摘要:
发展生物兼容的金属催化剂用于芳烃的选择性氧化生成醌的方法在有机合成中极为重要.本文以过硫酸氢钾为终端氧化剂,一系列的位阻金属卟啉为仿生催化剂用于2-甲基萘的氧化进行了探究,结果表明:铁卟啉的催化活性远远高于锰卟啉,其中氯化5,10,15,20-四(五氟苯基)铁卟啉催化活性明显地优于氯化5,10,15,20-四(2-氟苯基)铁卟啉、氯化5,10,15,20-四(2,4,6-三甲基苯基)铁卟啉、氯化5,10,15,20-四(2,6-二氯苯基)铁卟啉、氯化5,10,15,20-四(2,6-二氟苯基)铁卟啉;相应优化条件如下:乙腈为溶剂,底物2-甲基萘1 mmol,过硫酸氢钾3mmol,四丁基碘化铵0.1 mmol,氯化5,10,15,20-四(五氟苯基)铁卟啉0.2 mmol%,室温下2-甲基萘以100%的转化率选择性氧化得到18%的2-甲基-1,4-萘醌(维生素K3)和52%的6-甲基-1,4-萘醌;5,10,15,20-四(五氟苯基)卟啉结构通过1H NMR、19F NMR、13C NMR和X射线单晶衍射表征,相应目标产物的结构通过1H NMR、13C NMR和2D-NMR表征.%The development of bio-compatible metal catalysts for selective oxidation of Arene to Quinones,is of intrinsically importance in organic synthesis.In this paper,the oxidation of 2-Methylnaphthalene is investigated,employing a serious of hinder metalloporphyrins as biomimetic catalyst and Oxone as the terminal oxidant.The results show that the catalytic activity of iron porphyrin is much higher than that of manganese porphyrin,and Iron (]Ⅲ) complex of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin is markedly superior to Iron (Ⅲ) complex of 5,10,15,20-tetrakis (2,4,6-trimethylphenyl) porphyrin,Iron (Ⅲ) complex of 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin,Iron (Ⅲ) complex of 5,10,15,20-tetrakis(2-fluorophenyl)porphyrin and Iron (lⅢ) complex of 5,10,15,20-tetrakis (2,6-difluorophenyl)porphyrin.An optimized condition is followed:MeCN 10 mL,2-methylnaphthalene 1 mmol,Oxone 3 mmol,Bu4NI 0.1 mmol,Iron (Ⅲ) complex of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin 0.2 mmol%,and 2-Methylnaphthalene was selectively oxidized to 2-methyl-1,4-naphthaoquinone (vitamin K3) in 18% yield and 6-methyl-1,4-naphthaoquinone in 52% yield with 100% conversions.The structures of 5,10,15,20-tetrakis (pentafluorophenyl)porphyrin was determined by 1H-NMR,13C-NMR,19F-NMR and X-ray crystallography,and the structure of the corresponding target compounds was characterized by 1H-NMR,13C-NMR and 2D-NMR.