(4-(9-phenyl-9H-carbazol-3-yl)phenyl)boronic acid

In this example, an example in which 3-[4-(9-phenanthryl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPPn) represented by Structural Formula (102) in Embodiment 1 is manufactured will be described. Step 1: Synthesis Method of 4-(9-phenyl-9H-carbazol-3-yl)phenylboronic acidInto a 300-mL three-neck flask was put 8.0 g (20 mmol) of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole obtained in Reaction Scheme (F1-2), the atmosphere in the flask was replaced with nitrogen, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was then added to the flask, and the temperature was lowered to -78° C. To this mixture, 3.4 mL (30 mmol) of trimethyl borate was added, and the mixture with the trimethyl borate added was stirred at -78° C. for 2 hours and at room temperature for 18 hours. After the reaction, 1M diluted hydrochloric acid was added to this reaction solution until the solution became acid, and the solution with the diluted hydrochloric acid added was stirred for 7 hours. This solution was subjected to ethyl acetate extraction, and an organic layer obtained was washed with a saturated saline. After the washing, magnesium sulfate was added to the organic layer to remove moisture. This suspension was filtrated, and the obtained filtrate was concentrated, and hexane was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 6.4 g of white powder that was an objective substance in a yield of 88percent. The reaction scheme of Step 1 is shown (F2-1).Step 1: Synthesis of 4-(9-Phenyl-9H-carbazol-3-yl)phenylboronic acid In a 300 mL three-neck flask, 8.0 g (20 mmol) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole was placed, the air in the flask was replaced with nitrogen, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was added, and the temperature was lowered to -78 °C. Into this mixture solution, 15 mL (24 mmol) of a 1.65 mol/L n-butyllithium hexane solution was dropped, and the mixture solution with the n-butyllithium hexane solution added was stirred for 2 hours. To this mixture, 3.4 mL (30 mmol) of trimethyl borate was added, and the mixture was stirred at -78 °C for 2 hours and at room temperature for 18 hours. After the reaction, a 1M diluted hydrochloric acid was added to this reaction solution until the solution became acid, and the solution with the diluted hydrochloric acid added was stirred for 7 hours. This solution was subjected to extraction with ethyl acetate, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution. After the washing, magnesium sulfate was added to the organic layer to adsorb moisture. This suspension was filtered, and the obtained filtrate was concentrated, and hexane was added thereto. The mixture was irradiated with supersonic waves and then recrystallized to give 6.4 g of a white powder, which was the object of synthesis, in a yield of 88 percent. A reaction scheme of Step 1 described above is illustrated below. [0360] [0361] The Rf values of the substance that was the object of synthesis and 3-(4-bromophenyl)-9-phenyl-9H-carbazole were respectively 0 (origin) and 0.53, which were found by silica gel thin layer chromatography (TLC) (developing solvent: ethyl acetate/hexane in a 1 :10 ratio). In addition, the Rf values of the object of the synthesis and 3-(4-bromophenyl)-9-phenyl-9H-carbazole were respectively 0.72 and 0.93, which were found by silica gel thin layer chromatography (TLC) using ethyl acetate as a developing solvent.Step 2: Synthesis Method of 4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acidA synthetic scheme for 4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acid is illustrated in the following (F-2). Into a 300-mL three-neck flask, 8.0 g (20 mmol) of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole obtained in Step 1 described above was put, the atmosphere in the flask was replaced with nitrogen, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was then added to the flask, and the temperature was lowered to -78° C. Into this mixture solution, 15 mL (24 mmol) of a 1.65 mol/L n-butyllithium hexane solution was dropped, and the mixture solution with the n-butyllithium hexane solution added was stirred for 2 hours. To this mixture, 3.4 mL (30 mmol) of trimethyl borate was added, and the mixture with the trimethyl borate added was stirred at -78° C. for 2 hours and at room temperature for 18 hours. After the reaction, 1M diluted hydrochloric acid was added to this reaction solution until the solution became acid, and the solution with the diluted hydrochloric acid added was stirred for 7 hours. This solution was subjected to ethyl acetate extraction, and the obtained organic layer was washed with a saturated saline. After the washing, magnesium sulfate was added to the organic layer to adsorb moisture. This suspension was filtrated, and the obtained filtrate was concentrated, and hexane was added thereto. The mixture was exposed to supersonic waves and then recrystallized to obtain an intended white powder with a yield of 6.4 g at 88percent.The Rf value of the intended product obtained by silica gel thin layer chromatography (TLC) (developing solvent, ethyl acetate:hexane=1:10) was 0 (origin), and the Rf value of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole was 0.53. In addition, the Rf value of the intended product obtained by silica gel thin layer chromatography (TLC) using ethyl acetate as the developing solvent was 0.72, and the Rf value of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole was 0.93. In any case of the developing solvents, no spot derived from the 3-(4-bromophenyl)-9-phenyl-9H-carbazole was observed. Therefore, it is determined that the implementation of the reaction in Step 2 provided the intended product with a higher degree of purity in a simple manner with an extremely high yield.In Step 2, the 3-(4-bromophenyl)-9-phenyl-9H-carbazole as a raw material halide was reacted with n-butyllithium whose amount (1.2 equivalents) is larger than that of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole as a lithiating agent so that the raw material halide was not left. In addition, the raw material halide is more likely to dissolve in a nonpolar solvent such as hexane, than the boron compound (4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acid) as the intended product, and can be thus easily separated by recrystallization. This allows for preventing an impurity from being produced by a coupling reaction between the boron compound (4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acid) synthesized in Step 2 and a halide (3-(4-bromophenyl)-9-phenyl-9H-carbazole), which was an impurity in the boron compound, in the next step of a reaction with a halogenated anthracene compound.A solution of 8.0 g (20 mmol) of 3- (4-bromophenyl) -9-phenyl-9H-carbazole was placed in a 300 mL three-And the gas atmosphere in the flask was replaced with nitrogen. Then, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was added, The temperature was set to -78 ° C.And the mixture was added dropwise to the above-mentioned mixed solution1.65mol / LofN-butyllithiumHexane solution (15 mL) was added and stirred for 2 hours.To the above mixture was added trimethyl borate (3.4 mL, 30 mmol), and the mixture was stirred at -78 ° C for 2 hours.And stirred at room temperature for 18 hours. After the reaction, 1M dilute hydrochloric acid was added to the reaction solution until the solution became acidic, and the mixture was stirred for 7 hours. The extract was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine. After washing, magnesium sulfate was added to the organic layer to adsorb moisture. The suspension was filtered, and the resulting filtrate was concentrated, hexane was added and an ultrasonic wave was applied, followed by recrystallization, and a white powder of the desired product was obtained at a yield of 6.4 g and a yield of 88percent.Round bottom flask was charged with 9-Phenyl-9H-carbazole-3-boronic acid 15g (52.25mmol), 4-chloro-Phenylboronicacid8.98g (57.47mmol) and the mixture of toluene (174ml) and the mixture was then dissolved in 21.66g of potassium carbonate (156.74 mmol) was added to a stirred aqueous solution of dissolved 87ml. Followed by adding thereto tetrakis triphenylphosphine palladium 1.20g (1.04mmol) was stirred and refluxed for 24 hours under a nitrogen atmosphere. After the end of the reaction the extract was concentrated to dryness and extracted with ethyl acetate and filtered through a magnesium sulfate, and the filtrate under reduced pressure. The product n- hexane / dichloromethane (6: 4 by volume) was purified by a silica gel column chromatography to give the intermediate (I) as 16.13g (85percent yield).Round bottom flask was charged with 9-Phenyl-9H-carbazole-3-boronic acid 15g (52.25mmol), 4-chloro-Phenylboronicacid 8.98g dissolved in an aqueous solution of potassium carbonate 21.66g (156.74mmol) was dissolved was added to (57.47mmol) in toluene (174ml) into theIt was added to 87ml and stirred. Here tetrakistriphenylphosphine palladium was added to 1.20g (1.04mmol) of nitrogen atmosphere It was stirred under reflux for 24 hours under a group. After completion of the reaction, magnesium sulfate, the extract was then extracted with ethyl acetateIt was dried, filtered and concentrated under reduced pressure to the filtrate. Silica gel with: a product n- hexane / dichloromethane (volume ratio 4 6)The desired compound was purified by column chromatography of the intermediate (I) to give a 16.13g (85percent yield).The experimental device is fully dried, In a 1L three-necked flask, 30 g of intermediate A was added.Add 300ml of dry tetrahydrofuranAfter dissolution, the temperature was lowered to -78°C, and 33 ml of 2.5M n-BuLi was added dropwise.After stirring for one hour at the temperature, 10.1 g of trimethyl borate was added dropwise at this temperature.After the addition was completed, the mixture was stirred at room temperature overnight.After the reaction is over, Add 4N hydrochloric acid solution, Extract with dichloromethane, The organic phase is washed to neutral with saturated saline solution.dry, Remove the solvent, Purify the crude product with ethyl acetate, The filter cake is the boric acid product.19.2 g of intermediate B with a yield of 70percent.Preparation of compound 1-2 [152] After dissolving compound 1-1 (17.9 g, 44.8 mmol) in tetrahydrofuran (THF) 200 mL, the mixture was cooled to -78°C, 2.5 M n-butyl lithium (23 mL, 58.3 mmol) was slowly added to the mixture, and the mixture was stirred for 1 hour. Next, isopropyl borate (15.5 mL, 67.2 mmol) was added to the mixture, and the mixture was slowly heated and stirred at room temperature for 17 hours. After completing the reaction, the mixture was extracted with ethylacetate (EA) and HExample 2;In this example, an example in which 3-[4-(9-phenanthryl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPPn) represented by Structural Formula (102) in Embodiment 1 is manufactured will be described. Step 1: Synthesis Method of 4-(9-phenyl-9H-carbazol-3-yl)phenylboronic acidInto a 300-mL three-neck flask was put 8.0 g (20 mmol) of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole obtained in Reaction Scheme (F1-2), the atmosphere in the flask was replaced with nitrogen, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was then added to the flask, and the temperature was lowered to -78° C. To this mixture, 3.4 mL (30 mmol) of trimethyl borate was added, and the mixture with the trimethyl borate added was stirred at -78° C. for 2 hours and at room temperature for 18 hours. After the reaction, 1M diluted hydrochloric acid was added to this reaction solution until the solution became acid, and the solution with the diluted hydrochloric acid added was stirred for 7 hours. This solution was subjected to ethyl acetate extraction, and an organic layer obtained was washed with a saturated saline. After the washing, magnesium sulfate was added to the organic layer to remove moisture. This suspension was filtrated, and the obtained filtrate was concentrated, and hexane was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 6.4 g of white powder that was an objective substance in a yield of 88percent. The reaction scheme of Step 1 is shown (F2-1).Step 1: Synthesis of 4-(9-Phenyl-9H-carbazol-3-yl)phenylboronic acid In a 300 mL three-neck flask, 8.0 g (20 mmol) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole was placed, the air in the flask was replaced with nitrogen, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was added, and the temperature was lowered to -78 °C. Into this mixture solution, 15 mL (24 mmol) of a 1.65 mol/L n-butyllithium hexane solution was dropped, and the mixture solution with the n-butyllithium hexane solution added was stirred for 2 hours. To this mixture, 3.4 mL (30 mmol) of trimethyl borate was added, and the mixture was stirred at -78 °C for 2 hours and at room temperature for 18 hours. After the reaction, a 1M diluted hydrochloric acid was added to this reaction solution until the solution became acid, and the solution with the diluted hydrochloric acid added was stirred for 7 hours. This solution was subjected to extraction with ethyl acetate, and the obtained organic layer was washed with a saturated aqueous sodium chloride solution. After the washing, magnesium sulfate was added to the organic layer to adsorb moisture. This suspension was filtered, and the obtained filtrate was concentrated, and hexane was added thereto. The mixture was irradiated with supersonic waves and then recrystallized to give 6.4 g of a white powder, which was the object of synthesis, in a yield of 88 percent. A reaction scheme of Step 1 described above is illustrated below. [0360] [0361] The Rf values of the substance that was the object of synthesis and 3-(4-bromophenyl)-9-phenyl-9H-carbazole were respectively 0 (origin) and 0.53, which were found by silica gel thin layer chromatography (TLC) (developing solvent: ethyl acetate/hexane in a 1 :10 ratio). In addition, the Rf values of the object of the synthesis and 3-(4-bromophenyl)-9-phenyl-9H-carbazole were respectively 0.72 and 0.93, which were found by silica gel thin layer chromatography (TLC) using ethyl acetate as a developing solvent.Step 2: Synthesis Method of 4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acidA synthetic scheme for 4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acid is illustrated in the following (F-2). Into a 300-mL three-neck flask, 8.0 g (20 mmol) of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole obtained in Step 1 described above was put, the atmosphere in the flask was replaced with nitrogen, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was then added to the flask, and the temperature was lowered to -78° C. Into this mixture solution, 15 mL (24 mmol) of a 1.65 mol/L n-butyllithium hexane solution was dropped, and the mixture solution with the n-butyllithium hexane solution added was stirred for 2 hours. To this mixture, 3.4 mL (30 mmol) of trimethyl borate was added, and the mixture with the trimethyl borate added was stirred at -78° C. for 2 hours and at room temperature for 18 hours. After the reaction, 1M diluted hydrochloric acid was added to this reaction solution until the solution became acid, and the solution with the diluted hydrochloric acid added was stirred for 7 hours. This solution was subjected to ethyl acetate extraction, and the obtained organic layer was washed with a saturated saline. After the washing, magnesium sulfate was added to the organic layer to adsorb moisture. This suspension was filtrated, and the obtained filtrate was concentrated, and hexane was added thereto. The mixture was exposed to supersonic waves and then recrystallized to obtain an intended white powder with a yield of 6.4 g at 88percent.The Rf value of the intended product obtained by silica gel thin layer chromatography (TLC) (developing solvent, ethyl acetate:hexane=1:10) was 0 (origin), and the Rf value of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole was 0.53. In addition, the Rf value of the intended product obtained by silica gel thin layer chromatography (TLC) using ethyl acetate as the developing solvent was 0.72, and the Rf value of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole was 0.93. In any case of the developing solvents, no spot derived from the 3-(4-bromophenyl)-9-phenyl-9H-carbazole was observed. Therefore, it is determined that the implementation of the reaction in Step 2 provided the intended product with a higher degree of purity in a simple manner with an extremely high yield.In Step 2, the 3-(4-bromophenyl)-9-phenyl-9H-carbazole as a raw material halide was reacted with n-butyllithium whose amount (1.2 equivalents) is larger than that of the 3-(4-bromophenyl)-9-phenyl-9H-carbazole as a lithiating agent so that the raw material halide was not left. In addition, the raw material halide is more likely to dissolve in a nonpolar solvent such as hexane, than the boron compound (4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acid) as the intended product, and can be thus easily separated by recrystallization. This allows for preventing an impurity from being produced by a coupling reaction between the boron compound (4-(9-phenyl-9-H-carbazol-3-yl)phenylboronic acid) synthesized in Step 2 and a halide (3-(4-bromophenyl)-9-phenyl-9H-carbazole), which was an impurity in the boron compound, in the next step of a reaction with a halogenated anthracene compound.A solution of 8.0 g (20 mmol) of 3- (4-bromophenyl) -9-phenyl-9H-carbazole was placed in a 300 mL three-And the gas atmosphere in the flask was replaced with nitrogen. Then, 100 mL of dehydrated tetrahydrofuran (abbreviation: THF) was added, The temperature was set to -78 ° C.And the mixture was added dropwise to the above-mentioned mixed solution1.65mol / LofN-butyllithiumHexane solution (15 mL) was added and stirred for 2 hours.To the above mixture was added trimethyl borate (3.4 mL, 30 mmol), and the mixture was stirred at -78 ° C for 2 hours.And stirred at room temperature for 18 hours. After the reaction, 1M dilute hydrochloric acid was added to the reaction solution until the solution became acidic, and the mixture was stirred for 7 hours. The extract was extracted with ethyl acetate, and the resulting organic layer was washed with saturated brine. After washing, magnesium sulfate was added to the organic layer to adsorb moisture. The suspension was filtered, and the resulting filtrate was concentrated, hexane was added and an ultrasonic wave was applied, followed by recrystallization, and a white powder of the desired product was obtained at a yield of 6.4 g and a yield of 88percent.Round bottom flask was charged with 9-Phenyl-9H-carbazole-3-boronic acid 15g (52.25mmol), 4-chloro-Phenylboronicacid8.98g (57.47mmol) and the mixture of toluene (174ml) and the mixture was then dissolved in 21.66g of potassium carbonate (156.74 mmol) was added to a stirred aqueous solution of dissolved 87ml. Followed by adding thereto tetrakis triphenylphosphine palladium 1.20g (1.04mmol) was stirred and refluxed for 24 hours under a nitrogen atmosphere. After the end of the reaction the extract was concentrated to dryness and extracted with ethyl acetate and filtered through a magnesium sulfate, and the filtrate under reduced pressure. The product n- hexane / dichloromethane (6: 4 by volume) was purified by a silica gel column chromatography to give the intermediate (I) as 16.13g (85percent yield).Round bottom flask was charged with 9-Phenyl-9H-carbazole-3-boronic acid 15g (52.25mmol), 4-chloro-Phenylboronicacid 8.98g dissolved in an aqueous solution of potassium carbonate 21.66g (156.74mmol) was dissolved was added to (57.47mmol) in toluene (174ml) into theIt was added to 87ml and stirred. Here tetrakistriphenylphosphine palladium was added to 1.20g (1.04mmol) of nitrogen atmosphere It was stirred under reflux for 24 hours under a group. After completion of the reaction, magnesium sulfate, the extract was then extracted with ethyl acetateIt was dried, filtered and concentrated under reduced pressure to the filtrate. Silica gel with: a product n- hexane / dichloromethane (volume ratio 4 6)The desired compound was purified by column chromatography of the intermediate (I) to give a 16.13g (85percent yield).The experimental device is fully dried, In a 1L three-necked flask, 30 g of intermediate A was added.Add 300ml of dry tetrahydrofuranAfter dissolution, the temperature was lowered to -78°C, and 33 ml of 2.5M n-BuLi was added dropwise.After stirring for one hour at the temperature, 10.1 g of trimethyl borate was added dropwise at this temperature.After the addition was completed, the mixture was stirred at room temperature overnight.After the reaction is over, Add 4N hydrochloric acid solution, Extract with dichloromethane, The organic phase is washed to neutral with saturated saline solution.dry, Remove the solvent, Purify the crude product with ethyl acetate, The filter cake is the boric acid product.19.2 g of intermediate B with a yield of 70percent.Preparation of compound 1-2 [152] After dissolving compound 1-1 (17.9 g, 44.8 mmol) in tetrahydrofuran (THF) 200 mL, the mixture was cooled to -78°C, 2.5 M n-butyl lithium (23 mL, 58.3 mmol) was slowly added to the mixture, and the mixture was stirred for 1 hour. Next, isopropyl borate (15.5 mL, 67.2 mmol) was added to the mixture, and the mixture was slowly heated and stirred at room temperature for 17 hours. After completing the reaction, the mixture was extracted with ethylacetate (EA) and H

Molecular Weight:363.2
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:3
Exact Mass:363.1430590
Monoisotopic Mass:363.1430590
Topological Polar Surface Area:45.4
Heavy Atom Count:28
Complexity:515
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes