二氯-苯基-亚硫基-lambda5-磷烷

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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.

实验步骤: 投料: 取250ml干燥三口瓶，加入4-硝基苯酚（6.92g 49.75mmol 2.1eq）和甲苯（30ml），室温搅拌溶解完全，再加入40%氢氧化钠溶液（30ml）和苄基三乙基氯化铵（1.08g 4.74mmol 0.2eq），室温搅拌下逐滴加入M-CCPD102149-SM1（5.00g 23.69 1.0eq），添加完毕后，室温下搅拌反应1h。\n监测: lcms，tlc点板检测（pe：ea=5：1），结果显示，原料反应完全，有产物ms生成。\n后处理: 停止反应，往反应液中加入水（100ml）和乙酸乙酯（100ml）萃取，静置分层，取有机相，水相再加入乙酸乙酯进行萃取（100ml×2），合并有机相并用饱和食盐水洗涤（100ml×1），无水硫酸钠干燥，抽滤，滤液经减压浓缩得到黄色溶液5.6g。

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:300.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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.

反应条件: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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.