【作者】 杨义文；

【导师】 陈慧宗；

【作者基本信息】 江西师范大学 ， 有机化学， 2005， 硕士

【摘要】 本文叙述了纳米固体超强酸催化剂的研究进展及其在有机合成中的应用。比较系统地研究了纳米固体超强酸催化合成乙酸冰片酯的反应,并对反应的动力学进行了初探。对纳米固体超强酸催化合成系列正、异冰片酯及其它酯的反应作了一定的研究,论文分析了正、异冰片酯化反应的差异,并用TEM、BET、XRD、IR及酸标指示剂等方法和手段对纳米固体超强酸的粒度、比表而积、形貌变化及其酸性大小进行了分析和测定,通过IR、¹H NMR、^?C NMR等测试手段对各酯化反应的主产物进行了结构确证。 1.通过IR、TEM、BET、XRD、酸标指示剂等手段对纳米固体超强酸的结构、粒度、比表而积、形貌变化及其酸性大小进行了分析和测定,并对其催化机理进行了初步的探讨。 2.在纳米固体超强酸的催化下,乙酸和冰片的酯化反应能顺利进行,反应酯化率高,选择性好。实验考察了反应时间、反应温度、醇酸摩尔比、催化剂载休的配比、处理催化剂所用的浸泡液浓度、催化剂的焙烧温度、用量等因素对催化剂催化性能的影响,并由此得出酯化反应的最佳反应条件和催化剂的最佳制备条件。对反应的动力学进行了分析,采用孤立法分別测出乙酸和冰片各自的反应级数,通过测定T₁、T₂两个不同温度的反应速率常数,求出反应的活化能,并最终得出乙酸和冰片酯化反应的速率方程。 3.以合成乙酸冰片酯的最佳反应条件为基准,采用纳米固体超强酸S₂O₈^2-/ZrO₂或SO₄^2-/ZrO₂-La₂O₃为催化剂,以冰片、异冰片、乙酸、丙酸、丁酸、异丁酸为原料,合成了系列正、异冰片酯（其中6个末见文献报道）。对正、异冰片酯化反应的差异进行了分析。 4.采用纳米稀土复合固体超强酸SO₄^2-/ZrO₂-Gd₂O₃,SO₄^2-,^/ZrO₂-Nd₂O₃分别合成了乙酸戊酯和乙酸苄酯两种香料,实验考察了反应时间、反应温度、醇酸比及催化剂的用量对酯化率的影响,并由此得出反应的最佳条件。更多还原

【Abstract】 In this dissertation ,we stated the recent development of nanometer solid superacids and their appliance in organic synthesis. The preparation of borneolacetate catalyzed by nanometer solid superacid and its reaction kinetics were studied. The synthesis of eight compounds （ borneol ester and isoborneol ester） and other esters catalyzed by nanometer solid superacids were also researched. In addition, we still analyzed the distinction of esterification yield of borneol ester and isoborneol ester. The particle size, surface area, changes of profile and acidity of nanometer solid superacids were mensurated and analyzed by TEM, BET, XRD, IR and acid indicator. The structures of the main products of every esterification reaction were characterized by IR, 1^H NMR, and （13）^HNMR spectra.Firstly, the structures, particle size, surface area, changes of profile and the acidity of nanometer solid superacids were determined and analyzed by IR, TEM, BET, XRD and acid indicator. We also preliminarily studied the catalytic mechanism of nanometer solid superacids.Secondly, using nanometer solid superacids as the catalyst, the esterification reaction of acetic acid and borneol could proceed smoothly, the yield was very high and it had good reaction preference. The effects of reaction time, reaction temperature, the molar ratio of borneol to acetic acid, the mass percent of rare earth oxide in carrier, the mol concentration of dipping solution, baking temperature and the use level of catalyst on catalytic activity of nanometer solid superacid were discussed. The optimal conditions of preparation of catalyst and the optimal reaction conditions were obtained. Furthermore, we investigated its reaction kinetics, using isolated method we gained the reaction order of acetic acid and borneol. We also obtained the activation energy of the reaction through assaying the reaction rate constant of two temperatures （T₁, T₂）. At last, the reaction rate equation was acquired.Thirdly, on the basis of the optimal reaction conditions of synthesis of borneolacetate, using borneol 、 isoborneol, acetic acid, propionate、 butyrate and isobutyric acid as the starting material and nanometer solid superacid （S₂O₈）^2-/ZrO₂ or （SO₄）^2-/ZrO₂-La₂O₃ as the catalyst ,a series of compounds （ borneol ester and isoborneol ester ） which had six new compounds were prepared. The difference of esterification yield of borneol ester and isoborneol ester was analyzed.Finally, pentyl acetate and benteine could be respectively synthesized by esterification reaction in the presence of nanometer rare earth composite solid superacids （SO₄）^2-/ZrO₂-Gd₂O₃ and （SO₄）^2-/ZrO₂-Nd₂O₃. The effects of reaction time, reaction temperature, the mol ratio of acid to alcohol and the use level of catalyst on esterification yield were discussed. In the end, we obtained their optimal reaction conditions.更多还原