【作者】 王俊科；

【导师】 王喜存； 李政；

【作者基本信息】 西北师范大学 ， 有机化学， 2004， 硕士

【摘要】 本论文共分五章： 第一章 综述了PEG在有机合成方法学上的优势及其在有机合成方面的主要成就：包括生物大分子的合成，有机小分子的合成，杂环化合物的合成与PEG支载的催化剂和试剂。 第二章 利用PEG6000作载体，通过脱水剂DCC在室温下将对羟基苯甲酸以酯键连接在PEG6000上，再与氯乙酸在较温和的条件下生成PEG6000支载的芳氧乙酸，然后，依次与亚硫酰氯、硫氰酸铵、芳胺反应，生成PEG6000支载的硫脲，最后用甲醇钠的甲醇溶液切割PEG，得到了十一种1，3-二取代硫脲。 第三章 为了拓宽第二章方法的应用范围和得到结构更为多样的硫脲类化合物，我们用芳甲酰肼和芳氧乙酰肼替代芳胺作亲核试剂，得到了二十一种取代氨基硫脲。 第四章 以第三章的工作为基础，用冰醋酸处理PEG6000支载的氨基硫脲，顺利地脱水环合，进一步用甲醇钠的甲醇溶液切割PEG，得到二十种2，5-二取代-1，3，4-噻二唑。 第五章 以三氯氧磷作作脱水剂，在微波辐射条件下，利用PEG6000支载的芳氧乙酸与芳甲酰肼反应，得到PEG6000支载的啞二唑，用甲醇钠的甲醇溶液切割PEG，得到了十种2，5-二取代-1，3，4-啞二唑，并选出了最佳反应条件。我们试图用芳氧乙酰肼替代芳甲酰肼来合成2，5-二取代-1，3，4-啞二唑。不幸的是，没有得到预期产物。 总之，PEG 6000作为载体可以合成以上四类化合物。所有化合物均为未见文献报道的新化合物，其组成和结构经元素分析、红外光谱和核磁共振谱得到确证。与传统的方法相比，整个反应过程中，反应条件温和，提纯方法简单，分离容易；目标化合物中带有一个甲酯键，可以方便地对其进行转化和进一步的修饰。更多还原

【Abstract】 This paper is divided into five chapters.Chapter one The superiority of PEG in organic synthetic methodology and the main achievements in organic synthesis are reviewed, including the synthesis of biological macromolecules, organic small molecules and heterocyclic compounds and the PEG bound catalysts and reagents.Chapter two 4-Hydroxybenzoic acid is connected with PEG6000 through defoliant DCC at rooom temperature, then the product is refluxed with chloroacetic acid in acetone to afford PEG-bound phenyloxyacetic acid, which is reacted with thionyl chloride, ammonium thiocyanate and arylamines in turn to give PEG-bound disubstituded thioureas. After the cleavage with sodium methoxide in methanol, the eleven disubstituted thioureas are obtained.Chapter three In order to extend the scope of the method in chapter two and to obtain substituded diversiformly thioureas, we substitute the arylamines for aroylhydrazines and aryloxyacetyl hydrazines as nucleophilic reagents to afford twenty-one thiosemicarbazides.Chapter four In term of the works in chapter three, PEG-bound thiosemicarbazides are further reacted with glacial acetic acid before the cleavage of PEG with sodium methoxide in methanol and the dehydrating cyclization proceeds successfully to give twenty 2,5-disubstituded thiadizoles.Chapter five PEG-bound phenyloxyacetic acid is reacted with aroyl hydrazines in the presence of phosphorus oxychloride as catalyst under microwave irradiation to obtain PEG-bound oxadiazoles, which are incised with sodium methoxide in methanol to afford ten 2,5-disubstituted oxadiazoles. The best condition are chosen. Unfortunately, after aryloxyacetic acid hydrazines are treated with PEG-bound phenyloxyacetyl chloride and with POCl3 in turn, the predicted compounds cannot be afforded.In sum, the above four kinds of compounds may be synthesized on PEG6000 support. All compounds have not been reported in the literature. Their structure are confirmed by elemental analyses, IR, NMR and MS. Compared with conventional methods, the condition of PEG supporting reaction is mild and the procedures of purification and separation are simple. Moreover, the target compounds still involve an ester group and can be further modified and convert into other useful groups.更多还原