(4-broMophenyl)diphenylphosphineoxide

After dissolving formula 1-2E (20g, 58mmol) and trichloromethane (200 ml), after addition of hydrogen peroxide solution (20 ml), and stirred for 12 hours. After removing the water and stirred to put MgSO4, was obtained by filtered and concentrated and recrystallized from hexane structural formula 1-2F (18g, 85percent yield).Was dissolved dibromobenzene (20g, 85mmol) in tetrahydrofuran (100ml), it cooled to -78 . Were added dropwise n-BuLi (2.5M, 37ml, 93mmol) was slowly stirred for 30 minutes. Chloro-diphenylphosphine (17g, 76mmol) was added dropwise slowly and then the mixture was stirred for 3 hours and then raised to room temperature, added to water (100ml), and extracted with tetrahydrofuran. After the organic layer was concentrated and the trichlorosilane obtained after the white solid was recrystallized with hexane methane (200ml) Enoch, after addition of aqueous hydrogen peroxide (20ml) was stirred for 12 hours. Put and stirred with MgSO4 filtered and concentrated to remove the water and re-crystallized with hexane to give the compound of Formula 1-35A (18g, 85percent yield).After chemical formula 1 - D (20g, 58mmol) weremelted in the chloroform (200ml) followed by the addition of aqueous hydrogenperoxide (20ml) was stirred for 12 hours.. After it put in the MgSO General procedure: Dibromobenzene (20 g, 85 mmol) was dissolved in tetrahydrofuran (100 ml) -78'ColdRespectively.N-BuLi (2.5 M, 37 ml, 93 mmol) was slowly added dropwise Stir for 30 min.Chlorodiphenylphosphine (17 g, 76 mmol) was slowly added dropwise, and the mixture was stirred for 3 hours. After the temperature was raised to room temperature, water (100 ml)And extracted with tetrahydrofuran.The organic layer was concentrated and recrystallized with hexane to obtain a white solid, which was dissolved in trichloromethane (200 ml)Aqueous hydrogen peroxide (20 ml) was added, followed by stirring for 12 hours. The reaction mixture was poured into MgSO4 and stirred to remove water. The solution was concentrated by filtration and recrystallized with hexane to obtain the compound 1-32A (18 g, yield 85percent)dibromobenzene (20g, 85mmol) was dissolved in tetrahydrofuran (100ml), cooled to -78°C, n-BuLi (2.5M, 37ml, 93mmol) was slowly added dropwise and stirred for 30 minutes. Chloro-diphenylphosphine (17g, 76mmol) was slowly added dropwise and then the temperature was raised to room temperature, the mixture was stirred for 3 hours, then add water (100ml) and extracted with tetrahydrofuran. The organic layer was concentrated and dissolved in trichloromethane and then methane (200ml), after the addition of hydrogen peroxide solution (20ml) it was stirred for 12 hours. Stirring with MgSO4 and then filtered to remove water, concentrated and recrystallized from hexane to obtain the compound of Formula 1-16A (18g, 85percent yield).1, 4-Dibromobenzene (20 g, 85 mmol) was dissolved in tetrahydrofuran (100 ml) and then cooled to -78 °C. N-Butyllithium (n-BuLi) (2.5 M, 37 ml, 93 mmol) was slowly added dropwise and stirred for 30 minutes. Chlorodiphenylphosphine (17 g, 76 mmol) was slowly added dropwise and stirred for 3 hours. After warming to room temperature, water (100 ml) was added, and the mixture was extracted with tetrahydrofuran. The organic layer was concentrated and recrystallized from hexane to obtain a white solid. This was dissolved in trichloromethane (200 ml), hydrogen peroxide solution (20 ml) was added, and the mixture was stirred for 12 hours. Magnesium sulfate (MgSO4) was added and stirred to remove water, followed by filtration, concentration and recrystallization from hexane to obtain the compound of Formula 2-1C (18 g, yield 85percent).20.0 g (70.6 mmol) of 1-bromo-4-iodobenzene was added to a three-necked 1.0 L flask, and a nitrogen atmosphereDissolve in 500 mL of THF under nitrogen. After cooling the reaction temperature to -78 ° C, 31 mL (77.7 mmol) of 2.5 M n-BuLi solutionAnd the mixture was stirred at room temperature. After the dropwise addition was completed, the mixture was stirred at -78 ° C for one hour, and then chlorodiphenylphosphine13.9 mL (77.7 mmol) of chlorodiphenylphosphine was slowly added dropwise. After stirring for two hours, 10 mL of H2O was added. After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure. To the concentrate was added methylene chloride 500ML and 500 mL of H2O, and the organic layer was separated and washed with water and brine. The reaction of the resulting intermediate mixtureAfter cooling the temperature to 0 ° C, 85.8 mL (0.988 mol) of hydrogen peroxide (H 2 O 2) was slowly added dropwise. The reaction temperature was raised to room temperatureAnd the mixture was stirred for 18 hours. When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO4, filteredThe filtrate was concentrated under reduced pressure. The obtained concentrate was solidified and purified by using a solvent to obtain 18 g of a white solid compound (Intermediate (4)): 71.4percent).Into the 3-neck 1.0 L flask was charged with 1-bromo-4-iodo-benzene (1-bromo-4-iodobenzene ) 20.0 g (70.6 mmol)are dissolved in 500 mL THF under nitrogen atmosphere.After cooling the reaction temperature to -78 °C, a 2.5M n-BuLi solution, 31 mL (77.7mmol) was slowly added dropwise thereto and stirred. After the addition was terminated after han hour at -78°C , it was added dropwise the chloro-diphenylphosphine (chlorodiphenylphosphine) 13.9 mL (77.7mmol) slowly.After two hours stirring, HIn a three-necked 1.0 L flask20.0 g (70.6 mmol) of 1-bromo-4-iodobenzene was dissolved in 500 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78 °C, 31 mL (77.7 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred. After the dropwise addition was completed, the mixture was stirred at -78 ° C for 1 hour, 13.9 mL (77.7 mmol) of chlorodiphenylphosphine was slowly added dropwise.After stirring for two hours, 10 mL of H2O was added. After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure. To the concentrate was added 500 mL of dichloromethane and 500 mL of H2O, The organic layer was separated and washed with water and brine.The reaction temperature of the obtained intermediate mixture was kept at 0 ° C, 85.8 mL (0.988 mol) of hydrogen peroxide (H2O2) was slowly added dropwise.The reaction temperature was raised to room temperature and stirred for 18 hours. When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure.The obtained concentrate was solidified and purified by using a solvent to obtain 18 g (yield: 71.4percent) of a white solid compound (intermediate (1)).A three-necked 1.0 L flask was charged with 1-bromo-4-iodobenzene20.0 g (70.6 mmol)And dissolved in 500 mL of THF under a nitrogen atmosphere.After cooling the reaction temperature to -78 ° C, 31 mL (77.7 mmol) of 2.5 M n-BuLi solution was slowly added dropwiseAnd stirred. After the dropwise addition was completed, the mixture was stirred at -78 ° C for 1 hour, 13.9 mL (77.7 mmol) of & lt; RTI ID = 0.0 & gt; chlorodiphenylphosphine &Was slowly added dropwise. After stirring for two hours, 10 mL of H2O was added.After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure.After adding 500 mL of dichloromethane and 500 mL of H2O to the concentrate, the organic layer was separated and washed with water and brine.After the reaction mixture was cooled to 0 , hydrogen peroxide (H 2 O 2) 85.8ML (0.988 mol) was slowly added dropwise. After the reaction temperature was raised to room temperature, And stirred for 18 hours.When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure. The obtained concentrate was solidified and purified by using a solvent to obtain 18 g (yield: 71.4percent) of a white solid compound (intermediate (1))4-Bromophenyldiphenylphosphane oxide was synthesized without the isolation of the intermediate phosphane 1. Following the procedure described in [46], a solution of 4.42g (18.7mmol) of 1, 4-dibromobenzene in 25mL of dry diethylether was added dropwise into a slurry of 450mg (18.5mmol) of Mg turnings in 5mL of ether. When all the Mg was consumed, the mixture was cooled to −10°C and, maintaining the temperature below 0°C, 3.97g (18mmol) of PhGeneral procedure: The halogen compound was dissolved in THF. 2.5M n-BuLi solution inhexane was slowly dropped to this solution chilled to —80°C. (temperature measured directly in the solution). The stirring was continued for one hour. Diphenyl phosphine chloride or phenylphosphine dichloride, respectively, was added slowly at —80° C. The reaction mixture was allowed to warm to room temperature (RT) and stirred overnight. After methanol addition and reduction to dryness, the residue was dissolved in dichloromethane (DCM). The organic phase was washed with water, dried over Na2504 and reduced to dryness. The residue was dissolved in DCM again and oxidized with 30 wt. percent aqueous hydrogen peroxide solution. After stirring overnight, the organic solution was washed with water, dried over Na2504 and reduced to dryness. The crude product was purified by column chromatography. According to general procedure A) (0093) 1, 4-dibromobenzene: 10.00 g (42.4 mmol, 1.0 eq) (0094) n-butyllithium, 2.5M in hexane: 17 mL (42.4 mmol, 1.0 eq) (0095) chlorodiphenylphosphine: 9.35 g (42.4 mmol, 1.0 eq) (0096) THF: 50 mL (0097) DCM: 50 mL (0098) H(I-1)