1-PyreneboronicAcid(containsvaryingamountsofAnhydride)

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of Intermediate A (1.41 g, 4 mmol), pyrene-1-boronic acid (0.49 g, 2.0 mmol), tetrakis(triphenylphosphine)palladium (0) (0.50 g, 0.43 mmol), sodium carbonate (2.12 g, 20 mmol) in water (10 mL), n-butanol (30 mL), and toluene (30 mL) was heated under argon at 110° C. for 5 hours. The reaction mixture was poured into water (200 mL), treated with 5 N NaOH (20 mL), stirred for 1 hour, and extracted with dichloromethane (2×200 mL). The extract was dried over anhydrous sodium carbonate, and the volatiles were removed under reduced pressure. The residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:10) to give 4-bromo-7-(4-(pyren-1-yl)phenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (purity 90%, 650 mg, 53% yield) as yellow crystals. 1H NMR (400 MHz, CDCl3): δ 8.72 (m, 2H, pyridine), 8.31 (d, J=7.7 Hz, 1H, pyrene), 8.24 (dd, J=7.7 and 1.1 Hz, 1H, pyrene), 8.16-8.20 (m, 6H, pyrene and pyridine), 8.04 (t, J=7.7 Hz, 1H, pyrene), 8.00 (m, 2H, pyrene), 7.86 (d, J=7.7 Hz, 1H, benzotriazole), 7.86 (d, J=7.3 Hz, 1H, benzotriazole). extracted with dichloromethane (2×200 mL) The extract was dried over anhydrous sodium carbonate the volatiles were removed under reduced pressure The residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:10)

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of Intermediate A (1.41 g, 4 mmol), pyrene-1-boronic acid (0.49 g, 2.0 mmol), tetrakis(triphenylphosphine)palladium (0) (0.50 g, 0.43 mmol), sodium carbonate (2.12 g, 20 mmol) in water (10 mL), n-butanol (30 mL), and toluene (30 mL) was heated under argon at 110° C. for 5 hours. The reaction mixture was poured into water (200 mL), treated with 5 N NaOH (20 mL), stirred for 1 hour, and extracted with dichloromethane (2×200 mL). The extract was dried over anhydrous sodium carbonate, and the volatiles were removed under reduced pressure. The residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:10) to give 4-bromo-7-(4-(pyren-1-yl)phenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (purity 90%, 650 mg, 53% yield) as yellow crystals. 1H NMR (400 MHz, CDCl3): δ 8.72 (m, 2H, pyridine), 8.31 (d, J=7.7 Hz, 1H, pyrene), 8.24 (dd, J=7.7 and 1.1 Hz, 1H, pyrene), 8.16-8.20 (m, 6H, pyrene and pyridine), 8.04 (t, J=7.7 Hz, 1H, pyrene), 8.00 (m, 2H, pyrene), 7.86 (d, J=7.7 Hz, 1H, benzotriazole), 7.86 (d, J=7.3 Hz, 1H, benzotriazole). extracted with dichloromethane (2×200 mL) The extract was dried over anhydrous sodium carbonate the volatiles were removed under reduced pressure The residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:10)

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of Intermediate A (1.41 g, 4 mmol), pyrene-1-boronic acid (1.23 g, 5.0 mmol), 4-methoxyphenylboronic acid (0.76 g, 5.0 mmol), sodium carbonate (2.12 g, 20 mmol) in water (10 mL), tetrakis(triphenylphosphine)palladium (0) (0.50 g, 0.43 mmol), n-butanol (30 mL), and toluene (20 mL) was heated under argon at 110° C. for 4 hours. Thin layer chromatography (TLC) of the reaction mixture indicated no starting material left. The reaction mixture was poured into water (200 mL) and extracted with dichloromethane (3×200 mL). The extract was dried over anhydrous sodium carbonate, and the volatiles were removed under reduced pressure. The residue was chromatographed (silica gel, dichloromethane/ethyl acetate 95:5). The first fraction gave 4,7-di(pyren-1-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 4) (610 mg, 25%) as orange crystals. 1H NMR (400 MHz, CDCl3): δ 8.60 (m, 2H, pyridine), 8.38 (m, 4H, pyrene), 8.22-8.29 (m, 6H, pyrene), 8.20 (m, 4H, pyrene), 8.05-8.10 (m, 6H, pyrene and pyridine), 7.90 (s, 2H, benzotriazole). UV-vis spectrum (dichloromethane): λmax=381 nm. Fluorimetry (dichloromethane): λmax=524 nm. left extracted with dichloromethane (3×200 mL) The extract was dried over anhydrous sodium carbonate the volatiles were removed under reduced pressure The residue was chromatographed (silica gel, dichloromethane/ethyl acetate 95:5)

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Bromopyrene (2.00 g, 7.12 mmol) was dissolved in anhydrous THF (150 ml) and anhydrous ether (150 ml). The light yellow solution was cooled to −78° C. in nitrogen. n-Butyllithium (4.9 ml, 7.83 mmol) was slowly dripped into the solution. At this time, the solution became murky. This mixture was kept at −78° C. for ten minutes, 0° C. for ten minutes, and then −78° C. for thirty minutes. Then, triisopropyl borate (4.93 ml, 21.36 mmol) was slowly dripped into the solution, and the mixture was kept at −78° C. for thirty minutes. Finally, the mixture underwent reaction at room temperature for 1.5 days. Next, water was added into the reaction mixture, and the resulting mixture was stirred vigorously for one hour. The water layer and the organic layer were separated, the water layer was then extracted by ethyl ether (2×25 ml), and the organic layer was water washed (2×50 ml). The combined organic solution was contact with MgSO4 to remove water, then filtered, and concentrated on a rotary evaporator to obtain a pyreneboronic acid solid product. This mixture was kept at −78° C. for ten minutes, 0° C. for ten minutes −78° C. for thirty minutes the mixture was kept at −78° C. for thirty minutes Finally, the mixture underwent reaction at room temperature for 1.5 days The water layer and the organic layer were separated the water layer was then extracted by ethyl ether (2×25 ml) washed (2×50 ml) to remove water filtered concentrated on a rotary evaporator

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Bromopyrene (2.00 g, 7.12 mmol) was dissolved in anhydrous THF (150 ml) and anhydrous ether (150 ml). The light yellow solution was cooled to −78° C. in nitrogen. n-Butyllithium (4.9 ml, 7.83 mmol) was slowly dripped into the solution. At this time, the solution became murky. This mixture was kept at −78° C. for ten minutes, 0° C. for ten minutes, and then −78° C. for thirty minutes. Then, triisopropyl borate (4.93 ml, 21.36 mmol) was slowly dripped into the solution, and the mixture was kept at −78° C. for thirty minutes. Finally, the mixture underwent reaction at room temperature for 1.5 days. Next, water was added into the reaction mixture, and the resulting mixture was stirred vigorously for one hour. The water layer and the organic layer were separated, the water layer was then extracted by ethyl ether (2×25 ml), and the organic layer was water washed (2×50 ml). The combined organic solution was contact with MgSO4 to remove water, then filtered, and concentrated on a rotary evaporator to obtain a pyreneboronic acid solid product. This mixture was kept at −78° C. for ten minutes, 0° C. for ten minutes −78° C. for thirty minutes the mixture was kept at −78° C. for thirty minutes Finally, the mixture underwent reaction at room temperature for 1.5 days The water layer and the organic layer were separated the water layer was then extracted by ethyl ether (2×25 ml) washed (2×50 ml) to remove water filtered concentrated on a rotary evaporator

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under an atmosphere of argon, 4-bromoiodobenzene (7.0 g, 25 mmole), 1-pyreneboronic acid (5.7 g, 23 mmole) and tetrakis(triphenyl-phosphine)palladium(0) (0.5 g, 0.43 mmole, 1.7% Pd) were dissolved into toluene (50 ml). To the obtained solution, an aqueous solution of sodium carbonate (7.3 g, 69 mmole, 3 eq/35 ml) was added. The resultant solution was heated under refluxing for 10 hours and left standing for one night. The formed organic layer was separated, washed with a saturated aqueous solution of sodium chloride (50 ml) and dried with anhydrous magnesium sulfate. Then, the solvent was removed by distillation and a yellow oil was obtained. The obtained oil was purified by the column chromatography (silica gel/hexane, hexane+3% dichloromethane and hexane+10% dichloromethane, successively) and white needle crystals (6.6 g, 80%) were obtained. under refluxing for 10 hours left standing for one night The formed organic layer was separated washed with a saturated aqueous solution of sodium chloride (50 ml) dried with anhydrous magnesium sulfate Then, the solvent was removed by distillation a yellow oil was obtained The obtained oil was purified by the column chromatography (silica gel/hexane, hexane+3% dichloromethane and hexane+10% dichloromethane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under an atmosphere of argon, 4-bromoiodobenzene (7.0 g, 25 mmole), 1-pyreneboronic acid (5.7 g, 23 mmole) and tetrakis(triphenyl-phosphine)palladium(0) (0.5 g, 0.43 mmole, 1.7% Pd) were dissolved into toluene (50 ml). To the obtained solution, an aqueous solution of sodium carbonate (7.3 g, 69 mmole, 3 eq/35 ml) was added. The resultant solution was heated under refluxing for 10 hours and left standing for one night. The formed organic layer was separated, washed with a saturated aqueous solution of sodium chloride (50 ml) and dried with anhydrous magnesium sulfate. Then, the solvent was removed by distillation and a yellow oil was obtained. The obtained oil was purified by the column chromatography (silica gel/hexane, hexane+3% dichloromethane and hexane+10% dichloromethane, successively) and white needle crystals (6.6 g, 80%) were obtained. under refluxing for 10 hours left standing for one night The formed organic layer was separated washed with a saturated aqueous solution of sodium chloride (50 ml) dried with anhydrous magnesium sulfate Then, the solvent was removed by distillation a yellow oil was obtained The obtained oil was purified by the column chromatography (silica gel/hexane, hexane+3% dichloromethane and hexane+10% dichloromethane

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4.92 g (20 mmol) of pyrene-1-boronic acid, 5.94 g (21 mmol) of 3-bromoiodobenzene, and 0.46 g (0.4 mmol, 2 mol %) of tetrakis(triphenylphosphine)palladium(0) were loaded into a 300-ml three-necked flask, and air in the container was replaced with argon. Further, 10 ml of toluene and 30 ml (3 eq) of a 2M aqueous solution of sodium carbonate were added to the mixture, and the whole was refluxed under heat in an oil bath at 100° C. for 8 hours. After one night, the resultant was extracted with toluene/ion-exchanged water and purified by column chromatography, whereby 5.61 g of 3-pyrenylbromobenzene were obtained (79% yield). the whole was refluxed After one night the resultant was extracted with toluene/ion-exchanged water purified by column chromatography

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 10 (700 mg, 1.61 mmol), pyren-1-ylboronic acid (434 mg, 1.76 mmol), Palladium tetrakis triphenylphoshine (186 mg, 0.16 mmol) and potassium carbonate (1.34 g, 9.66 mmol) were introduced in a flask together with 17 mL toluene, 8.8 mL ethanol and 2.6 mL distilled water. This mixture is stirred at 80° C. during 24 hours before being filtered. The solid is then washed with hexane, water and some mL of chloroform before being dried. distilled water before being filtered The solid is then washed with hexane, water some mL of chloroform before being dried

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under the atmosphere of argon gas, 6 g of tribromobenzene available as a commercial reagent, 9.4 g of 1-pyrenyl boronic acid and 0.88 g of tetrakis(triphenylphophine)palladium were dissolved in 150 ml of toluene, and then the 57 ml of 2M sodium carbonate aqueous solution was added therein, followed by 7 hours reflux on heating. After standing to cool, the precipitated solid was separated through filtration, and then followed by washing with water and methanol, and drying. The obtained solid was refined through a silica gel chromatography (developing solvent: toluene/hexane=1/3) and then 4.1 g of 3,5-dipyrenylbromobenzene of pale yellow solid was obtained (Yield: 38%). reflux on heating to cool the precipitated solid was separated through filtration by washing with water and methanol drying

反応条件: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under the atmosphere of argon gas, 9 g of 1-(3,5-dibromophenyl)pyrene synthesized from 3,5-diboromoiodobenzene and 1-pyrenyl boronic acid was dissolved into 100 ml of anhydrous tetrahydrofuran (THF) and cooled down to −70° C. 14 ml of 1.6M n-butyllithium hexane solution was dropped therein and the resultant was stirred for 30 minutes. 5.9 g of 1,2-diiodoethane was added therein and the resultant was stirred for 5 hours. After the resultant was left overnight, water and methylene chloride were added therein, and then sodium bisulfite was added therein until the burned umber of the reaction solution was changed to yellow. The organic layer was extracted therefrom, and then it was washed by water and saturated salt water. Subsequently the organic layer was dried by using anhydrous sodium sulfate, and then the solvent was removed by distillation. The residue was refined through a silica gel chromatography (developing solvent: toluene/hexane=1/3) and then 8.4 g of 1-(3-bromo-4-iodophenyl)pyrene of cream color solid was obtained (Yield: 84%). the resultant was stirred for 5 hours After the resultant was left overnight The organic layer was extracted it was washed by water and saturated salt water Subsequently the organic layer was dried the solvent was removed by distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under the atmosphere of argon gas, 6 g of tribromobenzene available as a commercial reagent, 9.4 g of 1-pyrenyl boronic acid and 0.88 g of tetrakis(triphenylphophine)palladium were dissolved in 150 ml of toluene, and then the 57 ml of 2M sodium carbonate aqueous solution was added therein, followed by 7 hours reflux on heating. After standing to cool, the precipitated solid was separated through filtration, and then followed by washing with water and methanol, and drying. The obtained solid was refined through a silica gel chromatography (developing solvent: toluene/hexane=1/3) and then 4.1 g of 3,5-dipyrenylbromobenzene of pale yellow solid was obtained (Yield: 38%). reflux on heating to cool the precipitated solid was separated through filtration by washing with water and methanol drying