氯(二甲基)磷烷

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of chlorodimethylphosphine (250 mg, 2.60 mmol) in THF (0.7 mL) was added dropwise to a stirred suspension of sodium ethoxide (194 mg, 2.85 mmol) in THF (0.8 mL) at 0° C. The resulting mixture was stirred at room temperature for 30 min. then treated with 1-(bromomethyl)-3-nitrobenzene (560 mg, 2.59 mmol). The mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h., concentrated in vacuo and the residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane to afford 153 mg of dimethyl(3-nitrobenzyl)phosphane oxide (yield: 28%). 1H-NMR (CDCl3, 400 MHz): δ=1.53 (d, J=12.4 Hz, 6 H), 3.27 (d, J=14.0 Hz, 2 H), 7.55 (t, J=7.6 Hz, 1 H), 7.71 (d, J=7.6 Hz, 1 H), 8.11 (d, J=2.0 Hz, 1 H), 8.16 (dd, J=0.8, 7.2 Hz, 1 H). MS (ES+): m/z 214.00 (MH+). HPLC: tR=2.16 min (ZQ3, polar—5 min). The mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h. concentrated in vacuo the residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane

反应条件: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of chlorodimethylphosphine, ClPMe2, (1.0 g, 10.39 mmol) in 20 ml of pentane was added at −70° C. over 10 min through a cannula to a suspension of fluorenyllithium, (C13H9)Li, (1.788 g, 10.39 mmol) in 30 ml of dry pentane. After brief stirring at −70° C., the cooling bath was removed and the mixture was stirred for 4 hours at room temperature under an Ar atmosphere (with occasional heating by means of a hairdryer). 20 ml of toluene were added to the suspension to assist the dissolution of the product. The pale yellow suspension was filtered and volatile components were removed from the filtrate under vacuum to leave 2.34 g (99.6%) of 9-dimethylphosphinofluorene in the form of a pale yellow oil, which is pure according to 1H and 31P NMR. The product, 9-dimethylphosphinofluorene, (2.34 g, 10.34 mmol) was diluted in 25 ml of pentane and cooled to −70° C. BuLi (4.20 ml of a 2.5 molar solution, 10.5 mmol) was added to the cooled solution and the mixture was stirred briefly at −70° C. and then at room temperature. The clear yellow solution slowly becomes turbid at room temperature and a yellow precipitate begins to form. After a reaction time of 5 hours at room temperature, the mixture was filtered through a cannula and the yellow solid was washed with dry pentane (3×5 ml) and dried under high vacuum to leave 1.91 g (80%) of a loose orange-yellow solid, which is the title compound, 9-dimethylphosphinofluorenyllithium, according to 1H and 31P NMR spectroscopy. the cooling bath was removed the mixture was stirred for 4 hours at room temperature under an Ar atmosphere ( with occasional heating by means of a hairdryer) 20 ml of toluene were added to the suspension the dissolution of the product The pale yellow suspension was filtered volatile components were removed from the filtrate under vacuum

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 150 ml of ether were introduced into a round-bottomed flask which contained 5.5 g (0.047 mol) of indene; the mixture was cooled to −20° C. 20.8 ml of a 2.3 molar solution of butyl-lithium in hexane (0.048 mol) were added to this solution in the course of 5 minutes, a yellow solution being formed. After removal of the cooling bath, the solution was warmed to room temperature and subsequently stirred for 1 hour. After the reaction mixture had been cooled to −30° C., 4.6 g of chlorodimethylphosphine (0.048 mol) in 30 ml of ether were added in the course of 20 minutes, a precipitate forming. After stirring at −20° C. for 2 hours, 20.8 ml of a 2.3 molar solution of butyl-lithium in hexane (0.048 mol) were added drop-wise. When the addition was complete, the cooling bath was removed and the solution was warmed slowly to room temperature and subsequently stirred for 1.5 hours. After the suspension had been cooled to 0° C., 15.6 g of chlorotributyltin (0.048 mol) were added dropwise. The suspension formed was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo and the crude product was dissolved again in hexane, the solution was filtered and the filtrate was dried in vacuo, 17.4 g of the compound 3 (yield: 78%) remaining as a heavy yellow oil. 1H NMR (400 MHz, CD2Cl2) δ 7.67 (d, J=7.5 Hz, 1 H), 7.47 (d, J=7.4 Hz, 1 H), 7.18 (m, 2 H), 6.83 (m, 1 H), 4.28 (s with Sn satellites, 1 H), 1.43-0.78 (m, 33 H). 31P NMR (161.9 MHz, CD2Cl2): δ-61.6 ppm. a yellow solution being formed After removal of the cooling bath the solution was warmed to room temperature After the reaction mixture had been cooled to −30° C. a precipitate forming After stirring at −20° C. for 2 hours When the addition the cooling bath was removed the solution was warmed slowly to room temperature subsequently stirred for 1.5 hours After the suspension had been cooled to 0° C. The suspension formed was warmed to room temperature stirred for 1.5 hours The ether was removed in vacuo the crude product was dissolved again in hexane the solution was filtered

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of chlorodimethylphosphine (250 mg, 2.60 mmol) in THF (0.7 mL) was added dropwise to a stirred suspension of sodium ethoxide (194 mg, 2.85 mmol) in THF (0.8 mL) at 0° C. The resulting mixture was stirred at room temperature for 30 min. then treated with 1-(bromomethyl)-3-nitrobenzene (560 mg, 2.59 mmol). The mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h., concentrated in vacuo and the residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane to afford 153 mg of dimethyl(3-nitrobenzyl)phosphane oxide (yield: 28%). 1H-NMR (CDCl3, 400 MHz): δ=1.53 (d, J=12.4 Hz, 6 H), 3.27 (d, J=14.0 Hz, 2 H), 7.55 (t, J=7.6 Hz, 1 H), 7.71 (d, J=7.6 Hz, 1 H), 8.11 (d, J=2.0 Hz, 1 H), 8.16 (dd, J=0.8, 7.2 Hz, 1 H). MS (ES+): m/z 214.00 (MH+). HPLC: tR=2.16 min (ZQ3, polar—5 min). The mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h. concentrated in vacuo the residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 100 ml of ether were placed in a round-bottomed flask containing 6.76 a (0.052 moles) of 2-methylindene (compound 1); the solution was cooled to −20° C. 21 ml of a 2.5 molar solution of butyllithium in hexane (0.052 moles) were added over 5 min to form a yellow solution. After removal of the cooling bath, the solution was heated to room temperature and subsequently stirred for 1 hour. After cooling of the reaction mixture to −20° C., 5.0 g (0.052 moles) of chlorodimethylphosphine were added over 5 min to form a precipitate. The cooling bath was then removed and the reaction mixture was stirred for 1 h at room temperature. After cooling to −20° C., 21.0 ml of a 2.5 molar solution of butyllithium in hexane (0.052 moles) were added dropwise. When the addition was complete, the cooling bath was removed, after which the solution was heated slowly to room temperature and stirred for 1.5 h. After cooling of the suspension to 0° C., 16.9 g (0.052 moles) of chlorotributyltin were added dropwise. The suspension formed was heated to room temperature and stirred for 1.5 h. After removal of the ether under vacuum, the crude product was dissolved in hexane again, the solution was filtered and the filtrate was concentrated to dryness under vacuum to leave 24.3 g (yield: 98%) of compound 19 in the form of a heavy yellow oil. 31P NMR (161.9 MHz, CDCl2): δ=−68.5 (s). to form a yellow solution After removal of the cooling bath the solution was heated to room temperature After cooling of the reaction mixture to −20° C. to form a precipitate The cooling bath was then removed the reaction mixture was stirred for 1 h at room temperature After cooling to −20° C. When the addition the cooling bath was removed after which the solution was heated slowly to room temperature stirred for 1.5 h After cooling of the suspension to 0° C. The suspension formed was heated to room temperature stirred for 1.5 h After removal of the ether under vacuum the crude product was dissolved in hexane again the solution was filtered the filtrate was concentrated to dryness under vacuum

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 100 ml of ether were placed in a round-bottomed flask containing 6.76 a (0.052 moles) of 2-methylindene (compound 1); the solution was cooled to −20° C. 21 ml of a 2.5 molar solution of butyllithium in hexane (0.052 moles) were added over 5 min to form a yellow solution. After removal of the cooling bath, the solution was heated to room temperature and subsequently stirred for 1 hour. After cooling of the reaction mixture to −20° C., 5.0 g (0.052 moles) of chlorodimethylphosphine were added over 5 min to form a precipitate. The cooling bath was then removed and the reaction mixture was stirred for 1 h at room temperature. After cooling to −20° C., 21.0 ml of a 2.5 molar solution of butyllithium in hexane (0.052 moles) were added dropwise. When the addition was complete, the cooling bath was removed, after which the solution was heated slowly to room temperature and stirred for 1.5 h. After cooling of the suspension to 0° C., 16.9 g (0.052 moles) of chlorotributyltin were added dropwise. The suspension formed was heated to room temperature and stirred for 1.5 h. After removal of the ether under vacuum, the crude product was dissolved in hexane again, the solution was filtered and the filtrate was concentrated to dryness under vacuum to leave 24.3 g (yield: 98%) of compound 19 in the form of a heavy yellow oil. 31P NMR (161.9 MHz, CDCl2): δ=−68.5 (s). to form a yellow solution After removal of the cooling bath the solution was heated to room temperature After cooling of the reaction mixture to −20° C. to form a precipitate The cooling bath was then removed the reaction mixture was stirred for 1 h at room temperature After cooling to −20° C. When the addition the cooling bath was removed after which the solution was heated slowly to room temperature stirred for 1.5 h After cooling of the suspension to 0° C. The suspension formed was heated to room temperature stirred for 1.5 h After removal of the ether under vacuum the crude product was dissolved in hexane again the solution was filtered the filtrate was concentrated to dryness under vacuum

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 150 ml of ether were placed in a round-bottomed flask containing 5.5 g (0. 047 moles) of indene; the solution was cooled to −20° C. 20.8 ml of a 2.3 molar solution of butyllithium in hexane (0.048 moles) were added over 5 min to form a yellow solution. After removal of the cooling bath, the solution was heated to room temperature and subsequently stirred for 1 h. After cooling of the reaction mixture to −30° C., 4.6 g of chlorodimethylphosphine (0.048 moles) in 30 ml of ether were added over 20 min to form a precipitate. After stirring for 2 hours at −20° C., 20.8 ml of a 2.3 molar solution of butyllithium in hexane (0.048 moles) were added dropwise. When the addition was complete, the cooling bath was removed and the solution was heated slowly to room temperature and stirred for 1.5 h. After cooling of the suspension to 0° C., 15.6 g of chlorotributyltin (0.048 moles) were added dropwise. The suspension formed was heated to room temperature and stirred for 1.5 h. The ether was removed under vacuum, the crude product was dissolved in hexane again, the solution was filtered and the filtrate was concentrated to dryness under vacuum to leave 17.4 g of compound 10 (yield: 78%) in the form of a heavy yellow oil. 1H NMR (400 MHz, CD2Cl2): δ=7.67 (d, J=7.5 Hz, 1H); 7.47 (d, J=7.4 Hz, 1H); 7.18 (m, 2H); 6.83 (m, 1H); 4.28 (s with Sn satellites, 1H); 1.43-0.78 (m, 33H); 3P NMR (161.9 MHz, CD2Cl2): δ=−61.6 ppm. to form a yellow solution After removal of the cooling bath the solution was heated to room temperature After cooling of the reaction mixture to −30° C. to form a precipitate After stirring for 2 hours at −20° C. When the addition the cooling bath was removed the solution was heated slowly to room temperature stirred for 1.5 h After cooling of the suspension to 0° C. The suspension formed was heated to room temperature stirred for 1.5 h The ether was removed under vacuum the crude product was dissolved in hexane again the solution was filtered the filtrate was concentrated to dryness under vacuum

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 150 ml of ether were placed in a round-bottomed flask containing 5.5 g (0. 047 moles) of indene; the solution was cooled to −20° C. 20.8 ml of a 2.3 molar solution of butyllithium in hexane (0.048 moles) were added over 5 min to form a yellow solution. After removal of the cooling bath, the solution was heated to room temperature and subsequently stirred for 1 h. After cooling of the reaction mixture to −30° C., 4.6 g of chlorodimethylphosphine (0.048 moles) in 30 ml of ether were added over 20 min to form a precipitate. After stirring for 2 hours at −20° C., 20.8 ml of a 2.3 molar solution of butyllithium in hexane (0.048 moles) were added dropwise. When the addition was complete, the cooling bath was removed and the solution was heated slowly to room temperature and stirred for 1.5 h. After cooling of the suspension to 0° C., 15.6 g of chlorotributyltin (0.048 moles) were added dropwise. The suspension formed was heated to room temperature and stirred for 1.5 h. The ether was removed under vacuum, the crude product was dissolved in hexane again, the solution was filtered and the filtrate was concentrated to dryness under vacuum to leave 17.4 g of compound 10 (yield: 78%) in the form of a heavy yellow oil. 1H NMR (400 MHz, CD2Cl2): δ=7.67 (d, J=7.5 Hz, 1H); 7.47 (d, J=7.4 Hz, 1H); 7.18 (m, 2H); 6.83 (m, 1H); 4.28 (s with Sn satellites, 1H); 1.43-0.78 (m, 33H); 3P NMR (161.9 MHz, CD2Cl2): δ=−61.6 ppm. to form a yellow solution After removal of the cooling bath the solution was heated to room temperature After cooling of the reaction mixture to −30° C. to form a precipitate After stirring for 2 hours at −20° C. When the addition the cooling bath was removed the solution was heated slowly to room temperature stirred for 1.5 h After cooling of the suspension to 0° C. The suspension formed was heated to room temperature stirred for 1.5 h The ether was removed under vacuum the crude product was dissolved in hexane again the solution was filtered the filtrate was concentrated to dryness under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of chlorodimethylphosphine (250 mg, 2.60 mmol) in THF (0.7 mL) was added dropwise to a stirred suspension of sodium ethoxide (194 mg, 2.85 mmol) in THF (0.8 mL) at 0° C. The resulting mixture was stirred at room temperature for 30 min. then treated with 1-(bromomethyl)-3-nitrobenzene (560 mg, 2.59 mmol). The mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h., concentrated in vacuo and the residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane to afford 153 mg of dimethyl(3-nitrobenzyl)phosphane oxide (yield: 28%). 1H-NMR (CDCl3, 400 MHz): δ=1.53 (d, J=12.4 Hz, 6H), 3.27 (d, J=14.0 Hz, 2H), 7.55 (t, J=7.6 Hz, 1H), 7.71 (d, J=7.6 Hz, 1H), 8.11 (d, J=2.0 Hz, 1H), 8.16 (dd, J=0.8, 7.2 Hz, 1H). MS (ES+): m/z 214.00 (MH+). HPLC: tR=2.16 min (ZQ3, polar—5 min). The mixture was then stirred under nitrogen at 100° C. in a sealed tube for 2 h. concentrated in vacuo the residue purified by chromatography over silica gel eluting with 5% MeOH in dichloromethane

反应条件: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of chlorodimethylphosphine, ClPMe2, (1.0 g, 10.39 mmol) in 20 ml of pentane was added at −70° C. over 10 min through a cannula to a suspension of fluorenyllithium, (C13H9)Li, (1.788 g, 10.39 mmol) in 30 ml of dry pentane. After brief stirring at −70° C., the cooling bath was removed and the mixture was stirred for 4 hours at room temperature under an Ar atmosphere (with occasional heating by means of a hairdryer). 20 ml of toluene were added to the suspension to assist the dissolution of the product. The pale yellow suspension was filtered and volatile components were removed from the filtrate under vacuum to leave 2.34 g (99.6%) of 9-dimethylphosphinofluorene in the form of a pale yellow oil, which is pure according to 1H and 31P NMR. The product, 9-dimethylphosphinofluorene, (2.34 g, 10.34 mmol) was diluted in 25 ml of pentane and cooled to −70° C. BuLi (4.20 ml of a 2.5 molar solution, 10.5 mmol) was added to the cooled solution and the mixture was stirred briefly at −70° C. and then at room temperature. The clear yellow solution slowly becomes turbid at room temperature and a yellow precipitate begins to form. After a reaction time of 5 hours at room temperature, the mixture was filtered through a cannula and the yellow solid was washed with dry pentane (3×5 ml) and dried under high vacuum to leave 1.91 g (80%) of a loose orange-yellow solid, which is the title compound, 9-dimethylphosphinofluorenyllithium, according to 1H and 31P NMR spectroscopy. the cooling bath was removed the mixture was stirred for 4 hours at room temperature under an Ar atmosphere ( with occasional heating by means of a hairdryer) 20 ml of toluene were added to the suspension the dissolution of the product The pale yellow suspension was filtered volatile components were removed from the filtrate under vacuum