diethylphosphane

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

実験手順: A mixture of n-PrP(CH=CH2)2 (1.29 g, 10.0 mmol), Et2PH (2.25 g, 25.0 mmol) and 2,2'-azobis(isobutyronitrile) (AIBN, 30 mg) in a closed flask under inert atmosphere was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours. The resulting colorless liquid was stripped of volatiles under vacuum and vacuum distilled to give 3.1 g (97% yield) of product collected at 132°-135° C./0.35 mmHg. 31P-NMR (toluene): δ-18.5 (2P); δ-22.8 (1P). was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours distilled

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

実験手順: To a stirred solution of diethylphosphine (6.72 g, 74,6 mmol) in THF (150 ml) at −35° C., was added 47 ml of n-BuLi (1.6 M). Next, bis(2-chloroethyl)trimethylsilylamine (8.18 g, 38.4 mmol) in 40 ml tetrahydrofuran was then added dropwise to the LiP(Et)2 in tetrahydrofuran at −50° C. The mixture was allowed to warm to room temperature and stirred for 30 minutes. It was then heated to 60° C. and stirred overnight after which 100 ml of water was added to hydrolyse the silyl groups and the reaction mixture heated to 60° C. for 1 hour to ensure complete removal of the silyl groups. The reaction mixture was dried by passing it through a small bed of MgSO4, which was subsequently washed through with 60 ml diethyl ether. The solvent was removed to give 6.96 g bis(2-diethylphosphino-ethyl)-amine (Yield: 73%). 1H-NMR (C6D6) δ 1.12 (12H, d of t, CH2CH3, J=7.2 and 14.1 Hz), 1.38 (8H, q, CH2CH3, J=7.2), 1.60 (4H, t, (CH2)P, J=7.2) and 2.84 (4H, q, (CH2)N, J=7.8). 31P-NMR (C6D6) δ −26.02. It was then heated to 60° C. was added the reaction mixture heated to 60° C. for 1 hour removal of the silyl groups The reaction mixture was dried was subsequently washed through with 60 ml diethyl ether The solvent was removed

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

実験手順: To a stirred solution of diethylphosphine (6.72 g, 74,6 mmol) in THF (150 ml) at −35° C., was added 47 ml of n-BuLi (1.6 M). Next, bis(2-chloroethyl)trimethylsilylamine (8.18 g, 38.4 mmol) in 40 ml tetrahydrofuran was then added dropwise to the LiP(Et)2 in tetrahydrofuran at −50° C. The mixture was allowed to warm to room temperature and stirred for 30 minutes. It was then heated to 60° C. and stirred overnight after which 100 ml of water was added to hydrolyse the silyl groups and the reaction mixture heated to 60° C. for 1 hour to ensure complete removal of the silyl groups. The reaction mixture was dried by passing it through a small bed of MgSO4, which was subsequently washed through with 60 ml diethyl ether. The solvent was removed to give 6.96 g bis(2-diethylphosphino-ethyl)-amine (Yield: 73%). 1H-NMR (C6D6) δ 1.12 (12H, d of t, CH2CH3, J=7.2 and 14.1 Hz), 1.38 (8H, q, CH2CH3, J=7.2), 1.60 (4H, t, (CH2)P, J=7.2) and 2.84 (4H, q, (CH2)N, J=7.8). 31P-NMR (C6D6) δ −26.02. It was then heated to 60° C. was added the reaction mixture heated to 60° C. for 1 hour removal of the silyl groups The reaction mixture was dried was subsequently washed through with 60 ml diethyl ether The solvent was removed

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

実験手順: A mixture of n-PrP(CH=CH2)2 (1.29 g, 10.0 mmol), Et2PH (2.25 g, 25.0 mmol) and 2,2'-azobis(isobutyronitrile) (AIBN, 30 mg) in a closed flask under inert atmosphere was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours. The resulting colorless liquid was stripped of volatiles under vacuum and vacuum distilled to give 3.1 g (97% yield) of product collected at 132°-135° C./0.35 mm Hg. 31P-NMR (toluene): δ--18.5 (2P); δ--22.8 (1P). was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours distilled

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

実験手順: A mixture of n-PrP(CH=CH2)2 (1.29 g, 10.0 mmol), Et2PH (2.25 g, 25.0 mmol) and 2,2'-azobis(isobutyronitrile) (AIBN, 30 mg) in a closed flask under inert atmosphere was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours. The resulting colorless liquid was stripped of volatiles under vacuum and vacuum distilled to give 3.1 g (97% yield) of product collected at 132-135° C./0.35 mm Hg. 31P-NMR (toluene): δ--18.5 (2P); δ--22.8 (1P). was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours distilled

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

実験手順: This compound was synthesized as above by using Et2PH instead of Ph2PH. Et2PH (2.00 mL, 17.4 mmol, d=0.7862) and N3SiMe3 (5.00 mL, 35.8 mmol, d=0.868, 95%) were refluxed overnight in a round bottom flask with a reflux condenser under a positive pressure of nitrogen. After 12 hours the product was distilled through a short path distillation apparatus (0.01 mm, 56-60° C.) to yield a clear liquid (3.30 g, 72%). 1H NMR (C6D6): δ 1.12 (overlapping dq, CH2, 4H), 0.84 (overlapping dt, CH3, JHP=17.3 Hz, JHH=7.4 Hz, 6H), 0.73 (br s, NH, 1H), 0.29 (s, SiCH3, 18H). 13C{1H} NMR (C6D6): δ 26.6 (d, PCH2CH3, JCP=78.2 Hz), 6.5 (d, PCH2CH3, JCP=3.7 Hz), 3.3 (exchange broadened s, SiMe3); 31P{1H} NMR (C6D6): δ 20.1. Analysis calculated for C10H29N2PSi2: C, 45.41; H, 6.06; N, 4.81. Found: C, 68.73; H, 6.13; N, 4.73. This compound was synthesized as above After 12 hours the product was distilled through a short path distillation apparatus (0.01 mm, 56-60° C.)

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

実験手順: A mixture of n-PrP(CH=CH2)2 (1.29 g, 10.0 mmol), Et2PH (2.25 g, 25.0 mmol) and 2,2'-azobis(isobutyronitrile) (AIBN, 30 mg) in a closed flask under inert atmosphere was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours. The resulting colorless liquid was stripped of volatiles under vacuum and vacuum distilled to give 3.1 g (97% yield) of product collected at 132°-135° C./0.35 mmHg. 31P-NMR (toluene): δ-18.5 (2P); δ-22.8 (1P). was irradiated by a GE Sunlamp (275 W) one foot away for 24 hours distilled

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

実験手順: To a stirred solution of diethylphosphine (6.72 g, 74,6 mmol) in THF (150 ml) at −35° C., was added 47 ml of n-BuLi (1.6 M). Next, bis(2-chloroethyl)trimethylsilylamine (8.18 g, 38.4 mmol) in 40 ml tetrahydrofuran was then added dropwise to the LiP(Et)2 in tetrahydrofuran at −50° C. The mixture was allowed to warm to room temperature and stirred for 30 minutes. It was then heated to 60° C. and stirred overnight after which 100 ml of water was added to hydrolyse the silyl groups and the reaction mixture heated to 60° C. for 1 hour to ensure complete removal of the silyl groups. The reaction mixture was dried by passing it through a small bed of MgSO4, which was subsequently washed through with 60 ml diethyl ether. The solvent was removed to give 6.96 g bis(2-diethylphosphino-ethyl)-amine (Yield: 73%). 1H-NMR (C6D6) δ 1.12 (12H, d of t, CH2CH3, J=7.2 and 14.1 Hz), 1.38 (8H, q, CH2CH3, J=7.2), 1.60 (4H, t, (CH2)P, J=7.2) and 2.84 (4H, q, (CH2)N, J=7.8). 31P-NMR (C6D6) δ −26.02. It was then heated to 60° C. was added the reaction mixture heated to 60° C. for 1 hour removal of the silyl groups The reaction mixture was dried was subsequently washed through with 60 ml diethyl ether The solvent was removed