2-dichlorophosphorylpropane

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:

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 20 L four-necked round bottom flask fitted with an overhead stirrer and dropping funnel, flame dried and cooled in a stream of nitrogen, was charged with isopropyl phosphonic dichloride (350.0 g, 2173 mmol) in THF (5000 mL). The mixture was cool to −78° C. and vinyl magnesium bromide (5217 mL, 5217 mmol, 1M in THF) was added dropwise over 4 h. The reaction mixture was stirred at −78° C. for additional 30 minutes. After completion, the reaction mixture was poured into cold saturated aqueous NH4Cl (3.5 L) and extracted with dichloromethane (4×1000 L). The organic layers were combined, washed with brine (2×15000 mL), dried over sodium sulfate and concentrated in vacuo to give diethenyl(propan-2-yl)phosphane oxide (250 g, 80%) as light-brown oil. A 20 L four-necked round bottom flask fitted with an overhead stirrer flame dried cooled in a stream of nitrogen extracted with dichloromethane (4×1000 L) washed with brine (2×15000 mL) dried over sodium sulfate concentrated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 20 L four-necked round bottom flask fitted with an overhead stirrer and dropping funnel, flame dried and cooled in a stream of nitrogen, was charged with isopropyl phosphonic dichloride (350.0 g, 2173 mmol) in THF (5000 mL). The mixture was cool to −78° C. and vinyl magnesium bromide (5217 mL, 5217 mmol, 1M in THF) was added dropwise over 4 h. The reaction mixture was stirred at −78° C. for additional 30 minutes. After completion, the reaction mixture was poured into cold saturated aqueous NH4Cl (3.5 L) and extracted with dichloromethane (4×1000 L). The organic layers were combined, washed with brine (2×15000 mL), dried over sodium sulfate and concentrated in vacuo to give diethenyl(propan-2-yl)phosphane oxide (250 g, 80%) as light-brown oil. A 20 L four-necked round bottom flask fitted with an overhead stirrer flame dried cooled in a stream of nitrogen extracted with dichloromethane (4×1000 L) washed with brine (2×15000 mL) dried over sodium sulfate concentrated in vacuo

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 20 L four-necked round bottom flask fitted with an overhead stirrer and dropping funnel, flame dried and cooled in a stream of nitrogen, was charged with isopropyl phosphonic dichloride (350.0 g, 2173 mmol) in THF (5000 mL). The mixture was cool to −78° C. and vinyl magnesium bromide (5217 mL, 5217 mmol, 1M in THF) was added dropwise over 4 h. The reaction mixture was stirred at −78° C. for additional 30 minutes. After completion, the reaction mixture was poured into cold saturated aqueous NH4Cl (3.5 L) and extracted with dichloromethane (4×1000 L). The organic layers were combined, washed with brine (2×15000 mL), dried over sodium sulfate and concentrated in vacuo to give diethenyl(propan-2-yl)phosphane oxide (250 g, 80%) as light-brown oil. A 20 L four-necked round bottom flask fitted with an overhead stirrer flame dried cooled in a stream of nitrogen extracted with dichloromethane (4×1000 L) washed with brine (2×15000 mL) dried over sodium sulfate concentrated in vacuo

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 20 L four-necked round bottom flask fitted with an overhead stirrer and dropping funnel, flame dried and cooled in a stream of nitrogen, was charged with isopropyl phosphonic dichloride (350.0 g, 2173 mmol) in THF (5000 mL). The mixture was cool to −78° C. and vinyl magnesium bromide (5217 mL, 5217 mmol, 1M in THF) was added dropwise over 4 h. The reaction mixture was stirred at −78° C. for additional 30 minutes. After completion, the reaction mixture was poured into cold saturated aqueous NH4Cl (3.5 L) and extracted with dichloromethane (4×1000 L). The organic layers were combined, washed with brine (2×15000 mL), dried over sodium sulfate and concentrated in vacuo to give diethenyl(propan-2-yl)phosphane oxide (250 g, 80%) as light-brown oil. A 20 L four-necked round bottom flask fitted with an overhead stirrer flame dried cooled in a stream of nitrogen extracted with dichloromethane (4×1000 L) washed with brine (2×15000 mL) dried over sodium sulfate concentrated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:26.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (8 g, 0.125 mol) in hexane was added to a solution of tetramethylethylenediamine (14.3 g, 0.123 mol) in 60 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-trimethylsilylbenzylamine (10.75 g, 0.06 mol) in 60 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. This suspension was stirred for 16.5 hours at 26° C. and then cooled to -72° C. using a solid carbon dioxide-acetone bath. A solution of isopropylphosphonic dichloride (10.3 g, 0.064 mol) in 60 ml. of anhydrous cyclohexane was rapidly added to the suspension causing the temperature of the reaction to increase to -10° C. The reaction mixture was allowed to cool to -72° C., after which time the solid carbon dioxide-acetone bath was removed and the reaction mixture was stirred for 1.5 hours at 26° C. The reaction mixture was cooled to 0° C. and then quenched with the rapid addition of 12 ml. of acetic acid. The reaction mixture was concentrated under vacuum and the resulting residue was partitioned between methylene chloride and water. The layers were separated and the methylene chloride layer was dried over magnesium sulfate and concentrated in vacuo to yield a red oil. The red oil was distilled at 180° C. and 0.2 mm to yield 1-isopropyl-2-trimethylsilyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide. While maintaining the temperature of the reaction at 0° C. to produce a suspension cooled to -72° C. the temperature of the reaction to increase to -10° C to cool to -72° C. after which time the solid carbon dioxide-acetone bath was removed the reaction mixture was stirred for 1.5 hours at 26° C The reaction mixture was cooled to 0° C. quenched with the rapid addition of 12 ml The reaction mixture was concentrated under vacuum the resulting residue was partitioned between methylene chloride and water The layers were separated the methylene chloride layer was dried over magnesium sulfate concentrated in vacuo to yield a red oil The red oil was distilled at 180° C.

反応条件: temp:0.00; pressure:0.00; stir: