dichloro-phenyl-sulfanylidene-lambda5-phosphane

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser carrying a CaCl2 -Drierite drying tube, and a heating mantle, was charged with 4-phenoxyphenol (8.64 g, 46.4 mmol), 4-dimethylaminopyridine (0.57 g, 4.7 mmol), and anhydrous pyridine (40 mL), and the stirred solution was treated slowly with benzenephosphonothioic dichloride (3.6 mL, 23.2 mmol) via syringe. The resulting mixture was stirred at ambient temperature for 64 hours, then was heated at reflux for 1 hour, and allowed to cool. The reaction was monitored periodically by HPLC. Workup consisted of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL), then washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine. Drying (MgSO4) filtration and concentration gave a red oily residue. Purification by chromatography on flash-grade silica gel (4"×2" i.d.), eluting with CH2Cl2 , afforded 9.3 g (79 percent yield) of the title compound as a yellow, viscous oil which had a PDSC (O2) onset/extrap (° C.) of 248/324. An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser was heated at reflux for 1 hour to cool of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL) washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine Drying (MgSO4) filtration and concentration gave a red oily residue Purification by chromatography on flash-grade silica gel (4"×2" i.d.) eluting with CH2Cl2

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

実験手順: An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser carrying a CaCl2 -Drierite drying tube, and a heating mantle, was charged with 4-phenoxyphenol (8.64 g, 46.4 mmol), 4-dimethylaminopyridine (0.57 g, 4.7 mmol), and anhydrous pyridine (40 mL), and the stirred solution was treated slowly with benzenephosphonothioic dichloride (3.6 mL, 23.2 mmol) via syringe. The resulting mixture was stirred at ambient temperature for 64 hours, then was heated at reflux for 1 hour, and allowed to cool. The reaction was monitored periodically by HPLC. Workup consisted of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL), then washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine. Drying (MgSO4) filtration and concentration gave a red oily residue. Purification by chromatography on flash-grade silica gel (4"×2" i.d.), eluting with CH2Cl2 , afforded 9.3 g (79 percent yield) of the title compound as a yellow, viscous oil which had a PDSC (O2) onset/extrap (° C.) of 248/324. An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser was heated at reflux for 1 hour to cool of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL) washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine Drying (MgSO4) filtration and concentration gave a red oily residue Purification by chromatography on flash-grade silica gel (4"×2" i.d.) eluting with CH2Cl2

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

実験手順: An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser carrying a CaCl2 -Drierite drying tube, and a heating mantle, was charged with 4-phenoxyphenol (8.64 g, 46.4 mmol), 4-dimethylaminopyridine (0.57 g, 4.7 mmol), and anhydrous pyridine (40 mL), and the stirred solution was treated slowly with benzenephosphonothioic dichloride (3.6 mL, 23.2 mmol) via syringe. The resulting mixture was stirred at ambient temperature for 64 hours, then was heated at reflux for 1 hour, and allowed to cool. The reaction was monitored periodically by HPLC. Workup consisted of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL), then washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine. Drying (MgSO4) filtration and concentration gave a red oily residue. Purification by chromatography on flash-grade silica gel (4"×2" i.d.), eluting with CH2Cl2 , afforded 9.3 g (79 percent yield) of the title compound as a yellow, viscous oil which had a PDSC (O2) onset/extrap (° C.) of 248/324. An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser was heated at reflux for 1 hour to cool of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL) washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine Drying (MgSO4) filtration and concentration gave a red oily residue Purification by chromatography on flash-grade silica gel (4"×2" i.d.) eluting with CH2Cl2

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

実験手順: Phenol is treated with an excess of thiophosphoryl chloride (at reflux) to yield phenyl thiophosphoryl dichloride ##STR16## and this product was condensed with p-nitroaniline and hydrogenated as set out in Example 1. The corresponding polymer is obtained by polycondensation with isophthaloyl chloride as in Example 2. The inherent viscosity was 0.9 dl/g.

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

実験手順: Phenol is treated with an excess of thiophosphoryl chloride (at reflux) to yield phenyl thiophosphoryl dichloride ##STR16## and this product was condensed with p-nitroaniline and hydrogenated as set out in Example 1. The corresponding polymer is obtained by polycondensation with isophthaloyl chloride as in Example 2. The inherent viscosity was 0.9 dl/g.

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:300.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The procedure of Example 10 was repeated using 33.6 grams (0.3 moles) of chlorobenzene, 41.1 grams (0.3 moles) of phosphorus trichloride and 22.2 grams (0.05 moles) of phosphorus pentasulfide. The reaction mixture was heated at 300° C. for 7 hours. The product, phenylphosphonothioic dichloride, in a yield of 18.3 grams, was isolated by distillation and redistillation, and had a boiling point of 58° C. and 62° C. (0.02 millimeters of mercury) and an nD25 of 1.6235 as against the reported nD25 of 1.6220 for phenylphosphonothioic dichloride.

反応条件: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 100 cc autoclave, 42.35 g (0.25 mole) of thiophosphoryl trichloride, 19.53 g (0.25 mole) of benzene were charged, and the mixture was heated with stirring at 200° C for 4 hours. The reaction mixture was treated in accordance with the process of Example 1. No phenylphosphonothioic dichloride was produced. the mixture was heated The reaction mixture was treated in accordance with the process of Example 1

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

実験手順: An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser carrying a CaCl2 -Drierite drying tube, and a heating mantle, was charged with 4-phenoxyphenol (8.64 g, 46.4 mmol), 4-dimethylaminopyridine (0.57 g, 4.7 mmol), and anhydrous pyridine (40 mL), and the stirred solution was treated slowly with benzenephosphonothioic dichloride (3.6 mL, 23.2 mmol) via syringe. The resulting mixture was stirred at ambient temperature for 64 hours, then was heated at reflux for 1 hour, and allowed to cool. The reaction was monitored periodically by HPLC. Workup consisted of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL), then washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine. Drying (MgSO4) filtration and concentration gave a red oily residue. Purification by chromatography on flash-grade silica gel (4"×2" i.d.), eluting with CH2Cl2 , afforded 9.3 g (79 percent yield) of the title compound as a yellow, viscous oil which had a PDSC (O2) onset/extrap (° C.) of 248/324. An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser was heated at reflux for 1 hour to cool of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL) washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine Drying (MgSO4) filtration and concentration gave a red oily residue Purification by chromatography on flash-grade silica gel (4"×2" i.d.) eluting with CH2Cl2

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

実験手順: Phenol is treated with an excess of thiophosphoryl chloride (at reflux) to yield phenyl thiophosphoryl dichloride ##STR16## and this product was condensed with p-nitroaniline and hydrogenated as set out in Example 1. The corresponding polymer is obtained by polycondensation with isophthaloyl chloride as in Example 2. The inherent viscosity was 0.9 dl/g.