9-(3-bromophenyl)carbazole

Carbazole 2.00 g (12.0 mmol), 1-bromo-3-iodobenzene, 2.02 mL (15.8mmol), copper (Cu) 2.29 g (36.0 mmol) of calcium carbonate and 4.98 g (36.0 mmol) of DMF in 30 mL insert heated at 130 It was stirred. After the completion of the reaction, it cooled to ambient temperature and diluted with ethyl acetate to a vacuum filter, and passed through a silica gelThe filtrate was concentrated under reduced pressure. Separating the product by silica gel column chromatography (ethyl acetate: n- hexane = 1: 20) to give the desired intermediate compound (C) 3.80 g (98percent yield).In a dry 2L three-necked flask, 42.3 g of m-bromo iodobenzene and 27.5 g of carbazole were added. Then dry and degassed 800 mL of toluene was added as a solvent. Add 43.2g of sodium tert-butoxide (3eq.), 0.67 g of palladium acetate (2percent mol) and 3.7 g of ligand 1, 1′-binaphthyl-2, 2′-bisdiphenylphosphine (BINAP, 4percent mol). The temperature was raised to 110°C and the reaction ended overnight. Cool to room temperature Activated carbon adsorption, suction filtration, solvent removal, recrystallization with toluene and ethanol, 40.9 g of intermediate I are obtained (yield 90percent).1-bromo-3 - iodo-benzene (145 ml, 53 mmol), carbazole (8.7 g, 52 mmol), copper powder (10.1 g, 159 mmol) and potassium carbonate (22 g, 159 mmol) dimethyl was dissolved in formamide (120 ml), it was stirred under argon for 24 hours in the presence of 130 . When complete the reaction, The reaction mixture was cooled to ambient temperature, filtered on Celite mukhyeo ethyl acetate. Filtered, poured in water, extracted with ethyl acetate, and wash the organic layer extracted with brine. The washed organic layer was dried over magnesium sulfate and purified by column chromatography (silica gel) to give the title compound (14.9 g, 89percent).Synthesis example 3:; Synthesis of N-(3-bromophenyl)carbazole (compound 4); (4) Under nitrogen, carbazole (24.3 g, 1 eq.) is added to a flask together with 1 -bromo-3- iodobenzene (98percent; 75.3 g, 1.9 eq.), potassium carbonate (48.2 g, 2.5 eq.) and copper (1 .77 g, 0.1 eq.). The reaction is heated to 150°C and stirred at 150°C for 48 h. The mixture is cooled to room temperature and diluted with 150 ml. of methylene chloride. 100 mL of demineralized water are added to the mixture, which is stirred. Removal of the aqueous phase is followed by washing a further 2x with demineralized water (100 mL). The organic phase is dried over sodium sulfate and concentrated. The excess 1 -bromo-3-iodobenzene is distilled off under reduced pressure. LC (Si0A mixture of 9-H carbazole (4.0 g, 24.1 mmol), 3-bromoiodobenzene (10.23 g, 36.1 mmol), copper (3.06 g, 48.2 mmol), potassium carbonate (13.3 g, 96.4 mmol), 18-crown-6 (636 mg, 2.41 mmol) and DMF (anhydrous, 50 mL) was degassed for about 40 minutes. The mixture was then further degassed by heating to about 150° C. overnight under argon. After cooling to room temperature (RT), solids from reaction mixture were then filtered off. The filtrate was then poured into dichloromethane (DCM) (250 mL) and then washed with water (3×200 mL). The organic layer was dried over sodium sulfate and loaded onto silica gel. A flash column (hexanes) gave 6.56 g (79percent yield) of product 1B; pure by HNMR.Under nitrogen flow, carbazole (7.00 g), 3-bromoiodobenzene (14.2 g), copper powder (2.66 g), potassium carbonate (5.79 g), and tetraglyme (10 ml) were stirred while heating to 140°C for 5 hr and then allowed to cool to room temperature. After the completion of the reaction, chloroform was added to the reaction solution, and the insoluble matter was removed by filtration. Chloroform contained in the filtrate was evaporated under reduced pressure, and the resulting matter was purified by silica-gel column chromatography (n-hexane/toluene = 4/1) and dried under reduced pressure to obtain a target compound 11 (10.5 g, yield: 78percent) as a colorless viscous liquid.In the reaction flask carbazole 3.0g, meta-bromoiodobenzene 10.15g, 2.39 g copper iodide, 4.95g of potassium carbonate and 40mL of dry xylene, the reaction was refluxed for 48 hours nitrogen, was added 50mL of water quench off the reaction, extracted with dichloromethane, the solvent was evaporated, purified by column chromatography to give a white colored final precipitate 9-(3-bromophenyl)-9H- carbazole 3.5g, 78percent yield.Under a nitrogen atmosphere (NIn 250mL three-necked flask, were added carbazole 16.72g, m-bromoiodobenzene 42.44g, cuprous iodide 1.9g, 1, 2- diaminocyclohexane 3.42g, 42.4g anhydrous potassium phosphate and solvent 1 , 4-dioxane 160mL, N2 replaced three times, heated to reflux and the reaction stopped after 16h.Cooled to room temperature, filtered, and the filtrate was collected, purified by column chromatography (dichloromethane: n-hexane = 1: 1-1: 0), the target receives the solid product 22g (69percent).Sigma aldrich in nitrogen (http://www. Sigmaaldrich. Com /) carbazole yarn (50 g, 299. 0 mmol) of toluene 0. 5 L senses a rotation velocity of the disk to, herein 1-bromo-3-iodobenzene sigma aldrich yarn (101. 5 g, 358. 8 mmol), bis (dibenzylideneacetone) palladium (0) (5. 16 g, 8. 97 mmol), tris-tert butylphosphine (3. 02 g, 15. 0 mmol) and sodium tert-butoxide (34. 5 g, 358. 8 mmol) in 100 °C sequentially and at the reflux by heating at a 16. Complete after reaction solution at a water doesn't have any error frames, then dichloromethane (DCM) extraction of water to the MgSO4 anhydride after triggers number, filter and was, concentrating it under reduced pressure. Thus-obtained residue number intermediate that is forward separated into flash column chromatography I-2 (33. 3 g, 35percent) a obtained250ml 3-neck round bottom flask was charged 1-3 (5g), palladium(0)diacetate (0.1g), tri-tert-butylphosphine (0.3g), put the toluene (100ml), 1 h on the atmosphere of argon at room temperature It was stirred. After the addition of potassium carbonate (7.2g), 3- bromo carbazole (6.3g) in the mixture was stirred at 80 °C for 6 hours. After the addition of water and extracted with ethyl acetate to give 1.9g the title 1-4 substituents through a separation column using hexane and the resulting material after removal of water.First, 1 times the equivalent of carbazole, 1 to 1.5 equivalents of dihalogenated benzene, such as m-dibromobenzene, 0.44 times the equivalent of Cu (electrolytic refined copper), 4.04 times the equivalent of K2CO3 into the reaction vessel, Nitrobenzene as the reaction solvent, Nitrogen protection under 120 ~ 160 reaction 12 ~ 48h, The reaction solution was distilled under reduced pressure to obtain a crude product, The pure product was obtained by column chromatography, The yield was 75-85percent.To a 500 mL reaction flask was charged 20 g (84.7 mmol) of m-dibromobenzene, 14 g (84.7 mmol) of carbazole, 1.6 g (8.77 mmol)Cuprous iodide, 1.5 g (16.9 mmol)ofN-dimethyl-1, 2-ethanediamine, 117 g (0.847 mol) of potassium carbonate and 300 ml of solvent xylene, Nitrogen protection Heating to 120 ° C, Insulation reaction for 24 hours.The water bath was cooled to 80 ° C and filtered while hot. The filter cake was washed with toluene and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column eluting with petroleum ether / dichloromethane to give 22.6 g of a white solid product. Yield: 83percentsee Kido, J.; Su, S. -J.; Sasabe, H.; Takeda, T.; Chem. Mater. 2008, 20(5), 1691-1693, which is incorporated by reference herein for its relevant teachings) was prepared as follows: a mixture of carbazole (4.000 g, 23.92 mmol), 1, 3-dibromobenzene (14.11 g, 59.81 mmol), KStep 1. Add 100 mmol of carbazole to the reaction vessel.m-dibromobenzene 100mmol, Potassium tert-butoxide 300mmol, Pd2 (dba) 3 1mmol, Ultrasonic deoxygenated xylene, Stir and dissolve, Replace the air three times, Adding ligand tri-tert-butylphosphine 4percent (4mmol, 50percent m/V), Replace the air three times, The reaction was refluxed for 6 h.Cool to room temperature, Add enough dichloromethane to completely dissolve the product.a small amount of silica gel funnel, Remove catalyst and salt.The filtrate is concentrated to a viscous state.Column chromatography, The product was obtained 3-1 80 mmol.General procedure: A mixture of a fluorinated aryl halide (2.0 mmol), a carbazole (0.5 mmol), and a base (2.0 mmol) in solvent (2 mL) was allowed to react under air atmosphere. The reaction mixture was heated to the specified temperature for 24 h. After reaction completion, the mixture was added to brine (15 mL) and extracted with CHIn a nitrogen atmosphere, 150.4 g (0.9 mol) of carbazole (B) was dissolved in 450 mL of dimethylimidazolidinone. 91 g (0.945 mol) of sodium t-butoxide was added and the temperature was raised to 110 ° C. with stirring. 173.3 g (0.99 mol) of 1-bromo-3-fluorobenzene (D) was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate / water, and the organic layer was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane / ethyl acetate (9/1 (mass ratio)) to obtain 192.9 g (yield 67percent) of compound (E).Synthesis Example 3General procedure: A mixture of a fluorinated aryl halide (2.0 mmol), a carbazole (0.5 mmol), and a base (2.0 mmol) in solvent (2 mL) was allowed to react under air atmosphere. The reaction mixture was heated to the specified temperature for 24 h. After reaction completion, the mixture was added to brine (15 mL) and extracted with CH2Cl2 (3 × 15 mL). The combined extract was concentrated under reduced pressure and the product was isolated by short chromatography on a silica gel (200-300 mesh) column.In a nitrogen atmosphere, 150.4 g (0.9 mol) of carbazole (B) was dissolved in 450 mL of dimethylimidazolidinone. 91 g (0.945 mol) of sodium t-butoxide was added and the temperature was raised to 110 C. with stirring. 173.3 g (0.99 mol) of 1-bromo-3-fluorobenzene (D) was added, and the mixture was heated and stirred at 120 C. for 5 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate / water, and the organic layer was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane / ethyl acetate (9/1 (mass ratio)) to obtain 192.9 g (yield 67%) of compound (E).Add carbazole (2g, 11.93mmol) to a 100mL reaction flask.2-bromo-4-fluorobenzene (2g, 11.36mmol), potassium carbonate (3.14g, 22.73 mmol), DMSO (30mL), Under nitrogen protection, heat to 140 C for 4 hours.The reaction was monitored by TLC until the reaction was complete.Filter under reduced temperature and rinse the filter cake with ethyl acetate and water.The aqueous phase was separated, the organic layer was dried and concentrated, 100 mL of n-hexane was added, and sonication was performed for 2 minutes. A white solid was precipitated and filtered to obtain 1.3 g of intermediate M4.b) 22 ml of 1.55M n-butyl lithium in heptane is added to 10.0 g (0.031 mol) 9-(3- bromophenyl) carbazole in 100 ml of THF at -78C under nitrogen. The resulting solution is stirred for 1 h at -78C. Then, 10.7 ml of triisopropyl borate is added to the reaction at -78C. The reaction mixture is stirred at -78C for 1 h, then warmed to 0C, and stirred for 3 h. 100ml of 1 M HCI aq. and 100ml of dichloromethane are added and the organic phase is separated. The organic phase is washed with water and dried with magnesium sulfate and evaporated under reduced pressure to give a crude material. The crude material is recrys- tallized from toluene/hexane to yield 5.30 g (59.5% of theory) 3-(carbazol-9- yl)phenylboronic acid as a white solid. 1 H-NMR (400 MHz, CDCIs): delta 8.26 - 8.25 (m, 4H), 8.05 - 7.93 (m, 2H), 7.67 - 7.64 (m, 2H), (1c) Preparation of 3-(9-carbazolyl)-aniline 8.5g 9-(3-bromophenyl)-carbazole from step (1 b) above, 0.12g Pd2DBA3 0.11g dicyclohexylphosphinebiphenyl and 50mL dioxane were stirred in a glove box (N2). 9.2g LiN[Si(Me)3]2 and a further 10mL dioxane were added and the reaction brought to reflux overnight. The reaction was cooled and remove from the glove and water was added slowly. The pH of the aqueous layer was brought to 9 with carbonate and then the mixture was extracted with DCM. The DCM layer was separated and dried over magnesium sulfate then chromatographed on silica eluting with 1:1 ethylacetate:heaxanes. The product elutes as a tan solution which on evaporation and addition of methanol produces a tan colored crystalline solid in ~90% yield. 1-H nmr shows it to be the desired aniline product.(1b) Preparation of 6-(9-Phenyl-9H-carbazol-3-yl)-9H-pyrido[2, 3-b]indole (1.1g, 0.27mmol)