2,3-Difluoro-4-ethoxyphenylboronicacid(containsvaryingamountsofAnhydride)

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.450 mol of sodium metaborate are introduced into 240 ml of water. 0.012 mol of bis(triphenylphosphine)palladium(II) chloride, 0.6 mol of 4-bromo-1-iodobenzene (11) and 0.012 mol of hydrazinium hydrochloride are added, and the mixture is stirred at about 20° C. for 5 minutes. 0.6 mol of 2,3-difluoro-4-ethoxyphenylboronic acid (12) dissolved in 600 ml of tetrahydrofuran are then added, and the mixture is refluxed for 4 hours, giving the compound of the formula 13. are then added the mixture is refluxed for 4 hours

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.450 mol of sodium metaborate are introduced into 240 ml of water. 0.012 mol of bis(triphenylphosphine)palladium(II) chloride, 0.6 mol of 4-bromo-1-iodobenzene (11) and 0.012 mol of hydrazinium hydrochloride are added, and the mixture is stirred at about 20° C. for 5 minutes. 0.6 mol of 2,3-difluoro-4-ethoxyphenylboronic acid (12) dissolved in 600 ml of tetrahydrofuran are then added, and the mixture is refluxed for 4 hours, giving the compound of the formula 13. are then added the mixture is refluxed for 4 hours

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: In a reactor under nitrogen atmosphere, 20.0 g of compound (a2)17.2 g of 4-bromo-2,3-difluorophenol (a3), 30.6 g of sodium carbonate, 0.54 g of palladium on carbon catalyst (Pd/C) were dissolved in 120 mL of 2-propanol (IPA). After stirring by refluxing for 10 hours, the reaction mixture was cooled to room temperature, and injected into a mixture of 500 ml of 1N hydrochloric acid and 300 ml of toluene which was cooled into 0° C. The mixture was separated into organic layer and aqueous layer and the organic layer was extracted. The resulting organic layer was washed with saturated chloride aqueous solution and dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to provide the residue. The resulting residue was purified by recrystallization from heptan, dried to provide 13.2 g of 4′-ethoxy-2,3,2′,3′-tetrafluorobiphenyl-4-ol (a4) as a white solid. by refluxing for 10 hours was cooled into 0° C The mixture was separated into organic layer and aqueous layer the organic layer was extracted The resulting organic layer was washed with saturated chloride aqueous solution dried over anhydrous magnesium sulfate the solvent was concentrated under reduced pressure to provide the residue The resulting residue was purified by recrystallization from heptan dried

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 8-(4-Bromophenyl)-1,4-dioxaspiro(4.5)dec-7-ene (s71) (30.0 g), 4-ethoxy-2,3-difluorophenylboronic acid (s70) (24.6 g), potassium phosphate (K3PO4; 64.7 g), dichlorobistriphenylphosphine palladium (II) (Pd(Ph3P)2Cl2; 2.1 g) and 1,4-dioxane (300 ml) were placed in a reaction vessel under an atmosphere of nitrogen, and heated to reflux for 2 hours. After the reaction mixture had been cooled to 25° C., it was treated with water, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography with toluene as an eluent and silica gel as a stationary phase powder. Pd/C (1.5 g) was added to the purified product, and the mixture was stirred at room temperature under a hydrogen atmosphere until hydrogen absorption had ceased. After the reaction had been completed, Pd/C was removed, and then solvent was distilled off. The residue was purified by column chromatography with toluene as an eluent and silica gel as a stationary phase powder, and then by recrystallization from a mixed solvent of toluene and heptane (toluene:heptane=1:1 by volume) to give 8-(4′-ethoxy-2′,3′-difluoro-(1,1′-biphenyl)-4-yl)-1,4-dioxaspiro(4.5)decane (s72) (28.8 g). The yield based on the compound (s71) was 75.7%. heated to reflux for 2 hours the aqueous layer was extracted with toluene The combined organic layers were washed with water dried over anhydrous magnesium sulfate The solution was concentrated under reduced pressure the residue was purified by column chromatography with toluene as an eluent Pd/C (1.5 g) was added to the purified product Pd/C was removed solvent was distilled off The residue was purified by column chromatography with toluene as an eluent silica gel as a stationary phase powder, and then by recrystallization from a mixed solvent of toluene and heptane (toluene:heptane=1:1 by volume)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-Iodoethyl benzoate (1) (25.0 g), 4-ethoxy-2,3-difluorophenylboronic acid (2) (20.1 g), potassium carbonate (25.0 g), palladium on carbon (NX type of 5% Pd/C; 50% wet; made by N. E. Chemcat; hereinafter referred to as Pd/C) (0.25 g), toluene (100 ml), ethanol (100 ml) and water (100 ml) were put in a reaction vessel under a nitrogen atmosphere, and heated under reflux for 2 hours. The reaction mixture was cooled to 25° C., and then poured into water (500 ml) and toluene (500 ml), and mixed. The mixture was then allowed to stand until it had separated into two phases of organic and aqueous phases, and extraction into an organic phase was carried out. The organic phase obtained was fractionated, washed with water, and then dried over anhydrous magnesium sulfate. The solution obtained was concentrated under reduced pressure, and the residue obtained was purified with a fractional operation by means of column chromatography using toluene as the eluent and silica gel as the stationary phase powder. The product was further purified by means of recrystallization from ethanol and dried, giving 18.8 g of ethyl 4-ethoxy-2,3-difluoro-4′-biphenylbenzoate (3). The yield based on the compound (1) was 67.9%. were put in a reaction vessel under a nitrogen atmosphere heated under reflux for 2 hours mixed had separated into two phases of organic and aqueous phases, and extraction into an organic phase The organic phase obtained washed with water dried over anhydrous magnesium sulfate The solution obtained was concentrated under reduced pressure the residue obtained was purified with a fractional operation by means of column chromatography The product was further purified by means of recrystallization from ethanol dried

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-Bromoiodobenzene (1) (20.0 g), 4-ethoxy-2,3-difluorophenylboronic acid (2) (14.4 g), potassium carbonate (29.3 g), Pd(Ph3P)2Cl2 (1.49 g), toluene (100 ml), Solmix A-11 (100 ml), and water (100 ml) were put in a reaction vessel under a nitrogen atmosphere, and heated under reflux for 2 hours. The reaction mixture was cooled to 25° C., and then poured into water (500 ml) and toluene (500 ml), and mixed. The mixture was then allowed to stand until it had separated into two phases of organic and aqueous phases, and an extractive operation to an organic phase was carried out. The organic phase obtained was fractionated, washed with water, and then dried over anhydrous magnesium sulfate. The solution obtained was concentrated under reduced pressure, and the residue obtained was purified with a fractional operation by means of column chromatography using toluene as the eluent and silica gel as the stationary phase powder. The product was further purified by means of recrystallization from Solmix A-11 and dried, giving 20.8 g of 4-ethoxy-4′-bromo-2,3-difluoro-1,1′-biphenyl (3). The yield based on the compound (1) was 94.0%. heated under reflux for 2 hours mixed had separated into two phases of organic and aqueous phases The organic phase obtained washed with water dried over anhydrous magnesium sulfate The solution obtained was concentrated under reduced pressure the residue obtained was purified with a fractional operation by means of column chromatography The product was further purified by means of recrystallization from Solmix A-11 dried

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Ethyl 4-iodobenzoate (1) (25.0 g), 4-ethoxy-2,3-difluorophenylboronic acid (2) (20.1 g), potassium carbonate (25.0 g), Pd/C (0.25 g), toluene (100 ml), ethanol (100 ml) and water (100 ml) were added to a reaction vessel under an atmosphere of nitrogen, and heated to reflux for 2 hours. After the reaction solution had been cooled to 25° C., it was poured into water (500 ml) and toluene (500 ml), and mixed with them. The mixture was then allowed to stand until it had separated into two phases of organic and aqueous phases, and the extraction into an organic phase was carried out. The resulting organic phase was separated, and washed with water, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the resulting residue was purified by column chromatography using silica gel as a stationary phase powder and toluene as an eluent. The product was further purified by recrystallization from ethanol and dried to give ethyl 4-ethoxy-2,3-difluoro-4′-biphenylbenzoate (3) (18.8 g). The yield based on the compound (1) was 67.9%. heated to reflux for 2 hours mixed with them had separated into two phases of organic and aqueous phases the extraction into an organic phase The resulting organic phase was separated washed with water dried over anhydrous magnesium sulfate The solution was concentrated under reduced pressure the resulting residue was purified by column chromatography The product was further purified by recrystallization from ethanol dried

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

実験手順: A mixture of 10.0 g (38.7 mmol) of 2-bromotellurophene, 8.0 g (39.6 mmol) of 4-ethoxy-2,3-difluorophenylboronic acid, 3.5 g (3.0 mmol) of tetrakis-(triphenylphosphine)palladium(0) and 100 ml of 2 N sodium carbonate soln. in 200 ml of toluene/ethanol (1:1) is heated under reflux for 1.5 h. After cooling, the organic phase is separated off, and the aqueous phase is extracted with toluene. The combined organic phases are washed with sat. sodium hydrogencarbonate soln., 1 N hydrochloric acid and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO2, n-heptane:toluene=3:2). Further purification is carried out by recrystallisation from ethanol; 2-(4-ethoxy-2,3-difluorophenyl)tellurophene is obtained as a yellow solid. under reflux for 1.5 h After cooling the organic phase is separated off the aqueous phase is extracted with toluene The combined organic phases are washed with sat. sodium hydrogencarbonate soln The solution is dried concentrated to dryness The residue is purified by column chromatography (SiO2, n-heptane:toluene=3:2) Further purification is carried out by recrystallisation from ethanol

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

実験手順: A mixture of 45.0 g (0.21 mol) of 2-bromoselenophene, 52.0 g (0.26 mol) of 4-ethoxy-2,3-difluorophenylboronic acid, 20.0 g (17.3 mmol) of tetrakis(triphenylphosphine)palladium(0) and 600 ml of 2 N sodium carbonate soln. in 1100 ml of toluene/ethanol (1:1) is heated under reflux for 20 h. After cooling, the organic phase is separated off, and the aqueous phase is extracted with toluene. The combined organic phases are washed with sat. sodium hydrogencarbonate soln., 1 N hydrochloric acid and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is purified by column chromatography (SiO2, n-heptane:toluene=3:2). Further purification is carried out by recrystallisation from ethanol; 2-(4-ethoxy-2,3-difluorophenyl)selenophene is obtained as a beige solid. under reflux for 20 h After cooling the organic phase is separated off the aqueous phase is extracted with toluene The combined organic phases are washed with sat. sodium hydrogencarbonate soln The solution is dried concentrated to dryness The residue is purified by column chromatography (SiO2, n-heptane:toluene=3:2) Further purification is carried out by recrystallisation from ethanol

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.450 mol of sodium metaborate are introduced into 240 ml of water. 0.012 mol of bis(triphenylphosphine)palladium(II) chloride, 0.6 mol of 4-bromo-1-iodobenzene (11) and 0.012 mol of hydrazinium hydrochloride are added, and the mixture is stirred at about 20° C. for 5 minutes. 0.6 mol of 2,3-difluoro-4-ethoxyphenylboronic acid (12) dissolved in 600 ml of tetrahydrofuran are then added, and the mixture is refluxed for 4 hours, giving the compound of the formula 13. are then added the mixture is refluxed for 4 hours