1-chloro-4-dichlorophosphorylbenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Chlorophenylphosphonic dichloride (0.4 g, 0.81 mmol) was added to a cooled (0° C.) solution of 1-H-tetrazole (0.056 g, 0.81 mmol) and 35 (0.113 g, 0.22 mmol) in dry pyridine (5 mL). The reaction mixture was left to stir under a nitrogen atmosphere at 20° C. for 3 h and then evaporated to dryness under reduced pressure. The residue was dissolved in dioxane and NH3.H2O (5 mL) was added. After stirring for 5 h at 20° C., the reaction mixture was evaporated to dryness under reduced pressure to afford 36 (0.2 g, crude). The reaction mixture was left evaporated to dryness under reduced pressure The residue was dissolved in dioxane NH3.H2O (5 mL) was added After stirring for 5 h at 20° C. the reaction mixture was evaporated to dryness under reduced pressure

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Chlorophenylphosphonic dichloride (0.4 g, 0.81 mmol) was added to a cooled (0° C.) solution of 1-H-tetrazole (0.056 g, 0.81 mmol) and 35 (0.113 g, 0.22 mmol) in dry pyridine (5 mL). The reaction mixture was left to stir under a nitrogen atmosphere at 20° C. for 3 h and then evaporated to dryness under reduced pressure. The residue was dissolved in dioxane and NH3.H2O (5 mL) was added. After stirring for 5 h at 20° C., the reaction mixture was evaporated to dryness under reduced pressure to afford 36 (0.2 g, crude). The reaction mixture was left evaporated to dryness under reduced pressure The residue was dissolved in dioxane NH3.H2O (5 mL) was added After stirring for 5 h at 20° C. the reaction mixture was evaporated to dryness under reduced pressure

Conditions: temp:26.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (4.03 g, 0.063 mol) in hexane was added to a solution of tetramethylethylenediamine (1.86 g, 0.016 mol) in 30 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-benzylaniline (5.5 g, 0.03 mol) in 30 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. The suspension was stirred for 2 hours at 26° C. and then cooled to 0° C. A solution of 4-chlorophenylphosphonic dichloride (7.35 g, 0.032 mol) in 30 ml. of anhydrous cyclohexane was rapidly added to the suspension. After stirring for 15 minutes at 0° C., the resulting mixture was stirred for 2 hours at 26° C. The reaction mixture was cooled to 0° C., then quenched with the rapid addition of 6 ml. of acetic acid. After stirring for 15 minutes, the cyclohexane was removed on a rotary evaporator and the resulting residue was partitioned between methylene chloride and water. The layers were separated and the methylene chloride layer was washed with 5% hydrochloric acid, then water, dried with sodium sulfate and concentrated in vacuo to yield a blue oil. The blue oil was separated on a silica gel column using first methylene chloride then a 3:1 mixture of methylene chloride:ethyl acetate as the eluant. Fractions containing the benzazaphosphole were combined and concentrated in vacuo to yield a crude product. The crude product was slurried in anhydrous diethyl ether to yield 1-(4-chlorophenyl)-2-phenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (1.0 g, 5% yield) as a white crystalline solid having a melting point of 180°-182° C. and the following analysis: While maintaining the temperature of the reaction at 0° C. to produce a suspension cooled to 0° C After stirring for 15 minutes at 0° C. the resulting mixture was stirred for 2 hours at 26° C The reaction mixture was cooled to 0° C. quenched with the rapid addition of 6 ml After stirring for 15 minutes the cyclohexane was removed on a rotary evaporator the resulting residue was partitioned between methylene chloride and water The layers were separated the methylene chloride layer was washed with 5% hydrochloric acid water, dried with sodium sulfate concentrated in vacuo to yield a blue oil The blue oil was separated on a silica gel column a 3:1 mixture of methylene chloride Fractions containing the benzazaphosphole concentrated in vacuo to yield a crude product

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

Procedure: Into a mixture of 67 g of p-chlorophenylphosphonic acid and 20 g of p-chlorophenylphosphonic acid dichloride phosgene was introduced at a temperature of from 180°-190°C for 20 hours. After blowing through nitrogen to remove excess phosgene the mixture was distilled under reduced pressure. 66 g of p-chlorophenylphosphonic acid dichloride were obtained corresponding to a yield of 84 percent of the theory. was introduced at a temperature of from 180°-190°C for 20 hours to remove excess phosgene the mixture was distilled under reduced pressure

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

Procedure: 167 g (0.73 mole) of p-chlorophenylphosphonic acid dichloride and 121 g (0.46 mole) of triphenylphosphane were stirred for 2 hours at 180° C. and for 10 hours at 200° C. under an atmosphere of nitrogen. Distillation was then carried out at 0.04 kPa until a top temperature of 140° C. was reached. This gave 145 g, containing 58.5% of p-chlorophenyldichlorophosphane and 41.5% of p-chlorophenylphosphonic acid dichloride (according to 31P-NMR spectrum). The distillate was fractionated using a 70 cm silvered-jacketed column, packed with Raschig rings. Pure p-chlorophenyldichlorophosphane (boiling point: 71° C./0.093 kPa) was obtained. This corresponds to a yield of 85% of theory, based on triphenylphosphane employed. Distillation was then carried out at 0.04 kPa until a top temperature of 140° C. This gave 145 g, containing 58.5% of p-chlorophenyldichlorophosphane and 41.5% of p-chlorophenylphosphonic acid dichloride (according to 31P-NMR spectrum)