摘要
醇氧化为相应的羰基化合物是一个重要的基本有机合成反应.通常的化学计量氧化、多相催化氧化和自由基氧化多有不足之处,在温和条件下通过络合催化途径来实现这种活泼官能团的转换,不但有深远的理论意义,更有广阔的应用前景.随着各种过渡金属络合物催化作用的研究开发及分子氧活化研究的不断深入,醇类的络合催化氧化也十分活跃,以过氧化物为氧源的Zr,V,Ti,Mo等络合物及以分子氧为氧源的Ru,V,Co等络合物的氧化醇的研究不少.用铜络合物、分子氧的工作中。
A Cu(Ⅱ) complex system for the catalytic oxidation of alcohols with di-oxygen to corresponding carbonyl compounds under mild conditions has been investigated. The oxidation rate of primary alcohols was greater than that of secondary alcohols. Steric hindrance effects were observed in the catalytic oxidation of some secondary alcohols by using cupric-N,N-disalicylidene-ethylene-diamine system. The multiplicity role of base was also studied. No oxidation of alcohols by Cu(II) complex was observed in the absence of base. The oxygen absorbed increased with increasing the amount of base, and the selectivity for carbonyl compounds decreased with increasing the amount of base. In the oxidation of benzyl alcohol to benzaldehyde, the conversion and selectivity were 65% and 90% respectively at a molar ratio of NaOH/alcohol 0.25. According to the relation of oxygen absorbed and conversion of benzyl alcohol, the reaction equation of the overall oxidation is proposed.
基金
国家自然科学基金
