2,4-dichloro-1-[chloro-(2,4-dichlorophenoxy)phosphoryl]oxybenzene

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

実験手順: The title compound was prepared by the general method of Example 1 with the following modifications. (1) The molar ratio of 2,4-dichlorophenol to phosphorus oxychloride was increased from 1.33 to 1.85 by using 189.99 g (1.165 mole) of 2,4-dichlorophenol and 96.60 g (0.63 mole) of phosphorus oxychloride. (2) The reaction time at 120° was increased to about 24 hours. (3) The product was crystallized using a larger quantity of hexane (570 ml, or 3 ml per gram of starting 2,4-dichlorophenol) at -15°. Analysis by GLPC indicated 82% purity (by weight) of bis(2,4-dichlorophenyl) phosphorochloridate, with contamination by a trace of 2,4-dichlorophenyl phosphorodichloridate and 18% (by weight) of tris(2,4-dichlorophenyl) phosphate. The yield of the bis(2,4-dichlorophenyl) phosphorochloridate when corrected for purity was 125 g (53%) (3) The product was crystallized at -15°

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

実験手順: To a melt of 2,4-dichlorophenol (400.0 g, 2.454 mole) at ca. 50° was added 4-dimethylamino-pyridine (6.93 g, 56 mmole), followed by phosphorus oxychloride (289.5 g, 1.887 mole). The mixture was heated under nitrogen to ca. 120°, at which temperature the mixture began to reflux and to generate hydrogen chloride (which was passed through a sodium hydroxide scrubber). After about twelve hours at 120°-125°, gas-liquid partition chromatography (GLPC) using a silica capillary indicated less than 1% (by weight) of unreacted 2,4-dichlorophenol and a mixture of 2,4-dichlorophenyl phosphorodichloridate, the desired bis(2,4-dichlorophenyl) phosphorochloridate, and tris(2,4-dichlorophenyl) phosphate. After the reaction mixture was cooled to ca. 40°, hexane (145 ml) was added and the mixture was cooled to ca. 20°. A precipitate containing 4-dimethylaminopyridine hydrochloride was removed by filtration. The filtrate was diluted with additional hexane (145 ml) and cooled to ca. -30°. After about eight hours the resultant precipitate was collected by filtration and washed with hexane (four 200-ml portions) at ca. -20°, all with careful exclusion of moisture. Drying for two hours at room temperature under a flow of nitrogen yielded 129.87 g (26% yield) of the desired bis(2,4-dichlorophenyl) phosphorochloridate as a white solid. Analysis by GLPC indicated 99% purity (by weight), with contamination by 0.3% (by weight) 2,4-dichlorophenyl phosphorodichloridate and 0.2% (by weight) tris(2,4-dichlorophenyl) phosphate. The mixture was heated under nitrogen to ca. 120°, at which temperature the mixture to reflux After about twelve hours at 120°-125° gas-liquid partition chromatography (GLPC) a mixture of 2,4-dichlorophenyl phosphorodichloridate After the reaction mixture was cooled to ca. 40° hexane (145 ml) was added the mixture was cooled to ca. 20° A precipitate containing 4-dimethylaminopyridine hydrochloride was removed by filtration The filtrate was diluted with additional hexane (145 ml) cooled to ca. -30° After about eight hours the resultant precipitate was collected by filtration washed with hexane (four 200-ml portions) at ca. -20° Drying for two hours at room temperature under a flow of nitrogen

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

実験手順: The title compound was prepared by the general method of Example 1 with the following modifications. (1) The molar ratio of 2,4-dichlorophenol to phosphorus oxychloride was increased from 1.33 to 1.85 by using 189.99 g (1.165 mole) of 2,4-dichlorophenol and 96.60 g (0.63 mole) of phosphorus oxychloride. (2) The reaction time at 120° was increased to about 24 hours. (3) The product was crystallized using a larger quantity of hexane (570 ml, or 3 ml per gram of starting 2,4-dichlorophenol) at -15°. Analysis by GLPC indicated 82% purity (by weight) of bis(2,4-dichlorophenyl)phosphorochloridate, with contamination by a trace of 2,4-dichlorophenyl phosphorodichloridate and 18% (by weight) of tris(2,4-dichlorophenyl)phosphate. The yield of the bis(2,4-dichlorophenyl)phosphorochloridate when corrected for purity was 125 g (53%). Subsequent reactions were unaffected by the presence of the tris(2,4-dichlorophenyl)phosphate, as illustrated by Examples 3 and 4. (3) The product was crystallized at -15°

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

実験手順: The title compound was prepared by the general method of Example 1 with the following modifications. (1) The molar ratio of 2,4-dichlorophenol to phosphorus oxychloride was increased from 1.33 to 1.85 by using 189.99 g (1.165 mole) of 2,4-dichlorophenol and 96.60 g (0.63 mole) of phosphorus oxychloride. (2) The reaction time at 120° was increased to about 24 hours. (3) The product was crystallized using a larger quantity of hexane (570 ml, or 3 ml per gram of starting 2,4-dichlorophenol) at -15°. Analysis by GLPC indicated 82% purity (by weight) of bis(2,4-dichlorophenyl) phosphorochloridate, with contamination by a trace of 2,4-dichlorophenyl phosphorodichloridate and 18% (by weight) of tris(2,4-dichlorophenyl) phosphate. The yield of the bis(2,4-dichlorophenyl) phosphorochloridate when corrected for purity was 125 g (53%) (3) The product was crystallized at -15°

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

実験手順: To a melt of 2,4-dichlorophenol (400.0 g, 2.454 mole) at ca. 50° was added 4-dimethylamino-pyridine (6.93 g, 56 mmole), followed by phosphorus oxychloride (289.5 g, 1.887 mole). The mixture was heated under nitrogen to ca. 120°, at which temperature the mixture began to reflux and to generate hydrogen chloride (which was passed through a sodium hydroxide scrubber). After about twelve hours at 120°-125°, gas-liquid partition chromatography (GLPC) using a silica capillary indicated less than 1% (by weight) of unreacted 2,4-dichlorophenol and a mixture of 2,4-dichlorophenyl phosphorodichloridate, the desired bis(2,4-dichlorophenyl) phosphorochloridate, and tris(2,4-dichlorophenyl) phosphate. After the reaction mixture was cooled to ca. 40°, hexane (145 ml) was added and the mixture was cooled to ca. 20°. A precipitate containing 4-dimethylaminopyridine hydrochloride was removed by filtration. The filtrate was diluted with additional hexane (145 ml) and cooled to ca. -30°. After about eight hours the resultant precipitate was collected by filtration and washed with hexane (four 200-ml portions) at ca. -20°, all with careful exclusion of moisture. Drying for two hours at room temperature under a flow of nitrogen yielded 129.87 g (26% yield) of the desired bis(2,4-dichlorophenyl) phosphorochloridate as a white solid. Analysis by GLPC indicated 99% purity (by weight), with contamination by 0.3% (by weight) 2,4-dichlorophenyl phosphorodichloridate and 0.2% (by weight) tris(2,4-dichlorophenyl) phosphate. The mixture was heated under nitrogen to ca. 120°, at which temperature the mixture to reflux After about twelve hours at 120°-125° gas-liquid partition chromatography (GLPC) a mixture of 2,4-dichlorophenyl phosphorodichloridate After the reaction mixture was cooled to ca. 40° hexane (145 ml) was added the mixture was cooled to ca. 20° A precipitate containing 4-dimethylaminopyridine hydrochloride was removed by filtration The filtrate was diluted with additional hexane (145 ml) cooled to ca. -30° After about eight hours the resultant precipitate was collected by filtration washed with hexane (four 200-ml portions) at ca. -20° Drying for two hours at room temperature under a flow of nitrogen

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

実験手順: The title compound was prepared by the general method of Example 1 with the following modifications. (1) The molar ratio of 2,4-dichlorophenol to phosphorus oxychloride was increased from 1.33 to 1.85 by using 189.99 g (1.165 mole) of 2,4-dichlorophenol and 96.60 g (0.63 mole) of phosphorus oxychloride. (2) The reaction time at 120° was increased to about 24 hours. (3) The product was crystallized using a larger quantity of hexane (570 ml, or 3 ml per gram of starting 2,4-dichlorophenol) at -15°. Analysis by GLPC indicated 82% purity (by weight) of bis(2,4-dichlorophenyl)phosphorochloridate, with contamination by a trace of 2,4-dichlorophenyl phosphorodichloridate and 18% (by weight) of tris(2,4-dichlorophenyl)phosphate. The yield of the bis(2,4-dichlorophenyl)phosphorochloridate when corrected for purity was 125 g (53%). Subsequent reactions were unaffected by the presence of the tris(2,4-dichlorophenyl)phosphate, as illustrated by Examples 3 and 4. (3) The product was crystallized at -15°

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

実験手順: The title compound was prepared by the general method of Example 1 with the following modifications. (1) The molar ratio of 2,4-dichlorophenol to phosphorus oxychloride was increased from 1.33 to 1.85 by using 189.99 g (1.165 mole) of 2,4-dichlorophenol and 96.60 g (0.63 mole) of phosphorus oxychloride. (2) The reaction time at 120° was increased to about 24 hours. (3) The product was crystallized using a larger quantity of hexane (570 ml, or 3 ml per gram of starting 2,4-dichlorophenol) at -15°. Analysis by GLPC indicated 82% purity (by weight) of bis(2,4-dichlorophenyl) phosphorochloridate, with contamination by a trace of 2,4-dichlorophenyl phosphorodichloridate and 18% (by weight) of tris(2,4-dichlorophenyl) phosphate. The yield of the bis(2,4-dichlorophenyl) phosphorochloridate when corrected for purity was 125 g (53%) (3) The product was crystallized at -15°

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

実験手順: To a melt of 2,4-dichlorophenol (400.0 g, 2.454 mole) at ca. 50° was added 4-dimethylamino-pyridine (6.93 g, 56 mmole), followed by phosphorus oxychloride (289.5 g, 1.887 mole). The mixture was heated under nitrogen to ca. 120°, at which temperature the mixture began to reflux and to generate hydrogen chloride (which was passed through a sodium hydroxide scrubber). After about twelve hours at 120°-125°, gas-liquid partition chromatography (GLPC) using a silica capillary indicated less than 1% (by weight) of unreacted 2,4-dichlorophenol and a mixture of 2,4-dichlorophenyl phosphorodichloridate, the desired bis(2,4-dichlorophenyl) phosphorochloridate, and tris(2,4-dichlorophenyl) phosphate. After the reaction mixture was cooled to ca. 40°, hexane (145 ml) was added and the mixture was cooled to ca. 20°. A precipitate containing 4-dimethylaminopyridine hydrochloride was removed by filtration. The filtrate was diluted with additional hexane (145 ml) and cooled to ca. -30°. After about eight hours the resultant precipitate was collected by filtration and washed with hexane (four 200-ml portions) at ca. -20°, all with careful exclusion of moisture. Drying for two hours at room temperature under a flow of nitrogen yielded 129.87 g (26% yield) of the desired bis(2,4-dichlorophenyl) phosphorochloridate as a white solid. Analysis by GLPC indicated 99% purity (by weight), with contamination by 0.3% (by weight) 2,4-dichlorophenyl phosphorodichloridate and 0.2% (by weight) tris(2,4-dichlorophenyl) phosphate. The mixture was heated under nitrogen to ca. 120°, at which temperature the mixture to reflux After about twelve hours at 120°-125° gas-liquid partition chromatography (GLPC) a mixture of 2,4-dichlorophenyl phosphorodichloridate After the reaction mixture was cooled to ca. 40° hexane (145 ml) was added the mixture was cooled to ca. 20° A precipitate containing 4-dimethylaminopyridine hydrochloride was removed by filtration The filtrate was diluted with additional hexane (145 ml) cooled to ca. -30° After about eight hours the resultant precipitate was collected by filtration washed with hexane (four 200-ml portions) at ca. -20° Drying for two hours at room temperature under a flow of nitrogen

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

実験手順: The title compound was prepared by the general method of Example 1 with the following modifications. (1) The molar ratio of 2,4-dichlorophenol to phosphorus oxychloride was increased from 1.33 to 1.85 by using 189.99 g (1.165 mole) of 2,4-dichlorophenol and 96.60 g (0.63 mole) of phosphorus oxychloride. (2) The reaction time at 120° was increased to about 24 hours. (3) The product was crystallized using a larger quantity of hexane (570 ml, or 3 ml per gram of starting 2,4-dichlorophenol) at -15°. Analysis by GLPC indicated 82% purity (by weight) of bis(2,4-dichlorophenyl)phosphorochloridate, with contamination by a trace of 2,4-dichlorophenyl phosphorodichloridate and 18% (by weight) of tris(2,4-dichlorophenyl)phosphate. The yield of the bis(2,4-dichlorophenyl)phosphorochloridate when corrected for purity was 125 g (53%). Subsequent reactions were unaffected by the presence of the tris(2,4-dichlorophenyl)phosphate, as illustrated by Examples 3 and 4. (3) The product was crystallized at -15°