非晶态雷尼镍论文：D-酒石酸修饰RaneyNi催化樟脑不对称加氢合成龙脑.doc

非晶态雷尼镍论文：D-酒石酸修饰RaneyNi催化樟脑不对称加氢合成龙脑【中文摘要】手性化合物是一类重要的化合物,在香料、医药、农药和功能材料等方面具有广泛用途。开展手性合成的新方法和新催化剂的研究具有十分重要的意义。多相手性催化剂具有产物易分离,催化剂可以重复使用等优点,符合绿色化学发展方向。因此近年来开发和探索高效率、高光学选择性的的多相手性催化剂已成为手性催化研究的重要课题。采用具有光学活性的酒石酸修饰雷尼镍催化剂可以制得一种高效催化剂,该催化剂体系对羰基手性加氢具有良好的催化活性和对映体选择性。本课题将该催化体系用于催化天然樟脑不对称【英文摘要】Chiral compounds are important compounds,which are broadly used in perfume,medicine,pesticide,functional materials and so on.It has great importance to produce new method and new catalyst for chiral synthesis.There are two kinds chiral catalyst,homogeneous and heterogeneous phase catalyst.Homogeneous phase catalyst has high reaction activity and enantio-selectivity,but its expensive and hard to reuse. Hetero-geneous phase catalysts are facile,easy operated and easy to reused, which are as green chemical catalyst.So it is important subject to develop new catalyst with high reaction activity and enantioselectivity.The system of Raney Ni modified by D-tartaric acid high reaction activity and enantio-selectivity on carbonyl compounds hydrogenation.Our subject trys to use RaneyNi/D-TA/NaBr as catalyst in hydrogenation of comphor.This is the main research contents:(1)Find new technical route. By read many abstract, we decide our technical route as this:research the effects of D-tartaric acid concentration,pH of modifying solution,selection of additives,temperature of modification and time of modification on Raney nickel catalyst.We find optimum modification conditions as: Raney Ni 3g, modified in 100ml solution with 1% D-tartaric acid concentration and 2% NaBr concentration,pH =4,which are achieved by adding1M NaOH,then modified 1hour at 100.(2)The influence of most important factors on the optical yield and hydrogenation activity varying the reaction temperature and pressure,solvent type,the reaction time and so on were systematically investigated.By many tests,We find optimum conditions as this:comphor 3g,modified Raney Ni 3g,ethanol-solution 500ml,acetoacetate2g,stirring speed as 800r/min,reaction10hour at 60.(3)Various physico-chemical methods,such as,infra-red spectroscopy (FTIR),X-ray diffractometry(XRD),scanning electron microscopy(SEM),BET surface area,and so on,were employed to gain a deeper understanding of the inherent problem of the factors effect.As a result, we found the loading amount of D-tartaric acid and crystal structure ware nearly same after hydrogenation,but Raney Ni surface became irregular,nickel atom dissolved.(4)To evaluate the mechanism of asymmetric hydrogenation of comphor, we consider many reference and our experimental data,and put forward chiral catalytic mechanism of RaneyNi/D-TA/NaBr system.【关键词】非晶态雷尼镍 D-酒石酸 修饰 不对称加氢 樟脑【英文关键词】Raney nickel D-Tartaric acid modification asymmetric hydrogenation comphor【目录】D-酒石酸修饰RaneyNi催化樟脑不对称加氢合成龙脑论文摘要8-10Abstract10-11第一章 绪论12-251.1 手性与手性合成技术12-141.1.1 手性技术12-131.1.2.对映体组成的表示方法和测定方法13-141.2 不对称催化加氢研究进展14-201.2.1 多相不对称催化加氢研究进展14-161.2.1.1 传统过渡金属催化剂催化加氢14-151.2.1.2 由手性分子修饰的多相催化加氢体系15-161.2.2 均相不对称催化加氢研究进展16-181.2.2.1 磷原子手性配体16-181.2.3 均相不对称加氢催化剂的多相化的发展18-191.2.4 不对称催化加氢未来研究的方向19-201.3 不对称合成龙脑研究现状20-221.3.1 课题背景20-211.3.2 樟脑不对称还原研究现状21-221.3.2.1 使用硅烷制取211.3.2.2 使用碱金属还原211.3.2.3 固体酸催化-蒎烯和松节油211.3.2.4 使用格氏试剂21-221.3.2.5 电还原樟脑合成龙脑221.3.2.6 其他还原剂221.4 课题研究思路22-251.4.1 课题研究的目的、内容22-231.4.2 课题研究的意义23-25第二章 实验研究方案25-352.1 技术路线的确定252.2 实验原理25-262.3 课题方法的构思26-272.3.1 课题方法的设想26-272.3.2 实验设计272.4 主要试剂和仪器27-292.4.1 主要试剂和原料27-282.4.2 主要仪器和设备28-292.5 TA-NaBr/RaneyNi 不对称催化剂的制备292.5.1 RaneyNi 的前处理292.5.2 RaneyNi 的预修饰过程292.6 加氢反应29-312.6.1 樟脑预处理29-302.6.2 试验方法302.6.3 产物的分析与测定30-312.7 数据分析31-332.7.1 催化剂性能考察办法312.7.2 产物测定结果的计算方法31-332.8 催化剂的表征33-342.8.1 催化剂表面酒石酸负载量的测定332.8.2 X 射线衍射研究332.8.3 催化剂表面NaBr 负载量的测定33-342.8.4 SEM 研究342.8.5 红外光谱研究342.9 本章小结34-35第三章 催化剂修饰条件对催化剂性能的影响35-473.1 修饰溶液 PH 值的影响35-373.2 修饰液中酒石酸浓度及其负载量的影响37-393.3 修饰温度的影响39-403.4 修饰时间的影响40-423.5 修饰助剂的影响42-443.6 其他条件对 RaneyNi 活性及光学选择性的影响44-463.6.1 修饰过程中引入空气的影响443.6.2 超声因素的影响44-463.7 本章小结46-47第四章 反应条件对催化剂活性的影响47-584.1 引言474.2 溶剂的影响47-484.3 反应温度的影响48-494.4 添加乙酸钠的影响49-514.5 氢气压力的影响51-524.6 反应时间的影响52-544.7 反应底物和催化剂之比的影响54-554.8 其他反应因素的影响554.9 催化剂催化寿命的考察55-564.10 本章小结56-58第五章 催化剂的表征及催化机理研究58-685.1