bis(4-bromophenyl)methanone

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a flask containing a mixture of 4,4'-dibromobenzophenone (5.0 g, 14.7 mmol), PdCl2 (PPh3)2 (0.42 mg, 0.60 mmol), and CuI (60 mg, 0.30 mmol) was added THF (100 mL), iPr2NH (20 mL) and trimethylsilylacetylene (4.6 mL, 32.5 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 40 hours. The solvent was removed under vacuum, and the residue was extracted with CH2Cl2 /H2O. The organic layer was collected, dried over MgSO4, filtered through Al2O3, and pumped dry. The residue was recrystallized from CH2Cl2 /hexane at -30° C. to afford pale brown crystalline 4,4'-bis(trimethylsilylethynyl)benzophenone in 96% yield (5.29 g). 1H NMR (300 MHz, C6D6, 25° C., TMS): δ=0.25 (s, 18 H, CH3), 7.53 (d, J=8.6 Hz, 4 H, C6H4), 7.69 (d, 4 H, C6H4). To a mixture of 4,4'-bis(trimethylsilylethynyl)benzophenone (1.0 g, 2.67 mmol) and KOH (0.30 g, 5.36 mmol) was added 50 mL of MeOH and the solution was stirred at room temperature for 3 hours. The solution was then extracted with Et2O. The Et2O solution was pumped dry and the residue was chromatographed using EtOAc/hexane (1:50 to 1:5) as eluent to afford 4,4'-diethynylbenzophenone in 68% yield (0.42 g). To a flask containing The solvent was removed under vacuum the residue was extracted with CH2Cl2 /H2O The organic layer was collected dried over MgSO4 filtered through Al2O3 pumped dry The residue was recrystallized from CH2Cl2 /hexane at -30° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 4-isopropylphenol (20.4 g.) in 30 ml of dimethylformamide was added slowly a slurry of sodium hydride, 60% in mineral oil (6.0 g.) in 150 ml of dimethylformamide. When the reaction was complete, 8.5 g. of 4,4'-dibromobenzophenone and 1.0 g. dendritic copper powder were added and the reaction mixture heated to reflux and held at reflux for 24 hours. The solvent was removed under vacuum and the residue poured into ice-water. The crude product was recrystallized from ethanol to give the desired compound, mp 104-105° C. Structure was confirmed by IR, NMR, C-13 NMR and MS. the reaction mixture heated to reflux at reflux for 24 hours The solvent was removed under vacuum the residue poured into ice-water The crude product was recrystallized from ethanol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: With stirring and with the exclusion of moisture, a solution of 20 ml of 1.6N n-butyllithium in hexane is added dropwise in the course of 30 minutes to a solution, cooled to -75°, of 5.2 g (33 mmol) of 5-bromopyrimidine and 10.7 g (31.2 mmol) of 4,4'-dibromobenzophenone in 130 ml of THF. The reaction mixture is stirred for a further 0.5 hours at -75° and then for 16 hours at room temperature; then, while cooling with ice, it is hydrolysed by the addition of 20 ml of water. The organic phase is separated off and diluted with ethyl acetate. The solution is washed with 2N HCl and a semi-saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by column chromatography (400 g of silica gel, methylene chloride/ethyl acetate 85:15) and recrystallised from ethyl acetate, m.p. 89°-90°, Rf value=0.11 (silica gel, methylene chloride/ethyl acetate 85:15). The reaction mixture is stirred for a further 0.5 hours at -75° then, while cooling with ice, it The organic phase is separated off diluted with ethyl acetate The solution is washed with 2N HCl a semi-saturated sodium chloride solution, dried over sodium sulfate filtered concentrated by evaporation The residue is purified by column chromatography (400 g of silica gel, methylene chloride/ethyl acetate 85:15) recrystallised from ethyl acetate, m.p. 89°-90°, Rf value=0.11 (silica gel, methylene chloride/ethyl acetate 85:15)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of triethyl phosphonoacetate (26.8 g, 120.0 mmol) in dry THF (100 mL) was added at 0° C. over a period of 25 min. to a stirred suspension of sodium hydride (60% in oil, 4.8 g, 120.0 mmol) in dry THF (100 ml). After stirring at 0° C. for 30 min. a solution of 4,4′-dibromobenzophenone (20.4 g, 60.0 mmol) in dry THF (200 ml) was added and the mixture slowly warmed to room temperature, and stirring continued for 48 h. The reaction mixture was diluted with 1N hydrochloric acid (400 ml) and ethyl acetate (100 ml). The organic phase was separated, and the aqueous phase further extracted with ethyl acetate (2×300 ml). The combined organic phases were washed with water (300 ml×3), dried (MgSO4), filtered and concentrated in vacuo. The product was purified by column chromatography on silica gel (15% ethyl acetate in n-heptane eluent) to give 24.5 g (99%) 3,3-bis-(4-bromophenyl)-acrylic acid ethyl ester as an off-white amorphous solid. was added The organic phase was separated the aqueous phase further extracted with ethyl acetate (2×300 ml) The combined organic phases were washed with water (300 ml×3) dried (MgSO4) filtered concentrated in vacuo The product was purified by column chromatography on silica gel (15% ethyl acetate in n-heptane eluent)

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6.96 g of 9-(2-bromophenyl)-9H-carbazole as the intermediate of Preparation Example 8 was dissolved in 10 mL of purified tetrahydrofuran, and the resulting solution was cooled to −78° C. and 8.64 mL of butyllithium was slowly added dropwise. The mixture was stirred at the same temperature for 30 min, and 6.12 g of 4,4′-dibromobenzophenone was added. The mixture was stirred at the same temperature for 40 min and then further stirred at room temperature for an additional 3 hours. The reaction was terminated with aqueous ammonium chloride, and the reaction mixture was extracted with ethyl ether. The organic layer was dewatered using anhydrous magnesium sulfate, and the organic solvent was then removed. The resulting solid was dispersed in ethanol, stirred for one day, filtered, and vacuum dried, thus obtaining an intermediate material. The solid thus obtained was dispersed in 10 mL of acetic acid, and 10 drops of concentrated sulfuric acid were added, after which the mixture was refluxed for 4 hours. The resulting solid was filtered, washed with ethanol, and vacuum dried, yielding a 8,8-bis(4-bromophenyl)-8H-indolo[3,2,1-de]acridine compound. The mixture was stirred at the same temperature for 40 min further stirred at room temperature for an additional 3 hours The reaction was terminated with aqueous ammonium chloride the reaction mixture was extracted with ethyl ether the organic solvent was then removed The resulting solid was dispersed in ethanol stirred for one day filtered vacuum dried thus obtaining an intermediate material The solid thus obtained after which the mixture was refluxed for 4 hours The resulting solid was filtered washed with ethanol, and vacuum dried

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6.96 g of 9-(2-bromophenyl)-9H-carbazole as the intermediate of Preparation Example 8 was dissolved in 10 mL of purified tetrahydrofuran, and the resulting solution was cooled to −78° C. and 8.64 mL of butyllithium was slowly added dropwise. The mixture was stirred at the same temperature for 30 min, and 6.12 g of 4,4′-dibromobenzophenone was added. The mixture was stirred at the same temperature for 40 min and then further stirred at room temperature for an additional 3 hours. The reaction was terminated with aqueous ammonium chloride, and the reaction mixture was extracted with ethyl ether. The organic layer was dewatered using anhydrous magnesium sulfate, and the organic solvent was then removed. The resulting solid was dispersed in ethanol, stirred for one day, filtered, and vacuum dried, thus obtaining an intermediate material. The solid thus obtained was dispersed in 10 mL of acetic acid, and 10 drops of concentrated sulfuric acid were added, after which the mixture was refluxed for 4 hours. The resulting solid was filtered, washed with ethanol, and vacuum dried, yielding a 8,8-bis(4-bromophenyl)-8H-indolo[3,2,1-de]acridine compound. The mixture was stirred at the same temperature for 40 min further stirred at room temperature for an additional 3 hours The reaction was terminated with aqueous ammonium chloride the reaction mixture was extracted with ethyl ether the organic solvent was then removed The resulting solid was dispersed in ethanol stirred for one day filtered vacuum dried thus obtaining an intermediate material The solid thus obtained after which the mixture was refluxed for 4 hours The resulting solid was filtered washed with ethanol, and vacuum dried

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 20 ml of 1.6N n-butyllithium in hexane is added dropwise within 30 minutes, with stirring and with the exclusion of moisture, to a solution, cooled to -75°, of 5.2 g (33 mmol) of 5-bromopyrimidine and 10.7 g (31.2 mmol) of 4,4'-dibromobenzophenone in 130 ml of THF. The reaction mixture is stirred for a further 0.5 hour at -75° and then for 16 hours at room temperature; then, while cooling with ice, it is hydrolysed by adding 20 ml of water. The organic phase is separated and diluted with ethyl acetate. The solution is washed with 2N HCl and a semi-saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by column chromatography (400 g of silica gel, methylene chloride/ethyl acetate 85:15) and recrystallised from ethyl acetate, m.p. 89°-90°, Rf value=0.11 (silica gel, methylene chloride/ethyl acetate 85:15). The reaction mixture is stirred for a further 0.5 hour at -75° then, while cooling with ice, it The organic phase is separated diluted with ethyl acetate The solution is washed with 2N HCl a semi-saturated sodium chloride solution, dried over sodium sulfate filtered concentrated by evaporation The residue is purified by column chromatography (400 g of silica gel, methylene chloride/ethyl acetate 85:15) recrystallised from ethyl acetate, m.p. 89°-90°, Rf value=0.11 (silica gel, methylene chloride/ethyl acetate 85:15)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 20 ml of 1.6N n-butyllithium in hexane is added dropwise within 30 minutes, with stirring and with the exclusion of moisture, to a solution, cooled to -75°, of 5.2 g (33 mmol) of 5-bromopyrimidine and 10.7 g (31.2 mmol) of 4,4'-dibromobenzophenone in 130 ml of THF. The reaction mixture is stirred for a further 0.5 hour at -75° and then for 16 hours at room temperature; then, while cooling with ice, it is hydrolysed by adding 20 ml of water. The organic phase is separated and diluted with ethyl acetate. The solution is washed with 2N HCl and a semi-saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by column chromatography (400 g of silica gel, methylene chloride/ethyl acetate 85:15) and recrystallised from ethyl acetate, m.p. 89°-90°, Rf value=0.11 (silica gel, methylene chloride/ethyl acetate 85:15). The reaction mixture is stirred for a further 0.5 hour at -75° then, while cooling with ice, it The organic phase is separated diluted with ethyl acetate The solution is washed with 2N HCl a semi-saturated sodium chloride solution, dried over sodium sulfate filtered concentrated by evaporation The residue is purified by column chromatography (400 g of silica gel, methylene chloride/ethyl acetate 85:15) recrystallised from ethyl acetate, m.p. 89°-90°, Rf value=0.11 (silica gel, methylene chloride/ethyl acetate 85:15)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a flask containing a mixture of 4,4'-dibromobenzophenone (5.0 g, 14.7 mmol), PdCl2 (PPh3)2 (0.42 mg, 0.60 mmol), and CuI (60 mg, 0.30 mmol) was added THF (100 mL), iPr2NH (20 mL) and trimethylsilylacetylene (4.6 mL, 32.5 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 40 hours. The solvent was removed under vacuum, and the residue was extracted with CH2Cl2 /H2O. The organic layer was collected, dried over MgSO4, filtered through Al2O3, and pumped dry. The residue was recrystallized from CH2Cl2 /hexane at -30° C. to afford pale brown crystalline 4,4'-bis(trimethylsilylethynyl)benzophenone in 96% yield (5.29 g). 1H NMR (300 MHz, C6D6, 25° C., TMS): δ=0.25 (s, 18 H, CH3), 7.53 (d, J=8.6 Hz, 4 H, C6H4), 7.69 (d, 4 H, C6H4). To a mixture of 4,4'-bis(trimethylsilylethynyl)benzophenone (1.0 g, 2.67 mmol) and KOH (0.30 g, 5.36 mmol) was added 50 mL of MeOH and the solution was stirred at room temperature for 3 hours. The solution was then extracted with Et2O. The Et2O solution was pumped dry and the residue was chromatographed using EtOAc/hexane (1:50 to 1:5) as eluent to afford 4,4'-diethynylbenzophenone in 68% yield (0.42 g). To a flask containing The solvent was removed under vacuum the residue was extracted with CH2Cl2 /H2O The organic layer was collected dried over MgSO4 filtered through Al2O3 pumped dry The residue was recrystallized from CH2Cl2 /hexane at -30° C.