4-(9H-Carbozol-9-yl)phenylboronic acid

Class white powder

After dissolving compound 3-1 (35 g, 108.6 mmol) in THF (600 mL), and adding n-BuLi (52 mL, 130.35 mmol, 2.5 M in hexane) to the reaction mixture at -78°C, the reaction mixture was stirred for 1 hour. The reaction mixture was stirred for 12 hours at room temperature with adding B(Oi-Pr)(ii)Then, 21.8 g (67.5 mmol) of 9-(4-bromophenyl)carbazole was put into a 500 mL three-necked flask, and the air in the flask was replaced with nitrogen. Then, 200 mL of tetrahydrofuran (THF) was added thereto. The temperature in the flask was set to be -78° C. and then, 48.9 mL (74.3 mmol) of n-butyllithium (1.52 mol/L, hexane solution) was dropped to the mixture and was stirred for 2 hours at the same temperature. Then, 17.4 mL (155 mmol) of trimethyl borate was added thereto. The mixture was stirred for one hour at the same temperature, then, was stirred for 24 hours while raising the temperature to room temperature. After the reaction, 200 mL of hydrochloric acid (1.0 mol/L) was added to the reaction mixture, and then stirred for one hour at room temperature. After that, the organic layer in the reaction mixture was washed with water and the product was extracted with ethyl acetate from the water which was used for the washing. The obtained extraction solution and the organic layer, which was washed with water, were mixed. The mixture was further washed with a saturated aqueous solution of sodium chloride, and then dried with magnesium sulfate. After the drying, the mixture was suction filtrated, and the filtrate was concentrated. The obtained residue was recrystallized with a mixed solvent of chloroform and hexane to give 12.8 g of a white powdered solid of 4-(carbazol-9-yl)phenylboronic acid (yield: 65.9percent). A synthesis scheme (f-3) of 4-(carbazol-9-yl)phenylboronic acid is shown below.After Compound B-2 (4 g, 12.4 mmol) was dissolved in THF (40 mL), the mixture was cooled to -78 To a 200 mL two-necked round bottom flask containing 2-2 (11.13 g, 34.67 mmol) in 150 mL dry THF, 2.4M n-BuLi in hexane (10 mL, 24 mmol) was added dropwise at -78 °C under N2 protection. After stirring for 1.5 hr with the temperature below -70 °C, B(OMe)3 (8 mL, 71.8 mmol) was added dropwise into the reaction mixture. The solution mixture was allowed to stir overnight and slowly warmed to ambient temperature. There after, the solution was quenched with water and extracted using ethyl acetate. The combined organic layer was washed with saturated NaCl (aq) and dried over Na2SO4. Thus, it was concentrated and purified using column chromatography to obtain a white solid 8.46 g in 85percent yield which was directly used in the next step.(2) 9-(4-bromophenyl)-9H-carbazole 4.00g of THF was added 50mL of dry, cooling to -78 deg.] C, n-butyllithium was slowly added 6mL (the 2.4M), for 1 hour, followed by after addition of trimethyl borate 1.8mL, reaction was continued for 2 hours. after the reaction warmed to room temperature overnight, cooled to 0 deg.] C, was added HCl (2.0 M) 40ml hydrolysis, and extracted with methylene chloride, the solvent was evaporated, to give 2.84g (4-(9H-carbazol-9-yl)phenyl)boronic acid in 80percent yield.(ii) Synthesis of 4-(carbazol-9-yl)phenylboronic acid A synthesis scheme of 4-(carbazol-9-yl)phenylboronic acid is shown in (B-4).; 21.8 g (67.5 mmol) of N-(4-bromophenyl)carbazole was put into a 500-mL three-neck flask and nitrogen substitution was carried out. After that, 200 mL of tetrahydrofuran (THF) was added to keep the reaction system at -78 3.44 g (10.72 mmol) of intermediate 1 was weighed250 mL of dry three-necked flask, 80 mL of dry tetrahydrofuran was added as the reaction solvent.Under nitrogen protection, This was cooled to -78 & lt; 0 & gt; C with liquid nitrogen acetone, The mixture was stirred at this temperature for 5 min, 10.0 mL (1.6 mol / L, 16.08 mmol) of n-butyllithium was added dropwise to the reaction system using a syringe.After 1 hour of reaction, A syringe was added dropwise to the reaction system2.4 mL (42.89 mmol) of trimethyl borate, And allowed to stir overnight with natural warming.After the reaction, the solution was quenched by adding dilute hydrochloric acid solution.After tetrahydrofuran was spin-dried, the reaction solution was extracted with methylene chloride (100 mL x 3)The extracts were combined and dried over anhydrous magnesium sulfate, The solvent was removed and dried.The crude product was purified by column chromatography using dichloromethane and ethyl acetate as the eluent gradient, To give 2.05 g of a white crystalline solid, Yield 66.5percent.[Step 2: Synthesis of 4-(9H-carbazol-9-yl)phenylboronic acid] Then, 21.8 g (67.5 mmol) of 9-(4-bromophenyl)carbazole was put into a 500 mL three-necked flask, and the air in the flask was replaced with nitrogen. Cz-PhBr (15 mmol) was solved into THF in flask with gasreplacement by Ar for three times. After cooling down to 78 °C for10 min. N-butyl lithium (t-BuLi, 11 mL, 1.6 mol L1 in hexane solution)was dropped into and stirred for 1 h at 78 °C. The Triisopropylborate (23 mmol) was dropped into flask and stirred foranother 1 h at 78 °C the slowly warmed to room temperature andstirred overnight. Hydrochloric acid (HCl, 30 mL, 2 mol L1) wasadded into the flask and stirred for another 30 min. The productswas extracted by Dichloromethane (CH2Cl2). After evaporation, thecrude product was washed with pure petroleum ether. A whitepowder achieved with yield of 86percent.Compound 1 (4.83g, 15.00mmol) was put into the flask. THF (60mL) was added with the syring. The air in the flask was replaced with Ar three times. Then the reaction solution was cooled down to−78°C for 10min. N-butyl lithium (11.25mL, 1.6mol/L in hexane solution) was dropped into above flask dropwise with the syring, then stirred for 1hat−78°C. Triisopropyl borate ([(CHUnder a nitrogen atmosphere, 9.8 g (0.030 mol) of the intermediate E compound and 152 mL (0.2 M) of tetrahydrofuran were placed in a 500 mL two-neck round bottom flask and the temperature was lowered to -78 ° C. To this, a n-butyllithium dilution solution (1.6M, 38.02 mL) was slowly added, and the mixture was stirred for 1 hour while maintaining the temperature at -78 ° C. 17.2 g (0.091 mol) of triisopropylborate was slowly added to the above mixed solution, the temperature of the mixed solution was slowly raised to room temperature, and the mixture was stirred for 12 hours. After the reaction was completed, 1N hydrochloric acid was added, and after 10 minutes, the reaction mixture was washed with water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The resulting material was separated by column separation using a mixed solvent of hexane and ethyl acetate to obtain 5.9 g (67percent) of intermediate F.Under nitrogen, 9.8 g (0.030 mol) of Intermediate-E compound and 152 mL (0.2 M) of tetrahydrofuran were added to a 500 mL 2-neck round bottom flask and the temperature was lowered to -78 ° C. To this, a n-butyllithium dilution solution (1.6M, 38.02 mL) was added slowly, and the mixture was stirred for 1 hour while maintaining the temperature at -78 ° C. 17.2 g (0.091 mol) of triisopropylborate was slowly added to the above mixture, the temperature of the mixture was slowly raised to room temperature, and the mixture was stirred for 12 hours. After the reaction was completed, 1N hydrochloric acid was added, and after 10 minutes, the reaction mixture was washed with water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The resulting material was separated by column separation using a mixed solvent of hexane and ethyl acetate to obtain 5.9 g (67percent) of intermediate F.In NWeigh 1.72 g (5.36 mmol) of intermediate 1 in 100 mL of dry two-necked flask, 50 mL of dry tetrahydrofuran was added as the reaction solvent. Under nitrogen protection, It was cooled to -78 °C with liquid nitrogen acetone and stirred at this temperature for 5 min, Under nitrogen, 5.0 mL (1.6 mol / L, 8.04 mmol) of n-butyllithium was added dropwise to the reaction system. After reacting at -78 °C for 1 hour, 1.2 mL (10.72 mmol) of trimethyl borate was added dropwise to the reaction system, and the mixture was stirred at room temperature overnight. After the completion of the reaction, dilute hydrochloric acid solution was added and the solution was made acidic. The reaction solution was extracted with dichloromethane (50 mL x 3) The extracts were combined and dried over anhydrous magnesium sulfate, and the solvent was taken out and dried. The crude product was purified by column chromatography using dichloromethane and ethyl acetate as the eluent gradient to give 1.02 g of a white crystalline solid in 66.5percent yield.Under nitrogen 9- (4-bromophenyl) -9H- carbazole THF was cooled to 150 ml of the mixture (10g, 1.0eq) in -78 . After dropwise addition of n-BuLi (18.6 ml, 1.5eq) it was slowly stirred for 1 hour. After adding the trimethyl borate (5.2ml, 1.5eq) it was stirred for 2 hours. Cooled to 0 back extracted with MC was added to 6M HCl. The concentrate EA: hexane = 1: 1 was obtained by column separation of white solid compound 70-5. (5.4g, 60percent)19.6 g (60.7 mmol) of N-(4-bromophenyl)carbazole synthesized in Step 1 of Example 3 was put into a 500 mL three-neck flask, and the atmosphere in the flask was substituted by nitrogen. 100 mL of tetrahydrofuran (THF) was added to the flask and cooled to -78° C. Into this solution, 66.8 mL (42.3 mmol) of n-butyllithium hexane solution (1.58 mol/L) wad dropped under a nitrogen gas flow, and the solution was stirred at the same temperature for three hours. Then, 13.5 mL (140 mmol) of trimethyl borate was added into this solution at the same temperature, and while the temperature of the solution was being increased to room temperature, the solution was stirred for about 24 hours. About 200 mL of 2.0 mol/L hydrochloric acid was added into this solution and stirred at room temperature for one hour. This solution was extracted with ethyl acetate and the extracted solution and an organic layer were washed together with a saturated brine and dried with magnesium sulfate. The mixture was filtrated, and the filtrate was concentrate to obtain a solid substance. The obtained solid substance was recrystallized with a mixed solvent of chloroform and hexane, so that 10.2 g of the white powder of 4(9H-carbazol-9-yl)phenylboronic acid was obtained in yield 58percent.

suzuki reaction

Molecular Weight:287.1
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:2
Exact Mass:287.1117589
Monoisotopic Mass:287.1117589
Topological Polar Surface Area:45.4
Heavy Atom Count:22
Complexity:361
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes