【作者】 刘永根；

【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】 本文对纳米固体超强酸催化α-蒎烯（β-蒎烯、松节油）酯化—皂化法合成正龙脑、以及纳米固体超强酸催化莰烯选择性合成异龙脑进行了研究。 一.在纳米固体超强酸的催化下,α-蒎烯与草酸的酯化反应能顺利进行,经皂化反应后,能高产率、高选择性地合成珔龙脑。文章分析了三种纳米固体超强酸So₄^2-/ZrO₂、S₂O₈^2-/ZrO₂、SO₄^2-/ZrO₂-CeO₂作催化剂时,α-蒎烯与草酸发生酯化反应的温度、时间、反应物配比、催化剂用量以及催化剂颗粒大小等条件对合成龙脑的影响,从而得出了酯化反应的最佳条件,对催化剂的再生方法和重复使用进行了研究,并对α-蒎烯酯化—皂化法合成龙脑的反应机理进行了探讨,从反应机理和α-蒎烯的分子结构出发解釋了一系列实验现象。简述了纳米固体超强酸的结构特征。探索出了柱层析分离下、异龙脑的方法,并对下龙脑进行了熔点、IR、¹H NMR、¹³C NMR等测试。 二.论文研究了以β-蒎烯或松节油为原料合成龙脑的方法。用大量实验事实对α-蒎烯、β-蒎烯、松节油合成龙脑的方法和结果进行了分析和比较,对SO4₄^2-/ZrO₂、S₂O₈^2-/ZrO₂、SO₄^2-/ZrO₂-CeO₂,三种催化剂催化特性进行了研究和对比。 三.论文研究了异龙脑的选择性合成。采用纳米固体超强酸为催化剂,以莰烯和草酸为原料合成异龙脑,取得令人满意的效果,从而为工合合成异龙脑的方法提供了新的思路。论文对酯化反应的最佳条件进行了探索,分析了该法合成异龙脑的反应机理以及各种因素对莰烯转化率、界龙脑产率和产品纯度的影响。同样也对异龙脑进行了熔点、IR、¹H NMR、¹³C NMR等测试。 本文的主要目的是探索立体选择性合成正、异龙脑的最佳工艺途径。更多还原

【Abstract】 The synthesis of borneol catalyzed by nanometer solid superacid from a-Pinene（ β -pinene or turpentine） by the way of esterification- saprification method was proposed in this dissertation. The preparation of isoborneol from β -pinene by the way of esterification- saprification method in the presence of nanometer solid superacid was also studied.Firstly, the esterification reaction of a-Pinene and oxalic acid could proceed smoothly in the presence of nanometer solid superacid. After saprification reaction, borneol with high yield or high content in crude product could be obtained. When we used nanometer solid superacid （SO₄）^2-/ZrO₂ or （S₂O₈）^2-/ZrO₂ or （SO₄）^2-/ Zr_O2-CeO₂ as the catalyst, the effects of esterification reaction temperature,reaction time, catalyst amount, molar ratio of a-Pinene to oxalic acid, size of catalyst on the experimental results were investigated, the optimal reaction conditions of esterification reaction were gained. We also studied the reuse and the revivification of the catalyst.The reaction mechanism of synthesis of borneol from a-Pinene by the way of esterification- saprification method was discussed , from the reaction mechanism and the molecular structure of β -pinene we explained a series of experimental phenomena . In addition, we stated the constitutional feature of nanometer solid superacid and got a good separation method of borneol and isoborneol by way of column chromatography from test. The melting point of borneol was tested.The structure of borneol was characterized by IR, 1^H NMR, and （13）^H NMR spectra.Secondly, we researched the preparation of borneol from P -pinene or turpentine in the presence of nanometer solid superacid . Using a great amount of experiment fact we analyzed and compared the results of three synthetical method of borneol from a-Pinene , β-pinene or turpentine. The catalytic activity of three nanometer solid superacid （SO₄）^2-/ ZrO₂, （S₂O₈）^2-/ ZrO₂, （SO₄）^2-/ ZrO₂-Ce₂O₃ was also compared and studied.Finnally, the selective synthesis of isoborneol was investigated. Using nanometer solid superacid as the catalyst and camplene , oxalic acid as the raw material, by the way of esterification- saprification method ,we could selectively prepared isoborneol with high yield. It provided the synthesis of isoborneol in industry with a new way .We explored the optimal reaction conditions of esterification reaction and analyzed the effects of the mechanism of esterification reaction and different factors on the conversion of camplene, the yield of isoborneol and the purity of products. The melting point of isoborneol was tested. The structure of isoborneol was characterized by IR, 1^H NMR, and （13）^H NMR spectra too .In short, exploring the best process of selective synthesis of bornel and isoborneol was the main motives of this dissertation.更多还原