N-(2-BroMophenyl)-9H-carbazole

(1) The carbazole 8.36g (0.05mol), o-dibromobenzene 17.69g (0.075mol), potassium carbonate 17.97g (0.13mol) placed in the reactor, stirred, purged with nitrogen for 30min, 1.91 g of cuprous iodide and 1.46 g of L-lysine were added and heated to 163 ° C. for 38 h.No raw material was detected by TLC, and a large amount of water was added to terminate the reaction. The solid was precipitated by stirring and dried under suction filtration to give 13.37 g of 9- (2-bromophenyl) carbazole as solid, yield 83percent.9-Carbazole (6.52 g, 39 mmol), 1, 2-dibromobenzene (8 mL, 66.3 mmol), copper(I) oxide (1.116 g, 7.8 mmol), N, N'-dimethylethylenediamine (1.70 mL, 15.6 mmol) and anhydrous potassium phosphate (18.21 g, 85.8 mmol) were mixed in 50 mL of anhydrous toluene and heated at 120 °C for 3 days. The crude reaction mixture was extracted with dichloromethane and water. The organic layerwas dried with anhydrous MgSO4, filtered, and evaporated. The crude product was purified by column chromatography on silica gelusing 1:30 dichloromethane/hexane. The white powder wasformed. (6.95 g, Yield 55percent) 1H NMR (300 MHz, CDCl3): δ (ppm)8.14-8.17 (d, 2H), 7.85-7.88 (d, 1H), 7.47-7.57 (m, 2H), 7.37-7.45(m, 3H), 7.27-7.32 (m, 2H), 7.05-7.08 (d, 2H).A 500-mL, three-necked round bottom flask was charged with 9.7 g (0.058 mol) of the compound carbazole in a nitrogen atmosphere and diluted with 200 mL of dimethylsulfoxide. 15 g of 1, 2-dibromobenzene, 3.7 g of copper powder and 12 g of potassium carbonate were added to the diluted solution, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was heated and refluxed for 20 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane and distilled water. The extract was dried and concentrated under reduced pressure to obtain 10.3 g (yield: 55percent) of Compound 11-1.Carbazole (1.6700 g, 10.0 mmol), o-dibromobenzene (2.40 mL, 20.0 mmol), Copper iodide (0.1900 g, 1.0 mmol), 18-crown-6 (0.1320 g, 0.5 mmol), 60mL o-dichlorobenzene was added to the reaction flask in turn, under nitrogen protection and dark conditions, Stir heated to 100-210°C, react for 5-100 hours, stop the reaction and slowly reduce to room temperature, Most of the solvent was distilled off under reduced pressure. The solid residue was suction filtered and washed with dichloromethane solution. The organic phase was combined. Concentration and column chromatography gave N-(2-bromophenyl)carbazole; (yield: 53percent)In a one-neck flask, carbazole (3.3g, 19.9mmol), o-dibromobenzene (4.5g, 19.9mmol), CuI (0.8g, 4.0mmol), 1, 10-phenanthroline monohydrate (0.8g, 4.0mmol) and KOH (2.3g, 40mmol)were dissolved in o-x1ylene (50mL). The mixture was heated to reflux for 8h under nitrogen. After the reaction had all reacted, the mixture was allowed to cool to room temperature and then CH20 g (119.61 mmol) of carbazole, 67.68 g (239.22 mmol) of 2-bromoidobenzene, 11.40 g (59.81 mmol) of copper iodide, and 33.06 g (239.22 mmol) of potassium carbonate were dissolved in xylene in a nitrogen atmosphere, and the mixture was refluxed while stirring. After 12 hours, the mixture was cooled to room temperature, distilled water was added thereto, and the mixture was subjected to extraction using methyl chloride (MC), dried using magnesium sulfate, and distilled under reduced pressure. The resultant was separation-purified using column chromatography to obtain 32.64 g (101.67 mmol, 85percent yield) of Intermediate 1-1.(1) In the reaction flask carbazole 3.0g, o-bromo-iodobenzene 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, a white precipitate was finally obtained 9- (2-bromophenyl) -9H- carbazole 2.5g, 56percent yield.Carbazole (1 eq) and o-bromoiodobenzene (3 eq) cuprous iodide (0.05 eq); 11 g potassium carbonate (4 eq) was added to a three-neck bottle.Add anhydrous N, N-dimethylformamide (DMF) and react at 140 ° C for 48 h.After the reaction was completed, the reaction system was poured into water to precipitate a large amount of solid, and the solid was dissolved in dichloromethane, and the mixture was applied to a white solid (47percent);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-2-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 20. 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-3 (27. 9 g, 29percent) a obtained.Carbazole (1.672 g, 10 mmol), l-bromo-2-iodobenzene (1.5 ml, 12 mmol), potassium carbonate (K CO , 2.7646 g, 20 mmol), copper iodide (CuI, 95 mg, 0.5 mmol), and 25 ml of xylene were refluxed in a nitrogen atmosphere. After cooling to normal temperature was conducted, a product was extracted with ethyl acetate, water was removed with anhydrous magnesium sulfate (MgSO ), and the solvent was removed at a reduced pressure. The resulting product was passed through a silica gel column using a hexane solvent to produce a compound, the solvent was removed at a reduced pressure, and vacuum drying was conducted to produce the resulting white solid compound of Formula a (800 mg, yield 25percent).[123] MS: [M+H]Preparation Example 1Preparation of Starting Material Represented by Formula aCarbazole (1.672 g, 10 mmol), 1-bromo-2-iodobenzene (1.5 ml, 12 mmol), potassium carbonate (KPreparation Example 1Preparation of Starting Material Represented by Formula aCarbazole (1.672 g, 10 mmol), 1-bromo-2-iodobenzene (1.5 ml, 12 mmol), potassium carbonate (KGeneral procedure: A mixture of carbazole(1.67 g, 10 mmol), 2-bromoiodobenzene (4.2 g, 15 mmol), K2CO3 (2.76 g, 20 mmol), CuI (0.95 g, 5 mmol) and DMA (100 mL) in a 250 mL three-necked flask was heated at 130 °C for 48 h under nitrogen. After cooling, it was poured into water (200 mL) and extracted with CH2Cl2, the combined organic phase was washed with water and dried over MgSO4. After workup, the crude product was isolated by column chromatography (PE) to afford white powder (1.5 g, 25 percent); Rf = 0.26 (PE); M. p.: 110 – 112 °C; 1H NMR (CDCl3, 500 MHz) δ: 8.17(d, J = 7.7 Hz, 2H), 7.88 (d, J = 8.0 Hz, 1H), 7.52 (m, 2H), 7.43 (m, 3H), 7.31 (t, J = 7.33 Hz, 2H), 7.08 (d, J = 8.1 Hz, 2H); 13C NMR (CDCl3, 125 MHz) δ: 140.84, 136.77, 134.23, 131.13, 130.14, 128.80, 125.92, 123.85, 123.25, 120.33, 119.98, 110.01.Carbazole (7.39 g, 0.0442 mol), 1-bromo-2-iodobenzene (25 g, 0.0883 mol), CuI (0.421 g, 2.22 mmol), K2CO3 (12.12 g, 0.0883 mol) in a 500 mL 2-neck flask Mol) were dissolved in xylene and refluxed and stirred at 120 ° C. The mixture was cooled to room temperature, extracted with CH2Cl2, dried over MgSO4, and then the solvent was removed. Hexane solvent to obtain 3.63 g (25.5percent) of a white solid.Under nitrogen atmosphere, a mixture of carbazole (1.7 g), 1-bromo-2-iodobenzene (1.5 ml), potassium carbonate (2.8 g), copper iodide (95 mg), and xylene (25 ml) was refluxed. After cooling to ordinary temperature, the reaction product was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and then, the solvent was removed under reduced pressure. The residue was passed through a silica gel column by using a hexane solvent, and then, the solvent was removed under reduced pressure. The obtained residue was vacuum-dried to obtain the intermediate a as a white solid (800 mg, 25percent yield). MS: [M+H]Under nitrogen atmosphere, a mixture of carbazole (1.7 g), 1-bromo-2-iodobenzene (1.5 ml), potassium carbonate (2.8 g), copper iodide (95 mg), and xylene (25 ml) was refluxed. After cooling to ordinary temperature, the reaction product was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and then, the solvent was removed under reduced pressure. The residue was passed through a silica gel column by using a hexane solvent, and then, the solvent was removed under reduced pressure. The obtained residue was vacuum-dried to obtain the intermediate a as a white solid (800 mg, 25percent yield). MS: [M+H]Carbazole (1.7 g), 1-bromo-2-iodobenzene (1.5 ml), Potassium carbonate (2.8 g), Copper iodide (95 mg) and xylene (25 ml) were refluxed under an atmosphere of nitrogen.After cooling to normal temperature, the product was extracted with ethyl acetate.After drying the extract with anhydrous magnesium sulfate, The solvent was removed under reduced pressure.Passed through a silica gel column using a hexane solvent, the solvent was removed under reduced pressure, The obtained residue was dried under vacuum to obtain an intermediate a (800 mg, 25percent yield) as a white solid.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 CHTo a 500 mL four-necked round-bottomed flask, a three-way stopcock, a mechanical stirrer, a condenser, and a thermometer were attached, and the inside was purged with nitrogen. To this flask, carbazole (19.4 g, 116. 3 mmol, 1.0 eq.), 1, 2-dibromobenzene (54.8 g, 232.6 mmol, 2.0 eq.), xylenes (120 mL), copper (I) oxide (3.3 g, 23.3 mmol, 0.2 eq.), N, N'-dimethylethylenediamine (5.0 mL, 46.5 mmol, 0.4 eq.), and potassium phosphate (54.3 g, 255.9 mmol, 2.2 eq.) were sequentially added, and the obtained suspension was stirred at 170°C for 24 hours. 9-(2-Bromophenyl)carbazole (4.5 g, 13.98 mmol) was added to a three-neck reaction flask, and THF (100 mL) was added to dissolve and stirred, and the mixture was replaced with nitrogen three times. The temperature was lowered to -78 C in a nitrogen atmosphere, and after the temperature was reached, the control temperature was slowly added dropwise to -65 C to n-BuLi (0.357 mL, 13.98 mmol), and the mixture was stirred for 30 min. Further, Compound A (2 g, 6.66 mmol) was dissolved in 30 mL of THF, and then slowly added dropwise to the reaction mixture. After the completion of the dropwise addition, the mixture was naturally allowed to react to room temperature for 6 hours. After the reaction was completed, ice water (100 mL) was added to quench the reaction. Further, DCM (80 mL × 2) was added for extraction, and finally extracted once with saturated brine. The organic phase was collected and rotary evaporated to give a pale yellow oil. 20 mL of acetic acid was added to the oil, and the mixture was heated to reflux for 6 hours. After the reaction was completed, H2O (100 mL) was added to the reaction mixture, and the mixture was filtered and washed with water.Dry to give a white solid M2 (1.8 g, 2.4 mmol), yield 36%

Molecular Weight:322.2
XLogP3:5.7
Rotatable Bond Count:1
Exact Mass:321.01531
Monoisotopic Mass:321.01531
Topological Polar Surface Area:4.9
Heavy Atom Count:20
Complexity:322
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes