Compound and method for producing same

Abstract

To provide a compound that has a cyclic tetradentate ligand skeleton, can form a metal complex, and can be used as a light-emitting device.SOLUTION: The present invention relates to a compound represented by general formula (1), and a compound as a partially reduced body thereof (where Ar is an aryl group).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a compound having a cyclic tetradentate ligand skeleton and a method for producing the same. [Background technology]

[0002] In general, polydentate (bidentate, tridentate) ligands have a large association constant with metal ions and are known to form more stable complexes than monodentate ligands. Compared to bidentate and tridentate ligands, tetradentate ligands are extremely rare due to the difficulty of synthesizing them.

[0003] Furthermore, porphyrin and phthalocyanine are known as tetradentate cyclic ligands having a rigid cyclic structure that can form strong complexes (see Non-Patent Document 1). Porphyrin and phthalocyanine are known to have structural features in that their skeletons are planar and lack chirality, and that they become tetradentate upon deprotonation of two NH groups, acting as negative divalent ligands. However, there have been almost no reports on tetradentate cyclic ligands other than porphyrins and phthalocyanines. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Chemical Review(2016)117.2910-3043 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to solve the above-mentioned conventional problems and achieve the following object: That is, the present invention aims to provide a compound that has a cyclic tetradentate ligand skeleton, is capable of forming a metal complex, and can be used as a light-emitting device. [Means for solving the problem]

[0006] The means for solving the above problems are as follows. The compound of the present invention is represented by either of the following general formula (1) or the following general formula (2). [ka] [ka] In the general formulas (1) and (2), Ar represents an aryl group. Effect of the Invention

[0007] According to the present invention, it is possible to solve the above-mentioned problems in the prior art and achieve the above-mentioned object, and it is possible to provide a compound that has a cyclic tetradentate ligand skeleton, is capable of forming a metal complex, and can be used as a light-emitting device. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing the side and top molecular structures of the compound represented by general formula (1) of the present invention (wherein two Ar are p-methoxybenzyl groups) in an X-ray structural analysis. [Diagram 2] FIG. 2 is a diagram showing the ultraviolet-visible spectrum of the compound (1-1) of the present invention. [Diagram 3] FIG. 3 is a diagram showing the ultraviolet-visible spectrum of the compound (1-1) of the present invention. [Figure 4A] FIG. 4A is a diagram showing the fluorescence emission spectrum of the compound (1-1) of the present invention. [Figure 4B] FIG. 4B is a diagram showing the fluorescence emission spectrum of the compound (1-1) of the present invention. [Diagram 5] FIG. 5 is a graph showing the relationship between the fluorescence of the compound (1-1) of the present invention at an emission wavelength of 461 nm and the amount of TFA. [Figure 6] FIG. 6 is a graph showing the relationship between the fluorescence of the compound (1-1) of the present invention at an emission wavelength of 461 nm and the amount of TFA. [Figure 7] FIG. 7 shows the fluorescence emission spectra of the compounds (1-1) and (1-2) of the present invention under acidic conditions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] (Compound represented by either general formula (1) or general formula (2)) The compound of the present invention is a compound represented by either of the following general formula (1) or the following general formula (2), and is a cyclic tetradentate pyridyl nitrogen ligand having a cyclic tetradentate ligand skeleton. Since the compound has four quinoline skeletons, the present inventors have classified the compound into tetraquinoline ( TE tra Q The researchers named it uinoline (TEQ).

[0010] [ka]

[0011] [ka] In the general formulas (1) and (2), Ar represents an aryl group.

[0012] The two Ar in the general formula (1) may be the same or different. The two Ar in the general formula (2) may be the same or different. The aforementioned Ar is not particularly limited so long as it is an aryl group and can be appropriately selected depending on the purpose, but is preferably a group represented by the following general formula (a) (a p-alkoxyphenyl group).

[0013] [ka] In the general formula (a), R is a hydrogen atom, an alkyl group, or a trifluoromethylsulfonyl group (CF3SO2 -), and * represents a bond. Examples of the alkyl group in R include a methyl group and an n-pentyl group.

[0014] FIG. 1 shows a schematic diagram of the side and top molecular structures of the compound represented by general formula (1) of the present invention (where Ar is a p-methoxyphenyl group) in an X-ray structural analysis. The compound represented by the general formula (1) and the compound represented by the general formula (2) have a non-planar tetraquinoline skeleton and have chirality, and in this respect, are different from known porphyrins (which have a planar skeleton and do not have chirality). In addition, the properties of the compound represented by the general formula (1) are different in that the compound represented by the general formula (2) is tetradentate upon deprotonation of the two NH groups and therefore acts as a negative divalent ligand. To make porphyrin chiral, it is necessary to introduce a chiral element into the substituent site on the outside of the porphyrin skeleton, but there is a large spatial dissociation from the metal center, which is the active body. The compound represented by the general formula (1) and the compound represented by the general formula (2) have a chiral three-dimensional main skeleton, and can form a chiral environment in the close vicinity of the metal center. In the compound represented by the general formula (1) and the compound represented by the general formula (2), it is also possible to derivatize the tetraquinoline skeleton with the Ar and introduce a substituent into an additional substituent site, and there is a high degree of freedom in molecular design for imparting functions and differentiating functions.

[0015] There are a large number of research examples on metalloporphyrin complexes formed from the porphyrin. Using these research examples, it is possible to emulate the compounds represented by the general formula (1) and the compounds represented by the general formula (2) by introducing modulation of the valence and chirality. As a result, it is highly likely that the ligand skeletons of the compounds represented by the general formula (1) and the compounds represented by the general formula (2) can be used as versatile ligand skeletons capable of developing molecular structures that are highly suitable for specific purposes.

[0016] The compound represented by the general formula (1) and the compound represented by the general formula (2) can form a metal complex. Among these, the compound represented by the general formula (1) can selectively incorporate copper(II) ions to form a copper complex. The metal complex formed from the compound represented by the general formula (1) is a compound represented by the general formula (3) described below. The metal complex formed from the compound represented by the general formula (2) is a compound represented by the general formula (4) described below. The compound represented by the general formula (1) selectively captures copper (II) ions, and is therefore useful as a remover for removing heavy metals from the environment, and as a Cu 2+ It can be used as a quantitative reagent.

[0017] The compound represented by the general formula (1) can emit fluorescence and can be used as a light-emitting element. In addition, the compound represented by the general formula (1) exhibits enhanced fluorescence intensity in an acidic environment. Since the enhanced fluorescence intensity is proportional to the acid concentration, the compound can be used as a probe for measuring the acidity in the environment.

[0018] (Compound represented by either general formula (3) or general formula (4)) The compound of the present invention is a compound represented by either of the following general formula (3) or the following general formula (4), and is a metal complex having a cyclic tetradentate ligand skeleton.

[0019] [ka] In the general formula (3), Ar represents an aryl group; - represents an anion. [ka] In the above general formula (4), Ar represents an aryl group, and M represents a metal.

[0020] Ar in the general formula (3) is the same as Ar in the general formula (1), and the preferred embodiments are also the same. B in the general formula (3) - The anion is not particularly limited and can be appropriately selected depending on the purpose. For example, TfO - , BF4 - , Cl - etc.

[0021] Ar in the general formula (4) is the same as Ar in the general formula (2), and the preferred embodiments are also the same. M in the general formula (4) is a metal. The metal is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include iron, cobalt, and zinc.

[0022] (Compound represented by structural formula 1d) The compound of the present invention is a compound represented by the following structural formula 1d, and is an intermediate compound in the process of producing a compound represented by any one of the general formulae (1) to (4) above.

[0023] [ka]

[0024] (Compound represented by structural formula 1D) The compound of the present invention is a compound represented by the following structural formula 1D, and is a metal complex of the compound represented by the structural formula 1d.

[0025] [ka]

[0026] (Method of producing the compound) The method for producing a compound of the present invention is a method for producing a compound represented by any one of the general formulas (1) to (4), which includes at least a reaction step of reacting a compound represented by the structural formula 1d with a compound represented by the following general formula (b), and further includes other steps as necessary.

[0027] [ka] In the above general formula (b), R 1 represents an alkyl group. R 1 Examples of the alkyl group in the above formula include a methyl group and an n-pentyl group. The compound represented by the general formula (b) is 4-ethynylanisole (R 1 : methyl group), 1-ethynyl-4-(n-pentyloxy)benzene (R 1 : n-pentyl group) is preferred.

[0028] <Reaction process> The reaction step is not particularly limited and can be appropriately selected depending on the purpose, but is preferably carried out in the presence of an amide activator and a base. The combination of the activator and base is preferably 2,4,6-trimethoxypyridine and trifluoromethanesulfonic anhydride. The amount of the catalyst used in the reaction step is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 2 to 10 molar equivalents relative to the compound represented by the structural formula 1d.

[0029] The solvent used in the reaction step is not particularly limited and can be appropriately selected depending on the purpose. Examples of the solvent include 1,2-dichloroethane, dichloromethane, and toluene.

[0030] The reaction temperature in the reaction step is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0°C to 80°C. The reaction time in the reaction step is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 hours to 30 hours. The pressure in the reaction step is not particularly limited and can be appropriately selected depending on the purpose, but atmospheric pressure is preferred. EXAMPLES

[0031] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples, "Me" stands for "methyl group", "Et" stands for "ethyl group", "TMS" stands for "trimethylsilyl group", "Tf" stands for "trifluoromethylsulfonyl group", "Ac" stands for "acetyl group", "Ph" stands for "phenyl group", and "rt" stands for room temperature. Mixing ratios in solutions such as various eluents are indicated by volume ratios.

[0032] Example 1 <Synthesis of compound (1-1)> <<Synthesis of Compound 1a: 2-Chloroquinoline-8-carboxylic acid>> In a three-neck flask under an argon atmosphere, 8-bromo-2-chloroquinoline (2.425 g, 10 mmol) and anhydrous tetrahydrofuran (THF, 40 mL) were placed. n-Butyl lithium (nBuLi, 3.85 mL, 10 mmol, 2.6 M hexane solution) was added at -78°C and stirred for 20 minutes. CO2 was bubbled through the reaction solution for 30 minutes. When the starting material disappeared, 1N HCl was added to stop the reaction, and 1N NaOH was added until the pH of the reaction solution reached 10. The reaction solution was extracted with water, and the aqueous layer was washed with ethyl acetate and dichloromethane. 1N HCl was added to the aqueous layer to produce a white solid. Dichloromethane was added to dissolve the solid, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with brine and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to give compound 1a (1.774 g, 85% yield) as a yellow solid.

[0033] [ka]

[0034] [ka]

[0035] The compound 1a (2-chloroquinoline-8-carboxylic acid) obtained above 1The H NMR spectrum is shown. 1 H NMR (400MHz, CDCl3): δ14.80(bs,1H),8.85(dd,J=7.6,1.6Hz,1H),8.35(d,J=8.8 Hz,1H),8.11(dd,J=8.0,1.2Hz,1H),7.78(t,J=7.6Hz,1H),7.59(d,J=8.8Hz,1H).

[0036] <<Synthesis of Compound 1b: Acidic Methyl 2-Chloroquinoline-8-carboxylate>> In a Schlenk tube under an argon atmosphere, the obtained compound 1a (4.67 g, 22.5 mmol), toluene (100 mL), and MeOH (20 mL) were placed. Trimethylsilyldiazomethane (TMSCHN2, 15.8 mL, 31.5 mmol, 2 M hexane solution) was added at 0°C and stirred for 30 min. The reaction solution was warmed to room temperature and stirred for another 22 h. When the starting material disappeared, 1N HCl was added to quench the reaction. Saturated NaHCO3 solution was added until the pH of the reaction solution reached 7.5. The reaction solution was extracted with ethyl acetate, washed with brine, and dried over anhydrous Na2SO4. The solution was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (eluent: hexane:ethyl acetate = 90:10 to 80:20 to 75:25) to obtain compound 1b (3.814 g, 76% yield) as a yellow solid.

[0037] [ka]

[0038] [ka]

[0039] The compound 1b (acidic methyl 2-chloroquinoline-8-carboxylate) obtained above 1 The H NMR spectrum is shown. 1H NMR (400MHz, CDCl3): δ8.12(d,J=8.8Hz,1H),8.09(dd,J=7.2,1.6Hz,1H),7.95( dd,J=8.4,1.6Hz,1H),7.59(t,J=7.2Hz,1H),7.44(d,J=8.4Hz,1H),4.05(s,3H).

[0040] <<Synthesis of Compound 1c: Methyl 2-(2-aminophenyl)quinoline-8-carboxylate>> Compound 1b (2.44 g, 11 mmol), (2-aminophenyl)boronic acid (1.656 g, 12.1 mmol), K2CO3 (11.40 g, 82.5 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 635.6 mg, 0.55 mol), dioxane (100 mL), and water (40 mL) were placed in a three-neck flask at room temperature under an argon atmosphere. The reaction solution was stirred at 70 °C for 20 h. When the starting material disappeared, water and ethyl acetate were added. The reaction solution was extracted with ethyl acetate, washed with brine, and dried over anhydrous Na2SO4. The solution was filtered through silica gel (eluent: ethyl acetate), evaporated under reduced pressure, and the residue was purified by silica gel chromatography (eluent: hexane:ethyl acetate = 5:1) to give compound 1c (2.82 g, 92% yield) as a yellow solid.

[0041] [ka]

[0042] [ka]

[0043] The compound 1c (methyl 2-(2-aminophenyl)quinoline-8-carboxylate) obtained above 1 The H NMR spectrum is shown. 1H NMR (400MHz, CDCl3): δ8.23(dd,J=7.6,1.6Hz,1H),8.18(d,J=8.8Hz,1H),7.94-7.92(m,2H),7.77 (dd,J=8.0,1.2Hz,1H),7.50(t,J=7.2Hz,1H),7.23-7.19(m,1H),6.82-6.74(m,4H),4.01(s,3H).

[0044] <<Synthesis of Compound 1d: 3,7-diaza-1(2,8),5(8,2)-diquinolina-2,6(1,2)-dibenzcyclooctaphane-4,8-dione>> The obtained compound 1c (278.3 mg, 1 mmol) and THF (60 mL) were placed in a three-neck flask under an argon atmosphere. Potassium tert-butoxide (t-BuOK, 3 mL, 3 mmol, 1 M THF solution) was added dropwise to the reaction solution at -78°C. The temperature was slowly raised to room temperature within 0.5 hours and stirred for another 1 hour. When the starting material disappeared, the reaction was stopped by adding saturated NH4Cl solution. The reaction solution was extracted with ethyl acetate, washed with brine, and dried over anhydrous Na2SO4. The solution was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (eluent: hexane:ethyl acetate = 1:1 to 1:2) to obtain compound 1d (149.5 mg, yield 61%) as a yellow solid.

[0045] [ka]

[0046] [ka]

[0047] The compound 1d (3,7-diaza-1(2,8),5(8,2)-diquinolina-2,6(1,2)-dibenzcyclooctaphane-4,8-dione) obtained above 1 The H NMR spectrum is shown. 1H NMR(400MHz,CDCl3):δ12.55(s,2H),8.53(dd,J=7.2,1.6Hz,2H),8.34(d,J=8.4Hz,2H), 7.91(dd,J=8.0,1.2Hz,2H),7.79(d,J=8.4Hz,2H),7.66-7.64(m,2H),7.57-7.48(m,8H).

[0048] <<Synthesis of compound (1-1): tetraquinoline (TEQ)>> Compound 1d (98.5 mg, 0.2 mmol), 2,4,6-trimethoxypyridine (2,4,6-(OMe)3-pyridine, 169.2 mg, 1 mmol), and 1,2-dichloroethane (DCE, 3 mL) were placed in a sealed tube under an argon atmosphere. Trifluoromethanesulfonic anhydride (Tf2O, 105 μL, 0.64 mmol) was added dropwise to the reaction solution at 0 °C and stirred for an additional 15 min. 4-Ethynylanisole (0.26 mL, 2 mmol) was added and the reaction solution was heated at 80 °C for 22 h. Upon completion of the reaction, Et3N was added to quench the reaction. The reaction solution was filtered through a silica gel pad (eluent: dichloromethane (DCM): ethyl acetate = 1:1). The solution was concentrated and filtered through basic Al2O3 (eluent: DCM: ethyl acetate = 20:1). The solution was evaporated under reduced pressure, and the residue was washed seven times with Et2O (solvent was removed by centrifugation), to give compound (1-1) (60.2 mg, 42% yield) as a pale gray solid. The Et2O solution was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (eluent: hexane:ethyl acetate = 1:1 to 1:3) to give a crude product, which was washed with a small amount of Et2O to give an additional 3.0 mg (2% yield) of compound (1-1) as a pale gray solid.

[0049] [ka]

[0050] [ka]

[0051] The compound (1-1) (TEQ) obtained above 1 The H NMR spectrum is shown. 1 H NMR(400MHz,DMF-d7):δ8.44(d,J=8.4Hz,2H),8.05-8.01(m,4H),7.75(dd,J=7. 2,1.6Hz,2H),7.67-7.58(m.12H),7.52(s,2H),7.17-7.15(m,4H),3.90(s,6H).

[0052] Example 2 <Synthesis of compound (1-2): TEQ-OH> Compound (1-1) (TEQ, 36.0 mg, 0.05 mmol) and pyridine hydrochloride (Py·HCl, 2.311 g, 20 mmol) were placed in a sealed tube under an argon atmosphere, and the reaction solution was stirred at 180 °C for 11 h. When the reaction was completed, 2N NaOH was added to quench the reaction at pH = 7. DCM and MeOH were added to almost dissolve the solid. The reaction solution was extracted with DCM, washed with brine, and dried over anhydrous Na2SO4. The solution was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (eluent: DCM:MeOH = 95:5) to give compound (1-2) (22.1 mg, 64% yield) as a pale yellow solid.

[0053] [ka]

[0054] [ka]

[0055] The compound (1-2) (TEQ-OH) obtained above 1 The H NMR spectrum is shown. 1H NMR(400MHz,DMF-d7):δ9.97(s,2H),8.44(d,J=8.4Hz,2H),8.07-8.02(m,4H) ,7.75-7.73(m,2H),7.66-7.57(m.8H),7.51-7.49(m,6H),7.06-7.02(m,4H).

[0056] Example 3 <Synthesis of compound (1-3): TEQ-OTf> Compound (1-2) (TEQ-OH, 27.7 mg, 0.04 mmol) and pyridine (2 mL) were placed in a sealed tube under argon atmosphere. Tf2O (52.5 μL, 0.32 mmol) was added dropwise to the reaction solution at 0°C. The reaction solution was warmed to room temperature and stirred for an additional 24 h. Upon completion of the reaction, saturated NH4Cl was added to quench the reaction. The reaction solution was extracted with DCM, washed with brine, and dried over anhydrous Na2SO4. The solution was evaporated under reduced pressure, and the residue was purified by basic Al2O3 chromatography (eluent: DCM:MeOH = 40:1) to give compound (1-3) (22.3 mg, 58% yield) as a white solid.

[0057] [ka]

[0058] [ka]

[0059] The compound (1-3) (TEQ-OTf) obtained above 1 The H NMR spectrum is shown. 1 H NMR(400MHz,DMF-d7):δ8.45(d,J=8.4Hz,2H),8.06-8.04(m,2H),7.92-7.88(m,6H),7.78-7.70(m.8H),7.66-7.61(m,8H).

[0060] Example 4 <Synthesis of compound (1-4): TEQ-OPently> Compound 1d (98.5 mg, 0.2 mmol), 2,4,6-trimethoxypyridine (2,4,6-(OMe)3-pyridine, 169.2 mg, 1 mmol), and 1,2-dichloroethane (DCE, 3 mL) were placed in a sealed tube under an argon atmosphere. Trifluoromethanesulfonic anhydride (Tf2O, 105 μL, 0.64 mmol) was added dropwise to the reaction solution at 0 °C and stirred for an additional 15 min. 1-Ethynyl-4-(n-pentyloxy)benzene (376.5 mg, 2 mmol) was added, and the reaction solution was heated at 80 °C for 22 h. Upon completion of the reaction, Et3N was added to quench the reaction. The reaction solution was filtered through a silica gel pad (eluent: dichloromethane (DCM): ethyl acetate = 1:1). The solution was concentrated and filtered through basic Al2O3 (eluent: DCM:ethyl acetate = 20:1). The solution was evaporated under reduced pressure, and the residue was washed with Et2O seven times (solvent was removed by centrifugation) to give compound (1-4) (45.2 mg, 27% yield) as a brown solid.

[0061] [ka]

[0062] The compound (1-4) (TEQ-OPently) obtained above 1 The H NMR spectrum is shown. 1 H NMR(400MHz,CDCl3)δ8.18(d,J=8.4Hz,2H),8.02(dd,J=8.4,1.2Hz,2H),7.82(dd,J=8.4,1.6Hz,2H),7.60-7.54(m,4H),7 .51-7.43(m,12H),7.01-6.98(m.4H),4.01(t,J=6.4Hz,4H),1.86-1.79(m,4H),1.49-1.37(m,8H),0.94(t,J=7.2Hz,6H).

[0063] Example 5 <Synthesis of compound (2-1): TEQ-8H> Compound (1-1) (TEQ, 36.0 mg, 0.05 mmol), phenylboronic acid (PhB(OH)2, 61.0 mg, 0.5 mmol), Hantzsch ester (126.6 mg, 0.5 mmol), and DCE (5 mL) were placed in a sealed tube under an argon atmosphere. The reaction solution was stirred at 80°C for 24 hours. When the reaction was completed, the solution was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (eluent: hexane:ethyl acetate = 10:1 to 4:1) to obtain a crude product. This was purified by solvent recycling preparative HPLC (eluent: chloroform) to obtain compound (2-1) (20.9 mg, 57% yield) as a yellow solid.

[0064] [ka]

[0065] [ka]

[0066] The compound (2-1) (TEQ-8H) obtained above 1 The H NMR spectrum is shown. 1 H NMR (400MHz, CDCl3): δ7.81(dd,J=8.4,1.2Hz,2H),7.75-7.73(m,2H),7.41(s,2H),7.39-7.35(m,6H),7.12-7.09(m,4H),7.00-6.96(m,4H),6.72( t,J=7.6,2H),6.03(s,2H),5.98(dd,J=12.0,2.8Hz,2H),3.85(s,6H),3. 33-3.25(m,2H),3.02-2.96(m,2H),2.64-2.54(m,2H),2.12-2.09(m,2H).

[0067] Example 6 <Synthesis of compound (3-1): TEQ-Cu-(OTf)2> Compound (1-1) (TEQ, 144.2 mg, 0.2 mmol), Cu(OTf)2 (72.3 mg, 0.2 mmol), and DCM (20 mL) were placed in a Schlenk tube under an argon atmosphere. The reaction solution was stirred at room temperature for 19 hours. When the reaction was completed, the reaction solution was filtered through Celite (eluent: DCM). The solution was evaporated under reduced pressure, and the residue was dissolved in acetone / toluene (1:3). This solution was left to stand at room temperature for 2 days, and compound (3-1) (192.6 mg, 89% yield) was obtained as a dark green solid.

[0068] [ka]

[0069] Example 7 <Synthesis of compound (3-2): TEQ-Cu-(BF4)2> In a Schlenk tube under an argon atmosphere, compound (1-1) (TEQ, 36.0 mg, 0.05 mmol), copper(II) tetrafluoroborate hydrate (Cu(BF4)2-xH2O, 15.5 mg, 0.05 mmol, 19% by mass to 22% by mass Cu), DCM (10 mL), and acetone (1 mL) were placed. The reaction solution was stirred at room temperature for 43 hours. When the reaction was completed, acetone was added to dissolve the precipitate, and the reaction solution was filtered through Celite (eluent: DCM). The solution was evaporated under reduced pressure, and the residue was dissolved in acetone / toluene (1:1). This solution was left to stand at room temperature for 2 days, and compound (3-2) (26.6 mg, 56% yield) was obtained as a dark green solid.

[0070] [ka]

[0071] Example 8 <Synthesis of Compound 1D: Copper 3,7-diaza-1(2,8),5(8,2)-diquinolina-2,6(1,2)-dibenzcyclooctaphane-4,8-dione> Compound 1d (49.3 mg, 0.1 mmol), Cu(OTf)2 (36.2 mg, 0.1 mmol), potassium acetate (KOAc, 19.6 mg, 0.2 mmol), and DCM (3 mL) were placed in a Schlenk tube under an argon atmosphere. The reaction solution was stirred at room temperature for 24 hours. When the reaction was completed, a small amount of MeOH was added to dissolve the precipitate, and the reaction solution was filtered through Celite (eluent: DCM), the solution was evaporated under reduced pressure, and the residue was dissolved in acetone / MeOH (1:1). This solution was left at room temperature for 2 days to obtain compound 1D (38.7 mg, 70% yield) as a dark green solid.

[0072] [ka]

[0073] Example 9 <UV-Visible light spectrum measurement> The ultraviolet-visible (UV-Vis) spectrum of the obtained compound was measured by the following procedure.

[0074] Each solution used in the measurement was prepared as follows. (1) Preparation of TFA solution (25 mL, 5 mmol / L) Trifluoroacetic acid (TFA, 9.3 μL, 0.125 mmol) was placed in a 25 mL measuring flask, and dichloromethane was added up to the marked line. (2) Preparation of compound (1-1) solution (10 mL, 0.2 mmol / L) Compound (1-1) (TEQ, 1.44 mg, 0.002 mmol) was placed in a 10 mL measuring flask, and dichloromethane was added up to the marked line. (3) Preparation of compound (1-1) + 4 equivalents of TFA solution (10 mL, 0.02 mmol / L) A compound (1-1) solution (1 mL, 0.2 mmol / L) and a TFA solution (0.16 mL, 5 mmol / L) were placed in a 10 mL measuring flask, and dichloromethane was added up to the marked line. (4) Compound (1-1) solution (10mL, 0.02mmol / L) A compound (1-1) solution (1 mL, 0.2 mmol / L) was placed in a 10 mL measuring flask, and dichloromethane was added up to the marked line. (5) Compound (1-2) solution (10mL, 0.2mmol / L) (6) Compound (1-2) solution (10mL, 0.02mmol / L) (7) Compound (1-3) solution (10mL, 0.2mmol / L) (8) Compound (1-3) solution (10mL, 0.02mmol / L) Solutions (5) to (8) were prepared in the same manner as in (2) and (4) above, except that compound (1-1) in (2) and (4) above was replaced with compound (1-2) or compound (1-3).

[0075] The ultraviolet-visible light spectrum was measured at room temperature in an air atmosphere using an ultraviolet-visible light spectrum measuring device (device name: V-670, manufactured by JASCO Corporation). For compound (1-1), compound (1-2), and compound (1-3), the ultraviolet-visible spectrum measured using a 0.02 mmol / L solution is shown in FIG. 2, and the ultraviolet-visible spectrum measured using a 0.2 mmol / L solution is shown in FIG. 3.

[0076] Solution (3): Absorption wavelength λ of compound (1-1) under acidic conditions determined from the ultraviolet-visible spectrum of compound (1-1) (0.02 mmol / L) + 4 equivalents of TFA solution abs The absorption wavelength was 370 nm and the molar absorption coefficient ε was 28,700 L / (cm*mol) (Figure 2). In addition, the absorption wavelength λ of compound (1-1) was calculated from the ultraviolet-visible spectrum of solution (2): compound (1-1) (0.2 mmol / L). abs was 385.5 nm and the molar absorption coefficient ε was 3,540 L / (cm*mol).

[0077] Example 10 <Measurement of fluorescence emission spectrum> The fluorescence emission spectrum was measured using a fluorescence emission spectrum measuring device (device name: V-670, manufactured by JASCO Corporation) at an excitation wavelength of 385.5 nm in an air atmosphere at room temperature. Fluorescence emission spectra measured using a 0.02 mmol / L DCM solution of compound (1-1) (when no TFA was added, no TFA) and a 0.02 mmol / L DCM solution of compound (1-1) to which 0.1 equivalent, 0.2 equivalent, 0.4 equivalent, 0.6 equivalent, 0.8 equivalent, 1.0 equivalent, 1.5 equivalent, 2.0 equivalent, 3.0 equivalent, 4.0 equivalent, 6.0 equivalent, and 8.0 equivalent of TFA (0.1 to 8.0 equiv TFA) are shown in Figures 4A and B.

[0078] From the fluorescence emission spectrum, the emission wavelength λ of compound (1-1) without the addition of TFA was em is 435 nm, and the emission quantum yield Φ F was 0.07. In addition, the emission wavelength λ of the compound (1-1) under acidic conditions when 4.0 equivalents of TFA were added was em is 461 nm, and the emission quantum yield Φ F was 0.63. Therefore, it was found that compound (1-1) can emit fluorescence, and the fluorescence intensity is enhanced under acidic conditions.

[0079] The relationship between the fluorescence at an emission wavelength of 461 nm and the amount of TFA, which was determined based on Figures 4A and B, is shown in Figures 5 and 6. It was found that the fluorescence intensity of compound (1-1) was proportional to the amount of TFA when no TFA was added to when 1.0 equivalent of TFA was added (coefficient of determination: R 2 =0.9945).

[0080] Example 11 <Measurement of fluorescence emission spectrum> Measurement of the fluorescence emission spectrum was carried out in the same manner as in Example 8, except that the following solutions were used. The measured fluorescence emission spectrum is shown in FIG. Compound (1-1) (0.02 mmol / L) + 4.0 equivalents of TFA solution, excitation wavelength λ ex :385.5nm Compound (1-2) (0.02 mmol / L) + 4.0 equivalents of TFA solution, excitation wavelength λ ex :360nm Acyclic pyridine tetramer (TetraPy) (0.02 mmol / L) + 4.0 equivalents of TFA solution, excitation wavelength λ ex :360nm

[0081] [ka]

[0082] Emission wavelength λ under acidic conditions when 4.0 equivalents of TFA are added to compound (1-1) em is 461 nm, and the emission quantum yield Φ F was 0.63. Emission wavelength λ under acidic conditions when 4.0 equivalents of TFA are added to compound (1-2) em is 461 nm, and the emission quantum yield Φ F was 0.24. Emission wavelength λ under acidic conditions when 4.0 equivalents of TFA are added to TetraPy em is 461 nm, and the emission quantum yield Φ F The fluorescence of TetraPy was very weak due to its weak absorption, but the luminescence quantum yield was moderate. Therefore, it was found that compound (1-1) and compound (1-2) can emit fluorescence, and the fluorescence intensity is enhanced under acidic conditions. [Industrial Applicability]

[0083] The compound represented by either of the general formula (1) and the general formula (2) of the present invention can form a metal complex and selectively capture copper (II) ions, and therefore can be used as a remover for removing heavy metals in the environment, and as a Cu 2+ The compound of the present invention represented by either of the general formula (1) and the general formula (2) can emit fluorescence and can be used as a light-emitting element.

[0084] For example, aspects of the present invention are as follows. <1> The compound is characterized by being represented by either of the following general formula (1) and the following general formula (2). [ka] [ka] In the general formulas (1) and (2), Ar represents an aryl group. <2> The compound is characterized by being represented by either of the following general formula (3) and the following general formula (4). [ka] In the general formula (3), Ar represents an aryl group; - represents an anion. [ka] In the above general formula (4), Ar represents an aryl group, and M represents a metal. Medium, B - represents an anion. <3> The aryl group is represented by the following general formula (a): <1> from <2> The compound according to any one of the preceding claims. [ka] In the general formula (a), R represents any one of a hydrogen atom, an alkyl group, and a trifluoromethylsulfonyl group, and * represents a bond. <4> The compound is characterized by being represented by either of the following structural formula 1d and the following structural formula 1D. [ka] <5> The above <1> from <3> A method for producing the compound according to any one of the above, The method for producing a compound includes a step of reacting a compound represented by the following structural formula 1d with a compound represented by the following general formula (b). [ka] [ka] In the above general formula (b), R 1 represents an alkyl group.

Claims

1. A compound represented by any one of the following general formulas (1) and (2): 【Chemistry 1】 【Chemistry 2】 In the general formulas (1) and (2), Ar represents an aryl group.

2. A compound represented by any one of the following general formulas (3) and (4): 【Chemistry 3】 In the general formula (3), Ar represents an aryl group; － represents an anion. 【Chemistry 4】 In the above general formula (4), Ar represents an aryl group, and M represents a metal.

3. The compound according to claim 1 , wherein the aryl group is represented by the following general formula (a): 【Chemistry 5】 In the above general formula (a), R represents any one of a hydrogen atom, an alkyl group, and a trifluoromethylsulfonyl group, and * represents a bond.

4. A compound represented by any one of the following structural formulas 1d and 1D. 【Chemistry 6】

5. A method for producing a compound according to any one of claims 1 to 3, comprising the steps of: A method for producing a compound, comprising a step of reacting a compound represented by the following structural formula 1d with a compound represented by the following general formula (b): 【Chemistry 7】 【Chemistry 8】 In the above general formula (b), R １ represents an alkyl group.

Images