diethoxyphosphoryl(phenyl)methanol

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: A solution of Compound 19 (1.00 g, 0.0041M) in thionyl chloride (1.63 g, 0.014M) is allowed to stir at room temperature for 16 hours. The thionyl chloride is removed in vacuo and the crude is poured over ice-water. The aqueous is extracted with ether (2 times). The ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water. The organic layer is dried (Na2SO4), filtered and concentrated to obtain 0.712 g of a clear oil. The crude is chromatographed over flash silica gel (0.040-063 mm, 100 g) and eluted with 1% acetone/CH2Cl2 to obtain 0.516 g (0.0020M, 48%) of the title compound as a clear oil. 1H NMR (CDCl3 /TMS): δ 7.56-7.52 (m, 2H, Ar), 4.40 -7.32 (m, 3H, ArH), 4.90 (d, J=14 Hz, 1H, CHCl), 4.23-4.12 (m, 2H, CH2), 4.10-4.00 (m, 1H, CH2), 3.95-3.84 (m, 1H, CH2), 1.32 (dt, J=7.0, 0.6 Hz, 3H, CH3), 1.17 (dt, J=7.0, 0.6 Hz, 3H, CH3); 13C NMR (CDCl3): δ 134.16 (d, J=3.0 Hz, Ar), 129.01-128.55 (m, Ar), 64.13-63.86 (m, CH2), 53.67 (d, J=53.7 Hz, CHCl), 16.45-16.19 (m, CH3); 31P NMR (CDCl3): δ 17.82. Anal. calc'd. for C11H16O3CIP: C, 50.30; H, 6.14; P, 11.79. Found: C, 50.06; H, 6.24; P, 11.66. The thionyl chloride is removed in vacuo the crude is poured over ice-water The aqueous is extracted with ether (2 times) The ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water The organic layer is dried (Na2SO4) filtered concentrated

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

実験手順: The procedure described for the preparation of Compound 19 is used except that 3-fluorobenzaldehyde (1.49 g, 0.012M) is used in place of benzaldehyde. The solid obtained is recrystallized from hexane to obtain 2.474 g (0.009 M, 79%) of colorless short needles: mp 81°-82° C. The solid obtained is recrystallized from hexane

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

実験手順: 90 g of bromine, dissolved in 250 ml of methylene chloride, were added dropwise to a solution of 131 g (0.5 mole) of triphenylphosphine in 500 ml of methylene chloride at 30° to 35° C., moisture being excluded. The mixture was subsequently stirred at room temperature for 1 hour, a solution of 122 g (0.5 mole) of α-hydroxybenzyl-phosphonic acid diethyl ester in 250 ml of methylene chloride was then added dropwise at -20° C. in the course of 1 hour, the mixture was subsequently stirred at -20° C. for 1 hour and 40 g of pyridine, dissolved in 250 ml of methylene chloride, were then added dropwise at -20° C. in the course of one hour. The mixture was subsequently stirred for 20 hours, whereupon the temperature rose slowly to +20° C. The reaction mixture was transferred to a pear-shaped flask and the solvent was distilled off under a waterpump vacuum. The residue was extracted by stirring with one liter of ether and the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory). The mother liquor was concentrated in vacuo and the residue distilled under a high vacuum. 112 g (72% of theory) of α-bromobenzylphosphonic acid diethyl ester were obtained as a light yellow oil with a boiling point of 110° C./0.01 mm Hg and a purity of 95.9% (gas chromatogram). the mixture was subsequently stirred at -20° C. for 1 hour were then added dropwise at -20° C. in the course of one hour The mixture was subsequently stirred for 20 hours, whereupon the temperature rose slowly to +20° C The reaction mixture was transferred to a pear-shaped flask the solvent was distilled off under a waterpump vacuum The residue was extracted by stirring with one liter of ether the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory) The mother liquor was concentrated in vacuo the residue distilled under a high vacuum

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

実験手順: 90 g of bromine, dissolved in 250 ml of methylene chloride, were added dropwise to a solution of 131 g (0.5 mole) of triphenylphosphine in 500 ml of methylene chloride at 30° to 35° C., moisture being excluded. The mixture was subsequently stirred at room temperature for 1 hour, a solution of 122 g (0.5 mole) of α-hydroxybenzyl-phosphonic acid diethyl ester in 250 ml of methylene chloride was then added dropwise at -20° C. in the course of 1 hour, the mixture was subsequently stirred at -20° C. for 1 hour and 40 g of pyridine, dissolved in 250 ml of methylene chloride, were then added dropwise at -20° C. in the course of one hour. The mixture was subsequently stirred for 20 hours, whereupon the temperature rose slowly to +20° C. The reaction mixture was transferred to a pear-shaped flask and the solvent was distilled off under a waterpump vacuum. The residue was extracted by stirring with one liter of ether and the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory). The mother liquor was concentrated in vacuo and the residue distilled under a high vacuum. 112 g (72% of theory) of α-bromobenzylphosphonic acid diethyl ester were obtained as a light yellow oil with a boiling point of 110° C./0.01 mm Hg and a purity of 95.9% (gas chromatogram). the mixture was subsequently stirred at -20° C. for 1 hour were then added dropwise at -20° C. in the course of one hour The mixture was subsequently stirred for 20 hours, whereupon the temperature rose slowly to +20° C The reaction mixture was transferred to a pear-shaped flask the solvent was distilled off under a waterpump vacuum The residue was extracted by stirring with one liter of ether the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory) The mother liquor was concentrated in vacuo the residue distilled under a high vacuum

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

実験手順: A solution of Compound 19 (1.00 g, 0.0041M) in thionyl chloride (1.63 g, 0.014M) is allowed to stir at room temperature for 16 hours. The thionyl chloride is removed in vacuo and the crude is poured over ice-water. The aqueous is extracted with ether (2 times). The ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water. The organic layer is dried (Na2SO4), filtered and concentrated to obtain 0.712 g of a clear oil. The crude is chromatographed over flash silica gel (0.040-063 mm, 100 g) and eluted with 1% acetone/CH2Cl2 to obtain 0.516 g (0.0020M, 48%) of the title compound as a clear oil. 1H NMR (CDCl3 /TMS): δ 7.56-7.52 (m, 2H, Ar), 4.40 -7.32 (m, 3H, ArH), 4.90 (d, J=14 Hz, 1H, CHCl), 4.23-4.12 (m, 2H, CH2), 4.10-4.00 (m, 1H, CH2), 3.95-3.84 (m, 1H, CH2), 1.32 (dt, J=7.0, 0.6 Hz, 3H, CH3), 1.17 (dt, J=7.0, 0.6 Hz, 3H, CH3); 13C NMR (CDCl3): δ 134.16 (d, J=3.0 Hz, Ar), 129.01-128.55 (m, Ar), 64.13-63.86 (m, CH2), 53.67 (d, J=53.7 Hz, CHCl), 16.45-16.19 (m, CH3); 31P NMR (CDCl3): δ 17.82. Anal. calc'd. for C11H16O3CIP: C, 50.30; H, 6.14; P, 11.79. Found: C, 50.06; H, 6.24; P, 11.66. The thionyl chloride is removed in vacuo the crude is poured over ice-water The aqueous is extracted with ether (2 times) The ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water The organic layer is dried (Na2SO4) filtered concentrated

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

実験手順: The procedure described for the preparation of Compound 19 is used except that 3-fluorobenzaldehyde (1.49 g, 0.012M) is used in place of benzaldehyde. The solid obtained is recrystallized from hexane to obtain 2.474 g (0.009 M, 79%) of colorless short needles: mp 81°-82° C. The solid obtained is recrystallized from hexane

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: 90 g of bromine, dissolved in 250 ml of methylene chloride, were added dropwise to a solution of 131 g (0.5 mol) of triphenylphosphine in 500 ml of methylene chloride at 30°-35° C., with exclusion of moisture. The mixture was subsequently stirred at room temperature for 1 hour, a solution of 122 g (0.5 mol) of α-hydroxybenzylphosphonic acid diethyl ester in 250 ml of methylene chloride was then added dropwise at -20° C. in the course of 1 hour, the mixture was subsequently stirred at -20° C. for 1 hour and 40 g of pyridine, dissolved in 250 ml of methylene chloride, were then added dropwise at -20° C. in the course of one hour. The mixture was subsequently stirred for 20 hours, the temperature slowly rising to +20° C. The reaction mixture was transferred to a pear-shaped flask and the solvent was distilled off under a waterpump vacuum. The residue was extracted by stirring with one liter of ether and the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory). The mother liquor was concentrated in vacuo and the residue was distilled under a high vacuum. 112 g (72% of theory) of α-bromobenzyl-phosphonic acid diethyl ester were obtained as a pale yellow oil with a boiling point of 110° C./0.01 mm Hg and a purity of 95.9% (gas chromatography). the mixture was subsequently stirred at -20° C. for 1 hour were then added dropwise at -20° C. in the course of one hour The mixture was subsequently stirred for 20 hours slowly rising to +20° C The reaction mixture was transferred to a pear-shaped flask the solvent was distilled off under a waterpump vacuum The residue was extracted by stirring with one liter of ether the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory) The mother liquor was concentrated in vacuo the residue was distilled under a high vacuum

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

実験手順: 90 g of bromine, dissolved in 250 ml of methylene chloride, were added dropwise to a solution of 131 g (0.5 mole) of triphenylphosphine in 500 ml of methylene chloride at 30° to 35° C., moisture being excluded. The mixture was subsequently stirred at room temperature for 1 hour, a solution of 122 g (0.5 mole) of α-hydroxybenzyl-phosphonic acid diethyl ester in 250 ml of methylene chloride was then added dropwise at -20° C. in the course of 1 hour, the mixture was subsequently stirred at -20° C. for 1 hour and 40 g of pyridine, dissolved in 250 ml of methylene chloride, were then added dropwise at -20° C. in the course of one hour. The mixture was subsequently stirred for 20 hours, whereupon the temperature rose slowly to +20° C. The reaction mixture was transferred to a pear-shaped flask and the solvent was distilled off under a waterpump vacuum. The residue was extracted by stirring with one liter of ether and the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory). The mother liquor was concentrated in vacuo and the residue distilled under a high vacuum. 112 g (72% of theory) of α-bromobenzylphosphonic acid diethyl ester were obtained as a light yellow oil with a boiling point of 110° C./0.01 mm Hg and a purity of 95.9% (gas chromatogram). the mixture was subsequently stirred at -20° C. for 1 hour were then added dropwise at -20° C. in the course of one hour The mixture was subsequently stirred for 20 hours, whereupon the temperature rose slowly to +20° C The reaction mixture was transferred to a pear-shaped flask the solvent was distilled off under a waterpump vacuum The residue was extracted by stirring with one liter of ether the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory) The mother liquor was concentrated in vacuo the residue distilled under a high vacuum

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

実験手順: A solution of Compound 19 (1.00 g, 0.0041M) in thionyl chloride (1.63 g, 0.014M) is allowed to stir at room temperature for 16 hours. The thionyl chloride is removed in vacuo and the crude is poured over ice-water. The aqueous is extracted with ether (2 times). The ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water. The organic layer is dried (Na2SO4), filtered and concentrated to obtain 0.712 g of a clear oil. The crude is chromatographed over flash silica gel (0.040-063 mm, 100 g) and eluted with 1% acetone/CH2Cl2 to obtain 0.516 g (0.0020M, 48%) of the title compound as a clear oil. 1H NMR (CDCl3 /TMS): δ 7.56-7.52 (m, 2H, Ar), 4.40 -7.32 (m, 3H, ArH), 4.90 (d, J=14 Hz, 1H, CHCl), 4.23-4.12 (m, 2H, CH2), 4.10-4.00 (m, 1H, CH2), 3.95-3.84 (m, 1H, CH2), 1.32 (dt, J=7.0, 0.6 Hz, 3H, CH3), 1.17 (dt, J=7.0, 0.6 Hz, 3H, CH3); 13C NMR (CDCl3): δ 134.16 (d, J=3.0 Hz, Ar), 129.01-128.55 (m, Ar), 64.13-63.86 (m, CH2), 53.67 (d, J=53.7 Hz, CHCl), 16.45-16.19 (m, CH3); 31P NMR (CDCl3): δ 17.82. Anal. calc'd. for C11H16O3CIP: C, 50.30; H, 6.14; P, 11.79. Found: C, 50.06; H, 6.24; P, 11.66. The thionyl chloride is removed in vacuo the crude is poured over ice-water The aqueous is extracted with ether (2 times) The ether layer is washed with sodium bicarbonate (saturated solution) (2 times) and water The organic layer is dried (Na2SO4) filtered concentrated

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

実験手順: The procedure described for the preparation of Compound 19 is used except that 3-fluorobenzaldehyde (1.49 g, 0.012M) is used in place of benzaldehyde. The solid obtained is recrystallized from hexane to obtain 2.474 g (0.009 M, 79%) of colorless short needles: mp 81°-82° C. The solid obtained is recrystallized from hexane