dichloro(methoxy)phosphane

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

実験手順: 5'-O-Dimethoxytritylthymidine (1.6 g, 2.9 mmol) in anhydrous tetrahydrofuran (5 ml) was added dropwise to a well stirred solution at -78° of CH3OPCl2 (0.33 ml, 2.5 mmol) and collidine (1.86 ml, 14.1 mmol) in anhydrous tetrahydrofuran (5 ml). A white precipitate formed during the addition. The mixture was stirred for 15 min at -78° and then filtered through a sintered glass funnel to remove collidine hydrochloride. The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml). The filtrate was then diluted with dry toluene and concentrated to a gum. After dry argon had been bled into the apparatus, a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added and the gum was allowed to dissolve completely in this solution. Solvent was removed by concentration in vacuo. This reconcentration using a solution of toluene and tetrahydrofuran was repeated three times. After the final concentration, the gum was dissolved in dry tetrahydrofuran (3 ml), cooled to -78° and a solution of tetrazole (0.18 g, 2.6 mmol) in dry tetrahydrofuran (3 ml) was added dropwise. A white precipitate of collidine hydrochloride formed during the addition. The mixture was stirred additional 10 min at -78° and then transferred using positive argon pressure and a cannula to a centrifuge tube filled with argon. The supernatant recovered after centrifugation contained the tetrazolylphosphite product which can be used directly for synthesis of deoxyoligonucleotides. Alternatively, the tetrazolylphosphite can be stored as a precipitate and reconstituted as needed. A white precipitate formed during the addition filtered through a sintered glass funnel to remove collidine hydrochloride The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml) The filtrate was then diluted with dry toluene concentrated to a gum a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added to dissolve completely in this solution Solvent was removed by concentration in vacuo After the final concentration the gum was dissolved in dry tetrahydrofuran (3 ml) cooled to -78°

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

実験手順: 5'-O-Dimethoxytritylthymidine (1.6 g, 2.9 mmol) in anhydrous tetrahydrofuran (5 ml) was added dropwise to a well stirred solution at -78° of CH3OPCl2 (0.33 ml, 2.5 mmol) and collidine (1.86 ml, 14.1 mmol) in anhydrous tetrahydrofuran (5 ml). A white precipitate formed during the addition. The mixture was stirred for 15 min at -78° and then filtered through a sintered glass funnel to remove collidine hydrochloride. The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml). The filtrate was then diluted with dry toluene and concentrated to a gum. After dry argon had been bled into the apparatus, a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added and the gum was allowed to dissolve completely in this solution. Solvent was removed by concentration in vacuo. This reconcentration using a solution of toluene and tetrahydrofuran was repeated three times. After the final concentration, the gum was dissolved in dry tetrahydrofuran (3 ml), cooled to -78° and a solution of tetrazole (0.18 g, 2.6 mmol) in dry tetrahydrofuran (3 ml) was added dropwise. A white precipitate of collidine hydrochloride formed during the addition. The mixture was stirred additional 10 min at -78° and then transferred using positive argon pressure and a cannula to a centrifuge tube filled with argon. The supernatant recovered after centrifugation contained the tetrazolylphosphite product which can be used directly for synthesis of deoxyoligonucleotides. Alternatively, the tetrazolylphosphite can be stored as a precipitate and reconstituted as needed. A white precipitate formed during the addition filtered through a sintered glass funnel to remove collidine hydrochloride The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml) The filtrate was then diluted with dry toluene concentrated to a gum a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added to dissolve completely in this solution Solvent was removed by concentration in vacuo After the final concentration the gum was dissolved in dry tetrahydrofuran (3 ml) cooled to -78°

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

実験手順: 5'-O-Dimethoxytritylthymidine (1.6 g, 2.9 mmol) in anhydrous tetrahydrofuran (5 ml) was added dropwise to a well stirred solution at -78° of CH3OPCl2 (0.33 ml, 2.5 mmol) and collidine (1.86 ml, 14.1 mmol) in anhydrous tetrahydrofuran (5 ml). A white precipitate formed during the addition. The mixture was stirred for 15 min at -78° and then filtered through a sintered glass funnel to remove collidine hydrochloride. The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml). The filtrate was then diluted with dry toluene and concentrated to a gum. After dry argon had been bled into the apparatus, a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added and the gum was allowed to dissolve completely in this solution. Solvent was removed by concentration in vacuo. This reconcentration using a solution of toluene and tetrahydrofuran was repeated three times. After the final concentration, the gum was dissolved in dry tetrahydrofuran (3 ml), cooled to -78° and a solution of tetrazole (0.18 g, 2.6 mmol) in dry tetrahydrofuran (3 ml) was added dropwise. A white precipitate of collidine hydrochloride formed during the addition. The mixture was stirred an additional 10 min at -78° and then transferred using positive argon pressure and a cannula to a centrifuge tube filled with argon. The supernatant recovered after centrifugation contained the tetrazolylphosphite product which can be used directly for synthesis of deoxyoligonucleotides. Alternatively, the tetrazolylphosphite can be stored as a precipitate and reconstituted as needed. A white precipitate formed during the addition filtered through a sintered glass funnel to remove collidine hydrochloride The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml) The filtrate was then diluted with dry toluene concentrated to a gum a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added to dissolve completely in this solution Solvent was removed by concentration in vacuo After the final concentration the gum was dissolved in dry tetrahydrofuran (3 ml) cooled to -78°

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

実験手順: 5'-O-Dimethoxytritylthymidine (1.6 g, 2.9 mmol) in anhydrous tetrahydrofuran (5 ml) was added dropwise to a well stirred solution at -78° of CH3OPCl2 (0.33 ml, 2.5 mmol) and collidine (1.86 ml, 14.1 mmol) in anhydrous tetrahydrofuran (5 ml). A white precipitate formed during the addition. The mixture was stirred for 15 min at -78° and then filtered through a sintered glass funnel to remove collidine hydrochloride. The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml). The filtrate was then diluted with dry toluene and concentrated to a gum. After dry argon had been bled into the apparatus, a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added and the gum was allowed to dissolve completely in this solution. Solvent was removed by concentration in vacuo. This reconcentration using a solution of toluene and tetrahydrofuran was repeated three times. After the final concentration, the gum was dissolved in dry tetrahydrofuran (3 ml), cooled to -78° and a solution of tetrazole (0.18 g, 2.6 mmol) in dry tetrahydrofuran (3 ml) was added dropwise. A white precipitate of collidine hydrochloride formed during the addition. The mixture was stirred an additional 10 min at -78° and then transferred using positive argon pressure and a cannula to a centrifuge tube filled with argon. The supernatant recovered after centrifugation contained the tetrazolylphosphite product which can be used directly for synthesis of deoxyoligonucleotides. Alternatively, the tetrazolylphosphite can be stored as a precipitate and reconstituted as needed. A white precipitate formed during the addition filtered through a sintered glass funnel to remove collidine hydrochloride The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml) The filtrate was then diluted with dry toluene concentrated to a gum a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added to dissolve completely in this solution Solvent was removed by concentration in vacuo After the final concentration the gum was dissolved in dry tetrahydrofuran (3 ml) cooled to -78°

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

実験手順: p-(3-phenylpropyl)phenyllithium (8.1 g, 40 mmol) in 150 ml solvent (Et2O/THF 1/1) was added dropwise to CH3OPCl2 (2.66 g, 20 mmol) in 70 ml solvent (Et2O/THF 1/1) at -70° C. The addition was completed in 2 h. The reaction mixture was stirred overnight at room temperature and then brought to reflux for 2 h. The precipitate was filtered and the solvent of the solution was removed by applying vacuum. PCl3 (15 ml) was added to the resulting viscous oil and stirred for 24 h. Then the mixture was kept at 70° C. and 1 mm Hg for 2 h to remove excess PCl3 and byproduct. The product, di[p-(3-phenylpropyl)phenyl]chlorophosphine, was obtained as a pale yellow viscous oil with 90% yield. The product was characterized by 31P NMR. 83.6 The addition to reflux for 2 h The precipitate was filtered the solvent of the solution was removed PCl3 (15 ml) was added to the resulting viscous oil stirred for 24 h was kept at 70° C. 1 mm Hg for 2 h to remove excess PCl3 and byproduct

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

実験手順: p-(3-phenylpropyl)phenyllithium (8.1 g, 40 mmol) in 150 ml solvent (Et2O/THF 1/1) was added dropwise to CH3OPCl2 (2.66 g, 20 mmol) in 70 ml solvent (Et2O/THF 1/1) at -70° C. The addition was completed in 2 h. The reaction mixture was stirred overnight at room temperature and then brought to reflux for 2 h. The precipitate was filtered and the solvent of the solution was removed by applying vacuum. PCl3 (15 ml) was added to the resulting viscous oil and stirred for 24 h. Then the mixture was kept at 70° C. and 1 mm Hg for 2 h to remove excess PCl3 and byproduct. The product, di[p-(3-phenylpropyl)phenyl]chlorophosphine, was obtained as a pale yellow viscous oil with 90% yield. The product was characterized by 31P NMR. 83.6 The addition to reflux for 2 h The precipitate was filtered the solvent of the solution was removed PCl3 (15 ml) was added to the resulting viscous oil stirred for 24 h was kept at 70° C. 1 mm Hg for 2 h to remove excess PCl3 and byproduct

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

実験手順: 5'-O-Dimethoxytritylthymidine (1.6 g, 2.9 mmol) in anhydrous tetrahydrofuran (5 ml) was added dropwise to a well stirred solution at -78° of CH3OPCl2 (0.33 ml, 2.5 mmol) and collidine (1.86 ml, 14.1 mmol) in anhydrous tetrahydrofuran (5 ml). A white precipitate formed during the addition. The mixture was stirred for 15 min at -78° and then filtered through a sintered glass funnel to remove collidine hydrochloride. The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml). The filtrate was then diluted with dry toluene and concentrated to a gum. After dry argon had been bled into the apparatus, a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added and the gum was allowed to dissolve completely in this solution. Solvent was removed by concentration in vacuo. This reconcentration using a solution of toluene and tetrahydrofuran was repeated three times. After the final concentration, the gum was dissolved in dry tetrahydrofuran (3 ml), cooled to -78° and a solution of tetrazole (0.18 g, 2.6 mmol) in dry tetrahydrofuran (3 ml) was added dropwise. A white precipitate of collidine hydrochloride formed during the addition. The mixture was stirred an additional 10 min at -78° and then transferred using positive argon pressure and a cannula to a centrifuge tube filled with argon. The supernatant recovered after centrifugation contained the tetrazolylphosphite product which can be used directly for synthesis of deoxyoligonucleotides. Alternatively, the tetrazolylphosphite can be stored as a precipitate and reconstituted as needed. A white precipitate formed during the addition filtered through a sintered glass funnel to remove collidine hydrochloride The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml) The filtrate was then diluted with dry toluene concentrated to a gum a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added to dissolve completely in this solution Solvent was removed by concentration in vacuo After the final concentration the gum was dissolved in dry tetrahydrofuran (3 ml) cooled to -78°

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

実験手順: p-(3-phenylpropyl)phenyllithium (8.1 g, 40 mmol) in 150 ml solvent (Et2O/THF 1/1) was added dropwise to CH3OPCl2 (2.66 g, 20 mmol) in 70 ml solvent (Et2O/THF 1/1) at -70° C. The addition was completed in 2 h. The reaction mixture was stirred overnight at room temperature and then brought to reflux for 2 h. The precipitate was filtered and the solvent of the solution was removed by applying vacuum. PCl3 (15 ml) was added to the resulting viscous oil and stirred for 24 h. Then the mixture was kept at 70° C. and 1 mm Hg for 2 h to remove excess PCl3 and byproduct. The product, di[p-(3-phenylpropyl)phenyl]chlorophosphine, was obtained as a pale yellow viscous oil with 90% yield. The product was characterized by 31P NMR. 83.6. The addition to reflux for 2 h The precipitate was filtered the solvent of the solution was removed PCl3 (15 ml) was added to the resulting viscous oil stirred for 24 h was kept at 70° C. 1 mm Hg for 2 h to remove excess PCl3 and byproduct

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

実験手順: 5'-O-Dimethoxytritylthymidine (1.6 g, 2.9 mmol) in anhydrous tetrahydrofuran (5 ml) was added dropwise to a well stirred solution at -78° of CH3OPCl2 (0.33 ml, 2.5 mmol) and collidine (1.86 ml, 14.1 mmol) in anhydrous tetrahydrofuran (5 ml). A white precipitate formed during the addition. The mixture was stirred for 15 min at -78° and then filtered through a sintered glass funnel to remove collidine hydrochloride. The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml). The filtrate was then diluted with dry toluene and concentrated to a gum. After dry argon had been bled into the apparatus, a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added and the gum was allowed to dissolve completely in this solution. Solvent was removed by concentration in vacuo. This reconcentration using a solution of toluene and tetrahydrofuran was repeated three times. After the final concentration, the gum was dissolved in dry tetrahydrofuran (3 ml), cooled to -78° and a solution of tetrazole (0.18 g, 2.6 mmol) in dry tetrahydrofuran (3 ml) was added dropwise. A white precipitate of collidine hydrochloride formed during the addition. The mixture was stirred additional 10 min at -78° and then transferred using positive argon pressure and a cannula to a centrifuge tube filled with argon. The supernatant recovered after centrifugation contained the tetrazolylphosphite product which can be used directly for synthesis of deoxyoligonucleotides. Alternatively, the tetrazolylphosphite can be stored as a precipitate and reconstituted as needed. A white precipitate formed during the addition filtered through a sintered glass funnel to remove collidine hydrochloride The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml) The filtrate was then diluted with dry toluene concentrated to a gum a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added to dissolve completely in this solution Solvent was removed by concentration in vacuo After the final concentration the gum was dissolved in dry tetrahydrofuran (3 ml) cooled to -78°

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

実験手順: 5'-O-Dimethoxytritylthymidine (1.6 g, 2.9 mmol) in anhydrous tetrahydrofuran (5 ml) was added dropwise to a well stirred solution at -78° of CH3OPCl2 (0.33 ml, 2.5 mmol) and collidine (1.86 ml, 14.1 mmol) in anhydrous tetrahydrofuran (5 ml). A white precipitate formed during the addition. The mixture was stirred for 15 min at -78° and then filtered through a sintered glass funnel to remove collidine hydrochloride. The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml). The filtrate was then diluted with dry toluene and concentrated to a gum. After dry argon had been bled into the apparatus, a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added and the gum was allowed to dissolve completely in this solution. Solvent was removed by concentration in vacuo. This reconcentration using a solution of toluene and tetrahydrofuran was repeated three times. After the final concentration, the gum was dissolved in dry tetrahydrofuran (3 ml), cooled to -78° and a solution of tetrazole (0.18 g, 2.6 mmol) in dry tetrahydrofuran (3 ml) was added dropwise. A white precipitate of collidine hydrochloride formed during the addition. The mixture was stirred an additional 10 min at -78° and then transferred using positive argon pressure and a cannula to a centrifuge tube filled with argon. The supernatant recovered after centrifugation contained the tetrazolylphosphite product which can be used directly for synthesis of deoxyoligonucleotides. Alternatively, the tetrazolylphosphite can be stored as a precipitate and reconstituted as needed. A white precipitate formed during the addition filtered through a sintered glass funnel to remove collidine hydrochloride The collidine hydrochloride was washed with dry tetrahydrofuran (1 ml) The filtrate was then diluted with dry toluene concentrated to a gum a solution (6 ml) containing toluene:tetrahydrofuran (2:1) was added to dissolve completely in this solution Solvent was removed by concentration in vacuo After the final concentration the gum was dissolved in dry tetrahydrofuran (3 ml) cooled to -78°

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

実験手順: p-(3-phenylpropyl)phenyllithium (8.1 g, 40 mmol) in 150 ml solvent (Et2O/THF 1/1) was added dropwise to CH3OPCl2 (2.66 g, 20 mmol) in 70 ml solvent (Et2O/THF 1/1) at -70° C. The addition was completed in 2 h. The reaction mixture was stirred overnight at room temperature and then brought to reflux for 2 h. The precipitate was filtered and the solvent of the solution was removed by applying vacuum. PCl3 (15 ml) was added to the resulting viscous oil and stirred for 24 h. Then the mixture was kept at 70° C. and 1 mm Hg for 2 h to remove excess PCl3 and byproduct. The product, di[p-(3-phenylpropyl)phenyl]chlorophosphine, was obtained as a pale yellow viscous oil with 90% yield. The product was characterized by 31P NMR. 83.6 The addition to reflux for 2 h The precipitate was filtered the solvent of the solution was removed PCl3 (15 ml) was added to the resulting viscous oil stirred for 24 h was kept at 70° C. 1 mm Hg for 2 h to remove excess PCl3 and byproduct

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

実験手順: p-(3-phenylpropyl)phenyllithium (8.1 g, 40 mmol) in 150 ml solvent (Et2O/THF 1/1) was added dropwise to CH3OPCl2 (2.66 g, 20 mmol) in 70 ml solvent (Et2O/THF 1/1) at -70° C. The addition was completed in 2 h. The reaction mixture was stirred overnight at room temperature and then brought to reflux for 2 h. The precipitate was filtered and the solvent of the solution was removed by applying vacuum. PCl3 (15 ml) was added to the resulting viscous oil and stirred for 24 h. Then the mixture was kept at 70° C. and 1 mm Hg for 2 h to remove excess PCl3 and byproduct. The product, di[p-(3-phenylpropyl)phenyl]chlorophosphine, was obtained as a pale yellow viscous oil with 90% yield. The product was characterized by 31P NMR. 83.6. The addition to reflux for 2 h The precipitate was filtered the solvent of the solution was removed PCl3 (15 ml) was added to the resulting viscous oil stirred for 24 h was kept at 70° C. 1 mm Hg for 2 h to remove excess PCl3 and byproduct