| 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-/ ZrO2-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, 1H 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, 1H 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. |
