【作者】 李浩然；

【导师】 马学兵；

【作者基本信息】 西南大学 ， 有机化学， 2011， 硕士

【摘要】 本文以廉价的1R,2R-环己二胺为原料,通过一系列(磺酰胺化、烯烃聚合)化学反应,合成不同聚合度含有机膦酸官能团的聚合物载体。通过氮原子的配位络合作用将[RuCl2(p-cymene)]负载于该有机聚合物载体上,制备了在酸性介质中能溶于四氢呋喃、乙腈、氯仿和N,N-二甲基甲酰胺等有机溶剂的有机聚合物负载钌催化剂。在催化反应结束后,加入乙酸乙酯等有机溶剂,该负载钌催化剂可从均相反应体系中析出,通过过滤可回收(87-93%)。用IR, TEM, XRD和N2等温吸附曲线对有机聚合物载体和负载手性催化剂的结构和表面形貌进行了分析,并确定了其组成。实验表明：与其他有机高分子载体不同,含有机膦酸官能团的聚合物载体具有微孔结构(1-20 A)、线形(宽20-50 nm)的网状结构。负载过渡金属钉后,载体的线状形貌结构被打断,形成了团簇状结构。将该负载钌手性催化剂应用于苯乙酮及其衍生物的不对称转移氢化,探索了不同钌负载量、溶剂、温度和反应时间等条件对催化性能的影响,筛选了最佳的催化反应条件。在最佳的催化反应条件下(10 wt%钌负载量、m苯乙酮/mRu=100：1、V甲酸/V三乙胺=1：3,底物浓度为1.72 mol/mL,甲醇溶剂、50℃、反应6 h),反应产物的转化率和对映选择性分别为41.3-99%和80.1-97.3%ee,没有其它副产物产生。更多还原

【Abstract】 In this article, the organosoluble polystyrene polymer containing phosphonate group had been synthesized by using 1R,2R-Diaminocyclohexane as raw material through several steps (p-toluenesulfonyl and radical polymerization reaction). Upon the immobilization of [RuCl2(p-cymene)]2 on the synthesized polystyrene polymer by the complexation reaction of amino group with metal ruthenium, catalysts 4a-c organosoluble in THF, DMF, DMSO, CH2Cl2, CHCl3, CH3CN, CH3OH and so on in acidic medium were prepared. After the catalytic reaction was completed, ethyl acetate was added, and then supported ruthenium catalyst 4c precipitated out and recycled in 87-93% yield.The structure and surface morphology had been characteried by IR, TG, XPRD, SEM, TEM, and N2 adsorption-desorption isotherm. It was shown that 3c is a novel type of catalyst support possessed the filiform and microporous structure with 20-50 nm width and 1-20A micropores.In the asymmetric transfer hydrogenation of acetophenone and it derivatives, the optinum catalytic conditions such as the supported amount of transitional metal ruthenium, solvent, temperature and reaction time were screened in details. The products of acetophenone and it derivatives in 41.3-99% conversion and 80.1-97.3% ee without side-products (100% chemical selectivity) were obtained at 50℃for 6 h in methanol containing 1.72 mol/mL substrates by using 10 wt% Ru catalyst (S/C=100).更多还原