Ciriminna Rosaria, Hesemann Peter, Moreau Joël J E, Carraro Massimo, Campestrini Sandro, Pagliaro Mario
Istituto per lo Studio dei Materiali Nanostrutturati, CNR, via Ugo La Malfa 153, 90146 Palermo, Italy.
Chemistry. 2006 Jul 5;12(20):5220-4. doi: 10.1002/chem.200501556.
The replacement of toxic Cr(VI) for O2 and of chlorinated solvents for supercritical carbon dioxide (or ionic liquids) in the oxidation of alcohols remains hindered by the low selectivity and activity of the current heterogeneous catalysts. Using an integrated approach that combines sol-gel entrapped perruthenate as aerobic catalyst, an encapsulated ionic liquid as solubility promoter, and scCO2 as the reaction solvent, we have developed a system capable of rapidly converting different alcohols into carbonyl compounds with complete selectivity, including substrates which are otherwise difficult to oxidise. The methodology is generally applicable and may easily be extended to other waste-free, catalytic syntheses of fine chemicals.
在醇类氧化反应中,用氧气替代有毒的六价铬(Cr(VI))以及用超临界二氧化碳(或离子液体)替代氯化溶剂,目前仍受到多相催化剂选择性和活性较低的阻碍。通过采用一种综合方法,即将溶胶 - 凝胶包裹的高钌酸盐用作需氧催化剂、将封装的离子液体用作溶解度促进剂以及将超临界二氧化碳用作反应溶剂,我们开发出了一种能够将不同醇类快速转化为羰基化合物且具有完全选择性的体系,包括那些原本难以氧化的底物。该方法具有普遍适用性,并且可以很容易地扩展到其他无废物的精细化学品催化合成中。