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固体酸催化的有机合成反应的研究及其产物结构的表征

Studies on the Organic Synthesis Reactions Catalyzed by Solid Acids and Structural Analysis

【作者】 张素玲

【导师】 靳通收;

【作者基本信息】 河北大学 , 有机化学, 2002, 硕士

【摘要】 本文共分三部分: 第一部分:固体超强酸ZrO2/SO42-作为一种价廉易得的酸性催化剂已被用于多种有机化学反应,几乎对所有的酸催化反应均表现出较高的反应活性和较好的选择性,有其特殊的催化性能。在ZrO2/SO42-催化下,对醛酮与邻苯二酚作用生成2-取代或2,2-二取代苯骈-1,3-二氧五环来保护醛酮的羰基和酚羟基的反应进行了研究。该方法优于传统方法,具有无污染、反应条件温和、选择性好、产率高、以及操作简便、后处理容易等特点。 第二部分:在酸催化下,通过Biginelli缩合反应,以β-酮酸酯、醛和脲为原料,合成了具有抗癌性和抗病毒性等药理活性的3,4-二氢嘧啶-2-酮及其衍生物。Biginelli合成反应一般采用浓硫酸和盐酸为催化剂,容易发生氧化,聚合等副反应,并造成设备腐蚀,环境污染。本文采用氨基磺酸和对甲苯磺酸为合成该类化合物的催化剂,反应速度快,产率高,选择性好,并且解决了以上不足,为工业生产提供了一种经济实用新方法。 第三部分:在固体酸催化下,对β-酮酸酯与醇进行酯交换反应进行了研究。β-酮酸酯是一类重要的化学中间体,在有机合成中具有广泛的应用。用低沸点的醇的酯合成高沸点、高级醇的酯是合成酮酸酯的重要方法。完成此反应常采用硫酸、磷酸为催化剂,不仅腐蚀设备,污染环境,并且收率低。本文采用固体酸蒙脱土K-10为催化剂,环境友好,收率较高,操作简单,经济实用,催化剂可重复使用等特点。

【Abstract】 This thesis consists of three parts.In the first part, solid superacid ZrO2/SO42- is found to be cheap solid acidic catalyst for many organic reactions, it has much more efficient behavior in catalysis and work-up than conventional counterparts. An efficient and convenient method for preparation of 2,2-disubstituted and 2-monosubstituted 1,3-benzodioxoles from ketones and aldehydes with catechol catalysed by ZrO2/SO42- has been presented. The present methods have the additional advantages of non-corrosivity, mild reaction conditions, high yield and selectivity, easy of set-up and work-up over the classical methods.In the second part, dihydropyrimidines are prepared by a one-pot cyclocondensation of aldehydes, p-ketoesters and urea with aminosulfonic acid and p-toluenesulfonic acid-catalyzed condensation reaction. They have been the focus of considerable due to their therapeutic and pharmacological properties. Excellent yields with short reaction time, non-side reaction, non-corrosive and easy experimental and product isolation procedures make this an important alternation to traditional Biginelli catalyst.In the third part, transesterification of β-ketoesters with alcohols catalyzed by Montmorillonite K-10 in good yields. β-Ketoesters are of interest as chemical intermediates in the pharmaceutical, agrichemical, chemical and polymer industries, it is well known that traditional acidic catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid can cause severe environmental problems. The obvious advantages of the catalyst are easy and simple operation in the workup, inexpensive, non-toxic, non-corrosive, recyclable, more economical and environmental.

  • 【网络出版投稿人】 河北大学
  • 【网络出版年期】2004年 02期
  • 【分类号】O621.2
  • 【下载频次】358
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