![]() |
Under an argon stream, 3.58 g (12.0 mmol) of the compound (1-10) synthesized by the above reaction, 11.32 g (48.0 mmol) of 1, 4-dibromobenzene and 0.28 g (0.24 mmol) of tetrakis (triphenylphosphine) palladium (0) were dissolved in 80 ml of toluene and 10 ml of ethanol. Then, 18 ml of an aqueous solution containing 36.0 mmol of sodium carbonate was added, and the mixture was stirred under reflux for 18 hours. After cooling to room temperature, water was added to the reaction solution and extracted with toluene. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by column chromatography and a white solid (yield 2.50 g, yield 51percent) of the target compound (1-11) was obtained.Exemplary Synthesis 3; Synthesis of Compound 3; Synthesis of 9-phenyl-10-(4-bromophenyl)anthracene; An amount of 2.46 g (8.26 mmol) of 10-phenylanthracene-9-boronic acid synthesized in the same manner as in Exemplary Synthesis 2, 9.75 g (41.3 mmol) of p-dibromobenzene, and 250 mg of tetrakis triphenylphosphine palladium as catalysis were dissolved in a mixed solvent of 60 ml of toluene and 15 ml of ethanol. Then, 30 ml of 2M sodium carbonate solution was added and allowed to react at 90° C. for 12 hours. After the reaction was completed, the organic layer was separated and purified by column chromatography to obtain 1.48 g (3.62 mmol) of 9-phenyl-10-(4-bromophenyl)anthracene. The yield was 43.8percent. Synthesis of 7, 12-Diphenylbenzofluoranthene-9-Boronic Acid; An amount of 3 g (6.21 mmol) of 9-bromo-7, 12-diphenylbenzofluoranthene synthesized in the same manner as in Exemplary Synthesis 1 was dissolved in dehydrated THF and cooled to -80° C. Then, 4.3 ml (6.8 mmol) of a solution of n butyllithium in n-hexane was added dropwise. Forty minutes later, 1.81 g (12.4 mmol) of triethyl borate was added. After two-hour reaction, a diluted hydrochloric acid solution was passed and allowed to stand for 12 hours. Then, the separated organic layer was recrystallized to obtain 1.51 g (3.37 mmol) of 7, 12-diphenylbenzofluoranthene-9-boronic acid. The yield was 54.3percent. (Synthesis of Compound 3); An amount of 1.38 g (3.37 mmol) of 9-phenyl-10-(4-bromophenyl)anthracene, 1.51 g (3.37 mmol) of 7, 12-diphenylbenzofluoranthene-9-boronic acid, and 100 mg of tetrakis triphenylphosphine palladium as catalysis were dissolved in a mixed solvent of 60 ml of toluene and 15 ml of ethanol. Then, 30 ml of 2M sodium carbonate solution was added and allowed to react at 90° C. for 12 hours. After the reaction was completed, the organic layer was separated and purified by column chromatography to obtain 2.01 g (2.75 mmol) of Compound 3. The yield was 81.6percent.The obtained Compound 3 was identified by the mass spectrum, infrared absorption spectrum, and NMR.(iv) Next, a synthetic method of 9-phenyl-10-(4-bromophenyl) anthracene using 9-iodo- 10-phenylanthracene prepared by the above method as a starting material will be shown. A mixture of 1.0 g (2.63 mmol) of 9-iodo- 10-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of tetrakis (triphenylphosphine) palladium, 2M potassium carbonate solution (3 mL), and 10 mL of toluene is agitated at 80 °C 9 hours. After reaction, toluene is added and filtration is carried out using Florisil, celite, and alumina. After the filtrate is rinsed with water and saturated salt solution, it is dried with magnesium sulfate. After natural filtration, the filtrate is condensed, and when it is recrystallized with chloroform and hexane, 562 mg of 9-phenyl-10-(4-bromophenyl) anthracene is obtained as alight brown solid at a yield of 45 percent. A synthetic scheme of 9-phenyl-10-(4-bromophenyl) anthracene from 9-iodo- 10-phenylanthracene is shown below.First, 1.0 g (2.63 mmol) of 9-iodine-10-phenylanthracene, 542 mg (2.70 mmol) of /7-bromophenyl boronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium (O) (abbreviation: Pd(PPh(iv) Synthesis of 9-phenyl-10-(4-bromophenyl)anthracene (abbreviation: PA).; A mixture of 1.0 g (2.63 mmol) of 9-iodo-lO-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of Pd(PPli(iv) (iv) 1.0 g (2.63 mmol) of 9-iodo-lO-phenylanthracene, 542 mg (2.70 mmol) of p-bromophenylboronic acid, 46 mg (0.03 mmol) of Pd(PPli(4) (4) Synthesis of 9-(4-Bromophenyl)-10-phenylanthracene (abbreviation: PA)Were mixed 1.0 g (2.6 mmol) of 9-iodine-lO-phenylanthracene obtained by the above Step 1(3), 540 mg (2.7 mmol) of /?-bromophenylboronic acid, 46 mg (30 μmol) of tetrakis(triphenylphosphine)palladium(0), 3.0 mL(6.0 mmol) of 2.0 mol/L potassium carbonate aqueous solution, and 10 mL of toluene, and the mixture was stirred at 80 In a 50 mL three-necked flask were put 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromophenyl boronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium(0), 3 mL of an aqueous potassium carbonate solution (2 mol/l), and 10 mL of toluene. [Step 1] Step 3: Step 3: (4) Synthesis of 9-phenyl-10-(4-bromophenyl)anthracene; A mixture of 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium, 3 mL of a 2 mol/L aqueous potassium carbonate solution, and 10 mL of toluene was stirred for 9 hours at 80 A mixture of 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium (abbreviation: Pd(PPliA mixture containing 1.0 g (2.6 mmol) of 9-iodine-10-phenylanthracene, 540 mg (2.7 mmol) of p-bromophenylboronic acid, 46 mg (30 μmol) of tetrakis(triphenylphosphine)palladium(0) (abbreviated to Pd(PPhA 300 mL reactor was charged with 2, 5-dibromobenzaldehyde (15.3 g, 58 mmol)9, 9-dimethyl-9H-fluoren-2-ylboronic acid (14.7 g, 62 mmol)Potassium carbonate (16 g, 116 mmol), Tetrakis triphenylphosphine palladium (2.2 g, 1 mmol), H2O 30 mL, Add 75 mL of toluene and 75 mL of 1, 4-dioxane, and stir at reflux for 12 hours. After completion of the reaction, the reaction product was separated, and the organic layer was concentrated under reduced pressure, and the resultant product was separated by column chromatography to obtain (11 g, 50percent). (Intermediate 2-a) (27.2 g, 88.1percent) was obtained in the same manner as in Synthesis Example 1-4, except that 1-bromo-4-iodobenzene was used instead of Intermediate 1-c.2 L reactor was charged with 90 g (446 mmol) of 1-bromo-4-iodobenzene, 92 g (535 mmol) of phenylanthraceneboronic acid, 123.2 g (891 mmol) of potassium carbonate, 17.2 g (9 mmol) of tetrakis (triphenylphosphine) palladium, 180 mL of H 2 O and 720 mL of toluene were added and the mixture was stirred under reflux for 24 hours.The reaction mixture is separated at room temperature and the organic layer is concentrated under reduced pressure. Separation by column chromatography gave 103 g (yield 77percent).
![]() |
![]() |
![]() |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|