Selective Synthesis of Unsaturated Alcohols over Heterogeneous Metal-Ion Catalysts

以十六烷基三甲基溴化铵为模板剂合成了介孔分子筛MCM-41。用锡盐、锆盐浸渍MCM-41、SiO_2、Al_2O_3、TiO_2和一些沸石。在30 ml不锈钢高压釜中，巴豆醛和苯乙酮与仲醇进行选择性还原反应，巴豆醛在金属催化剂上加氢生成大量的丁醛和正丁醇，它们是C=C双键的氢化产物。锡的加入能有效地提高巴豆醇的选择性，从而提高金属催化剂上羰基的选择性。负载型Sn和Zr催化剂表明，以仲醇为溶剂，通过氢转移反应选择性地还原羰基（MPV还原）。研究了载体和起始盐对反应的影响。含MCM-41的SiO2适合作为Sn和Zr的载体。酸性或碱性的支持是无效的。活性炭负载的锆也具有很高的活性。应选择中性多孔材料作为支撑体。Sn催化剂的醋酸锡和Zr催化剂的氧氯化锆分别是最好的起始盐之一。还原温度对不饱和醇收率的依赖性表明Sn（II）和Zr（IV）是羰基化合物选择性还原的活性物种。辛可尼定的加入改善了S-1-苯基乙醇的对映体过量。

Mesoporous silicate, MCM-41 was synthesized by using hexadecyl trimethyl ammonium bromide as a template. MCM-41, SiO_2, Al_2O_3, TiO_2 and some zeolites were impregnated with some kinds of tin and zirconium salts. The catalyst were calcined and reduced at prescribed temperatures.The selective reductions of crotonaldehyde and acctophenone were carried out with a secondary alcohol in stainless steel autoclave (30 ml).Hydrogenation of crotonaldehyde over metallic catalysts produces significant amount of butyraldehyde and 1-butanol, corresponding hydrogenates of C=C doublc bond. The addition of Sn was effective to improve the selectivity of crotyl alcohol, corresponding hydrogenate of carbonyl group over metallic catalysts. The supported Sn and Zr catalysts indicated that carbonyl groups were selectivcly reduced via hydrogen transfer reaction from secondary alcohol added as a solvent (MPV reduction). The effects of support and starting salts were investigated. Silica including MCM-41 was suitable for the support of Sn and Zr. Acidic or basic support was not effective. Zirconium supported on active carbon was also highly active. Neutral porous materials should be selected for the supports. Tin acetate for Sn catalysts and zirconium oxychloride for Zr catalysts were ones of the best starting salts, respectively Dependence of reduction temperature on the yicld of unsaturated alcohol indicated that Sn (II) and Zr (IV) were active species for the selective reduction of carbonyl compounds. Enatiomeric-excess of S-1-phenyl ethanol was improved by the addition of cinconidine in the reation mixture.