3-Bromo-9H-carbazole

White to light yellow solid

The intermediate F was synthesized through Reaction Scheme 3A below as follows: 8.708 g (50.00 mmol) of carbazole, 8.899 g (50.00 mmol) of NBS and 100 ml of THF were stirred at room temperature (about 25° C.) to obtain 11.70 g of Intermediate F with a yield of 95percent. (0152) First, carbazole (16.7 g, 100.0 mmol)Placed in 250mL external constant pressure dropping funnel single-ported bottle A, Vacuum, nitrogen cycle three times, After adding 50mLDMF dissolved, The single-necked flask A was placed in ice-salt bath (ice volume ratio:Saline saturated solution = 10: 1, Temperature is about -10 ° C)After full cooling, NBS (17.7 g, 100.0 mmol)DMF solution was slowly added dropwise to the carbazole solution through a constant pressure dropping funnel.Drip and add ice salt bath, Keep cold.Device does not move, Reaction 18-24h.After the reaction is completed, Pour into a large amount of water sedimentation, After filtration take the solid, Ethanol recrystallized.(The solid and a small amount of ethanol was heated to boiling, If there is still a lot of solid, Then continue to add ethanol, Until completely dissolved - at this time directly placed cooling recrystallization or only a small amount of solid - at this time filtered hot cooling recrystallization, Recrystallization can be added 2/3 amount of water) Yield: 95percent.The 16.7g (0.1mol) carbazole was dissolved in tetrahydrofuran (THF, 500mL) in, and then the resulting solution was stirred at 0 10 minutes. Thereto was added N- bromosuccinimide (NBS, 18.68g, 0.105mol), the resulting mixture was stirred at normal temperature for 12 hours, then extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous magnesium sulfate (MgSO4) was dried, then the solvent was removed, and subjected to silica gel column chromatography to give 22.4g (91percent) Compound A-1.General procedure: In a round-bottomed flask, the substrate (1 mmol) and aqueous HBr(48percent) (1 mL) were mixed in DMSO (1 mL). The mixture was stirredat corresponding temperature for 1–4 h. After cooling to roomtemperature, the reaction was adjusted to pH 7–8 with aqueous NaOHsolution (4 M). Then the mixture was washed twice with EtOAc, andthe combined organic extracts were dried, filtered and concentratedunder reduced pressure to give bromination products.A mixture of carbazole (1, 52.6 mmol) and N-bromosuccinimide (50.0 mmol) in tetrahydrofuran (100 mL) was stirred at room temperature for 5 h. The reaction mixture was evaporated under reduced pressure and the resulting residue was purified by crystallization from hexane-acetone mixture to obtain 3-bromo-9H-carbazole (5).Yield 86.1 percent; White solid, mp: 194.4 , RCarbazole (8.25 g, 0.05 mol) was added into 50 ml of DMF anddissolved in stirring. Then the mixed solution of N-bromosuccinimide(NBS) (8.90 g, 0.05 mol) and 50 ml of DMF was added dropwiseinto reaction flask in ice-water bath. The mixture wasstirred at room temperature for 2 h. The solution was poured into500 ml of ice water and the white precipitate was filtered, washedby distilled water, recrystallized by ethanol and dried under vacuum. white powder (10.45 g, 85percent) was obtained. 1H NMR(CDCl3, d, ppm): 8.13 (s, 2H), 7.52-7.54 (d, 2H), 7.31-7.35 (d, 3H).Carbazole (1.002 g, 5.997 mmol) was added into DMF solution (50 mL). Then the mixture of N-bromosuccinimide (NBS) (1.068 g, 6.000 mmol) and DMF (20 mL) was added dropwise into reaction flask in ice-water bath. After filtration and washed by water, white powder was obtained [29] (1.254 g, 85.0percent). Mp: 199 °C. 3-Bromocarbazole (1 ). To DMF (67 ml) was added carbazole (10 g, 59.80 mmol) and mixture was stirred at room temperature for 15 minutes. N-bromosuccinimide (10.6 g, 59.56 mmol) in DMF (100 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for two hours. White precipitates were formed after the mixture was poured into water. The precipitates were filtered and dissolved in dichloromethane. The organic layer was washed with water to remove water soluble impurities. The organic fraction was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The resulting white solid was purified by recrystallization from ethanol to give colorless crystals (10.65 g, 72 percent yield). 1H-NMR (CDCIs, 400 MHz): δ 8.34(bs, 1 H), 8.15(d, J=7.8Hz, 1 H), 7.48(d, J=8.2, 1 H), 7.45(m, 1H), 11.42(s, 1H). (MS, ESI) m/z 246 (MCarbazole (52.26 g, 0.30 mol) was dissolved in dichloromethane (3 L) and silicagel (60 mesh, 600 g) was added to the mixture and the mixture was cooled to 10 In the procedures shown in Scheme 1, the preparation of 3-bromocarbazole 1 using N-bromosuccinimide was contaminated by some starting material and 3, 6-dibromocarbazole, both of which could be removed by fractional recrystallization from toluene. The preparation of 3 was accomplished in good yield by dropwise introduction of the lithiated TBDMS-protected 3-bromocarbazole 2 intermediate to excess 1, 4-diiodobutane.[Step 1: Synthesis of 3-bromo-9H-carbazole] (1) Carbazole (16.7 g, 100 mmol) was dissolved in 100 mL of DMF, In a 500 mL four-necked flask was mechanically stirred, The temperature was controlled with an ice-salt bath-5 ° C to -10 ° C, Further, 100 mL of a DMF solution of NBS (18.7 g, 105 mmol) was added, Stirring was continued and the reaction was continued overnight.The reaction was poured vigorously into water, stirred, filtered and the filter cake was allowed to dry. Ethyl acetate, To give 16.6 g of 3-bromocarbazole in 67.6percent yield.To a suspension of 9.153 g (54.7 mmol) of carbazole in 100 ml of HPLC grade acetonitrile at O[169] Carbazole (20 g, 119.6 mmol) was dissolved in dimethylformamide (DMF) 200 mL, and N-bromosuccinimide (NBS) (21.2 g, 119.6 mmol) was added at 0°C. After stirring for 12 hours, distilled water was added, and the obtained solid was filtered under reduced pressure. The obtained solid was added to methanol, and after stirring, the solution was filtered under reduced pressure. The re-obtained solid was added to ethyl acetate (EA) and methanol, and stirred. Then, the mixture was filtered under reduced pressure to obtain compound 1-6 (17 g, 69.07 mmol, 58.04 percent).After dissolving carbazole 20 g (119.6 mmol) in dimethylfomiamide (DMF) 200 mL, N-bromosuccineimide (NBS) 21.2 g (119.6 mmol) was added to the mixture at 0°C. After stirring the mixture for 12 hours, distilled water was added to the mixture, and the produced solid was filtered under reduced pressure. The obtained solid was added to methanol, and the mixture was stuffed, and filtered under reduced pressure. Then, the obtained solid was added to a mixture of EA, and methanol, the mixture was stilTed, and filtered under reduced pressure to obtain compound C-3-2 17 g (58.04 percent).N-Bromosuccinimide (21 .63 g, 121 .53 mmol) was added portionwise to a stirred solution of 9 - -carbazole (19.00 g, 1 13.6 mmol) in acetonitrile (420 ml_) at room temperature. The reaction mixture was stirred at room temperature for 16 hours. After complete consumption of the starting material, as indicated by TLC, the reaction mixture was precipitated and filtered. The precipitate was washed with n-pentane to afford 3- bromo-9 - -carbazole as an off-white solid (14.7 g, 53percent). Synthesis of 3-bromocarbazole. NBS (12.77 g, 71.8 mmol) in DMF was added to 9H-carbazole (12 g, 71.8 mmol) in 200 mL at 0 °C dropwise. The reaction was monitored by HPLC. After 2 h, HPLC indicated 76percent of desired product and 6percent of dibrominated compound. The reaction was quenched by adding 500 mL of ice water. The internal temperature was controlled to be lower than 10 °C. The precipitate formed was collected by filtration. The solid was stirred in 400 mL of warm methanol. (-40 °C). The solid was collected by filtration. The solid was dissolved in 150 mL of DCM. 200 mL of methanol was added. The DCM was boiled off. The solvent level was down to 150 mL. The slurry was stirred at room temperature overnight. The solid was collected by filtration. 9 g (51percent yield) of solid was collected.A solution of N-bromosuccinimide (10.64 g, 59.8 mol) dissolved in NN-dimethylformamide (DMF) (20 ml) was treated with a constant pressure dropping solution The funnel was added dropwise to a solution of carbazole (10 g, 59.8 mol) in DMF (20 ml)in. After completion of the drop, the ice bath was removed and the reaction was conducted overnight at room temperature. The reaction solution was then washed with deionized water, the solid was precipitated, and the solid was filtered off and the product was recrystallized from ethanol (2). Yield: 47percent.16 g (grams) of carbazole was dissolved in 80 mL ) n, n ′-dimethylformamide, to this was added 18 g n-bromosuccinimide, and the reaction was stirred at room temperature overnight. The reaction mixture was poured into water and the precipitate filtered. a white solid, washed with methanol and dried under vacuum to obtain 20 g of 3-bromocarbazole.Under nitrogen atmosphere, intermediate F 2.78g (10 mmol) was dissolved in o- dichlorobenzene 20ml and triphenylphosphine 6.56g (25mmol) was added and reflux. After completion of the reaction, MC 200ml, H2O 200ml was added and then the the MC layer was extracted, concentrated and separated by column chromatography using Hex : EA =5 : 1 and dried over anhydrous MgSO4 to give the intermediate G 1.94g (79percent).Intermediate E 2.78g (10mmol) was dissolved in o-dichlorobenzene 40ml under nitrogen, triphenylphosphine 6.56g (25mmol) was added and the mixture was refluxed. After completion of the reaction, 200ml MC and 200ml H2O was added, the MC layer was extracted and dried over anhydrous MgSO4 and concentrated by column with Hex: EA = 5: 1 to give the intermediate F 1.94 g(79percent).Then dissolved under nitrogen the intermediates B 2.78g (10mmol) in 20ml o-dichlorobenzene triphenylphosphine 6.56g (25mmol) and the mixture was refluxed.To 1: After completion of the reaction, 200ml MC, the MC layer then was extracted by the addition of 200ml H2O and dried over anhydrous MgSO4 and concentrated to Hex: MC = 5Column with intermediate CTo give a 1.94g (79percent).Synthesis of Intermediate 27 (0166) (0167) Under a nitrogen atmosphere, Intermediate 26 (2.78 g, 10 mmol) was dissolved in o-DCB (40 mL), and then triphenylphosphine (6.56 g, 25 mmol) was added dropwise and refluxed. (0168) After the reaction was terminated, MC (200 mL) and HUnder a nitrogen atmosphere, Intermediate 22 (2.78 g, 10 mmol) was dissolved in o-DCB (40 mL), and then triphenylphosphine (6.56 g, 25 mmol) was added and refluxed. After the reaction was terminated, MC (200 mL) and HThe intermediate F 1mol Was dissolved in o-dichlorobenzene was added to 2.5mol and triphenylphosphine at 200°C It was stirred. After completion of reaction, after the removal o-dichlorobenzene by distillation and extracted with water and CH2Cl2 and the organic layer no It is dried with MgSO4, and concentrated by column chromatography and recrystallization to the resulting product and then to obtain the desired intermediate G (Yield: 77percent).Said Sub 1-I-1 obtained in the synthesis (168.52g, 606mmol) senses a rotation velocity of the disk to in round bottom flasko- dichlorobenzene in a, triphenylphosphine (397.35g, 1514.9mmol) adding an 200 °C stirring section. When reaction is completed the via fractional distillation to remove the dichlorobenzene- o CH Wherein the Sub 1-I-1 (66.39 g, 238.7mmol) after a round bottom flask was dissolved in o-dichlorobenzene (1194ml), it was added triphenylphosphine (156.54 g, 596.8 mmol) and stirred at 200 . After completion ofreaction was removed by distillation and the o-dichlorobenzene and water, extracted CH2Cl2. The resulting compound and the organic layer was dried overMgSO4 and concentrated to silicagel column and the product was recrystallizedfrom 35.25 g (yield: 60percent) was obtained.General procedure: A mixture of starting compound (2.69 mmol), CuCl

Molecular Weight:246.10
XLogP3:4.4
Hydrogen Bond Donor Count:1
Exact Mass:244.98401
Monoisotopic Mass:244.98401
Topological Polar Surface Area:15.8
Heavy Atom Count:14
Complexity:218
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes