【作者】 张丽；

【导师】 肖元晶；

【作者基本信息】 华东师范大学 ， 有机化学， 2015， 硕士

【摘要】 本论文的主要工作是多取代含氟异噁唑类化合物的合成研究,论文包括两大部分,第一部分是NIS促进的4-多氟烷基-5-酰基异嗯唑衍生物的合成；第二部分是质子酸促进的4-多氟烷基-5-烷基异嗯唑衍生物的合成。我们首先发展了一种新的合成4-多氟烷基-5-酰基异嗯唑衍生物的方法。该方法利用廉价易得的各种含氟含炔基羟胺为原料,通过加入NIS作为氧化剂,产生肟中间体,然后发生亲电环化反应可以实现一锅法合成4-多氟烷基-5-酰基异嗯唑衍生物。这种新方法原料易得,操作方便,条件温和,而且具有一定的实用价值。在前面工作基础上发现,我们在肟中间体的形成之后,直接加入适量的硫代硫酸钠固体将体系存在的碘离子淬灭或还原,利用体系形成的质子酸来促进下一步的亲电环化反应。从而发展了一种合成4-多氟烷基-5-烷基异噁唑衍生物的方法。更多还原

【Abstract】 The main work of this dissertation is focused on synthesis of multi-substituted fluorinated isoxazole derivatives, which includes two parts:the first part is to synthesize 4-polyfluoroalkyl isoxazole-5-acyl derivatives, which was promoted by NIS; The second part is to synthesis of 4 polyfluoroalkyl isoxazole-5-alkyl derivatives, which was promoted by protonic acid.first, in the first part of this dissertation, we have developed a new method for the synthesis of 4-polyfluoroalkyl isoxazole-5-acyl derivatives. This method makes use of a variety of cheap and readily available fluorinated alkyne-containing hydroxylamine as starting material, NIS as an oxidant to produce oxime intermediates and subsequent electrophilic cyclization reaction, which provide a one-pot method for synthesis of 4-polyfluoroalkyl-5-acyl isoxazole derivative. This novel synthetic method was featured with readily available starting materials, good yields and ease of operation under mild reactions condition and the ease of further transformation of the products.Based on the first part of this dissertation, we find that oxime intermediate could undergo electrophilic cyclization to afford 4-polyfluoroalkyl isoxazole-5-acyl derivatives by adding an appropriate amount of sodium thiosulfate to the reaction system timely to quench the iodide ions. Therefore, a new method for the synthesis of 4-polyfluoroalkyl isoxazole-5-acyl derivatives was developed in the second part of this dissertation.更多还原