3,6-DIBROMO-9-PHENYLCARBAZOLE

off-white powder

To a solution of 9-phenyl-9H-carbazole (2.04 g, 8.05 mmol) in CClFirst, into a 200-mL Mayer flask were put 3.7 g (15 mmol) of 9-phenyl-9H-carbazole, 5.4 g (30 mmol) of N-bromosuccinimide (abbreviation: NBS), and75 mL of ethyl acetate. At room temperature, this solution was stirred in the air for 52 hours. Then, water was added thereto and this mixture was furtherstirred. An aqueous layer of the mixture was subjected to extraction with ethyl acetate three times. The extracted solution and an organic layer werecombined, the mixture was washed with water and saturated saline, and then magnesium sulfate was added thereto. The obtained mixture was gravityfilteredand the filtrate was concentrated, so that 5.5 g of the target white powder was obtained in a yield of 92percent.Under nitrogen protection, N-phenylcarbazole (48.6 g, 0.2 mol) was dissolved in 500 mL DMF (N, N-dimethylformamide) in a 1 L three-necked flask, NBS (N-bromosuccinimide, 78.3 g, 0.44 mol) was slowly added to the reaction system at a temperature of 20 to 25 ° C, 0.5h plus completed.The reaction system was stirred at 20-25 ° C for 24 hours.After completion of the reaction to the reaction systemAn aqueous solution of sodium sulfite (500 mL, 0.05 mol / L) was added, Quenching reaction, Filter cake, After washing with deionized water, Crystallization is carried out with toluene or absolute ethanol, To give a white solid, Namely the intermediate C01-a, The yield was 90.3percent.Under nitrogen protection, N-phenylcarbazole (48.6 g, 0.2 mol) was dissolved in 500 mL of DMF (N, N-dimethylformamide) in a 1 L three-necked flask, To the reaction system was slowly added NBS (N-bromosuccinimide, 78.3 g, 0.44 mol) as a solid at a controlled temperature of 20-25 ° C, 0.5h plus completed.The reaction system was incubated at 20-25 ° C for 24 hours with stirring.After completion of the reaction, an aqueous solution of sodium sulfite (500 mL, 0.05 mol / L) was added to the reaction system, The reaction mixture was quenched and the filter cake was suction filtered to obtain a cake. The residue was washed with deionized water and then crystallized from toluene or absolute ethanol to give a white solid, which was 3, 6-dibromo-N-phenylcarbazole in 90percent yield.Preparation of Structural Formula 1B; The Structural Formula 1A (13.2 g, 54.3 mmol) was dissolved in chloroform (300 ml), and N-bromo succinimide (20.3 g, 114.0 mmol)) was added thereto, and agitated for 3 hours at normal temperature. Distilled water was put into the reaction solution, the termination of the reaction was carried out, and the organic material layer was extracted. The reaction solution was concentrated, and recrystallized with EtOH to obtain the Structural Formula 1B (18.9 g, yield 87 percent). MS: [M+H]0.1640 mol of N-phenyl-9H-carbazole was charged into a 2000 ml three-necked flask, washed with 320 ml of acetic acid and 960 ml of dichlorMethane dissolved, placed in ice water bath; slowly dropping 0.3280mol liquid bromine, room temperature reaction overnight, The reaction solution was neutralized with 1.5 L of 1 mol / L aqueous sodium hydroxide solution to the remaining liquid bromine, and the organic phase was separated to obtain an organic phase, Respectively, washed three times with water, liquid to take organic phase, spin dry, Washed with 300 ml PE (60-90), suction filtered, vacuum dried at 55 ° C, To give the product 3, 6-dibromo-9-phenylcarbazole 0.1440 mol, 87.8percent yield.N-bromosuccinimide (15.00 g, 84 mmol, 2.05 eq) is dissolved in 30 ml of dimethylformamide and then slowly added to a flask in which 30 ml of 9-phenyl-9Hcarbazole (10 g, 41 mmol, 1.0 eq) is dissolved in 30 ml of dimethylformamide. After 5 hours of reaction, the reaction product was precipitated with 200 ml of distilled water, filtered and dried to obtain 13.03 g (yield: 79.04percent) of the target compound.Example 3 Synthesis of Carbozole-Based (2-Arm) Fluorescent Molecular Rotor (0310) Synthesis of Intermediate E; 3.25 g (10.0 mmol) of 3, 6-dibromocarbazole, 10.2 g (50.0 mmole) iodobenzene, 190 mg (1.0 mmole) of Cul, 132 mg (0.5 mmole) of 18-C-6, 2.76 g (20.0mmole) of KTo a round bottom flask Sub 2-1-6 (6.5g, 20mmol), Sub 2-1-2-1 (4.1g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol ), NaOt-Bu (5.8g, 60mmol), were addedto toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100 ° C.The organic layer was dried and the ether was extracted with water over MgSO4 andconcentrated and to the resulting organic silicagel column and recrystallized from a Sub2-1-7-1 6.0g (yield: 75percent) was obtained.2.5 g (14.9 mmol) ofcarbazole was used (utilized) to perform an NI3S bromination to synthesize 2, 5-dibromocar- bazole. Then, the 2, 5-dibromocarbazole and iodinated phenyl were used (utilized) to synthesize 3.72 g (9.28 mmol) of Intermediate E through a buchwald reaction.A.3, 6-dibromocarbazole (200 mg, 0.62 mmol) was dissolved in DMF solvent, Then iodobenzene (188.3 mg, 0.92 mmol) was added, DL-piperidinecarboxylic acid (11.88 mg, 0.09 mmol), Cuprous oxide (8.27 mg, 0.04 mmol), Cesium carbonate (299.75 mg, 0.92 mmol), Under nitrogen protection, The reaction system was placed at 110 ° C under reflux for 12 h, After the reaction is complete, Ethyl acetate extraction, Organic layer washed three times, Dried over anhydrous sodium sulfate, The solvent is evaporated under reduced pressure;The crude product was purified by column chromatography with ethyl acetate and petroleum ether mixed solvent (20: 1)To obtain compound 3, 6-dibromo-9-phenylcarbazole (white solid, 225 mg, yield 90.5percent).To a 1 L reaction flask was added toluene solvent (450 ml), In a nitrogen atmosphere, a flask containing Synthesis Synthesis of H1-1 compound: 1.6 g of 3, 6-dibromo-9-phenyl-9oxazole, 2.4 g of 9-phenyl-3-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-9Eta-carbazole under a nitrogen atmosphere , 0.23 g of tetrakis(triphenylphosphine)palladium, 6 ml of 2M aqueous potassium carbonate solution, 20 ml of toluene and 5 ml of ethanol were placed in a reaction vessel, and then heated and stirred at reflux temperature for 5 hours.After cooling to 40 C, the insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure to give a crude product.The crude product was purified by recrystallization (solvent: toluene/methanol) and dried.1.76 g (yield: 60.9%) of 3, 6-bis(9'-phenyl-9Eta-carbazol-3-yl)-9-phenyl-9H-carbazole (Compound H1-1) is obtained as a brownish white powder.

An important intermediate for the synthesis of optoelectronic materials

Molecular Weight:401.1
XLogP3:6.4
Rotatable Bond Count:1
Exact Mass:400.92378
Monoisotopic Mass:398.92582
Topological Polar Surface Area:4.9
Heavy Atom Count:21
Complexity:342
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes