2,7-DIBROMO-9H-CARBAZOLE

White to light yellow powder or crystals

2.5 g (8 mmol) 4, 4’-dibromo biphenyl was used(utilized) to perform a cyclization reaction to synthesize 2.08g (80percent) of 4, 4’-dibromo carbazole. The 4, 4’-dibromo carbazole and iodinated phenyl were dissolved in 40 ml of toluene to synthesize Intermediate C through a buchwald reaction.Dibromo-2-nitrobiphenyl (17.85 g, 50 mmol) and triphenylphosphine (32.75 g, 125 mmol) were dissolved in 300 mL of N, N-dimethylacetamide under an argon atmosphere The reaction was refluxed overnight. The reaction was stopped and cooled to room temperature. The mixture was extracted with methylene chloride and washed with water four to five times. After drying, the residue was purified by silica gel column chromatography (petroleum ether / methylene chloride = 2: 1) using 200 to 300 mesh, and recrystallized from ethanol to give white Solid (12 g, 73.8percent).4, 4’-Dibromo-2-nitro-biphenyl (2.04 g, 5.42 mmol) and PPh3 (3.80g, 14.3 mmol) were refluxing in 1, 2-dichlorobenzen (14 mL) under Ar over night. Then the solvent is removed byevaporation under vacuum. The residue was purified with silica chromatography (eluent:dichloromethane/hexanes = 0percent to 44percent). A brown solid (1.29 g, 70percent) was obtained asintermediate 1.2, 7-dibromo-9-H-carbazole (8): In a 100 mL flame-dried flask, 4, 4'-Dibromo-2-nitrobiphenyl (10 g, 28 mmol) was solubilized in 35 mL of triethyl phosphite (P(OEt)Into the 4, 4'-dibromo-2-nitrobiphenyl (compound f-1) to 16.5g 2-neck RBF takes a vacuum. After all caught the Vacuum fill with nitrogen gas. After that, insert the triethyl phosphite (triethyl phospite) 60mL was refluxed for 18 hours. After the reaction was terminated with vacuum distillation to remove the solvent as much as possible The residue was purified by column chromatography: to give the (nucleic acid eluent) to give the 2, 7-dibromo-9H-carbazole (compound f-2). (Yield: 62percent)A solution of (7) (4.0 g, 11.21 mmol) and triphenylphosphine(7.20 g, 27.45 mmol) in 45 mL of chlorobenzene was stirred at120 C for 16 h. The solution was extracted with ethyl acetate andwater, and the organic phasewas dried with anhydrous MgSO4. Thecrude product was concentrated in vacuo and purified by gelchromatography (silica gel, DCM/hexane 1/2 in volume ratio asthe eluant) to give a white solid (1.86 g, 51percent). 1H NMR (CDCl3, ppm):7.35e7.36 (d, J 8.0 Hz, 2H, aromatic protons), 7.58 (s, 2H, aromaticprotons), 7.86e7.88 (d, J 8.0 Hz, 2H, aromatic protons), 8.10 (s, 1H, eNH). 13C NMR (CDCl3, ppm): 113.83, 119.73, 121.45, 121.79, 132.29, 140.29. MASS (EI): m/z 325.Under nitrogen protection, In 250mlA solution of A3 (10 g, 28.0 mmol), triphenylphosphine (18. 4 g, 70 mmol) and 110 ml of o-dichlorobenzene were added successively under reflux to reflux and reacted for 18 hours with stirring. After completion of the reaction, the reaction solution was allowed to cool to room temperature and then poured into an appropriate amount of water and extracted with methylene chloride. The resulting organic phase was dried over anhydrous magnesium sulfate and the organic solvent was removed by rotary evaporator. The initial product was purified by chromatography And the eluent was petroleum ether / ethyl acetate to give 4.7 g of a pale yellow solid (yield: 51.2percent).7.8 g of Compound 1 was dissolved in 30 mL of triethylphosphite and stirred well. The above will be under the protection of nitrogen The system was heated to 150 ° C for 24 hours. After vacuum distillation to remove excess solvent, the residue was purified by column chromatography. most A white solid was obtained as a pure product in 48percent yield.In a 100 mL jar, 1.00 g (5.99 mmol) of carbazole was added, dissolved in tetrahydrofuran, and the jar was placed in an ice bath and protected from light.Then, 2.67 g (15 mmol) of NBS was dissolved in tetrahydrofuran and poured into a constant pressure dropping funnel. The solution was slowly dropped into a 100 mL single-mouth flask, and the mixture was stirred in an ice bath under nitrogen for 4 h.The reaction was poured into 100 mL of water and extracted three times with ethyl acetate.The resulting liquid was spin-dried and subjected to column chromatography with ethyl acetate: petroleum ether = 1:200 to give 1.56 g (4.8 mmol) of white.Solid, compound 2, 80percent yield.General procedure: The 4, 4'-dihalo-2-nitrobiphenyl (0.004 mol) and 4-nitrotoluene (0.006 mol) were heated at 160 °C with an excess of trialkyl phosphite (0.05 mol) under argon for 5 h (a-h, j, k) or 17 h (i, m). After cooling the excess of trialkyl phosphite and the trialkyl phosphate were removed under vacuum. The reaction mixture was chromatographed (column 3.x.60 cm) on silica gel in toluene/heptane (1:1 by vol). The main product 7 (R

Molecular Weight:325.00
XLogP3:4.8
Hydrogen Bond Donor Count:1
Exact Mass:324.89247
Monoisotopic Mass:322.89452
Topological Polar Surface Area:15.8
Heavy Atom Count:15
Complexity:222
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes