【作者】 翁建全；

【导师】 沈德隆；

【作者基本信息】 浙江工业大学 ， 工业催化， 2005， 博士

【摘要】 噻唑类杂环化合物具有良好的生物活性,广泛应用于农药和医药领域。本论文以1,3-噻唑烷为先导化合物,催化合成了66个1,3-噻唑烷衍生物,其中56个为新化合物,所有化合物结构均经红外光谱、核磁共振氢谱、质谱和元素分析表征;同时,对其晶体结构和生物活性进行了研究。具体研究内容如下: 1.参照文献方法,以乙醇胺和二硫化碳为原料合成了2-硫代-1,3-噻唑烷,继而利用其与氯乙醇的硫氧交换反应合成了2-氧代-1,3-噻唑烷,并对其工艺条件进行了优化;参考相关文献,设计了一条以2-氧代-1,3-噻唑烷和O,O-二乙基硫代磷酰氯为原料合成杀线虫剂噻唑磷的工艺路线,成功得到了噻唑磷样品;该路线未见有文献报道,具有原料易得、操作简便、反应条件温和等优点。 2.在三乙胺的催化下,通过2-取代-1,3-噻唑烷与氯甲酸酯的缩合反应得到26个2-取代-1,3-噻唑烷-3-甲酸酯类化合物,其中24个为新化合物;通过对代表性化合物的X-射线单晶结构分析,证实了2-硫代-1,3-噻唑烷与氯甲酸酯的缩合产物为硫酮式,而非硫酯式结构,并发现其分子中酰胺键长显著长于典型的酰胺键长。 3.在三乙胺的催化下,通过2-取代-1,3-噻唑烷与酰氯的缩合反应得到22个3-酰基-2-取代-1,3-噻唑烷类化合物,其中16个为新化合物;通过对代表性化合物的X-射线单晶结构分析,对其结构进行了确证,同时也发现此类化合物分子中的酰胺键长较典型的酰胺键要长得多。 4.在三乙胺的催化下,通过2-取代-1,3-噻唑烷与取代苯基异氰酸酯的偶联反应得到17个N-取代苯基-2-取代-1,3-噻唑烷-3-甲酰胺类化合物,其中16个为新化合物;通过对代表性化合物的X-射线单晶结构分析,对其结构进行了确证,在发现较长的酰胺键特征的同时,还发现了此类化合物存在分子内氢键作用。 5.对以上所合成的2,3-位取代-1,3-噻唑烷衍生物进行了初步生物活性(杀虫、杀菌及除草)研究。研究结果表明,大部分化合物对部分供试菌种表现出一定的抑制活性,其中化合物3c在500mg/L浓度下对小麦白粉病菌的抑制率达到90%;更多还原

【Abstract】 The thiazole derivatives have been widely used in pesticidal and medicinal fields because of their good biological activities. Sixty-six 1,3-thiazolidine derivatives, fifty-six of which are novel compounds, were prepared based on 1,3-thiazolidine as the lead compound and their structures were confirmed by IR, ¹H NMR, MS and elemental analysis. Their crystal structures and biological activities were also studied. It may be summarized as follows:1. According to the literature method, 2-thiono-l,3-thiazolidine was prepared with ethanolamine and carbon bisulfide as raw materials and 2-oxo-1,3-thiazolidine was further prepared by the exchange reaction between the oxygen of chloroethanol and sulphur atom of 2-thiono-1,3-thiazolidine. A new route of preparing nematocide fosthiazate was designed with 2-oxo-1,3-thiazolidine and O,O-diethyl chlorido-phosphorothioate as starting materials, and fosthiazate was successfully obtained. The remarkable advantages of the designed route are mild reaction condition, simple operation, easy obtain of the raw materials, etc.2. Twenty-six 2-substituted-1,3-thiazolidine-3-carboxylates, twenty-four of which are novel compounds, were prepared from a condensation reaction of 2-substituted-1,3-thiazolidine and chloroformate catalyzed by Et₃N; The structure of the condensation products of 2-thiono-1,3-thiazolidine and chloroformate were proven to be 2-thiono-1,3-thiazolidine-3-carboxylate rather than the ester of mercaptothiazoline by single-crystal X-ray diffraction of representative compound, and it was found that the C-N bond length to carbonyl groups is longer than the C-N bond length of a typical acylamine group.更多还原