(4-chlorophenyl)-diethoxyphosphorylmethanol

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:

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

実験手順: 9.2 g (0.0768 mole) of thionyl chloride were added to a mixture of 20.2 g (0.0725 mole) of 4-chloro-α-hydroxy-benzylphosphonic acid diethyl ester, 65 g of methylene chloride and 5.8 g (0.0725 mole) of pyridine at 20° to 40° C. in the course of about 1 hour, while cooling slightly with water. The reaction mixture was then heated under reflux for 3 hours and was subsequently stirred for 12 hours without further heating. The mixture was poured onto about 100 g of ice-water and the organic phase was separated off and dried. After distilling off the solvent, the residue was concentrated under 6 mm Hg and at 45° C. 21 g (97.7% of theory) of 4-chloro-α-chloro-benzyl-phosphonic acid diethyl ester were obtained as a yellow viscous oil with a purity of 98.6% (gas chromatogram) and a refractive index nD24 of 1.5250. The reaction mixture was then heated under reflux for 3 hours the organic phase was separated off dried After distilling off the solvent the residue was concentrated under 6 mm Hg and at 45° C

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

実験手順: 9.2 g (0.0768 mol) of thionyl chloride were added to a mixture of 20.2 g (0.0725 mol) of 4-chloro-α-hydroxybenzylphosphonic acid diethyl ester, 65 g of methylene chloride and 5.8 g (0.0725 mol) of pyridine at 20°-40° C. in the course of about 1 hour, while cooling slightly with water. The reaction mixture was then heated under reflux for 3 hours and subsequently stirred for 12 hours, without further action of heat. The mixture was poured onto about 100 g of ice-water and the organic phase was separated off and dried. After distilling off the solvent, the residue was concentrated under 6 mm Hg and at 45° C. 21 g (97.7% of theory) of 4-chloro-α-chloro-benzylphosphonic acid diethyl ester were obtained as a yellow viscous oil with a purity of 98.6% (gas chromatogram) and a refractive index of nD24 : 1.5250. The reaction mixture was then heated under reflux for 3 hours of heat the organic phase was separated off dried After distilling off the solvent the residue was concentrated under 6 mm Hg and at 45° C

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

実験手順: 22.8 g (0.1 mol) of benzylphosphonic acid diethyl ester were added dropwise to a solution, cooled to 0° to 5° C., of 22.4 g (0.2 mol) of potassium tert.-butylate in 100 ml of tetrahydrofuran (dried over sodium) in the course of 15 l minutes. The mixture was stirred for one hour; a solution of 28 g (0.1 mol) of α-hydroxy-4-chlorobenzylphosphonic acid diethyl ester in 50 ml of tetrahydrofuran was then added to the mixture, while cooling to 0° to 5° C., and the mixture was stirred at room temperature (about 20° C.) for a further 15 hours. It was then poured into 1 liter of ice-water, filtered off and dried. 18 g (84% of theory) of 1-(4-chlorophenyl)-2-phenyl-ethylene were thus obtained in the form of colorless crystals of melting point 130° C. while cooling to 0° to 5° C. the mixture was stirred at room temperature (about 20° C.) for a further 15 hours filtered off dried

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

実験手順: 9.2 g (0.0768 mol) of thionyl chloride were added to a mixture of 20.2 g (0.0725 mol) of 4-chloro-α-hydroxybenzylphosphonic acid diethyl ester, 65 g of methylene chloride and 5.8 g (0.0725 mol) of pyridine at 20°-40° C. in the course of about 1 hour, while cooling slightly with water. The reaction mixture was then heated under reflux for 3 hours and subsequently stirred for 12 hours, without further action of heat. The mixture was poured onto about 100 g of ice-water and the organic phase was separated off and dried. After distilling off the solvent, the residue was concentrated under 6 mm Hg and at 45° C. 21 g (97.7% of theory) of 4-chloro-α-chloro-benzylphosphonic acid diethyl ester were obtained as a yellow viscous oil with a purity of 98.6% (gas chromatogram) and a refractive index of nD24 : 1.5250. The reaction mixture was then heated under reflux for 3 hours of heat the organic phase was separated off dried After distilling off the solvent the residue was concentrated under 6 mm Hg and at 45° C

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

実験手順: 22.8 g (0.1 mol) of benzylphosphonic acid diethyl ester were added dropwise to a solution, cooled to 0° to 5° C., of 22.4 g (0.2 mol) of potassium tert.-butylate in 100 ml of tetrahydrofuran (dried over sodium) in the course of 15 minutes. The mixture was stirred for one hour; a solution of 28 g (0.1 mol) of α-hydroxy-4-chlorobenzylphosphonic acid diethyl ester in 50 ml of tetrahydrofuran was then added to the mixture, while cooling to 0° to 5° C., and the mixture was stirred at room temperature (about 20° C.) for a further 15 hours. It was then poured into 1 liter of ice-water, filtered off and dried. 18 g (84% of theory) of 1-(4-chlorophenyl)-2-phenyl-ethylene were thus obtained in the form of colorless crystals of melting point 130° C. while cooling to 0° to 5° C. the mixture was stirred at room temperature (about 20° C.) for a further 15 hours filtered off dried

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

実験手順: A stirred solution of 38.0 grams (0.136 mole) of diethyl (4-chlorophenyl)hydroxymethylphosphonate in 250 ml of methylene chloride was cooled to 0° C., and a solution of 18.8 grams (0.158 mole) of thionyl chloride in 12 ml of methylene chloride was added via syringe. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it was stirred for 60 hours. After this time the reaction mixture was washed with two portions of aqueous 1N hydrochloric acid. The organic layer was filtered through silica gel. The silica gel was eluted with 1:1-hexane/ethyl acetate. The combined filtrates were concentrated under reduced pressure, yielding 40.5 grams of diethyl (4-chlorophenyl)chloromethylphosphonate. The nmr spectrum was consistent with the proposed structure. Upon completion of addition After this time the reaction mixture was washed with two portions of aqueous 1N hydrochloric acid The organic layer was filtered through silica gel The silica gel was eluted with 1 The combined filtrates were concentrated under reduced pressure

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

実験手順: Under a nitrogen atmosphere a solution of 20.0 grams (0.143 mole) of 4-chlorobenzaldehyde and 19.7 grams (0.142 mole) of diethyl phosphite was stirred at ambient temperature for 4 days. Gas chromatographic analysis of the reaction mixture indicated the reaction had not gone to completion. Ten ml of triethylamine was added, and the reaction mixture was stirred at ambient temperature for an additional 4 days. Gas chromatographic analysis of the reaction mixture indicated the reaction mixture still had not gone to completion. The reaction mixture was warmed to 40°-50° C. where it was stirred for 24 hours. After this time the reaction mixture was concentrated under reduced pressure, yielding 39.2 grams of diethyl (4-chlorophenyl)hydroxymethylphosphonate. The reaction mixture was warmed to 40°-50° C. where it was stirred for 24 hours After this time the reaction mixture was concentrated under reduced pressure

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

実験手順: 9.2 g (0.0768 mole) of thionyl chloride were added to a mixture of 20.2 g (0.0725 mole) of 4-chloro-α-hydroxy-benzylphosphonic acid diethyl ester, 65 g of methylene chloride and 5.8 g (0.0725 mole) of pyridine at 20° to 40° C. in the course of about 1 hour, while cooling slightly with water. The reaction mixture was then heated under reflux for 3 hours and was subsequently stirred for 12 hours without further heating. The mixture was poured onto about 100 g of ice-water and the organic phase was separated off and dried. After distilling off the solvent, the residue was concentrated under 6 mm Hg and at 45° C. 21 g (97.7% of theory) of 4-chloro-α-chloro-benzyl-phosphonic acid diethyl ester were obtained as a yellow viscous oil with a purity of 98.6% (gas chromatogram) and a refractive index nD24 of 1.5250. The reaction mixture was then heated under reflux for 3 hours the organic phase was separated off dried After distilling off the solvent the residue was concentrated under 6 mm Hg and at 45° C

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

実験手順: 9.2 g (0.0768 mol) of thionyl chloride were added to a mixture of 20.2 g (0.0725 mol) of 4-chloro-α-hydroxybenzylphosphonic acid diethyl ester, 65 g of methylene chloride and 5.8 g (0.0725 mol) of pyridine at 20°-40° C. in the course of about 1 hour, while cooling slightly with water. The reaction mixture was then heated under reflux for 3 hours and subsequently stirred for 12 hours, without further action of heat. The mixture was poured onto about 100 g of ice-water and the organic phase was separated off and dried. After distilling off the solvent, the residue was concentrated under 6 mm Hg and at 45° C. 21 g (97.7% of theory) of 4-chloro-α-chloro-benzylphosphonic acid diethyl ester were obtained as a yellow viscous oil with a purity of 98.6% (gas chromatogram) and a refractive index of nD24 : 1.5250. The reaction mixture was then heated under reflux for 3 hours of heat the organic phase was separated off dried After distilling off the solvent the residue was concentrated under 6 mm Hg and at 45° C