N-[chloro-[di(propan-2-yl)amino]phosphanyl]-N-propan-2-ylpropan-2-amine

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: Bis(diisopropylamino)chlorophosphine was synthesized by reacting phosphorous trichloride and diisopropylamine in toluene. Fifty ml of the resulting bis(diisopropylamino)phosphine was placed in a 250 ml flask and 3.01 ml of ethanol added slowly over a two minute period and the reaction allowed to proceed for several days. After filtering the mixture and removing the solvent, the structure of the bis(diisopropylamino)ethylphosphite ester reagent was analyzed by 31P and 1H NMR (31P NMR in CD3CN 125.9 ppm). to proceed for several days After filtering the mixture removing the solvent

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

実験手順: Phthalyl alcohol (1.15 g, 8.31 mmol) was dissolved in 5 ml of THF, and bisdiisopropylaminochlorophosphine (2.21 g, 8.31 mmol) which was dissolved in 5 ml of THF was added dropwise to the solution at -15° C. under a nitrogen atmosphere. Afterward, the temperature of the solution was adjusted to room temperature, and after the disappearance of phthalyl alcohol had been confirmed, hydrochloride of diisopropylamine was washed with ether. The wash liquor was concentrated and then distilled in order to obtain the desired product having a melting point of from 150° to 155° C. (0.7 mmHg). was added dropwise to the solution at -15° C. under a nitrogen atmosphere was adjusted to room temperature hydrochloride of diisopropylamine was washed with ether The wash liquor was concentrated distilled in order

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

実験手順: Phthalyl alcohol (1.15 g, 8.31 mmol) was dissolved in 5 ml of THF, and bisdiisopropylaminochlorophosphine (2.21 g, 8.31 mmol) which was dissolved in 5 ml of THF was added dropwise to the solution at -15° C. under a nitrogen atmosphere. Afterward, the temperature of the solution was adjusted to room temperature, and after the disappearance of phthalyl alcohol had been confirmed, hydrochloride of diisopropylamine was washed with ether. The wash liquor was concentrated and then distilled in order to obtain the desired product having a melting point of from 150° to 155° C. (0.7 mmHg). was added dropwise to the solution at -15° C. under a nitrogen atmosphere was adjusted to room temperature hydrochloride of diisopropylamine was washed with ether The wash liquor was concentrated distilled in order

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Bis(diisopropylamino)chlorophosphine (19, 250.1 g, 937 mmol) was dissolved in anhydrous ethyl ether (3.6 L) and triethylamine (190 g, 1.87 mol) was introduced. The turbid mixture was cooled at 0° C. and a solution of 2-propanol (225 g, 287 mL) in ether (200 mL) was added via a funnel. The resulting cloudy mixture was stirred at room temperature for 5.5 hours. The reaction was complete by checking with 31P NMR (δ=116.10 ppm, S). White solid (triethylamine HCl salt) was removed by filtration. The filtrate was concentrated to furnish a pale brown liquid (272 g, quantitative) and used for next step without further purification. Note that the P(III)-reagent can be purified by vacuum distillation (bp 84-86° C., 5 mm Hg) if desired to furnish a colorless clear oil. 1H NMR (CDCl3): δ 3.91 (m, 1H), 3.51 (m, 4 H), 1.19 (d, 6 H, J=6 Hz), 1.16 (24 H, m). 31P NMR (CDCl3): δ 116.1. White solid (triethylamine HCl salt) was removed by filtration The filtrate was concentrated to furnish a pale brown liquid (272 g, quantitative) used for next step without further purification can be purified by vacuum distillation (bp 84-86° C., 5 mm Hg) to furnish a colorless clear oil

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

実験手順: Bis(diisopropylamino)chlorophosphine was synthesized by reacting phosphorous trichloride and diisopropylamine in toluene. Fifty ml of the resulting bis(diisopropylamino)phosphine was placed in a 250 ml flask and 3.01 ml of ethanol added slowly over a two minute period and the reaction allowed to proceed for several days. After filtering the mixture and removing the solvent, the structure of the bis(diisopropylamino)ethylphosphite ester reagent was analyzed by 31P and 1H NMR (31P NMR in CD3CN 125.9 ppm). to proceed for several days After filtering the mixture removing the solvent

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

実験手順: Bis(diisopropylamino)chlorophosphine was synthesized by reacting phosphorous trichloride and diisopropylamine in toluene. Fifty ml of the resulting bis(diisopropylamino)phosphine was placed in a 250 ml flask and 3.01 ml of ethanol added slowly over a two minute period and the reaction allowed to proceed for several days. After filtering the mixture and removing the solvent, the structure of the bis(diisopropylamino)ethylphosphite ester reagent was analyzed by 31P and 1H NMR (31P NMR in CD3CN 125.9 ppm). to proceed for several days After filtering the mixture removing the solvent

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

実験手順: Phthalyl alcohol (1.15 g, 8.31 mmol) was dissolved in 5 ml of THF, and bisdiisopropylaminochlorophosphine (2.21 g, 8.31 mmol) which was dissolved in 5 ml of THF was added dropwise to the solution at -15° C. under a nitrogen atmosphere. Afterward, the temperature of the solution was adjusted to room temperature, and after the disappearance of phthalyl alcohol had been confirmed, hydrochloride of diisopropylamine was washed with ether. The wash liquor was concentrated and then distilled in order to obtain the desired product having a melting point of from 150° to 155° C. (0.7 mmHg). was added dropwise to the solution at -15° C. under a nitrogen atmosphere was adjusted to room temperature hydrochloride of diisopropylamine was washed with ether The wash liquor was concentrated distilled in order

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

実験手順: Bis-(N,N-Diisopropylamino) chlorophosphine, 10 grams (37 mmols), was dissolved in 500 ml of anhydrous acetonitrile. Phosphorus trichloride, 5.16 grams (37 mmols), was added to the solution and the reaction was allowed to stir over-night at room temperature. The reaction was assayed for completion by 31P NMR of an aliquot of the reaction using an external lock. Complete conversion of the starting material at δ 134 ppm to the product at δ 165 ppm was observed. The solvent was evaporated from the reaction mixture on a rotary evaporator and the resulting oil distilled under vacuum yielding 5.7 grams of product (81% yield). The solvent was evaporated from the reaction mixture on a rotary evaporator the resulting oil distilled under vacuum

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

実験手順: A 5-liter, 3-neck, round-bottom flask was equipped with a Fredrich's condenser, a ground glass stirrer bearing, a silicon rubber septum, and placed under dry argon. Two liters (1,600 grams, 15.9 mmols, 7.0 eq) of anhydrous diisopropyl amine was added to the flask. The diisopropyl amine was diluted by the addition of two liters of anhydrous acetonitrile. The solution was mixed with a mechanical stirrer attached to a glass stir rod and Teflon blade. An ice/water bath was placed under the 5-liter flask, and the amine solution allowed to cool for 30 min. Phosphorus trichloride (313 grams, 2.3 mmols, 1.0 eq) was dissolved in 1 liter of anhydrous acetonitrile in a separate dry 1-liter flask. The mechanical stirrer was set to vigorous stirring and the phosphorus trichloride solution added slowly to the stirring flask by cannula. Once the addition was complete, the ice/water bath was removed, and the reaction was allowed to warm to room temperature. The reaction was stirred overnight and the extent of the reaction determined by 31P NMR of an aliquot of the reaction mixture using an external lock. Complete conversion of the starting material, phosphorus trichloride (δ 201 ppm), into the product at δ 134 ppm, demonstrated completion of the desired reaction. The reaction mixture was filtered to remove the bulk of the diisopropylamine hydrochloride, which had precipitated. The precipitate was washed with anhydrous ether and the filtrates evaporated into a 2-liter round-bottom flask. The resulting evaporated product was a semi-crystalline solid, which was suspended in 1 liter of anhydrous hexanes. The flask was heated on a mantel, to allow the hexanes to boil. The hot liquid was filtered through a Schlenk filter-funnel to remove residual amine hydrochloride. This resulting clear yellow liquid was evaporated to one half the original volume and placed in a freezer to allow the product to recrystallize. The recrystallized product was isolated by filtration and dried in a vacuum desiccator, yielding 447 grams (74% yield). A 5-liter, 3-neck, round-bottom flask was equipped with a Fredrich's condenser, a ground glass stirrer bearing The solution was mixed with a mechanical stirrer An ice/water bath was placed under the 5-liter flask to cool for 30 min dry 1-liter flask the phosphorus trichloride solution added slowly to the stirring flask by cannula Once the addition the ice/water bath was removed The reaction was stirred overnight reaction The reaction mixture was filtered to remove the bulk of the diisopropylamine hydrochloride, which had precipitated The precipitate was washed with anhydrous ether the filtrates evaporated into a 2-liter round-bottom flask The resulting evaporated product The flask was heated on a mantel The hot liquid was filtered through a Schlenk filter-funnel to remove residual amine hydrochloride This resulting clear yellow liquid was evaporated to one half the original volume to recrystallize The recrystallized product was isolated by filtration dried in a vacuum desiccator yielding 447 grams (74% yield)