3,3'-Bicarbazole

Carbazole (10 g, 59.8 mmol), iron (III) chloride (38.8 g, 239.3 mmol) and chloroform (200 mL) were sequentially added to a 400 mL four-necked flask and stirred at room temperature for 30 minutes.After completion of the reaction, the organic solvent was removed under reduced pressure, and the solid obtained was washed by adding methanol.The solid was collected by filtration, and then the same methanol washing was repeated twice to obtain Intermediate 3 (16.7 g, yield 84percent).Bicarbazole (BCz) was prepared by chemical oxidation of 9H-carbazole in the presence of FeCl3. To a solution of 9H-carbazole (8.35 g, 100 mmol) in chloroform (150 ml) Iron chloride (anhydrous FeCl 3, 20 g, 120 mmol) was added thereto and stirred at room temperature for 30 minutes. The chloroform was removed from the reaction mixture and concentrated.After filtration with an excess amount of water, BCz (5.5 g, 62percent) was obtained through column chromatography (hexane: ethyl acetate = 2: 1 to 1: 1).Carbazole (12.0 g, 72.0 mmol) and anhydrous FeCl3 (47.0 g, 288 mmol) were dissolved in 240 mLof chloroform and stirred for 30 min under nitrogen. The solution was subsequently poured into alarger quantity of methyl alcohol. The precipitated green powder and zinc powder (18.7 g, 288 mmol)were dissolved in a solution of acetic acid and ethyl acetate (180 mL, 1:1) under nitrogen. The mixturewas heated at 50 °C overnight. The reaction mixture was filtered and washed with hot ethyl acetate.The filtered solution was poured into water and extracted with ethyl acetate. The organics werecombined, washed with brine, and dried with sodium sulfate. After solvent removal, 5.94 g of a brownpowder was obtained. This crude product was purified via vacuum sublimation. Obtained as a whilesolid was 2.53 g (8.0 mmol, 22percent) of BCz. 1H-NMR (400 MHz, DMSO-d6): δ (ppm) 11.28 (s, 2H), 8.51(s, 2H), 8.25 (d, J = 7.7 Hz, 2H), 7.81 (dd, J = 8.4 Hz, J = 1.4 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.1 Hz, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.4 Hz, 2H). 13C-NMR (100 MHz, DMSO-d6): δ (ppm)140.7, 139.2, 132.8, 126.1, 125.4, 123.6, 123.2, 120.9, 119.0, 118.6, 111.7, 111.5.In a 300 mL eggplant flask, 20 g of iron chlorideAnd 5 g of carbazole, and the mixture was vigorously stirred.After disappearance of carbazole was confirmed by TLC (thin layer chromatograph), the reaction mixture was added to 2 L of methanol. This operation was carried out ten times, and the mixture was stirred in methanol at room temperature for 22 hours. The green solid was collected by suction filtration to obtain a dark green solid. The obtained solid was treated with a large sublimation purifier at 1.2 × 10 -2 torr, at a heating rate of 1 ° C./min, Purification was carried out at a sublimation temperature of 250 ° C. to obtain a white solid (yield 2.8 g, yield 11percent). Identification of the target product was carried out by 1 H-NMR (400 MHz, DMSO). A chart of 1 H-NMR is shown in FIG. 1.Under nitrogen flow , at room temperature, the32.0 g of cardazole, Anhydrous ferric chloride [III] 93.13g with 400 ml of chloroform mixture solution was stirred for 22h. The mixed solution wasplaced in 1000 ml of methanol, stirred for 1 hour and then filtered. Into the resultingpowder added tetrahydrofuran (600 rrd) then mixture was refluxed for 30 minutesand followed by filtration to remove the insoluble matter. After evaporation, the mixture was dissolved in 100 ml of DMI (l, 3-Dimethyl-2-Imidazolidinone)and recrystallized at 5 ° C to obtain 14.0 g of 9H, 9'H-3, 3'- DicarbazoleA mixture solution of 3-bromo-9H-carbazole (6.75 g, 27.4 mmol), 9-phenyl-3-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-9H-carbazole (12.15 g, 32.9 mmol), PdCarbazole (10 g, 59.8 mmol), iron (III) chloride (38.8 g, 239.3 mmol) and chloroform (200 mL) were sequentially added to a 400 mL four-necked flask and stirred at room temperature for 30 minutes.After completion of the reaction, the organic solvent was removed under reduced pressure, and the solid obtained was washed by adding methanol.The solid was collected by filtration, and then the same methanol washing was repeated twice to obtain Intermediate 3 (16.7 g, yield 84%).To a suspended solution of ferric chloride (FeCl3) (12.88 g, 79.85 mmol) in 100 mL of dry chloroform (CHCl3) under nitrogen atmosphere, a solution of carbazole (1) (5.55 g, 17.89 mmol) in CHCl3 (50 mL) was slowly added at 25 C. After 3 h of stirring, methanol (MeOH) (300 mL), and dichloromethane (DCM) (100 mL) were added, and the mixture extracted using distilled water (2×200 mL). Brine solution was used to wash the combined organic layers which were then dried using anhydrous sodium sulphate (Na2SO4), filtered, and the solvent was removed to dryness. Column chromatography was done to purify the desired product, using a mixture of ethyl acetate and n-hexanes.Bicarbazole (BCz) was prepared by chemical oxidation of 9H-carbazole in the presence of FeCl3. To a solution of 9H-carbazole (8.35 g, 100 mmol) in chloroform (150 ml) Iron chloride (anhydrous FeCl 3, 20 g, 120 mmol) was added thereto and stirred at room temperature for 30 minutes. The chloroform was removed from the reaction mixture and concentrated.After filtration with an excess amount of water, BCz (5.5 g, 62%) was obtained through column chromatography (hexane: ethyl acetate = 2: 1 to 1: 1).Carbazole (12.0 g, 72.0 mmol) and anhydrous FeCl3 (47.0 g, 288 mmol) were dissolved in 240 mLof chloroform and stirred for 30 min under nitrogen. The solution was subsequently poured into alarger quantity of methyl alcohol. The precipitated green powder and zinc powder (18.7 g, 288 mmol)were dissolved in a solution of acetic acid and ethyl acetate (180 mL, 1:1) under nitrogen. The mixturewas heated at 50 C overnight. The reaction mixture was filtered and washed with hot ethyl acetate.The filtered solution was poured into water and extracted with ethyl acetate. The organics werecombined, washed with brine, and dried with sodium sulfate. After solvent removal, 5.94 g of a brownpowder was obtained. This crude product was purified via vacuum sublimation. Obtained as a whilesolid was 2.53 g (8.0 mmol, 22%) of BCz. 1H-NMR (400 MHz, DMSO-d6): delta (ppm) 11.28 (s, 2H), 8.51(s, 2H), 8.25 (d, J = 7.7 Hz, 2H), 7.81 (dd, J = 8.4 Hz, J = 1.4 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.1 Hz, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.4 Hz, 2H). 13C-NMR (100 MHz, DMSO-d6): delta (ppm)140.7, 139.2, 132.8, 126.1, 125.4, 123.6, 123.2, 120.9, 119.0, 118.6, 111.7, 111.5.In a 300 mL eggplant flask, 20 g of iron chlorideAnd 5 g of carbazole, and the mixture was vigorously stirred.After disappearance of carbazole was confirmed by TLC (thin layer chromatograph), the reaction mixture was added to 2 L of methanol. This operation was carried out ten times, and the mixture was stirred in methanol at room temperature for 22 hours. The green solid was collected by suction filtration to obtain a dark green solid. The obtained solid was treated with a large sublimation purifier at 1.2 × 10 -2 torr, at a heating rate of 1 C./min, Purification was carried out at a sublimation temperature of 250 C. to obtain a white solid (yield 2.8 g, yield 11%). Identification of the target product was carried out by 1 H-NMR (400 MHz, DMSO). A chart of 1 H-NMR is shown in FIG. 1.Under nitrogen flow , at room temperature, the32.0 g of cardazole, Anhydrous ferric chloride [III] 93.13g with 400 ml of chloroform mixture solution was stirred for 22h. The mixed solution wasplaced in 1000 ml of methanol, stirred for 1 hour and then filtered. Into the resultingpowder added tetrahydrofuran (600 rrd) then mixture was refluxed for 30 minutesand followed by filtration to remove the insoluble matter. After evaporation, the mixture was dissolved in 100 ml of DMI (l, 3-Dimethyl-2-Imidazolidinone)and recrystallized at 5 C to obtain 14.0 g of 9H, 9'H-3, 3'- Dicarbazole3-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-9H-carbazole(1.52 g, 5mmol), 3-bromo-9H- carbazole (1.23 g, 5 mmol), K2CO3(2.09 g, 15 mmol), pd(pph3)4 (0.029 g, 0.025 mmol) are added into around-bottom flask (100 mL), then adding the mixture of toluene(18 mL), ethanol (9 mL) and ultrapure water (3 mL) under N2, themixture is stirred to reflux overnight at 78 C. After completion of thereaction, the solution is separated by rotary evaporator, methylenechloride is added to the residue solid and the organic layer is dried overNa2SO4, then concentrated in vacuo [18]. The residue solid is purifiedby column chromatography to give the product as yellow solid powder(1.198 g, 72.2%): 1H NMR (500 MHz, DMSO): delta11.26 (s, 2 H), 8.50 (s, 2 H), 8.34-8.31(m, 2 H), 7.91-7.88 (m, 2 H), 7.59-7.46 (m, 6 H), 7.30-7.25 (m, 2 H). EI MS (m/z): 333.35, calcd for C24H16N2, 332.13. (0.5 g, 5 mmol), 1-(4-bromophenylsulfonyl)benzene (1.125 g, 12 mmol), potassium carbonate (1.25 g, 30 mmol), cuprous iodide (0.11 g, 2 mmol), 1, 10-phenanthroline(0.06 g, 2 mmol) are dissolved in 30 ml of N, N-dimethylformamide(DMF) under N2, stirring for 24 h under 160 C. After completion of thereaction, dichloromethane and water are added to the cooled mixture.The organic layer is separated and dried over Na2SO4, then concentratedin vacuo. The residue solid is purified by column chromatographyto give the product as pale yellow solid (2.08 g, 62.3%): 1H NMR (500 MHz, CDCl3: 8.43 (s, 2 H), 8.27-8.19 (m, 6 H), 8.09 (d, J=7.4 Hz, 4 H), 7.82 (d, J=8.5 Hz, 4 H), 7.77 (dd, J=8.5, 1.6 Hz, 2 H), 7.67 (t, J=7.4 Hz, 2 H), 7.62 (t, J=7.6 Hz, 4 H), 7.56 (d, J=8.5 Hz, 2 H), 7.51-7.44 (m, 4 H), 7.37 (t, J=7.3 Hz, 2 H). 13C NMR(500 MHz, CDCl3, delta): 144.2, 143.7, 141.4, 138.6, 138.2, 137.6, 137.1, 133.5, 128.9, 128.5, 127.6, 127.1, 126.8, 124.5, 123.9, 121.5, 116.6, 115.6, 109.1. EI MS (m/z): 764.16, calcd for C48H32N2O4S2, 764.18.3, 3?-bicarbazole (0.50 g, 1.5 mmol), potassium carbonate (0.99 g, 7.2 mmol), 6-methyl-2-fluorobenzonitrile (0.43 g, 3.3 mmol), DMSO 6 ml, heated at 140 C 12h.After cooling to room temperature and pouring into 200 ml of water, a large amount of solids were precipitated and stirred for 0.5 h. A white solid was obtained by suction filtration and purified by column chromatography to obtain a white solid with a yield of 85%.3, 3?-bicarbazole (0.50 g, 1.5 mmol), potassium carbonate (0.99 g, 7.2 mmol), 2-fluorobenzonitrile (0.39 g, 3.3 mmol), DMSO 6 ml, and heated at 140 C for 12 h.Cool to room temperature and pour into 200ml water to precipitate a large amount of solid and stir for 0.5h.A white solid was obtained by suction filtration and purified by column chromatography to obtain a white solid with a yield of 84%.The first compound (0.33 g, 1 mml), the second compound (1.39 g, 2.2 mml), cuprous iodide (0.02 g, 5 mml), 1, 10-phenanthroline (0.02 g, 5 mml), potassium carbonate (1.8 g, 10 mml) and N, N-dimethylformamide (20 ml). Nitrogen gas was introduced into the eggplant-shaped flask, and the reaction was refluxed for 24 hours at a reaction temperature of 150 to 180 C to obtain a first mixture. After the reaction, the first mixture is allowed to reach room temperature, and the first mixture is extracted with dichloromethane several times, and after each extraction, it is washed with water to obtain an organic phase; and the organic phase is dried over anhydrous sodium sulfate, Filtration, removing the solvent by a rotary evaporation method to obtain a crude product of the bipolar host material, and purifying the crude product of the bipolar host material by silica gel column chromatography to obtain petroleum ether and dichloro Methane and ethanol were rinsed as a rinse to give 0.78 g of a white solid, i.e., the bipolar host material, yield 58%, and the resulting bipolar host material was labeled as the fourth product.

Molecular Weight:332.4
XLogP3:6.8
Hydrogen Bond Donor Count:2
Rotatable Bond Count:1
Exact Mass:332.131348519
Monoisotopic Mass:332.131348519
Topological Polar Surface Area:31.6
Heavy Atom Count:26
Complexity:472
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes