3-(9H-Carbazol-9-yl)phenylboronic acid

off-white solid

9-(3-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 adding 1.8ml of trimethyl borate, the 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 2.96g (3-(9H-carbazol-9-yl)phenyl)boronic acid in 83percent yield.The experimental apparatus was thoroughly dried and 40.9 g was added to a 2L three-necked flask The product Intermediate I obtained by Reaction Formula 13, Add 800 mL of dried tetrahydrofuran, After dissolution, the temperature was lowered to -78°C, and 56 mL of 2.5 M n-BuLi was added dropwise. After stirring for one hour at the temperature, Then at this temperature, 17 g (1.3 eq.) of trimethyl borate was added dropwise. After the addition was completed, the mixture was stirred at room temperature overnight. After the reaction is completed, add 4M hydrochloric acid solution, Extract with dichloromethane and wash the organic phase with saturated brine until neutral. Dry, remove solvent, and cook the crude product with ethyl acetate. The filter cake is the boric acid product, intermediate J, 26.2g (product The rate is 72percent).After dissolved in 100ml 3 neck round bottom flask tetrahydrofuran (60ml) purifying the intermediates 1-4 (3.0g) was stirred for 30 minutes in an argon atmosphere at -78°C and on low temptarure . 2 molar concentration in the mixture after the n-butyl lithium (5.6ml) was slowly dropped from the atmosphere and stirred for 1 hour. Slowly added dropwise to triethyl borate (2.3ml) at the same temperature, to this reaction solution and stirred for 12 hours at room temperature and then stirred for 2 hours. After completion of the reaction by the addition of water after the addition of hydrochloric acid until pH 5 was added, stirred for 15 minutes and stirred for 4 hours. After removal of the water of the solution obtained was extracted with ether, and vacuum drying the resulting material to obtain 2.2g of the title 2 to 4 substituents.2.00 g of 3-boronic acid-9-phenylcarbazole (6.97 mmol) and 2.08 g of 4-(9-bromoanthracene)benzonitrile (5.80 mmol) was added to a clean three-necked flask, and nitrogen was pumped three times , Then 0.14 g of tetra-triphenylphosphine palladium (0.12 mmol) was added to the flask, and nitrogen was pumped three times, and then 30 ml of a 2M potassium carbonate solution, 30 ml of ethanol, and 60 ml of toluene were added to the flask., nitrogen was pumped three times, and then the reaction was stirred at 110 degrees Celsius for 12 hoursStop the reaction, reduce the temperature to room temperature, then use a rotary evaporator to evaporate the ethanol and toluene.The residue was extracted three times with water and dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, Dichloromethane was then distilled off, and the crude product was recrystallized from toluene to obtain 2.88 g of the product. (Yield: 95.36%)2, 4-Dichloro-6-phenyl-1, 3, 5-triazine (19.5g, 86.26mmol), (3-(carbazole-9H)Phenyl)Pinacol ester (35.04g, 94.89mmol), K2CO3 (23.84g, 172.52mmol) and Pd(PPh3)4 (2.99g, 2.59mmol) were added to a round bottom flask and dissolved in THF (250ml) and distilled water (85ml) and stirred under reflux for 12 hours at 60 C. After the reaction, the water layer was removed and column chromatography (Hexane: DCM (30%)) was used.24.68 g (66%) of an intermediate (Int-19) was obtainedS13. The 3, 7-dibromo-10-hexyl-10H-phenothiazine (intermediate product 2), 3- (9H-carbazole-9-yl) phenylboronic acid, Potassium carbonate and tetrakis (triphenylphosphine) palladium are dissolved in a molar ratio of 2: 1: 4: 0.05 in 1, 4-dioxane / water (1: 1) which is purged with nitrogen, Under the protection of nitrogen at 80 C for 16 hours, after cooling to room temperature, pour into water.The organic phase was extracted and separated by silica gel column chromatography to obtain a blue-green solid.3- (3- (9H-carbazole-9-yl) phenyl) -7-bromo-10-hexyl-10H-phenothiazine (intermediate product 3), the yield was 70%.30.29 g (105 mmol) of 3- (9H-carbazole-9-yl) phenyl boronic acid and 20 g (105 mmol) of 1-Bromo-4-chlorobenzene, Pd (PPh 3) 4 0.03 eq, K 2 CO 3 2 eq was suspended in THF and distilled water and stirred under reflux for 12 hours.After the completion of the reaction, the mixture was extracted, and the organic layer was concentrated and subjected to silica gel column to obtain 35 g (yield: 94%) of the intermediate compound B.2, 5-Dibromobenzene-1, 4-dinitrile (0.278 g, 0.972 mmol) obtained in the same manner as in synthesis Example 1, 3-(9-carbazolyl)phenylboronic acid (0.640 g, 2.23 mmol), and dehydrated toluene (30 mL) were placed in a Schlenk flask under a nitrogen atmosphere, to which Pd(PPh3)4 (0.06 g, 0.05 mmol) and K2CO3aq (2M, 15 mL) were then added, followed by stirring at 80 C. for 72 hours. After returning to room temperature, the deposit was filtered and rinsed with water, hexane, and methanol to provide the compound 3 as white powder (0.57 g, 93%). 1H MNR (500 MHz, CDCl3): delta 8.17 (d, J=7.5 Hz, 4H), 8.03 (s, 2H), 7.83-7.77 (m, 6H), 7.68 (d, J=7.3 Hz, 2H), 7.55 (d, J=8.1 Hz, 4H), 7.45 (t, J=7.2 Hz, 4H) 7.32 (t, J=7.35 Hz, 4H)

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:369
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes