2-BROMO-9H-XANTHEN-9-ONE

0.3 mmol of 2-p-bromophenoxy-5-chlorobenzaldehyde (82.8 mg), 0.03 mmol of CuCl2 (4.05 mg) and 0.6 mmol of NFSI (189 mg) were placed in a 15 mL thick-walled pressure-resistant reaction tube, and 3 mL of acetonitrile was added as a solvent.Then, magnetic stirring was carried out at 100 ° C for 24 hours.After cooling to room temperature. After completion of the reaction, 10mL of water was added, extracted with dichloromethane (3 * 10mL), the organic phases were combined and dried over anhydrous Na2SO4, After the filtrate was removed by filtration, the mixture was separated by column chromatography, and the eluent containing the product was collected by using petroleum ether/ethyl acetate in a volume ratio of 20:1 as an eluent.The eluent was evaporated to give 2-bromoxanthone. This material was a white solid with a yield of 70percent.method one:WeighTrifluoromethanesulfonic acidP-bromophenyl iodonium salt (1 mmol, 505 mg), Trifluoromethanesulfonic acid ketone(0.1 mmol, 36.2 mg) in a 25 mL sealed tube, add a magnet, After replacing three times with high purity nitrogen, methyl o-hydroxybenzoate (1 mmol, 127 l), 3 mL of dichloroethane, Tighten the tube, move it into a 110 ° C oil bath and stir, and allow to react overnight. The reaction was monitored by TLC and after the reaction was over, the tube was cooled to room temperature. Add to the system Into 5 mL of distilled water, stirred; extracted with ethyl acetate (5 mL × 3). The organic phases are combined and the solvent removed on a rotary evaporator to give Crude product; the crude product is loaded on silica gel, the eluant is purified by column chromatography with the volume ratio of petroleum ether: ethyl acetate = 7: 1, Pure 7-bromo accounted for tons of ketone, a white solid, isolated in 92percent yield.General procedure: The aryne precursor (1.5 equiv) was added to a mixture of carboxylic acid (0.25 mmol) and CsF (4.0 equiv) in 15 mL of freshly distilled THF, and the reaction mixture was then stirred in a closed vial at 125 °C for 18 h. After the reaction mixture was allowed to cool to room temperature, it was eluted through a plug of silica gel with ethyl acetate and the solvent was removed under reduced pressure. The residue was purified by flash chromatography on silica gel using hexanes/EtOAc as the eluent to afford the desired o-hydroxyaryl ketone.The 2-phenoxy-5-bromo - benzoic acid (10.3g, 35.2mmol) was dissolved in methylene chloride 20mL, under a nitrogen atmosphere, in an ice bath was added dropwise trifluoroacetic anhydride and 10mL trifluoride boron has ether (0.25g, 1.75mmol), the ice bath for 1 hour, triethylamine was added, stirring was continued to warm slowly to room temperature and then 10mL saturated NaHCO3 solution was added the reaction was quenched, the reaction was washed with water, saturated brine washed, and dried. It was purified by silica gel column chromatography to obtain a solid compound 31-a (6.9g, 25.2mmol), 73percent yield.Example 1Synthesis of Example Compound A-7[0143][Chem. 19]CUnder a nitrogen atmosphere, 2.5 g (8.9 mmol) of 1- (2-bromophenyl) naphthalene and 150 mL of anhydrous tetrahydrofuran were added to a dry, clean 250 mL three-necked flask, and dissolved at room temperature with stirring. The system was cooled to -78 C, and 3.9 mL (2.5 M, 9.8 mmol) of n-butyllithium was added dropwise at this temperature, and stirring was continued at this temperature for 1.5 h after the addition was completed. Subsequently, 2.2 g (8.1 mmol) of 3-bromoxanthone was added in one portion. After the addition, the cooling bath was removed, and the reaction was allowed to warm to room temperature by itself and continued to stir overnight. After completion of the reaction, it was washed with water, dried and spin-dried to obtain a white solid. The white solid was transferred to a 250 mL single-necked flask equipped with a reflux condenser, 100 mL of glacial acetic acid was added and heated to reflux, 3 mL of concentrated hydrochloric acid was added dropwise, and the reflux reaction was continued overnight. After the reaction was completed, the heating was turned off and the mixture was cooled to room temperature. The reaction solution was poured into ice water and filtered to obtain a white solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane = 5: 1 (V / V)) to obtain 2.8 g of white crystals in a yield of 75%.Compound A-1 (10 g, 22.2 mmol), In a 250-ml three-necked flask, under the protection of nitrogen, add 0.01 mol of raw material A3, 0.012 mol of intermediate D6, 150 ml of toluene and mix, then add 0.02 mol of sodium carbonate, 1 × 10-4 mol of Pd (PPh3) 4, Heating to 105 C, refluxing for 24 hours, sampling the plate, showing no bromide remaining, the reaction is complete; naturally cooling to room temperature, filtering, filtering the filtrate under reduced pressure spin (-0.09MPa, 85 C), passing through a neutral silica gel column To obtain the target product, with a purity of 99.1% by HPLC and a yield of 74.3%;3) Under a nitrogen atmosphere, 0.01 mol of intermediate III-13 and 0.015 mol of raw material I-3 were added to a 250 mL three-necked flask, dissolved in a mixed solvent (90 mL of toluene, 45 mL of ethanol), and then 0.03 mol of Na2CO3 aqueous solution ( 2M), stirred under nitrogen for 1 h, then added 1 × 10-4 mol Pd (PPh3) 4, heated under reflux for 15 h, sampled the plate, and the reaction was complete. It was left to cool, filtered, and the filtrate was spin-evaporated and passed through a silica gel column to obtain the target product with a purity of 99.6% and a yield of 78.6%.3) Under a nitrogen atmosphere, add 500 mol of the prepared intermediate II-11, 0.012 mol of raw material I-3, 0.03 mol of sodium tert-butoxide, 5 × 10-5 mol of Pd2 (dba) 3 and 5 to a 500 mL three-necked flask. × 10-5 mol of tri-tert-butyl phosphorus, then 150 mL of toluene was added to dissolve it, heated to 100 C, refluxed for 24 h, and the reaction was observed by TLC until the reaction was completed. It was left to cool to room temperature, filtered, and the filtrate was rotary distilled to no fractions. The obtained substance was purified through a silica gel column to obtain the titled target product, with a purity of 99.9% and a yield of 78.9%.5) Under a nitrogen atmosphere, 0.01 mol of intermediate III-9 and 0.015 mol of raw material I-3 were added to a 250 mL three-necked flask, dissolved in a mixed solvent (90 mL of toluene, 45 mL of ethanol), and then 0.03 mol of Na2CO3 aqueous solution was added. (2M), stir with nitrogen for 1 h, then add 1 × 10-4 mol Pd (PPh3) 4, heat and reflux for 15 h, sample the plate, and the reaction is complete. It was left to cool, filtered, and the filtrate was spin-evaporated and passed through a silica gel column to obtain the target product with a purity of 99.8% and a yield of 74.9%.

Molecular Weight:275.10
XLogP3:4.3
Hydrogen Bond Acceptor Count:2
Exact Mass:273.96294
Monoisotopic Mass:273.96294
Topological Polar Surface Area:26.3
Heavy Atom Count:16
Complexity:292
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes