3-Bromo-9-phenylcarbazole

off-white powder

To a flask including 3-bromo-9H-carbazole and iodobenzene, 0.03 eq. of tris(dibenzilideneacetone)dipalladium(0) (PdTo a round bottom flask 3-bromo-9H-carbazole (4.9g, 20mmol), iodobenzene (4.1g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu ( 5.8g, 60mmol), and the reaction allowed to proceed at 100 after the into toluene (210mL). After completion of reaction, the organic layer was dried over MgSO4, and extracted with water and ether and recrystallized silicagel column and the resulting organics concentrated and the product was 5.5g: (yield: 86percent).2-neck flask (Two neck flask) the material 1-a '(Cas No. 1592-95-6, 20g, 81.3mmol, 1eq) and iodo benzene (Iodobenzene) (18.23g, 89.4mmol, 1.1eq) was added to . Here, copper iodide (CuI) (3.1g, 16.3mmol, 0.2eq), 1, 10- phenanthroline (1, 10-phenanthroline) (3.0g, 16.3mmol, 0.2eq), and xylene (xylene) to 150ml then added and stirred under reflux for 6 hours. After the reaction cooled to room temperature, then the solvent was distilled off under reduced pressure and purified by column chromatography to give a 1-b '(22.4g, yield 86percent).Under nitrogen atmosphere, intermediate G 2.46g (10mmol) and iodobenzene 3.06g (15mmol) were dissolved in 25ml nitrobenzene, KUnder nitrogen intermediates C 2.46g (10mmol) and iodo-benzene 3.06g (15mmol) dissolved in 25ml of nitrobenzene and then, 4.15g K2CO3 (30mmol) and 0.19g Cu (3mmol) were added andIt was refluxed for 16 hours When the reaction is complete, remove the nitrobenzene via distillation, and 200ml MC, was added 200ml of H2O, extract the MC layer was dried over anhydrous MgSO4 and concentrated to Hex: MC = 5: 1 column with an intermediate D 2.61g (81percent to ) to giveintermediate G and 1mol iodobenzene nitrobenzene in the 1.5mol It was dissolved, Na2SO4, K2CO3, and the addition of Cu, which was stirred at 200 °. After the reaction is complete when the nitrobenzene removed by distillation and extracted with water and CH2Cl2 and the organic layer over anhydrous MgSO4 In dry, concentrated, and then the desired product was produced by column chromatography and recrystallization To give the intermediate H (Yield: 79percent).To a round bottom flask Sub 2-1-1 (4.9g, 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.ether and with water, dried over MgSO4 and the organic layer was extracted andconcentrated and to the resulting organic silicagel column and recrystallized Sub the 2-1-3-1 5.0g (yield: 78percent) was obtained.To a round bottom flask Sub 1-1-1 (4.9g, 20mmol), Sub 1-2-1 (4.1g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), and the reaction proceeds at 100°C after the into toluene (210mL). After the reaction was completed with water and extracted with ether. The organic layer was dried over MgSO4, concentrated and the resulting organic matter by silicagel column and recrystallized 4.8g of Sub 1 (1) (yield: 75percent) was obtained.In round bottom flask SM-1 (4.9g, 20mmol), SM-2-1 (4.48g, 22mmol), PdThe Sub 1-II-1 (35.25 g, 143.2 mmol) toa round bottom flask in nitrobenzene (1790ml) to dissolve and then, iodobenzene(43.83 g, 214.9 mmol), Na2SO4 (20.35 g, 143.2 mmol), K2CO3 (19.80 g, 143.2mmol), was added Cu (2.73g, 43.0 mmol) and stirred at 200 . After completion ofreaction was removed by distillation to nitrobenzene and extracted with waterand CH2Cl2. The resulting compound and the organic layer was dried over MgSO4and concentrated to silicagel column and the product was recrystallized from 33.69 g (yield: 73percent) was obtained.Said Sub 1-II-1 obtained in the synthesis (110.36g, 448.4mmol) senses a rotation velocity of the disk in nitrobenzene for in round bottom flask , iodobenzene (137.23g, 672.7mmol), Nabromo-9H-carbazole (50.0 g, 203 mmol) and iodobenzene (49g, 240 mmol), 800 mL of toluene to the mixture after the Cu (764mg, 12 mmol) , 18-Crown-6 (6.3 g, 24 mmol), NaOt- Bu (57.6 g, 600mmol) each added one after, 100°C in 24 hours stirring under reflux causes. ether and water and the organic layer was extracted and then dried with MgSO4 and then concentrated to produce an organic silicagel column and recrystallized Sub 1-1(1) to give 36.6g). (Yield: 57percent)250ml 3 neck round bottom flask the compound 1-3 (5g), Palladium (II) diacetate (0.1g), Tri-tert-butylphosphine (0.3g), toluene(100ml) was stirred into the atmosphere of argon at room temperature for 1 hour. A mixture of potassium carbonate (7.2g), 3-bromo carbazole (6.3g) it was stirred for 6 hours at 80°C. After the addition of water extracted with ethyl acetate and the title through a separation column using hexane and the resulting material water was removed to give a substituent 1-4 1.9g3-bromo-9H-carbazole (2.5 g, 0.010 mol) in bromobenzene (1.6 g, 0.010 mol), dibenzo-18-crown-6 (1.1 g, 0.0030 mol), copper (2) (1.2 g, 0.020 mol) , into a 100 mL DMF to potassium acetate (2.8 g, 0.020 mol) it was reacted with stirring for 4 hours at 120 degree . After the reaction cooled to H20: After layer separation the MC column purification (n-Hexane: MC) to give to 2.3 g (yield 71percent).[Step 3: Synthesis of 3-bromo-9-phenyl-9H-carbazole] [Step 2-1: Synthesis of 3-bromo-9-phenyl-9H-carbazole][0274]A synthetic scheme of 3-bromo-9-phenyl-9H-carbazole in Step 2-1 is shown in the following (D-2-1). [0275][0276]In a 1000 mL conical flask, 24 g (100 mmol) of 9-phenyl-9H-carbazole, 18 g(100 mmol) of JV-bromo succinimide, 450 mL of toluene, and 200 mL of ethyl acetate were added, and the mixture was stirred at room temperature for 45 hours. This suspension was washed with water and then magnesium sulfate was added thereto to remove moisture. This suspension was filtrated, and the obtained filtrate was concentrated and dried. Accordingly, 32 g of a caramel-like object, 3-bromo-9-phenyl-9H-carbazole, was obtained at a yield of 99 percent.[Step 3: Synthesis of 3-bromo-9-phenyl-9H-carbazole]Into a 1000 mL three-neck flask were put 24 g (100 mmol) of 9-phenylcarbazole, 18 g (100 mmol) of N-bromosuccinimide, 450 mL of toluene, and 200 mL of ethyl acetate, and the mixture was stirred for 45 hours at room temperature. This suspending solution was washed with water, and magnesium sulfate was added Step 1: [Step 2-1: Synthesis of 3-bromo-9-phenyl-9H-carbazole] The synthesis scheme of 3-bromo-9-phenyl-9H-carbazole in Step 2-1 is illustrated in the following (D-2-1). In a 1L conical flask, 24 g (100 mmol) of 9-phenyl-9H-carbazole, 18 g (100 mmol) of N-bromosuccinimide, 450 mL of toluene, and 200 mL of ethyl acetate were stirred at room temperature for 45 hours. This suspension was washed with water, and magnesium sulfate was added thereto, so that moisture was removed. This suspension was filtered, and the obtained filtrate was concentrated and dried. The amount and yield of a solid, which was the substance to be produced, were 32 g and 99percent, respectively.In a 1-L reactor, 9-phenyl carbazole (50 g, 205 mmol), N-bromosuccinimide (36.5 g, 205 mmol), toluene (700 ml), and ethylacetate (300 ml) were placed and stirred together at room temperature for 45 hours. After completion of the reaction, the organic layer was extracted and concentrated at a reduced pressure. Purification by column chromatography afforded Intermediate 12-a (60.7 g): yield 92percentFirstly, 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 600 ml of glacial acetic acid, and 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto. The mixture was stirred overnight at a room temperature. This glacial acetic acid solution was dropped in 1 L of ice water while stirring it. A precipitated white solid was washed three times with water. This solid was dissolved in 150 ml of diethyl ether, and washed with a saturated sodium hydrogencarbonate solution and water. This organic layer was dried with magnesium sulfate, and filtered. The obtained filtrate was concentrated. About 50 ml of methanol was added into the thus obtained EPO Firstly, 24.3 g (100 mmol) of N-phenylcarbazole was dissolved in 600 ml of glacial, acetic acid, and 17.8 g (100 mmol) of N-bromo succinic acid imide was slowly added thereto. The mixture was stirred for overnight at a room temperature. This glacial acetic acid solution was dropped in 1 L of ice water while stirring them. A precipitated white solid was washed three times with water. This white solid was dissolved in 150 ml of diethyl ether, and washed with a saturated sodium hydrogencarbonate solution and water. This organic layer was dried with magnesium sulfate, and filtered. The obtained filtrate was concentrated. The thus obtained EPO First, 24.3 g (100 mmol) of N-phenylcarbazole was dissolved in 600 mL of gracial acetic acid, and 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto. Then, the mixture was stirred for 24 hours at room temperature. This gracial acetic acid solution was dropped into 1 L of ice water while being stirred. The precipitated white solid was washed with water three times. This solid was dissolved in 150 mL of diethylether, and washed with a saturated sodium hydrogen carbonate solution and water in this order. This organic layer was dried with magnesium sulfate and then filtrated to obtain a filtrate. The filtrate was concentrated. The obtained residue was added with about 50 mL of methanol and was irradiated with ultrasonic waves so as to be dissolved uniformly. This solution was left at rest, and a white solid was precipitated. This solution was filtered, and the precipitate was dried to obtain 28.4 g (in a yield of 88percent) of a white powder, which was 3-bromo-9-phenylcarbazole.A method for synthesizing N, N', N-triphenyl-N, N', N-tris(9-phenylcarbazol-3-yl)-benzene-1, 3, 5-triamine (abbr.: PCA3B) represented by Structural Formula (21) as an example of the aromatic amine compound of the present invention is explained.; [Step 1]; First, a method for synthesizing 3-bromo-9-phenylcarbazole is explained. A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (B-1).; 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 600 mL of a glacial acetic acid, 17.8 g (100 mmol) of N-bromosuccinimide was gradually added thereto, and the mixture was stirred for approximately 20 hours at a room temperature. This glacial acetic acid solution was dropped into 1 L of ice water while stirring. The precipitated white solid was washed with water three times. This solid was dissolved in 150 mL of diethyl ether and the solution was washed with a saturated aqueous sodium hydrogen carbonate solution and water. An organic layer thereof was dried with magnesium sulfate. The organic layer was filtered, and the obtained filtrate was concentrated, where about approximately 50 mL of methanol was added and dissolved uniformly. The white solid was precipitated by leaving this solution at rest. This solid was recovered and dried, thereby obtaining 28.4 g (yield: 88percent) of 3-bromo-9-phenylcarbazole as a white powder.Step 2: Synthesis of N-phenyl-(9-phenylcarbazol-3-yl)amine (abbreviation: PCA; In Step 2, PCA was synthesized according to (i) and (ii) shown below.; (i) [Step 1: Synthesis Method of N-phenyl-(9-phenylcarbazole-3-yl)amine (Hereinafter, Referred to as PCA)] First, 24.3 g (100 mmol) of iV-phenylcarbazole was dissolved in 600 mL of EPO (i) (i) Synthesis of 3-bromo-9-phenylcarbazole;. A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (C-5).[0293](C-5) [Step 1] (i) [Step 2] Synthesis of N, 9-diphenyl-9H-carbazol-3-amine (abbreviation: PCA); (i) Synthesis of 3-bromo-9-phenylcarbazole; A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (C-5). 24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2 L Meyer flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added, and the solution was stirred for about 12 hours at room temperature. This solution was dropped into 1 L of ice water while stirring. A white solid precipitated was collected by suction filtration, and then washed with water three times. This solid was dissolved in 150 mL of diethyl ether, and the solution was washed with a saturated aqueous solution of sodium bicarbonate and then with water. The organic layer was dried over magnesium sulfate, filtered, and concentrated, and then the residue was dissolved in ca. 50 mL of ethanol. The precipitate formed as a white solid was collected by suction filtration and dried, giving 28.4 g (88percent yield) of 3-bromo-9-phenylcarbazole as white powder.(i) 24.3 g (100 mmol) of jV-phenylcarbazole was dissolved in 600 mL of glacial acetic acid, and 17.8 g (100 mmol) of -V-bromosuccinimide was slowly added thereto. The mixture was stirred for about 12 hours at a room temperature. This glacial acetic acid solution was dropped into 1 L of ice water while stirring it. A precipitated white solid was washed with water three times. This solid was dissolved in 150 mL of diethyl ether, and washed with a saturated sodium hydrogen carbonate solution and water. This organic layer was dried with magnesium sulfate. A mixture is filtered and a filtrate was concentrated. When an obtained residue was recrystallized with methanol, 28.4 g of 3-bromo-9-phenylcarbazole that was a target substance and was white powder was obtained in a yield of 88 percent (Synthesis Scheme (c-1)).24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2-L Erlenmeyer flask and dissolved by addition of 600 mL of glacial acetic acid. 17.8 g (100 mmol) of N-bromosuccinimide was slowly added into this solution and stirred for about 12 hours at room temperature. By dripping this reaction solution into 1 L of ice water while being stirred, a white solid was separated out. This separated white solid was recovered by suction filtration and washed three times with water. This solid was dissolved in 150 mL of diethyl ether and washed with a saturated sodium acid carbonate solution and water. This organic layer was dried with magnesium sulfate. Suction filtration of the mixture was performed, and the resulting filtrate was enriched. Recrystallization thereof was performed by addition of about 50 mL of methanol into this enriched solution and being left standing, whereby 28.4 g of a white powder solid of 3-bromo-9-phenylcarbazole was obtained at a yield of 88percent.24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2 L Meyer flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto, and the solution was stirred at room temperature for about 12 hours. This glacial acetic acid solution was dropped into 1 L of ice water while being stirred. A white solid substance precipitated was collected by suction filtration, and then washed with water three times. This solid substance was dissolved in 150 mL of diethyl ether, and the solution was washed with a saturated sodium hydrogen carbonate aqueous solution and then with water. The organic layer was dried with magnesium sulfate, the mixture was filtered by suction filtration, and the filtrate was concentrated. Thus, an oily substance was obtained. The oily substance was dissolved in about 50 mL of methanol. A precipitate of a white solid substance was produced by keeping this solution still. This solid substance was collected by suction filtration and dried. Then, 28.4 g (88percent yield) of 3-bromo-9-phenylcarbazole was obtained as white powder.Preparation of Structural Formula 33A; The Structural Formula 1A (15 g, 61.6 mmol) was dissolved in chloroform (300 ml), and N-bromo succinimide (11.0 g, 61.6 mmol) was added thereto, and agitated for 1 hour 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 n-hexane to obtain the Structural Formula 33A (17 g, yield 86percent). MS: [M+H]Intermediate I-4 5.47 g (22.5 mmol) and 80 mL CH2Cl2 to completely dissolved the solution N-bromosuccinimide (N-bromosuccinimide) 4.00 g (22.5 mmol) gave after the into room temperature in 12 hours dongan stirring. Was added to 60 mL of water to the reaction solution was extracted three times with 50 mL CH2Cl2. The obtained organic layer was dried with magnesium sulfate and evaporation of the solvent was recrystallized from methanol to give the intermediate I-5 6.16 g (yield 85percent). The resulting compound was confirmed by LC-MS.Intermediate I-1 5.47 g (22.5 mmol) to a CH2Cl2 solution was completely dissolved in 80 mL N- bromosuccinimide 4.00 g (22.5mmol) was stirred for 12 hours at room temperature gave put. 60 mL of water was added to the reaction solution in CH2Cl2 50 mLAnd extracted three times. After the collected organic layer was dried with magnesium sulfate and evaporation of the solvents, recrystallized from methanol andI-2 6.16 g (yield: 85percent).Intermediate I-1 5.47 g (22.5 mmol) ofCH2Cl2 80 mLCompletely dissolved in the solutionAfter N- bromo-succinimide 4.00 g (22.5mmol) was stirred at room temperature for 12 hours. 60 mL of water was added to the reaction solution was extracted three times with 50 mL CH2Cl2. The combined organic layers were dried over magnesium sulfate, and the solvent was recrystallized in methanol to give after evaporation 6.16 g of intermediate I-2 (yield: 85percent). The resulting compound was confirmed by LC-MS. C18H12BrN: MGeneral procedure: Intermediate I-1 5.47 g (22.5 mmol) ofCH2 Cl 2 80 mLthe solution was completely dissolved in N-bromosuccinimide 4.00 g (22.5 mmol) gave after the into room temperature in 12 hours stirring.It was added to 60 mL of water to the reaction mixture CHIntermediate I-1 5.47 g (22.5 mmol) N-bromosuccinimide4.00 g put (22.5mmol) in a CH2Cl2 solution was completely dissolved in 80 mL at room temperature gave It was stirred for 12 hours.Was added to 60 mL of water to the reaction solution was extracted three times with 50 mL CH2Cl2.After the collected organic layer was dried with magnesium sulfate and evaporation of the solvent was recrystallized with methanol Intermediate I-2. It was a 6.16 g (85percent yield).To a solution of 5.47 g (22.5 mmol) of Intermediate I-1 in 80 mL of methylene chloride, 4.00 g (22.5 mmol) of Nbromosuccinimide was added and the mixture was stirred at room temperature for 12 hours. To the reaction solution was added 60 mL of water and extracted three times with 50 mL of methylene chloride. The organic layer thus obtained was dried over magnesium sulfate, the solvent was evaporated, and the residue was recrystallized from methanol to obtain 6.16 g (yield: 85percent) of Intermediate I-2. The resulting compound was identified via LC-MS.4.00 g (22.5 mmol) of N-bromosuccinimide was added to a solution of 5.47 g (22.5 mmol)Of the intermediate I-3 was completely dissolved in 80 mL of CH2Cl2, The reaction solution was stirred at room temperature for 12 hours.The organic layer was extracted three times from the reaction solution by using 60 mL of water and 50 mL of CH2Cl2.The organic layer thus collected was dried with magnesium sulfate, The residue obtained after evaporation of the solvent from it was recrystallized using methanol, To obtain 6.16 g of intermediate I-4 (yield: 85percent).The compounds thus produced were determined by using LC-MS.9-phenyl-9Hcarbazole(6 g, 27 mmol), N-Bromosuccinimide (4.3 g, 27 mmol) wereadded to 30 mL of chloroform solution in 3-neck round bottom flaskand stirred for 30 min at room temperature. After vaporizing the solvent, the crude product was recrystallized using hexane. (7.4 g, Yield85percent) 1H NMR (300 MHz, CDCl3): δ(ppm) 8.25–8.24 (d, 1H), 8.10–8.07(d, 1H), 7.64–7.58 (t, 2H), 7.54–7.45 (m, 4H), 7.44–7.37 (m, 2H), 7.32–7.27 (m, 2H).Three necked flask were successively added to the 9-phenyl-carbazole (6.08g, 0.025mol), 1, 2- dichloroethane 80ml; stirred to dissolve, was added NBS (4.45g, 0.025mol), - 5 ~ 0 for 12h after stirring added an aqueous sodium bisulfate, 0.5H; stratification, the organic phase washed with saturated brine until neutral, dried over anhydrous sodium sulfate by filtration, the solvent was removed by rotary evaporation to give a yellow viscous liquid; silica gel column, eluted agent petroleum ether rotary evaporation to give a viscous yellow liquid, yield 83percent.7.10 g (29.2 mmol) of Intermediate A-1 was completely dissolved in 100 mL of CH2Cl2 (methylene chloride), 5.20 g (29.2 mmol) of N-bromosuccinimide was added thereto, and the resultant solution was stirred at room temper store for 12 hours. 80 mL of water was added to the reaction solution, and then an extraction was performed thereon three times by using 60 mL of methylene chloride. An organic layer obtained therefrom was dried by using magnesium sulfate, a solvent was evaporated therefrom, and then, the resultant solution was re-crystallized by using methanol to obtain 7.70 g (yield 82percent) of Intermediate A-2.Sub-1-1 (48.66 g, 200 mmol) obtained in the above synthesis was dissolved in 600 mL of methylene chloride. NBS (N-bromosuccinimide) (59.4 g, 210 mmol) was slowly added thereto and stirred at room temperature for 24 hours. After the reaction was completed, 300 mL of 5percent HCl was added, and 300 mL of water was added to remove residual NBS. The organic layer wasextracted with ether and water, dried over MgSO 4 and concentrated. To obtain 47.7 (74percent) of the product.Compound 9-4 63.4 g (260.58 mmol) was put into a 1-neck flask, which is then filled with argon under vacuum ambient. Tetrahydrofurane 500 mL was added thereinto, and then stirred at 0 for 10 minutes. NBS 7.35 g (40.78 mmol) was added thereinto, and stirred at room temperature for 1 day. Upon completion of the reaction, the resultant reaction material was extracted with distilled water and EA. The organic layer was dried over MgSO55 g (226.1 mmol) of intermediate product 7, 44.2 g (248.7 mmol) of NBS was suspended in 500 ml of dimethylformamide, followed by stirring at room temperature for 12 hours. Add the reaction mixture to distilled water and stir at room temperature for 6 hours. The filtrate is filtered under reduced pressure, the solid is dissolved in methyl alcohol, and the mixture is stirred at room temperature. After filtration under reduced pressure, 45 g (yield: 62percent) of the intermediate product (8) was obtained.1) in a 250ml three-neck bottle, under the protection of nitrogen, add 0.05mol 3-bromo-9H-carbazole, 0.06mol iodobenzene, 150ml toluene, stir and mix, then add 0.015mol Cu, 0.15mol potassium carbonate, heated to 150 °C , reflux reaction for 24 hours, Sampling point plate, showing no remaining 3-bromo-9H-carbazole, complete reaction; naturally cooled to room temperature, filtered, The filtrate was evaporated under reduced pressure (-0.09 MPa, 85°C) and passed through a neutral silica gel column to give 3-bromo-9-phenyl-9H-carbazole, HPLC purity 99.3percent, yield 78.8percent;

An important intermediate for the synthesis of optoelectronic materials.3-Bromo-N-phenylcarbazole is a heterocyclic organic substance and can be used as an intermediate in synthetic materials.

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:338
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes