钨(钼)过氧酸双季铵盐的合成和催化H_2O_2氧化醇类的反应

Synthesis of Bis-quaternary Ammonium Peroxotungstates (Peroxomolybdates) and their Catalytic Activity in Oxidation of Alcohols by Aqueous H_2O_2

设计合成了3种新型的钼、钨过氧配合物的双季铵盐PhCH2N(CH2)6NCH2Ph[W(O2)4].2H2O、PhCH2N(CH2)6NCH2Ph[WO(O2)2(C2O4)]和PhCH2N(CH2)6NCH2Ph[MoO(O2)2(C2O4)]。并利用元素分析、红外光谱、激光拉曼光谱测试技术对其进行了表征,研究了它们在无有机溶剂、无卤素、无相转移催化剂的清洁条件下催化30%稀H2O2氧化苯甲醇、环己醇分别生成苯甲醛(苯甲酸)和环己酮的反应。实验结果表明,在温和条件下,钨过氧配合物的双季铵盐对上述反应有很好的催化作用。而含钼过氧配合物的双季铵盐的催化活性相对较弱。其中,苯甲酸、苯甲醛、环己酮的最高产率可分别达到93.0%、93.6%和91.7%。

Several bis-quatemary ammonium salts of peroxotungstate and peroxomolybdate, such asPhCH2N（CH2）6NCH2Ph[W（O2）4]·2H2O、PhCH2N（CH2）6NCH2Ph[WO（O2）2（C2O4）] and PhCH2N（CH2）6NCH2Ph[MoO（O2）2（C2O4）] and PhCH2 N （ CH2 ） 6- NCH2 Phi MoO（O2）2 （C2O4 ）], have been synthesized and characterized. Their catalytic activities in the oxidation of cyclohexanol and benzyl alcohol with aqueous 30% hydrogen peroxide were investigated. The results show that the bis-quatemary ammonium peroxotungstates are excellent catalysts in the oxidation of benzyl alcohol and cyclohexanol under moderate conditions. However, the catalytic activity of bis-quatemary ammonium peroxomolybadates is relatively weak. The yields of benzyl acid, benzaldehyde and cyclohexanone were 93.0%, 93.6% and 91.7% respectively.