dichloro(methyl)phosphane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 12.6 g. of magnesium turnings was gradually added a solution containing 96 g. (0.50 mole) of p-chlorobromobenzene and 180 cc. tetrahydrofuran. The reaction mixture was stirred and maintained under a nitrogen atmosphere during the addition, following which the contents of the vessel were heated to reflux temperature for two hours. When the reaction mixture had cooled, a solution of methyldichlorophosphine (29.3 g., 0.25 mole) in 25 cc. tetrahydrofuran was gradually added. Following completion of this addition the reaction mixture was heated to reflux temperature for two hours. When the mixture had cooled it was slowly poured into 500 cc. of cold water and then acidified to a pH of 5 using aqueous hydrochloric acid. The resultant aqueous solution was extracted using chloroform. The organic layer was then dried over anhydrous magnesium sulfate and the chloroform removed under reduced pressure. The residue remaining following removal of the chloroform weighed 64 g. and was distilled, the fraction boiling at between 155 and 160 under a pressure of 0.5 mm. Hg being collected. This distillate converted to a white solid upon cooling. The solid material weighed 34 g. and exhibited the following analysis: containing 96 g maintained under a nitrogen atmosphere during the addition were heated to reflux temperature for two hours When the reaction mixture had cooled completion of this addition the reaction mixture was heated to reflux temperature for two hours When the mixture had cooled it was slowly poured into 500 cc The resultant aqueous solution was extracted The organic layer was then dried over anhydrous magnesium sulfate the chloroform removed under reduced pressure removal of the chloroform and was distilled being collected upon cooling

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 12.6 g. of magnesium turnings was gradually added a solution containing 96 g. (0.50 mole) of p-chlorobromobenzene and 180 cc. tetrahydrofuran. The reaction mixture was stirred and maintained under a nitrogen atmosphere during the addition, following which the contents of the vessel were heated to reflux temperature for two hours. When the reaction mixture had cooled, a solution of methyldichlorophosphine (29.3 g., 0.25 mole) in 25 cc. tetrahydrofuran was gradually added. Following completion of this addition the reaction mixture was heated to reflux temperature for two hours. When the mixture had cooled it was slowly poured into 500 cc. of cold water and then acidified to a pH of 5 using aqueous hydrochloric acid. The resultant aqueous solution was extracted using chloroform. The organic layer was then dried over anhydrous magnesium sulfate and the chloroform removed under reduced pressure. The residue remaining following removal of the chloroform weighed 64 g. and was distilled, the fraction boiling at between 155 and 160 under a pressure of 0.5 mm. Hg being collected. This distillate converted to a white solid upon cooling. The solid material weighed 34 g. and exhibited the following analysis: containing 96 g maintained under a nitrogen atmosphere during the addition were heated to reflux temperature for two hours When the reaction mixture had cooled completion of this addition the reaction mixture was heated to reflux temperature for two hours When the mixture had cooled it was slowly poured into 500 cc The resultant aqueous solution was extracted The organic layer was then dried over anhydrous magnesium sulfate the chloroform removed under reduced pressure removal of the chloroform and was distilled being collected upon cooling

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl dichlorophosphine (1.3 g) in ether (10 ml) and triethylamine (2 ml) were added to a stirred solution of N-benzoyl-N'-t-butyl hydrazine (1.0 g) in methylene chloride (3 ml). After stirring 5 minutes at room temperature, o-chloroaniline was added neat producing a mild exotherm. The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml), separated and the organic washed with 0.1N HCl, dried over MgSO4, filtered and rotavapped to a colorless oil weighing 0.5 g. producing a mild exotherm The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml) separated the organic washed with 0.1N HCl dried over MgSO4 filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 86 g (1 mol) of methacrylic acid were added dropwise to 117 g (1 mol) of methyldichlorophosphine at a temperature from 40° to 45° C. The mixture was stirred for 1 hour at said temperature. Phosphinic-carboxylic acid dichloride was then decomposed with 18 ml of H2O at a temperature of from 40° to 60° C., whereby a considerable formation of hydrogen chloride occurred. The residual quantity of hydrogen chloride in the reaction mixture was removed in a water-jet vacuum at 150° C. The residue was distilled under reduced pressure. 126 g of 2,4-dimethyl-2,5-dioxo-1,2-oxa-phospholane were obtained, which corresponds to a yield of 85.1% of the theory. The residual quantity of hydrogen chloride in the reaction mixture was removed in a water-jet vacuum at 150° C The residue was distilled under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 86 g (1 mol) of methacrylic acid were added dropwise to 117 g (1 mol) of methyldichlorophosphine at a temperature from 40° to 45° C. The mixture was stirred for 1 hour at said temperature. Phosphinic-carboxylic acid dichloride was then decomposed with 18 ml of H2O at a temperature of from 40° to 60° C., whereby a considerable formation of hydrogen chloride occurred. The residual quantity of hydrogen chloride in the reaction mixture was removed in a water-jet vacuum at 150° C. The residue was distilled under reduced pressure. 126 g of 2,4-dimethyl-2,5-dioxo-1,2-oxa-phospholane were obtained, which corresponds to a yield of 85.1% of the theory. The residual quantity of hydrogen chloride in the reaction mixture was removed in a water-jet vacuum at 150° C The residue was distilled under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl dichlorophosphine (1.3 g) in ether (10 ml) and triethylamine (2 ml) were added to a stirred solution of N-benzoyl-N'-t-butyl hydrazine (1.0 g) in methylene chloride (3 ml). After stirring 5 minutes at room temperature, o-chloroaniline was added neat producing a mild exotherm. The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml), separated and the organic washed with 0.1N HCl, dried over MgSO4, filtered and rotavapped to a colorless oil weighing 0.5 g. producing a mild exotherm The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml) separated the organic washed with 0.1N HCl dried over MgSO4 filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl dichlorophosphine (1.3 g) in ether (10 ml) and triethylamine (2 ml) were added to a stirred solution of N-benzoyl-N'-t-butyl hydrazine (1.0 g) in methylene chloride (3 ml). After stirring 5 minutes at room temperature, o-chloroaniline was added neat producing a mild exotherm. The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml), separated and the organic washed with 0.1N HCl, dried over MgSO4, filtered and rotavapped to a colorless oil weighing 0.5 g. producing a mild exotherm The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml) separated the organic washed with 0.1N HCl dried over MgSO4 filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 12.6 g. of magnesium turnings was gradually added a solution containing 96 g. (0.50 mole) of p-chlorobromobenzene and 1.80 cc. tetrahydrofuran. The reaction mixture was stirred and maintained under a nitrogen atmosphere during the addition, following which the contents of the vessel were heated to reflux temperature for two hours. When the reaction mixture had cooled, a solution of methyldichlorophosphine (29.3 g., 0.25 mole) in 25 cc. tetrahydrofuran was gradually added. Following completion of this addition the reaction mixture was heated to reflux temperature for two hours. When the mixture had cooled it was slowly poured into 500 cc. of cold water and then acidified to a pH of 5 using aqueous hydrochloric acid. The resultant aqueous solution was extracted using chloroform. The organic layer was then dried over anhydrous magnesium sulfate and the chloroform removed under reduced pressure. The residue remaining followng removal of the chloroform weighed 64 g. and was distilled, the fraction boiling at between 155 and 160 under a pressure of 0.5 mm Hg being collected. This distillate converted to a white solid upon cooling. The solid material weighed 34 g. and exhibited the following analysis: containing 96 g maintained under a nitrogen atmosphere during the addition were heated to reflux temperature for two hours When the reaction mixture had cooled completion of this addition the reaction mixture was heated to reflux temperature for two hours When the mixture had cooled it was slowly poured into 500 cc The resultant aqueous solution was extracted The organic layer was then dried over anhydrous magnesium sulfate the chloroform removed under reduced pressure removal of the chloroform and was distilled being collected upon cooling

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 43 g (0.5 mole) of methacrylic acid and 69 g (0.5 mole) of 3-hydroxypropyl-methyl-phosphinic acid is added to 58.5 g (0.5 mole) of methyldichloro-phosphine at 50°-60° C., while hydrogen chloride is discharged. Subsequently heating takes place under water jet vacuum to an internal temperature of up to 150° C. The residue is distilled under reduced pressure. 35 g of 2-methyl-2-oxo-1,2-oxa-phospholane (boiling point at 1.5 mm Hg: 120°-130° C.) and 55 g of 2,4-dimethyl-2,5-dioxo-1,2-oxa-phospholane (boiling point at 0.7 mm Hg: 150°-155° C.) are obtained. The yield in 2,4-dimethyl-2,5-dioxo-1,2-oxa-phospholane represents 71% of the theoretical yield. Subsequently heating up to 150° C The residue is distilled under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl dichlorophosphine (1.3 g) in ether (10 ml) and triethylamine (2 ml) were added to a stirred solution of N-benzoyl-N'-t-butyl hydrazine (1.0 g) in methylene chloride (3 ml). After stirring 5 minutes at room temperature, o-chloroaniline was added neat producing a mild exotherm. The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml), separated and the organic washed with 0.1N HCl, dried over MgSO4, filtered and rotavapped to a colorless oil weighing 0.5 g. producing a mild exotherm The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml) separated the organic washed with 0.1N HCl dried over MgSO4 filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 12.6 g. of magnesium turnings was gradually added a solution containing 96 g. (0.50 mole) of p-chlorobromobenzene and 180 cc. tetrahydrofuran. The reaction mixture was stirred and maintained under a nitrogen atmosphere during the addition, following which the contents of the vessel were heated to reflux temperature for two hours. When the reaction mixture had cooled, a solution of methyldichlorophosphine (29.3 g., 0.25 mole) in 25 cc. tetrahydrofuran was gradually added. Following completion of this addition the reaction mixture was heated to reflux temperature for two hours. When the mixture had cooled it was slowly poured into 500 cc. of cold water and then acidified to a pH of 5 using aqueous hydrochloric acid. The resultant aqueous solution was extracted using chloroform. The organic layer was then dried over anhydrous magnesium sulfate and the chloroform removed under reduced pressure. The residue remaining following removal of the chloroform weighed 64 g. and was distilled, the fraction boiling at between 155 and 160 under a pressure of 0.5 mm. Hg being collected. This distillate converted to a white solid upon cooling. The solid material weighed 34 g. and exhibited the following analysis: containing 96 g maintained under a nitrogen atmosphere during the addition were heated to reflux temperature for two hours When the reaction mixture had cooled completion of this addition the reaction mixture was heated to reflux temperature for two hours When the mixture had cooled it was slowly poured into 500 cc The resultant aqueous solution was extracted The organic layer was then dried over anhydrous magnesium sulfate the chloroform removed under reduced pressure removal of the chloroform and was distilled being collected upon cooling

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl dichlorophosphine (1.3 g) in ether (10 ml) and triethylamine (2 ml) were added to a stirred solution of N-benzoyl-N'-t-butyl hydrazine (1.0 g) in methylene chloride (3 ml). After stirring 5 minutes at room temperature, o-chloroaniline was added neat producing a mild exotherm. The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml), separated and the organic washed with 0.1N HCl, dried over MgSO4, filtered and rotavapped to a colorless oil weighing 0.5 g. producing a mild exotherm The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml) separated the organic washed with 0.1N HCl dried over MgSO4 filtered