chloro(diethoxy)phosphane

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:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Magnesium turnings (2.44 g, 0.10 mol) in 20 mL of dry diethyl ether under an atmosphere of nitrogen was added several iodine crystals. Phenylpropyl bromide (20.0 g, 0.10 mol) in 80 mL of diethyl ether was placed in a dropping funnel. Approximately 10 mL of the bromide solution was added to the magnesium turnings and stirring was initiated. After several minutes the iodine was consumed and additional phenylpropyl bromide was added while maintaining a temperature of 35° C. Once additional was complete (1.5 hours) the mixture was sealed and stored at 5° C. Diethylchlorophosphite (15.7 g, 0.1 mol) in 50 mL of dry diethyl ether was cooled to 5° C. under an atmosphere of nitrogen. Phenylpropylmagnesium bromide (100 mL, 0.1 mol, 1.0 M solution of in Et2O) was added dropwise over 2 hours while maintaining a temperature between 0-10° C. A thick white slurry formed and was stirred an additional 30 minutes. The mixture was filtered under a nitrogen atmosphere and the filtrate evaporated under reduced pressure to give a clear and colorless liquid. To the liquid was added 20 mL of water followed by 0.5 ml of concentrated hydrlochloric acid. An exothermic reaction was observed and stirring continued for 20 minutes followed by extraction with ethyl acetate. The organics were combined, washed with brine, dried (MgSO4) and evaporated. To the clear liquid was added sodium hydroxide (40 mL, 2.0 M NaOH), the resulting solution stirred for 1 hour and then washed with diethyl ether. The aqueous layer was acidified to pH 1.0 with concentrated hydrochloric acid and extracted twice with ethyl acetate. The organics were combined, dried (MgSO4) and evaporated to give 3-phenylpropylphosphinic acid (1,R=CH2CH2CH2Ph,R1=H)(9.8 g, 53%) as a clear and colorless oil. After several minutes the iodine was consumed additional phenylpropyl bromide was added (1.5 hours) was sealed stored at 5° C while maintaining a temperature between 0-10° C A thick white slurry formed was stirred an additional 30 minutes The mixture was filtered under a nitrogen atmosphere the filtrate evaporated under reduced pressure to give a clear and colorless liquid An exothermic reaction stirring followed by extraction with ethyl acetate washed with brine dried (MgSO4) evaporated To the clear liquid was added sodium hydroxide (40 mL, 2.0 M NaOH) the resulting solution stirred for 1 hour washed with diethyl ether extracted twice with ethyl acetate dried (MgSO4) evaporated

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Diethylchlorophosphite (15.6 g,0.1 mol) in 100 mL of dry diethyl ether was cooled to 5° C. under an atmosphere of nitrogen. Phenethylmagnesium chloride (100 mL, 0.1 mol, 1.0 M in THF) was added dropwise over 2 hours while maintaining a temperature between 0-10° C. A thick white slurry formed and stirred at room temperature overnight. The mixture was filtered under a nitrogen atmosphere and the filtrate evaporated under reduced pressure to give a clear and colorless liquid. The liquid was stirred as 15 mL of water was added followed by 0.5 mL of concentrated hydrlochloric acid. An exothermic reaction was observed and stirring continued for 15 minutes followed by extraction with ethyl acetate. The organics were combined, washed with brine, dried (MgSO4) and evaporated. The clear liquid was brought up in sodium hydroxide (40 mL, 2.0 M NaOH), stirred for 1 hour and washed once with diethyl ether. The aqueous layer was acidified to pH 1.0 with concentrated hydrochloric acid and extracted with ethyl acetate. The organics were combined, dried (MgSO4) and evaporated to give phenethylphosphinic acid (1,R=CH2CH2Ph, R1=H)(9.8 g, 58%) as a clear light yellow oil. A thick white slurry formed The mixture was filtered under a nitrogen atmosphere the filtrate evaporated under reduced pressure to give a clear and colorless liquid was added An exothermic reaction stirring continued for 15 minutes followed by extraction with ethyl acetate washed with brine dried (MgSO4) evaporated stirred for 1 hour washed once with diethyl ether extracted with ethyl acetate dried (MgSO4) evaporated

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

実験手順: Diethylchlorophosphite (25 g, 0.16 mol) in 100 mL of dry diethyl ether was cooled to 0° C. under an atmosphere of nitrogen. Benzylmagnesium chloride (80 mL, 0.16 mol, 2.0 M solution in Et2O) was added dropwise over two hours while maintaining a temperature below 10° C. A thick white slurry formed and stirring was continued at room temperature for 1 hour. The mixture was filtered under a nitrogen atmosphere and the filtrate evaporated under reduced pressure to give a clear and colorless liquid. The liquid was stirred as 15 mL of water was added followed by 0.5 ml concentrated hydrochloric acid. An exothermic reaction was observed and stirring was continued for an additional 30 minutes followed by extraction with ethyl acetate. The organics were combined, washed with brine, dried (MgSO4) and evaporated. The clear light golden liquid was added to sodium hydroxide (50 mL, 2.0 M NaOH), stirred for one hour and washed with diethyl ether. The aqueous layer was acidified to pH 1.0 with concentrated hydrochloric acid and extracted with ethyl acetate. The organics were combined, dried (MgSO4) and evaporated to give benzylphosphinic acid (1, R=CH2Ph, R1+H) (8 g, 32%) as a clear light golden oil. while maintaining a temperature below 10° C A thick white slurry formed The mixture was filtered under a nitrogen atmosphere the filtrate evaporated under reduced pressure to give a clear and colorless liquid was added An exothermic reaction stirring was continued for an additional 30 minutes followed by extraction with ethyl acetate washed with brine dried (MgSO4) evaporated The clear light golden liquid was added to sodium hydroxide (50 mL, 2.0 M NaOH) stirred for one hour washed with diethyl ether extracted with ethyl acetate dried (MgSO4) evaporated

反応条件: temp:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Magnesium turnings (2.44 g, 0.10 mol) in 20 mL of dry diethyl ether under an atmosphere of nitrogen was added several iodine crystals. Phenylpropyl bromide (20.0 g, 0.10 mol) in 80 mL of diethyl ether was placed in a dropping funnel. Approximately 10 mL of the bromide solution was added to the magnesium turnings and stirring was initiated. After several minutes the iodine was consumed and additional phenylpropyl bromide was added while maintaining a temperature of 35° C. Once additional was complete (1.5 hours) the mixture was sealed and stored at 5° C. Diethylchlorophosphite (15.7 g, 0.1 mol) in 50 mL of dry diethyl ether was cooled to 5° C. under an atmosphere of nitrogen. Phenylpropylmagnesium bromide (100 mL, 0.1 mol, 1.0 M solution of in Et2O) was added dropwise over 2 hours while maintaining a temperature between 0-10° C. A thick white slurry formed and was stirred an additional 30 minutes. The mixture was filtered under a nitrogen atmosphere and the filtrate evaporated under reduced pressure to give a clear and colorless liquid. To the liquid was added 20 mL of water followed by 0.5ml of concentrated hydrochloric acid. An exothermic reaction was observed and stirring continued for 20 minutes followed by extraction with ethyl acetate. The organics were combined, washed with brine, dried (MgSO4) and evaporated. To the clear liquid was added sodium hydroxide (40 mL, 2.0 M NaOH), the resulting solution stirred for 1 hour and then washed with diethyl ether. The aqueous layer was acidified to pH 1.0 with concentrated hydrochloric acid and extracted twice with ethyl acetate. The organics were combined, dried (MgSO4) and evaporated to give 3-phenylpropylphosphinic acid (1,R=CH2CH2CH2Ph,R1=H)(9.8 g, 53%) as a clear and colorless oil. After several minutes the iodine was consumed additional phenylpropyl bromide was added (1.5 hours) was sealed stored at 5° C while maintaining a temperature between 0-10° C A thick white slurry formed was stirred an additional 30 minutes The mixture was filtered under a nitrogen atmosphere the filtrate evaporated under reduced pressure to give a clear and colorless liquid An exothermic reaction stirring followed by extraction with ethyl acetate washed with brine dried (MgSO4) evaporated To the clear liquid was added sodium hydroxide (40 mL, 2.0 M NaOH) the resulting solution stirred for 1 hour washed with diethyl ether extracted twice with ethyl acetate dried (MgSO4) evaporated

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Diethylchlorophosphite (15.6 g,0.1 mol) in 100 mL of dry diethyl ether was cooled to 5° C. under an atmosphere of nitrogen. Phenethylmagnesium chloride (100 mL, 0.1 mol, 1.0 M in THF) was added dropwise over 2 hours while maintaining a temperature between 0-10° C. A thick white slurry formed and stirred at room temperature overnight. The mixture was filtered under a nitrogen atmosphere and the filtrate evaporated under reduced pressure to give a clear and colorless liquid. The liquid was stirred as 15 mL of water was added followed by 0.5 mL of concentrated hydrochloric acid. An exothermic reaction was observed and stirring continued for 15 minutes followed by extraction with ethyl acetate. The organics were combined, washed with brine, dried (MgSO4) and evaporated. The clear liquid was brought up in sodium hydroxide (40 mL, 2.0 M NaOH), stirred for 1 hour and washed once with diethyl ether. The aqueous layer was acidified to pH 1.0 with concentrated hydrochloric acid and extracted with ethyl acetate. The organics were combined, dried (MgSo4) and evaporated to give phenethylphosphinic acid (1,R=CH2CH2Ph, R1=H)(9.8 g, 58%) as a clear light yellow oil. A thick white slurry formed The mixture was filtered under a nitrogen atmosphere the filtrate evaporated under reduced pressure to give a clear and colorless liquid was added An exothermic reaction stirring continued for 15 minutes followed by extraction with ethyl acetate washed with brine dried (MgSO4) evaporated stirred for 1 hour washed once with diethyl ether extracted with ethyl acetate dried (MgSo4) evaporated

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

実験手順: Diethylchlorophosphite (25 g, 0.16 mol) in 100 mL of dry diethyl ether was cooled to 0° C. under an atmosphere of nitrogen. Benzylmagnesium chloride (80 mL, 0.16 mol, 2.0 M solution in Et2O) was added dropwise over two hours while maintaining a temperature below 10° C. A thick white slurry formed and stirring was continued at room temperature for 1 hour. The mixture was filtered under a nitrogen atmosphere and the filtrate evaporated under reduced pressure to give a clear and colorless liquid. The liquid was stirred as 15 mL of water was added followed by 0.5ml concentrated hydrochloric acid. An exothermic reaction was observed and stirring was continued for an additional 30 minutes followed by extraction with ethyl acetate. The organics were combined, washed with brine, dried (MgSo4) and evaporated. The clear light golden liquid was added to sodium hydroxide (50 mL, 2.0 M NaOH), stirred for one hour and washed with diethyl ether. The aqueous layer was acidified to pH 1.0 with concentrated hydrochloric acid and extracted with ethyl acetate. The organics were combined, dried (MgSO4) and evaporated to give benzylphosphinic acid (1, R=CH2Ph, R1+H) (8 g, 32%) as a clear light golden oil. while maintaining a temperature below 10° C A thick white slurry formed The mixture was filtered under a nitrogen atmosphere the filtrate evaporated under reduced pressure to give a clear and colorless liquid was added An exothermic reaction stirring was continued for an additional 30 minutes followed by extraction with ethyl acetate washed with brine dried (MgSo4) evaporated The clear light golden liquid was added to sodium hydroxide (50 mL, 2.0 M NaOH) stirred for one hour washed with diethyl ether extracted with ethyl acetate dried (MgSO4) evaporated

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (26.02 ml, 1.55M in hexane) was added dropwise over thirty minutes to a stirred solution of trimethylsilylacetylene (5.18 ml) in dry tetrahydrofuran (25 ml), whilst maintaining the temperature below -65° C. After twenty minutes, diethylchlorophosphite (4.71 ml) was added dropwise over twenty minutes, then stirring continued for a further ninety minutes at -65° C. The stirred mixture was allowed to warm to -20° C., quenched by dropwise addition of saturated ammonium chloride solution (10 ml), then allowed to reach room temperature, diluted with water (10 ml) and extracted with chloroform (4×25 ml). The extracts were dried over magnesium sulphate and evaporated under reduced pressure to give diethyl trimethylsilylethynylphosphonite as a brown oil (7.34 g, 83% pure by GC). whilst maintaining the temperature below -65° C After twenty minutes continued for a further ninety minutes at -65° C quenched by dropwise addition of saturated ammonium chloride solution (10 ml) to reach room temperature diluted with water (10 ml) extracted with chloroform (4×25 ml) The extracts were dried over magnesium sulphate evaporated under reduced pressure