双(二乙胺基)氯磷

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

实验步骤: To a solution of phosphorous trichloride (26 ml; 0.298 mol) in dry diethylether (500 ml) at −78° C., acetone/CO2 bath, under dry nitrogen gas atmosphere was added diethylamine (123.4 ml; 1.19 mol) dropwise via a pressure equalised dropping funnel over 2 hrs. A thick suspension formed, reaction allowed to warm to ambient temperature and stirred for an additional 2 hrs. After this time the suspension was filtered under dry nitrogen gas via an oven dried filter stick, washing with dry diethylether (3×100 ml). Filtrate was evaporated under high vacuum on the Schlenk line, using a cold-finger trap to condense solvent vapours, to give an oil. The oil was purified by distillation under reduced pressure to give the required product (b.p. 105° C. @ 10 mmHg; 49 g; 70% yield). 1H NMR (300 MHz, CDCl3), δ/ppm; 1.08 (6H, t J=7.0, CH3), 3.08 (4H, ap. br. d J=7.0, CH2); 31P NMR (121 MHz, CDCl3) δ/ppm; 159.9. over 2 hrs A thick suspension formed reaction After this time the suspension was filtered under dry nitrogen gas via an oven dried filter stick washing with dry diethylether (3×100 ml) Filtrate was evaporated under high vacuum on the Schlenk line to condense solvent vapours to give an oil The oil was purified by distillation under reduced pressure

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

实验步骤: To a solution of phosphorous trichloride (26 ml; 0.298 mol) in dry diethylether (500 ml) at −78° C., acetone/CO2 bath, under dry nitrogen gas atmosphere was added diethylamine (123.4 ml; 1.19 mol) dropwise via a pressure equalised dropping funnel over 2 hrs. A thick suspension formed, reaction allowed to warm to ambient temperature and stirred for an additional 2 hrs. After this time the suspension was filtered under dry nitrogen gas via an oven dried filter stick, washing with dry diethylether (3×100 ml). Filtrate was evaporated under high vacuum on the Schlenk line, using a cold-finger trap to condense solvent vapours, to give an oil. The oil was purified by distillation under reduced pressure to give the required product (b.p. 105° C. @ 10 mmHg; 49 g; 70% yield). 1H NMR (300 MHz, CDCl3), δ/ppm; 1.08 (6H, t J=7.0, CH3), 3.08 (4H, ap. br. d J=7.0, CH2); 31P NMR (121 MHz, CDCl3) δ/ppm; 159.9. over 2 hrs A thick suspension formed reaction After this time the suspension was filtered under dry nitrogen gas via an oven dried filter stick washing with dry diethylether (3×100 ml) Filtrate was evaporated under high vacuum on the Schlenk line to condense solvent vapours to give an oil The oil was purified by distillation under reduced pressure

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 50 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer, 0.36 g (14.8 mmol) of magnesium and 10 ml of anhydrous diethyl ether were charged at room temperature in a nitrogen gas atmosphere. After several drops of 1,2-dibromoethane were added so as to activate magnesium, 2.0 ml (14.2 mmol) of chloromethyltrimethylsilane were added dropwise carefully to avoid heat build-up. When the reaction solution was stirred for 1 hour while it was heated mildly with a drier, the solution darkened. Then, after the solution was cooled to −78° C., 3.0 g (14.2 mmol) of chlorobis(diethylamino)phosphine synthesized in (a) were added dropwise to the solution, and the resultant mixture was then returned to room temperature and refluxed for 1 hour. The resulting crystals were filtered off, washed with anhydrous diethyl ether, and purified by vacuum-distillation (0.2 kPa, 74.3-79.5° C.) to obtain 2.29 g of bis(diethylamino)(trimethylsilylmethyl)phosphine in the form of a colorless transparent liquid; the yield was 62%. In a 50 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer were added dropwise carefully to avoid heat was heated mildly with a drier were added dropwise to the solution was then returned to room temperature refluxed for 1 hour The resulting crystals were filtered off washed with anhydrous diethyl ether purified by vacuum-distillation (0.2 kPa, 74.3-79.5° C.)

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

实验步骤: In a 300 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer, 10.0 g (0.0728 mol) of phosphorus trichloride and 100 ml of anhydrous diethyl ether were charged at room temperature in a nitrogen gas atmosphere, and the mixture was cooled to 5° C. or less in an ice bath. While the resulting reaction mixture was stirred, 30.0 ml (0.291 mol) of diethylamine were slowly added dropwise to the reaction mixture over 3 hours. The resulting crystals were filtered off under pressure in a nitrogen gas atmosphere. After the crystals were washed with anhydrous diethyl ether three times, they were purified by vacuum-distillation (0.4 kPa, 77.8-78.2° C.), and 8.07 g of chlorobis(diethylamino)phosphine were obtained in the form of a transparent liquid; the yield was 53%. In a 300 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer the mixture was cooled to 5° C. or less in an ice bath While the resulting reaction mixture The resulting crystals were filtered off under pressure in a nitrogen gas atmosphere After the crystals were washed with anhydrous diethyl ether three times, they were purified by vacuum-distillation (0.4 kPa, 77.8-78.2° C.)

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

实验步骤: In a 300 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer, 10.0 g (0.0728 mol) of phosphorus trichloride and 100 ml of anhydrous diethyl ether were charged at room temperature in a nitrogen gas atmosphere, and the mixture was cooled to 5° C. or less in an ice bath. While the resulting reaction mixture was stirred, 30.0 ml (0.291 mol) of diethylamine were slowly added dropwise to the reaction mixture over 3 hours. The resulting crystals were filtered off under pressure in a nitrogen gas atmosphere. After the crystals were washed with anhydrous diethyl ether three times, they were purified by vacuum-distillation (0.4 kPa, 77.8-78.2° C.), and 8.07 g of chlorobis(diethylamino)phosphine were obtained in the form of a transparent liquid; the yield was 53%. In a 300 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer the mixture was cooled to 5° C. or less in an ice bath While the resulting reaction mixture The resulting crystals were filtered off under pressure in a nitrogen gas atmosphere After the crystals were washed with anhydrous diethyl ether three times, they were purified by vacuum-distillation (0.4 kPa, 77.8-78.2° C.)

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

实验步骤: At room temperature, 40.69 g (0.2186 mol) of ferrocene in 400 ml of abs. hexane is charged in a vessel. A mixture of 342 ml (0.547 mol) of 1.60 M n-butyllithium solution in hexane and 82.0 ml (63.6 g, 0.547 mol) of abs. N,N,N′,N′-tetramethylethylenediamine is added dropwise at room temperature within 6 h. The mixture is allowed to stir at room temperature for 18 h. The supernatant is filtered off through an immersion frit, and the orange filtration residue is suspended in 400 ml of abs. THF. At −78° C., a solution of 95.0 ml (94.6g, 0.481 mol) of bis(diethylamino)chlorophosphine in 200 ml of abs. THF is added dropwise within 4 h. The mixture is allowed to thaw to room temperature and stirred for another 15 h. The solution, which has now a red-brown color, is cooled down to −78° C., and 390 ml of 5.6 M HCl in diethyl ether is added dropwise within 5 h. After warming up to room temperature, the solvent is distilled off completely, and the residue is taken up in 2 l of diethyl ether, and the solution filtrated from insolubles through a P4 frit with Celite 545® as a filtering aid. The clear filtrate is again completely freed from solvent. The red-brown solid is finally recrystallized from 200 ml of toluene/pentane at −20° C.. After drying in an oil pump vacuum, 52.82 g of a coarse-crystalline solid (0.136 mol, 62%) is obtained. Analytical results: appropriate (see Example 2). At room temperature The supernatant is filtered off through an immersion frit At −78° C. thaw to room temperature stirred for another 15 h is cooled down to −78° C. After warming up to room temperature the solvent is distilled off completely the solution filtrated from insolubles through a P4 frit with Celite 545® as a filtering aid The red-brown solid is finally recrystallized from 200 ml of toluene/pentane at −20° C. After drying in an oil pump vacuum

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

实验步骤: To a solution of phosphorous trichloride (26 ml; 0.298 mol) in dry diethylether (500 ml) at −78° C., acetone/CO2 bath, under dry nitrogen gas atmosphere was added diethylamine (123.4 ml; 1.19 mol) dropwise via a pressure equalised dropping funnel over 2 hrs. A thick suspension formed, reaction allowed to warm to ambient temperature and stirred for an additional 2 hrs. After this time the suspension was filtered under dry nitrogen gas via an oven dried filter stick, washing with dry diethylether (3×100 ml). Filtrate was evaporated under high vacuum on the Schlenk line, using a cold-finger trap to condense solvent vapours, to give an oil. The oil was purified by distillation under reduced pressure to give the required product (b.p. 105° C. @ 10 mmHg; 49 g; 70% yield). 1H NMR (300 MHz, CDCl3), δ/ppm; 1.08 (6H, t J=7.0, CH3), 3.08 (4H, ap. br. d J=7.0, CH2); 31P NMR (121 MHz, CDCl3) δ/ppm; 159.9. over 2 hrs A thick suspension formed reaction After this time the suspension was filtered under dry nitrogen gas via an oven dried filter stick washing with dry diethylether (3×100 ml) Filtrate was evaporated under high vacuum on the Schlenk line to condense solvent vapours to give an oil The oil was purified by distillation under reduced pressure

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 50 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer, 0.36 g (14.8 mmol) of magnesium and 10 ml of anhydrous diethyl ether were charged at room temperature in a nitrogen gas atmosphere. After several drops of 1,2-dibromoethane were added so as to activate magnesium, 2.0 ml (14.2 mmol) of chloromethyltrimethylsilane were added dropwise carefully to avoid heat build-up. When the reaction solution was stirred for 1 hour while it was heated mildly with a drier, the solution darkened. Then, after the solution was cooled to −78° C., 3.0 g (14.2 mmol) of chlorobis(diethylamino)phosphine synthesized in (a) were added dropwise to the solution, and the resultant mixture was then returned to room temperature and refluxed for 1 hour. The resulting crystals were filtered off, washed with anhydrous diethyl ether, and purified by vacuum-distillation (0.2 kPa, 74.3-79.5° C.) to obtain 2.29 g of bis(diethylamino)(trimethylsilylmethyl)phosphine in the form of a colorless transparent liquid; the yield was 62%. In a 50 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer were added dropwise carefully to avoid heat was heated mildly with a drier were added dropwise to the solution was then returned to room temperature refluxed for 1 hour The resulting crystals were filtered off washed with anhydrous diethyl ether purified by vacuum-distillation (0.2 kPa, 74.3-79.5° C.)

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

实验步骤: In a 300 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer, 10.0 g (0.0728 mol) of phosphorus trichloride and 100 ml of anhydrous diethyl ether were charged at room temperature in a nitrogen gas atmosphere, and the mixture was cooled to 5° C. or less in an ice bath. While the resulting reaction mixture was stirred, 30.0 ml (0.291 mol) of diethylamine were slowly added dropwise to the reaction mixture over 3 hours. The resulting crystals were filtered off under pressure in a nitrogen gas atmosphere. After the crystals were washed with anhydrous diethyl ether three times, they were purified by vacuum-distillation (0.4 kPa, 77.8-78.2° C.), and 8.07 g of chlorobis(diethylamino)phosphine were obtained in the form of a transparent liquid; the yield was 53%. In a 300 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer the mixture was cooled to 5° C. or less in an ice bath While the resulting reaction mixture The resulting crystals were filtered off under pressure in a nitrogen gas atmosphere After the crystals were washed with anhydrous diethyl ether three times, they were purified by vacuum-distillation (0.4 kPa, 77.8-78.2° C.)