烷基磷酸单酯的合成

在醇溶液中,白磷与过氧化物分别进行非催化氧化和催化氧化反应合成了烷基磷酸单酯,分析了非催化氧化反应的机理。结果表明,醇和过氧化物的种类不同,产物中烷基磷酸单酯的含量不同。醇对烷基磷酸单酯选择性影响的大小顺序为:甲醇>正丁醇>苯酚;过氧化物对烷基磷酸单酯选择性影响的大小顺序为:叔丁基过氧化氢>过氧化(二)苯甲酰>过氧化氢。在甲醇溶液中,叔丁基过氧化氢和白磷进行非氧化反应的适宜条件为:n(白磷):n(叔丁基过氧化氢):n(甲醇)=1:10:12、反应温度80℃、反应时间2.5 h,在此条件下产物中烷基磷酸单酯的质量分数可达80.0%。以铜盐为催化剂可加速白磷的氧化;以Cu(acac)_2为催化剂,产物中烷基磷酸单酯的质量分数达95.0%。

Synthesis of Monoalkyl Phosphate

Oxidation of white phosphorus in alcoholic solutions by peroxides to produce phosphate was studied under non-catalytic or catalytic conditions.Depending on the reaction conditions, phosphorous acid,monoalkyl and dialkyl or trialkyl phosphates derivatives were prprepared.Results suggest the following order for activity of peroxides and solvents:ten-butyl hydroperoxide>(di) benzoylperoxide>hydroperoxide;methanol>n-butyl alcohol>phenol.Under optimal reaction conditions:n(white phosphorus):n(tert-butyl hydroperoxide):n(methanol)=1:10:12,reaction temperature 80 ℃,reaction time 2.5 h,in oxidation of white phosphorus by ten-butyl hydroperoxide in methanol solutions,content of monoalkyl phosphates in products is 80.0%(mass fraction).Cu(Ⅰ), Cu(Ⅱ)complexes as catalysts can significantly enhance oxidation of white phosphorus with increasing reaction rate.The order of catalyst activities is cupric acetylacetone>cupric acetate>cupric butyrate> cuprous iodide>cupric chloride.Noticeably,with cupric acetylacetone as catalyst,100% conversion of white phosphorus to organophosphorus products is achieved with high selectivity of monoalkyl phosphate(95.0%)under appropriate reaction conditions.Mechanism of the reaction is suggested to account for non-catalytic oxidation.