the group consisting of benzene, fused ring hydrocarbon compounds containing benzene, and fused ring hydrocarbon compounds containing benzene are directly bonded to one another.

[0022] Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, and a 4-phenylphenyl group.

[0023] The "substituted amino group" may be a secondary amino group or a tertiary amino group. Examples of groups that the substituted amino group has include alkyl groups, aryl groups, etc. These groups may have a substituent. When the substituted amino group has multiple groups, they may be the same or different, and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded.

[0024] The "substituent" is a group that can generally be taken in the field of organic chemistry. Examples of the substituent include a halogen atom, a hydroxy group, a carboxyl group, an amino group, a sulfonic acid group, a nitro group, a cyano group, an alkyl group, an aryl group, an alkoxy group, and a substituted amino group.

[0025] In this specification, Me represents a methyl group, Ph represents a phenyl group, DMF represents N,N-dimethylformamide, and DMSO represents dimethyl sulfoxide.

[0026] In this specification, room temperature refers to 25°C.

[0027] [Compound] The compound of this embodiment is a compound represented by formula (1).

[0028] [ka]

[0029] In formula (1), R 1 and R 2 R each independently represents a hydrogen atom, a halogen atom, a hydroxy group (-OH), an alkyl group, an alkoxy group, an amino group (-NH), or a substituted amino group.1 and R 2 may be the same or different from each other, but from the viewpoint of compound synthesis and symmetry, it is preferable that they are the same. 1 and R 2 R may be one selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, and a substituted amino group. 1 and R 2 From the viewpoint of lengthening the emission wavelength of the compound, may be an alkyl group or a hydrogen atom, or may be a hydrogen atom.

[0030] R 1 and R 2 The halogen atom in may be a chlorine atom.

[0031] R 1 and R 2 The alkyl group in may be a linear or branched alkyl group, or may be a linear alkyl group. The alkyl group may be an alkyl group having 1 to 6 carbon atoms, or may be a methyl group.

[0032] R 1 and R 2 The alkoxy group in may be a linear alkoxy group or a branched alkoxy group, or may be a linear alkoxy group. The alkoxy group may be an alkoxy group having 1 to 6 carbon atoms, or may be a methoxy group.

[0033] R 1 and R 2 The substituted amino group in may be a secondary amino group or a tertiary amino group, or may be a secondary amino group. The substituted amino group may be a secondary amino group having an alkyl group having 1 to 6 carbon atoms.

[0034] In formula (1), R 3 , R 4 , R 5 , and R 6 R each independently represents a hydrogen atom, an alkyl group, or an aryl group. 3 , R 4 , R5 , and R 6 R may be the same or different. 3 , R 4 , R 5 , and R 6 Two of the R groups may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. 3 , R 4 , R 5 , and R 6 may be the same or different from each other, but from the viewpoint of compound synthesis and symmetry, it is preferable that they are the same. 3 , R 4 , R 5 , and R 6 In the formula, the number of alkyl groups and aryl groups may be at least 1 (1 or more), or may be at least 3 (3 or more).

[0035] R 3 , R 4 , R 5 , and R 6 The alkyl group in may be a linear or branched alkyl group, or may be a linear alkyl group. The alkyl group may be an alkyl group having 1 to 6 carbon atoms, or may be a methyl group.

[0036] R 3 , R 4 , R 5 , and R 6 The aryl group in the formula (I) may be a group in which one hydrogen atom directly bonded to a carbon atom constituting the ring has been removed from an aromatic hydrocarbon having 6 to 10 carbon atoms, or may be a phenyl group.

[0037] Specific examples of the compound represented by formula (1) include compounds represented by formulas (1-1) to (1-6).

[0038] [ka]

[0039] [Method of manufacturing the compound] The method for producing the compound of this embodiment includes a step of subjecting a mixed solution containing a compound represented by formula (2) and a compound represented by formula (3) to an electrolytic reaction to obtain a compound represented by formula (1).

[0040] [ka]

[0041] In formula (2), R 1 and R 2 has the same meaning as above.

[0042] Specific examples of the compound represented by formula (2) include 2,5-dihydroxyterephthalaldehyde, 2,5-dihydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid dialkyl, 2,5-dihydroxy-N,N'-dialkylterephthalic acid amide, and 1,4-diacyl-2,5-dihydroxybenzene.

[0043] [ka]

[0044] In formula (3), R 3 , R 4 , R 5 , and R 6 has the same meaning as above.

[0045] R of the compound represented by formula (3) 3 , R 4 , R 5 , and R 6In the formula (3), the number of alkyl groups and aryl groups may be at least 1 (1 or more), or may be at least 3 (3 or more). In other words, the compound represented by formula (3) may be at least one selected from the group consisting of monosubstituted alkenes, disubstituted alkenes, trisubstituted alkenes, and tetrasubstituted alkenes, or may be at least one selected from the group consisting of trisubstituted alkenes and tetrasubstituted alkenes. The disubstituted alkene is preferably a 1,1-disubstituted alkene (terminal alkene).

[0046] Specific examples of the compound represented by formula (3) include monosubstituted alkenes such as styrene and its derivatives; disubstituted alkenes such as isobutene, α-methylstyrene, 2-ethyl-1-butene, methylenecyclohexane, methylenecyclopentane, methylenecyclobutane, methylenecyclopropane, 1,1-diphenylethylene, dibenzofulvene, and stilbene; trisubstituted alkenes such as 2-methyl-2-butene, 1-methyl-1-cyclohexene, 1-methyl-1-cyclopentene, and citronellic acid; and tetrasubstituted alkenes such as 2,3-dimethyl-2-butene, 1,2-dimethylcyclohexene, and 1,2-dimethylcyclopentene. Among these, the compound represented by formula (3) may be 2-methyl-2-butene or 2,3-dimethyl-2-butene from the viewpoint of synthesis.

[0047] The amount of the compound represented by formula (3) added may be, for example, 2 equivalents or more, 5 equivalents or more, or 8 equivalents or more relative to 1 equivalent of the compound represented by formula (2). The larger this ratio, the more excellent the reactivity tends to be. From the viewpoint of suppressing side reactions, this ratio may be, for example, 20 equivalents or less.

[0048] The mixed solution may further contain a solvent. The solvent is not particularly limited as long as it is applicable to an electrolytic reaction, and examples thereof include nitroalkane solvents such as nitromethane and nitroethane; and nitrile solvents such as acetonitrile. One solvent may be used alone, or two or more solvents may be mixed in any ratio. Among these, the solvent may be a nitroalkane solvent from the viewpoint of yield. The nitroalkane solvent may be nitromethane. That is, in one embodiment, the solvent may be nitromethane.

[0049] The concentration of the total amount of the compound represented by formula (2) and the compound represented by formula (3) relative to the total amount of the solvent may be, in molar concentration (mol / L), for example, 0.1 mmol / L to 5 mol / L, 0.5 mmol / L to 3 mol / L, or 1 mmol / L to 1 mol / L.

[0050] The mixed solution may further contain a supporting electrolyte from the viewpoint of increasing the conductivity in the electrolytic reaction. The supporting electrolyte is not particularly limited as long as it is applicable to the electrolytic reaction, and examples thereof include salts that are combinations of a cation moiety such as an alkali metal (e.g., Li) ion and an anion moiety such as a perchlorate ion. Among these, from the viewpoint of yield, the cation moiety may be a lithium ion and the anion moiety may be a perchlorate ion. That is, in one embodiment, the supporting electrolyte may be lithium perchlorate.

[0051] The concentration of the supporting electrolyte relative to the total amount of the solvent may be, for example, 0.5 to 10 mol / L, 1 to 8 mol / L, or 2 to 5 mol / L in molar concentration (mol / L).

[0052] The mixed solution may further contain various additives, such as organic acids.

[0053] Examples of organic acids include formic acid, acetic acid, propionic acid, benzoic acid, and trifluoroacetic acid. Use of an organic acid tends to improve the yield of the product, the compound represented by formula (1). Among these, the organic acid may be acetic acid.

[0054] In the method for producing a compound of this embodiment, an electrolytic reaction is applied to a mixed solution containing a compound represented by formula (2) and a compound represented by formula (3), and, as necessary, a solvent, a supporting electrolyte, an additive, etc. The electrolytic reaction can be a reaction (electrolytic oxidation reaction) that electrochemically oxidizes the compound represented by formula (2).

[0055] The electrolytic reaction can be carried out, for example, using an electrolytic cell equipped with electrodes. The electrolytic cell is equipped with at least two electrodes: an anode (working electrode) and a cathode (auxiliary electrode). Examples of the electrolytic cell include a single-compartment electrolytic cell (a diaphragm-less electrolytic cell) in which the two electrodes are installed in the same cell, and a two-compartment electrolytic cell (a diaphragm-equipped electrolytic cell) in which the two electrodes are installed in different cells. In the method for producing a compound of this embodiment, it is preferable to use a single-compartment electrolytic cell (a diaphragm-less electrolytic cell).

[0056] The electrolytic reaction may be performed by a two-electrode method using an anode (working electrode) and a cathode (auxiliary electrode), or by a three-electrode method using a reference electrode. Examples of the anode and cathode include electrodes made of glassy carbon, carbon felt, platinum, gold, palladium, graphite, ITO (indium tin oxide), and FTO (fluorine-doped tin oxide). Among these, from the viewpoint of yield, the anode may be carbon felt and the cathode may be platinum. Examples of the reference electrode include a reversible hydrogen electrode (RHE), a silver-silver chloride electrode (Ag / AgCl), and an Ag / Ag + Electrodes (e.g., silver-silver nitrate (Ag / Ag + )), calomel electrode (SCE), palladium-hydrogen electrode (Pd / H2), etc. Among these, the reference electrode may be a silver-silver chloride electrode (Ag / AgCl).

[0057] The atmosphere in which the electrolytic reaction is carried out is not particularly limited, but may be an inert gas atmosphere such as nitrogen or argon in order to avoid side reactions caused by oxygen molecules.

[0058] After the mixed solution is introduced into the electrolytic cell, an electrolytic reaction can be applied (progressed) by applying a potential to the mixed solution. The applied potential may be constant or may be varied. The electrolytic reaction may be constant potential electrolysis, in which the applied potential is constant.

[0059] The potential applied to the mixed solution can be set arbitrarily, but if the applied potential is too low, the compound represented by formula (2) may not be sufficiently oxidized, and if the applied potential is too high, the product may also be oxidized. The potential applied to the mixed solution may be, for example, 1 to 5 V versus a silver-silver chloride electrode (Ag / AgCl). The potential applied to the mixed solution may be 1.2 V or more, 1.3 V or more, or 1.5 V or more versus a silver-silver chloride electrode (Ag / AgCl), or may be 3 V or less, 2 V or less, or 1.8 V or less.

[0060] The amount of electricity applied in the electrolytic reaction may be 0.1 to 20 F / mol, 1 to 10 F / mol, or 3 to 5 F / mol relative to the compound represented by formula (2).

[0061] In one embodiment, the electrolysis reaction is preferably carried out using the following electrode materials under the following electrolysis conditions: By carrying out the electrolysis reaction under such conditions, an improved yield of the compound represented by formula (1) can be expected. Anode: Carbon felt ·Cathode: Platinum Applied potential: Constant potential of 1.5 to 1.8 V (vs. Ag / AgCl) ·Amount of current: 3~5F / mol

[0062] In this way, by applying an electrolytic reaction to a mixed solution containing the compound represented by formula (2) and the compound represented by formula (3), the compound represented by formula (1) can be efficiently obtained while suppressing side reactions.

[0063] The method for producing a compound of this embodiment may further include a step of purifying the obtained compound represented by formula (1). Examples of the purification method include commonly used purification methods such as filtration, extraction, crystallization, distillation, and various types of chromatography. These purification methods may be used alone or in combination.

[0064] [Fluorescent labeling agent] The fluorescent labeling agent of this embodiment includes a compound represented by the above formula (1).

[0065] The compound represented by formula (1) can be used as a fluorescent labeling agent. The substance to be fluorescently labeled with the compound represented by formula (1) is not particularly limited, and may be, for example, a physiologically active substance such as a peptide, a protein, a nucleic acid, a lipid, or a sugar chain; a polymer (polymer carrier) such as agarose or cellulose; or a resin (resin carrier) such as a natural resin or a synthetic resin.

[0066] [Substance labeling method] The method for labeling a substance of this embodiment includes a step of binding the compound represented by the above formula (1) to a substance (a substance that is fluorescently labeled with the compound represented by formula (1)).

[0067] The bond formed between the compound represented by formula (1) and a substance can be, for example, a chemical bond or a physical bond. A method for chemically bonding the compound represented by formula (1) to a substance includes, for example, reacting a group (e.g., a formyl group) possessed by the compound represented by formula (1) with a substance having a functional group (e.g., an amino group) capable of reacting with this group. In this case, an N=C bond is expected to be formed via an addition-dehydration reaction. The compound represented by formula (1) and the substance may be bonded directly or via a linker (linking group). The compound represented by formula (1) bound to a substance is expected to have a different emission wavelength from the compound represented by formula (1) not bound to the substance, making it possible to label the substance.

[0068] [Organic fluorescent materials] The organic fluorescent material of this embodiment contains a compound represented by the above formula (1).

[0069] The organic fluorescent material may further contain a resin such as a natural resin, a synthetic resin, etc. The organic fluorescent material of this embodiment can be used in various applications such as a fluorescent patterning material, a fluorescent switching material, a fluorescent sensor material, etc. [Example]

[0070] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0071] The structure of the compound was confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, and the luminescence properties of the compound were confirmed by known methods such as spectrophotometer.

[0072] For NMR measurement, a measurement sample was dissolved in deuterated chloroform (CDCl 3 ) and measured using an NMR apparatus (JNM-ECA500, manufactured by JEOL).

[0073] The fluorescence properties of the compounds (excitation wavelength (λex), fluorescence wavelength (λem), and fluorescence quantum yield (Φf)) were measured by dissolving the measurement sample in various solvents and using a spectrofluorometer (JASCO, FP-8300). -5 ~10 -4 The fluorescence quantum yield (Φf) was measured using an integrating sphere unit (manufactured by JASCO, Model ILF-835) on the spectrofluorometer.

[0074] Example 1 <Synthesis of Compound (1-1)> [ka]

[0075] Compound (2-1) was synthesized by demethylating the methoxy group of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (Sigma-Aldrich). 20 mL of a 3 mol / L lithium perchlorate / nitromethane solution was added to a single-chamber electrolytic cell, and Ar was bubbled through the solution. Subsequently, 0.050 mmol of compound (2-1), 10 molar equivalents of compound (3-1) (Tokyo Chemical Industry Co., Ltd.) relative to compound (2-1), and 915 μL (0.8 mol / L) of acetic acid were added to the single-chamber electrolytic cell to prepare a mixed solution. Next, an electrolytic reaction was carried out at a constant potential of 1.5 to 1.8 V (vs. Ag / AgCl) using carbon felt as the anode and platinum as the cathode. After applying a current of 4 F / mol, the mixed solution was diluted with water and extracted with ethyl acetate. The organic phase was then concentrated under reduced pressure and subjected to column chromatography to obtain the target product, compound (1-1) (yield: 53%). The NMR measurement results for compound (1-1) are shown below. Furthermore, the measurement results for the fluorescence properties of compound (1-1) in various solvents are shown in Table 1.

[0076] 1 HNMR (500MHz, CDCl3): δ10.33(2H,d,J=2.86Hz),3.49(2H,qui,J=28.07Hz),1. 51(6H,d,J=2.29Hz),1.34(6H,d,J=10.88Hz),1.13(6H,dd,J=12.60,6.87Hz). 13 C{ 1 H}NMR(125MHz,CDCl3):δ189.4,155.7,155.5,134.3,134.3,120.5,120.5,91.5,91.4,44.8,44.7,28.6,22.5,15.9,15.7.

[0077] [Table 1]

[0078] Example 2 <Synthesis of Compound (1-2)> [ka]

[0079] The electrolysis reaction was carried out in the same manner as in Example 1, except that compound (2-1) was replaced with compound (2-2) (Tokyo Chemical Industry Co., Ltd.), to obtain the target product, compound (1-2) (yield 14%). The NMR measurement results for compound (1-2) are shown below. Table 2 also shows the measurement results for the fluorescence properties of compound (1-2) in various solvents.

[0080] 1 HNMR(500MHz,CDCl3):δ10.78(2H,d,J=43.53Hz),3.28(2H,dqua,J=12.89,20.62,1 8.90Hz),1.56(6H,s),1.40(6H,d,J=3.44Hz),1.24(6H,dd,J=7.16,4.01,3.44Hz). 13 C{ 1 H}NMR(125MHz,CDCl3):δ168.7,168.7,149.6,149.5,130.6,130.2,118.7 ,112.4,112.3,85.1,84.9,34.8,34.7,27.5,27.5,25.7,25.7,15.9,15.7.

[0081] [Table 2]

[0082] Example 3 <Synthesis of compound (1-3)> [ka]

[0083] Compound (2-3) was synthesized by esterifying compound (2-2), a dicarboxylic acid, with methanol as the starting material. The electrolytic reaction was carried out in the same manner as in Example 1, except that compound (2-1) was replaced with compound (2-3), to obtain the target product, compound (1-3) (yield: 59%). The NMR measurement results for compound (1-3) are shown below. Table 3 also shows the measurement results for the fluorescence properties of compound (1-3) in various solvents.

[0084] 1 HNMR(500MHz, CDCl3): δ3.90(6H,d,J=4.01Hz),3.40(2H,dqua,J=14.32,21.19Hz) ,1.46(6H,d,J=14.89Hz),1.35(6H,d,J=21.19Hz),1.09(6H,dd,J=6.87,4.01Hz). 13 C{ 1 H}NMR(125MHz,CDCl3):δ165.7,165.6,151.8,151.8,135.4,135.2,114.7 ,114.7,89.6,89.6,52.0,52.0,45.9,28.4,28.3,22.5,22.5,16.4,16.3.

[0085] [Table 3]

[0086] Example 4 <Synthesis of Compound (1-4)> [ka]

[0087] Compound (2-4) was synthesized using the dicarboxylic acid compound (2-2) as the starting material according to the method described in Lett. Org. Chem. 2017, 14, 764-768. Except for replacing compound (2-1) with compound (2-4), the electrolytic reaction was carried out in the same manner as in Example 1 to obtain the target product, compound (1-4) (yield 28%). The NMR measurement results for compound (1-3) are shown below. Furthermore, the measurement results for the fluorescence properties of compound (1-4) in various solvents are shown in Table 4.

[0088] 1 HNMR(500MHz, CDCl3): δ8.04(2H,d,J=5.15Hz),3.82(2H,qua,J=21.19Hz),3.38(4H,m,J=69.88Hz),1.63(4H, m,J=37.23Hz),1.49(6H,s),1.32(6H,d,J=16.04Hz),1.15(6H,dd,J=12.60,6.87Hz),0.99(6H,t,J=7.40Hz). 13 C{ 1 H}NMR(125MHz, CDCl3): δ164.4,164.3,150.5,150.4,135.7,135.7,115.9,115. 9,90.8,90.7,45.4,45.3,41.2,28.5,28.5,22.7,22.7,16.7,16.6,11.6,11.5.

[0089] [Table 4]

[0090] Example 5 <Synthesis of compound (2-5)> [ka]

[0091] The dicarboxylic acid compound (2-2) was used as the starting material and reacted with methanol to esterify it, yielding compound (A). Compound (A) was then reacted with iodomethane to convert the phenolic hydroxyl group to a methoxy group, yielding compound (B). Compound (C) was then synthesized by hydrolysis of the ester of compound (B).

[0092] [ka]

[0093] The synthesized compound (C) was reacted with methyllithium to convert the carboxyl group to an acetyl group, thereby obtaining compound (D). The reaction from compound (C) to compound (D) was carried out with reference to the reaction conditions described in Bull. Korean Chem. Soc. 2005, 26, 9. Next, the methoxy group of compound (D) was demethylated using boron tribromide to obtain compound (2-5). The total yield was 16%.

[0094] <Synthesis of Compound (1-5)> [ka]

[0095] The electrolysis reaction was carried out in the same manner as in Example 1, except that compound (2-1) was replaced with compound (2-5), to obtain the target product, compound (1-5), (yield 30%). The NMR measurement results for compound (1-5) are shown below. Table 5 also shows the measurement results for the fluorescence properties of compound (1-5) in various solvents.

[0096] 1 HNMR(500MHz,CDCl3):δ3.52(2H,dqui,J=20.62,20.62Hz),2.60(6H,d,J=4.58Hz),1.44( 6H,d,J=6.87Hz),1.32(6H,d,J=28.64Hz),1.07(3H,d,J=7.45Hz),1.01(3H,d,J=6.87Hz). 13 C{ 1 H}NMR(125MHz,CDCl3):δ199.2,199.0,152.2,152.1,134.9,134.6,122.1,121.9,89.9,89.8,45.1,44.8,32.8,32.6,28.4,22.6,16.2,16.0.

[0097] [Table 5]

[0098] Example 6 <Synthesis of Compound (1-6)> [ka]

[0099] The electrolysis reaction was carried out in the same manner as in Example 1, except that compound (3-1) was replaced with compound (3-2) (Tokyo Chemical Industry Co., Ltd.), and the target product, compound (1-6), was obtained (yield 28%). The NMR measurement results for compound (1-6) are shown below. Furthermore, since compound (1-6) has a similar structure to compound (1-1), it is expected that the fluorescent properties of compound (1-6) in each solvent will be similar to those of compound (1-1).

[0100] 1 HNMR(500MHz, CDCl3): δ10.40(2H,s),1.34(12H,s),1.32(12H,s). 13 C{ 1 H}NMR(125MHz, CDCl3): δ189.8,155.9,136.9,121.5,93.5,47.8,22.9,22.2.

[0101] As described above, it was confirmed that the compounds of the present invention can be used as organic fluorescent dyes. Furthermore, it was found that the emission wavelengths of compounds (1-1) and (1-5) are longer, and in particular, compound (1-1) exhibits an emission wavelength of more than 500 nm in each solvent.

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 [In formula (1), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a substituted amino group. R ３ , R ４ , R ５ , and R ６ each independently represents a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R 3 , R 4 , R 5 , and R 6 is an alkyl group or an aryl group. R ３ , R ４ , R ５ , and R ６ Two selected from the group consisting of may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. There are two R ３ , R ４ , R ５ , and R ６ may be the same or different from each other.

2. A method for producing a compound represented by the following formula (1): A method for producing a compound, comprising a step of subjecting a mixed solution containing a compound represented by the following formula (2) and a compound represented by the following formula (3) to an electrolytic reaction: 【Chemistry 2】 In formula (1), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a substituted amino group. R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Two selected from the group consisting of R 3 , R 4 , R 5 and R 6 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. Two of R 3 , R 4 , R 5 , and R 6 may be the same or different.] 【Transformation 3】 [In formula (2), R １ and R ２ has the same meaning as above.] 【Chemistry 4】 [In formula (3), R ３ , R ４ , R ５ , and R ６ has the same meaning as above.]

3. A fluorescent labeling agent comprising a compound represented by the following formula (1): 【Transformation 5】 In formula (1), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a substituted amino group. R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Two selected from the group consisting of R 3 , R 4 , R 5 and R 6 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. Two of R 3 , R 4 , R 5 , and R 6 may be the same or different.]

4. A method for labeling a substance, comprising a step of binding a compound represented by the following formula (1) to the substance: 【Transformation 6】 In formula (1), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a substituted amino group. R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Two selected from the group consisting of R 3 , R 4 , R 5 and R 6 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. Two of R 3 , R 4 , R 5 , and R 6 may be the same or different.]

5. An organic fluorescent material comprising a compound represented by the following formula (1): 【Transformation 7】 In formula (1), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a substituted amino group. R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Two selected from the group consisting of R 3 , R 4 , R 5 and R 6 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. Two of R 3 , R 4 , R 5 , and R 6 may be the same or different.]

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