Di(1-adaMantyl)chlorophosphine

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

実験手順: An oven dried Schlenk tube was charged with magnesium turnings (240 mg, 9.89 mmol), 2-bromo-biphenyl (1.55 mL, 7.5 mmol). The tube was evacuated and backfilled with argon two times. To the above mixture THF (15 mL) was added through a rubber septum and the reaction mixture was heated to a mild reflux for 3 hours. The reaction mixture was then temporarily cooled to room temperature for the addition of cuprous chloride (930 mg, 9.45 mmol) followed by a solution of the di-1-adamantylchlorophosphine in 5 mL THF. Heating was resumed for an addtional 3 hours. The reaction mixture was cooled to room temperature, and ether (50 ml,) and pentane (50 mL) were added. The resulting suspension was stirred for 10 minutes, during which time a heavy dark-brown precipitate formed. The suspension was filtered and the solid was collected on a fritted funnel. The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 ml, 1:1). The mixture was vigorously shaken several times over 30 minutes. The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 ml,). The combined organic layers were washed with brine (2×50 mL), dried over anhydrous magnesium sulfate, decanted, and concentrated in vacuo. The product was crystallized from toluene/methanol to afford 450 mg (5.8%) product as a white solid. An oven dried Schlenk tube The tube was evacuated To the above mixture THF (15 mL) was added through a rubber septum the reaction mixture was heated to a mild reflux for 3 hours Heating formed The suspension was filtered the solid was collected on a fritted funnel The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 ml, 1:1) over 30 minutes The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 ml,) The combined organic layers were washed with brine (2×50 mL) dried over anhydrous magnesium sulfate decanted concentrated in vacuo The product was crystallized from toluene/methanol

反応条件: temp:-45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An oven-dried, round-bottom flask was charged with magnesium turnings (15.3 g, 0.63 mol) and 1-bromoadamantane (9.0 g, 0.041 mol). The flask was evacuated and backfilled with argon two times. To the reaction vessel 45 mL ether was added and the mixture was gently refluxed for 15 hours, without mechanical stirring. The resulting solution of Grignard reagent was taken up in a syringe, and added very slowly dropwise to a separate flame-dried, two-necked, round-bottom flask equipped with a reflux condenser which had been charged with PCl3 (0.9 mL, 10 mmol) and 15 mL ether which had been coooled to −40° C. During the addition the temperature was monitored and kept below −25° C. The resulting mixture was stirred for 30 minutes at −45° C., then the cooling bath was removed and the reaction mixture was allowed to warm slowly to room temperature. After stirring for an additional 30 minutes at room temperature, the reaction vessel was placed into a heated oilbath (37° C.) and was gently refluxed for 22 hours. The mixture was cooled to room temperature, and the solution was filtered through a cannula filter. The solvent as well as some of the adamantane byproduct was removed in vacuo, without exposing the product to air to afford crude di-1-adamantylchlorophosphine. The flask was evacuated To the reaction vessel 45 mL ether was added the mixture was gently refluxed for 15 hours, without mechanical stirring The resulting solution of Grignard reagent was taken up in a syringe added very slowly dropwise to a separate flame-dried two-necked, round-bottom flask equipped with a reflux condenser which had been coooled to −40° C During the addition the temperature kept below −25° C the cooling bath was removed to warm slowly to room temperature After stirring for an additional 30 minutes at room temperature was placed into a heated oilbath (37° C.) was gently refluxed for 22 hours The mixture was cooled to room temperature the solution was filtered through a cannula filter The solvent as well as some of the adamantane byproduct was removed in vacuo

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1.6 ml of TMEDA (15 mmol.) are added to a suspension of 1.43 g (10 mmol.) of N-phenylpyrrole in 30 ml of hexane. 6.25 ml of 1.6 molar n-butyllithium solution (10 mmol.) are added at room temperature. The mixture is then heated for 2.5 hours at reflux temperature (solution 1). In another flask, 3.36 g (10 mmol.) of di-1-adamantylchlorophosphane are mixed with 40 ml of hexane and heated to 76° C. (solution 2). The boiling solution 1 is then slowly transferred into solution 2, which is at 76° C., by means of a cannula. The mixture is then boiled for a further 2 hours at reflux, the solution is cooled, and 20 ml of water are added thereto. The organic phase is filtered off over magnesium sulfate. The solution is concentrated in vacuo; 15 ml of toluene are added thereto, and the mixture is heated to 60° C. and then cooled. After one day at room temperature, the product is filtered off. Yield: 3.3 g (75%). The mixture is then heated for 2.5 hours is at 76° C., by means of a cannula at reflux the solution is cooled The organic phase is filtered off over magnesium sulfate The solution is concentrated in vacuo 15 ml of toluene are added cooled After one day at room temperature the product is filtered off

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1.6 ml of TMEDA (15 mmol.) are added to a suspension of 1.43 g (10 mmol.) of N-phenylpyrrole in 30 ml of hexane. 6.25 ml of 1.6 molar n-butyllithium solution (10 mmol.) are added at room temperature. The mixture is then heated for 2.5 hours at reflux temperature (solution 1). In another flask, 3.36 g (10 mmol.) of di-1-adamantylchlorophosphane are mixed with 40 ml of hexane and heated to 76° C. (solution 2). The boiling solution 1 is then slowly transferred into solution 2, which is at 76° C., by means of a cannula. The mixture is then boiled for a further 2 hours at reflux, the solution is cooled, and 20 ml of water are added thereto. The organic phase is filtered off over magnesium sulfate. The solution is concentrated in vacuo; 15 ml of toluene are added thereto, and the mixture is heated to 60° C. and then cooled. After one day at room temperature, the product is filtered off. Yield: 3.3 g (75%). The mixture is then heated for 2.5 hours is at 76° C., by means of a cannula at reflux the solution is cooled The organic phase is filtered off over magnesium sulfate The solution is concentrated in vacuo 15 ml of toluene are added cooled After one day at room temperature the product is filtered off

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

実験手順: An oven dried Schlenk tube was charged with magnesium turnings (240 mg, 9.89 mmol), 2-bromo-biphenyl (1.55 mL, 7.5 mmol). The tube was evacuated and backfilled with argon two times. To the above mixture THF (15 mL) was added through a rubber septum and the reaction mixture was heated to a mild reflux for 3 hours. The reaction mixture was then temporarily cooled to room temperature for the addition of cuprous chloride (930 mg, 9.45 mmol) followed by a solution of the di-l-adamantylchlorophosphine in 5 mL THF. Heating was resumed for an addtional 3 hours. The reaction mixture was cooled to room temperature, and ether (50 mL) and pentane (50 mL) were added. The resulting suspension was stirred for 10 minutes, during which time a heavy dark-brown precipitate formed. The suspension was filtered and the solid was collected on a fritted funnel. The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1). The mixture was vigorously shaken several times over 30 minutes. The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL). The combined organic layers were washed with brine (2×50 mL), dried over anhydrous magnesium sulfate, decanted, and concentrated in vacuo. The product was crystallized from toluene/methanol to afford 450 mg (5.8%) product as a white solid. An oven dried Schlenk tube The tube was evacuated To the above mixture THF (15 mL) was added through a rubber septum the reaction mixture was heated to a mild reflux for 3 hours Heating formed The suspension was filtered the solid was collected on a fritted funnel The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1) over 30 minutes The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL) The combined organic layers were washed with brine (2×50 mL) dried over anhydrous magnesium sulfate decanted concentrated in vacuo The product was crystallized from toluene/methanol

反応条件: temp:-45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An oven-dried, round-bottom flask was charged with magnesium turnings (15.3 g, 0.63 mol) and 1-bromoadamantane (9.0 g, 0.041 mol). The flask was evacuated and backfilled with argon two times. To the reaction vessel 45 mL ether was added and the mixture was gently refluxed for 15 hours, without mechanical stirring. The resulting solution of Grignard reagent was taken up in a syringe, and added very slowly dropwise to a separate flame-dried, two-necked, round-bottom flask equipped with a reflux condenser which had been charged with PCl3 (0.9 mL, 10 mmol) and 15 mL ether which had been coooled to −40° C. During the addition the temperature was monitored and kept below −25° C. The resulting mixture was stirred for 30 minutes at −45° C., then the cooling bath was removed and the reaction mixture was allowed to warm slowly to room temperature. After stirring for an additional 30 minutes at room temperature, the reaction vessel was placed into a heated oilbath (37° C.) and was gently refluxed for 22 hours. The mixture was cooled to room temperature, and the solution was filtered through a cannula filter. The solvent as well as some of the adamantane byproduct was removed in vacuo, without exposing the product to air to afford crude di-1-adamantylchlorophosphine. The flask was evacuated To the reaction vessel 45 mL ether was added the mixture was gently refluxed for 15 hours, without mechanical stirring The resulting solution of Grignard reagent was taken up in a syringe added very slowly dropwise to a separate flame-dried two-necked, round-bottom flask equipped with a reflux condenser which had been coooled to −40° C During the addition the temperature kept below −25° C the cooling bath was removed to warm slowly to room temperature After stirring for an additional 30 minutes at room temperature was placed into a heated oilbath (37° C.) was gently refluxed for 22 hours The mixture was cooled to room temperature the solution was filtered through a cannula filter The solvent as well as some of the adamantane byproduct was removed in vacuo

反応条件: temp:-45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An oven-dried, round-bottom flask was charged with magnesium turnings (15.3 g, 0.63 mol) and 1-bromoadamantane (9.0 g, 0.041 mol). The flask was evacuated and backfilled with argon two times. To the reaction vessel 45 mL ether was added and the mixture was gently refluxed for 15 hours, without mechanical stirring. The resulting solution of Grignard reagent was taken up in a syringe, and added very slowly dropwise to a separate flame-dried, two-necked, round-bottom flask equipped with a reflux condenser which had been charged with PCl3 (0.9 mL, 10 mmol) and 15 mL ether which had been coooled to −40° C. During the addition the temperature was monitored and kept below −25° C. The resulting mixture was stirred for 30 minutes at −45° C., then the cooling bath was removed and the reaction mixture was allowed to warm slowly to room temperature. After stirring for an additional 30 minutes at room temperature, the reaction vessel was placed into a heated oilbath (37° C.) and was gently refluxed for 22 hours. The mixture was cooled to room temperature, and the solution was filtered through a cannula filter. The solvent as well as some of the adamantane byproduct was removed in vacuo, without exposing the product to air to afford crude di-1-adamantylchlorophosphine. The flask was evacuated To the reaction vessel 45 mL ether was added the mixture was gently refluxed for 15 hours, without mechanical stirring The resulting solution of Grignard reagent was taken up in a syringe added very slowly dropwise to a separate flame-dried two-necked, round-bottom flask equipped with a reflux condenser which had been coooled to −40° C During the addition the temperature kept below −25° C the cooling bath was removed to warm slowly to room temperature After stirring for an additional 30 minutes at room temperature was placed into a heated oilbath (37° C.) was gently refluxed for 22 hours The mixture was cooled to room temperature the solution was filtered through a cannula filter The solvent as well as some of the adamantane byproduct was removed in vacuo

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

実験手順: An oven dried Schlenk tube was charged with magnesium turnings (240 mg, 9.89 mmol), 2-bromo-biphenyl (1.55 mL, 7.5 mmol). The tube was evacuated and backfilled with argon two times. To the above mixture THF (15 mL) was added through a rubber septum and the reaction mixture was heated to a mild reflux for 3 hours. The reaction mixture was then temporarily cooled to room temperature for the addition of cuprous chloride (930 mg, 9.45 mmol) followed by a solution of the di-1-adamantylchlorophosphine in 5 mL THF. Heating was resumed for an addtional 3 hours. The reaction mixture was cooled to room temperature, and ether (50 ml,) and pentane (50 mL) were added. The resulting suspension was stirred for 10 minutes, during which time a heavy dark-brown precipitate formed. The suspension was filtered and the solid was collected on a fritted funnel. The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 ml, 1:1). The mixture was vigorously shaken several times over 30 minutes. The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 ml,). The combined organic layers were washed with brine (2×50 mL), dried over anhydrous magnesium sulfate, decanted, and concentrated in vacuo. The product was crystallized from toluene/methanol to afford 450 mg (5.8%) product as a white solid. An oven dried Schlenk tube The tube was evacuated To the above mixture THF (15 mL) was added through a rubber septum the reaction mixture was heated to a mild reflux for 3 hours Heating formed The suspension was filtered the solid was collected on a fritted funnel The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 ml, 1:1) over 30 minutes The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 ml,) The combined organic layers were washed with brine (2×50 mL) dried over anhydrous magnesium sulfate decanted concentrated in vacuo The product was crystallized from toluene/methanol

反応条件: temp:-45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An oven-dried, round-bottom flask was charged with magnesium turnings (15.3 g, 0.63 mol) and 1-bromoadamantane (9.0 g, 0.041 mol). The flask was evacuated and backfilled with argon two times. To the reaction vessel 45 mL ether was added and the mixture was gently refluxed for 15 hours, without mechanical stirring. The resulting solution of Grignard reagent was taken up in a syringe, and added very slowly dropwise to a separate flame-dried, two-necked, round-bottom flask equipped with a reflux condenser which had been charged with PCl3 (0.9 mL, 10 mmol) and 15 mL ether which had been coooled to −40° C. During the addition the temperature was monitored and kept below −25° C. The resulting mixture was stirred for 30 minutes at −45° C., then the cooling bath was removed and the reaction mixture was allowed to warm slowly to room temperature. After stirring for an additional 30 minutes at room temperature, the reaction vessel was placed into a heated oilbath (37° C.) and was gently refluxed for 22 hours. The mixture was cooled to room temperature, and the solution was filtered through a cannula filter. The solvent as well as some of the adamantane byproduct was removed in vacuo, without exposing the product to air to afford crude di-1-adamantylchlorophosphine. The flask was evacuated To the reaction vessel 45 mL ether was added the mixture was gently refluxed for 15 hours, without mechanical stirring The resulting solution of Grignard reagent was taken up in a syringe added very slowly dropwise to a separate flame-dried two-necked, round-bottom flask equipped with a reflux condenser which had been coooled to −40° C During the addition the temperature kept below −25° C the cooling bath was removed to warm slowly to room temperature After stirring for an additional 30 minutes at room temperature was placed into a heated oilbath (37° C.) was gently refluxed for 22 hours The mixture was cooled to room temperature the solution was filtered through a cannula filter The solvent as well as some of the adamantane byproduct was removed in vacuo

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

実験手順: An oven dried Schlenk tube was charged with magnesium turnings (240 mg, 9.89 mmol), 2-bromo-biphenyl (1.55 mL, 7.5 mmol). The tube was evacuated and backfilled with argon two times. To the above mixture THF (15 mL) was added through a rubber septum and the reaction mixture was heated to a mild reflux for 3 hours. The reaction mixture was then temporarily cooled to room temperature for the addition of cuprous chloride (930 mg, 9.45 mmol) followed by a solution of the di-1-adamantylchlorophosphine in 5 mL THF. Heating was resumed for an additional 3 hours. The reaction mixture was cooled to room temperature, and ether (50 mL) and pentane (50 mL) were added. The resulting suspension was stirred for 10 minutes, during which time a heavy dark-brown precipitate formed. The suspension was filtered and the solid was collected on a fritted funnel. The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1). The mixture was vigorously shaken several times over 30 minutes. The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL). The combined organic layers were washed with brine (2×50 mL), dried over anhydrous magnesium sulfate, decanted, and concentrated in vacuo. The product was crystallized from toluene/methanol to afford 450 mg (5.8%) product as a white solid. An oven dried Schlenk tube The tube was evacuated To the above mixture THF (15 mL) was added through a rubber septum the reaction mixture was heated to a mild reflux for 3 hours Heating formed The suspension was filtered the solid was collected on a fritted funnel The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1) over 30 minutes The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL) The combined organic layers were washed with brine (2×50 mL) dried over anhydrous magnesium sulfate decanted concentrated in vacuo The product was crystallized from toluene/methanol

反応条件: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: An oven-dried, round-bottom flask was charged with magnesium turnings (15.3 g, 0.63 mol) and 1-bromoadamantane (9.0 g, 0.041 mol). The flask was evacuated and backfilled with argon two times. To the reaction vessel 45 mL ether was added and the mixture was gently refluxed for 15 hours, without mechanical stirring. The resulting solution of Grignard reagent was taken up in a syringe, and added very slowly dropwise to a separate flame-dried, two-necked, round-bottom flask equipped with a reflux condenser which had been charged with PCl3 (0.9 mL, 10 mmol) and 15 mL ether which had been cooled to −40° C. During the addition the temperature was monitored and kept below −25° C. The resulting mixture was stirred for 30 minutes at −45° C., then the cooling bath was removed and the reaction mixture was allowed to warm slowly to room temperature. After stirring for an additional 30 minutes at room temperature, the reaction vessel was placed into a heated oil bath (37° C.) and was gently refluxed for 22 hours. The mixture was cooled to room temperature, and the solution was filtered through a cannula filter. The solvent as well as some of the adamantane byproduct was removed in vacuo, without exposing the product to air to afford crude di-1-adamantylchlorophosphine. The flask was evacuated To the reaction vessel 45 mL ether was added the mixture was gently refluxed for 15 hours, without mechanical stirring The resulting solution of Grignard reagent was taken up in a syringe added very slowly dropwise to a separate flame-dried two-necked, round-bottom flask equipped with a reflux condenser which During the addition the temperature kept below −25° C the cooling bath was removed to warm slowly to room temperature After stirring for an additional 30 minutes at room temperature the reaction vessel was placed into a heated oil bath (37° C.) and was gently refluxed for 22 hours The mixture was cooled to room temperature the solution was filtered through a cannula filter The solvent as well as some of the adamantane byproduct was removed in vacuo

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

実験手順: An oven dried Schlenk tube was charged with magnesium turnings (240 mg, 9.89 mmol), 2-bromo-biphenyl (1.55 mL, 7.5 mmol). The tube was evacuated and backfilled with argon two times. To the above mixture THF (15 mL) was added through a rubber septum and the reaction mixture was heated to a mild reflux for 3 hours. The reaction mixture was then temporarily cooled to room temperature for the addition of cuprous chloride (930 mg, 9.45 mmol) followed by a solution of the di-1-adamantylchlorophosphine in 5 mL THF. Heating was resumed for an additional 3 hours. The reaction mixture was cooled to room temperature, and ether (50 mL) and pentane (50 mL) were added. The resulting suspension was stirred for 10 minutes, during which time a heavy dark-brown precipitate formed. The suspension was filtered and the solid was collected on a fritted funnel. The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1). The mixture was vigorously shaken several times over 30 minutes. The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL). The combined organic layers were washed with brine (2×50 mL), dried over anhydrous magnesium sulfate, decanted, and concentrated in vacuo. The product was crystallized from toluene/methanol to afford 450 mg (5.8%) product as a white solid. An oven dried Schlenk tube The tube was evacuated To the above mixture THF (15 mL) was added through a rubber septum the reaction mixture was heated to a mild reflux for 3 hours Heating formed The suspension was filtered the solid was collected on a fritted funnel The solid was partitioned between ethyl acetate-ether (100 mL 1:1) and 38% ammonium hydroxide-water (100 mL 1:1) over 30 minutes The aqueos layer washed twice with ether-ethyl acetate (1:1, 100 mL) The combined organic layers were washed with brine (2×50 mL) dried over anhydrous magnesium sulfate decanted concentrated in vacuo The product was crystallized from toluene/methanol