摘要：活性开环易位聚合（ROMP）反应具有链长尺寸可控等优点，并且得到的聚合物中依然保留着单体中的双键，是制备功能化聚合物的最优方法之一。特别是有机化学家们经过一系列的研究，一些结构明确、化学性质稳定以及催化效率较高的催化剂开始逐渐被研发出来，这才使得通过聚合反应合成一些聚合物变得相对容易，尤其是一些含有复杂或者特殊官能团的聚合物，从而使得ROMP反应有一个较快的发展。ROMP反应中所用的单体种类有很多，而降冰片烯及其衍生物由于其自身的特点，在ROMP反应中被用作单体的次数较为频繁，但不同结构的单体由于自身的极性、空间位阻等方面会存在差异，因此这成为影响聚合反应的重要因素。由于糖分子具有水溶性、生物相溶性、生物降解性等特点，因此含糖化合物经常用于功能聚合物的合成。本论文主要研究新型含糖类7-氧杂降冰片烯衍生物的合成。首先是以四氢呋喃和马来酸酐为原料，经过一系列的反应得到含有炔基的氮杂降冰片烯衍生物，然后制备出葡萄糖、甘露糖、半乳糖的叠氮化合物，最后通过“点击化学”反应将叠氮化合物引入到降冰片烯衍生物上，从而得到新型含糖类7-氧杂降冰片烯衍生物单体。

关键词： 活性开环易位聚合；降冰片烯衍生物；含糖分子

Synthesis of Novel Sugar-containing 7-oxa Norbornene Derivatives for ROMP

Abstract：The active ring-opening metathesis polymerization (ROMP) reaction has advantages of controllable chain length, and the obtained polymer still retains double bonds in the monomer, and is one of the best methods for preparing functionalized polymers. In particular, after a series of studies by organic chemists, some catalysts with well-defined structures, stable chemical properties, and high catalytic efficiencies have been gradually developed. This has made it relatively easy to synthesize some polymers through polymerization, especially some Polymers containing complex or special functional groups, resulting in a rapid development of the ROMP reaction. There are many types of monomers used in the ROMP reaction, and due to its own characteristics, norbornene and its derivatives are frequently used as monomers in the ROMP reaction, but monomers of different structures have their own polarity. There may be differences in the steric hindrance and so on, so this has become an important factor affecting the polymerization reaction. Because sugar molecules are water-soluble, biocompatible, and biodegradable, sugar-containing compounds are often used in the synthesis of functional polymers. This dissertation mainly focuses on the synthesis of novel carbohydrate-containing 7-oxa-norbornene derivatives.Firstly, tetrahydrofuran and maleic anhydride are used as raw materials to obtain alkynyl-containing aza norbornene derivatives through a series of reactions, then glucose, mannose, galactose azide compounds are prepared, and finally, “click chemistry” The reaction incorporates an azide compound onto a norbornene derivative to give a novel saccharide-containing 7-oxabornene derivative.

KEY WORDS: ROMP; norbornene derivatives; sugar-containing molecules

目录

1 引言 1

1.1 开环易位聚合(ROMP)反应 1

1.1.1 开环易位聚合(ROMP)反应简介 1

1.1.2 开环易位聚合(ROMP)反应机理 2

1.1.3 开环易位聚合(ROMP)反应的主要应用 3

1.2 降冰片烯衍生物 3

1.2.1 降冰片烯衍生物简介 3

1.2.2 含糖7-氧杂降冰片烯衍生物 3

1.3 课题的研究意义及创新 5

1.3.1 研究意义 5

1.3.2 研究的创新 6

2 实验部分 7

2.1 课题的提出 7

2.2 合成路线 7

2.3 仪器和试剂 8

2.3.1 仪器 8

2.3.2 试剂 8

2.4 实验合成 10

2.4.1 制备含葡萄糖的7-氧杂降冰片烯衍生物的单体 11

2.4.2 制备含甘露糖的7-氧杂降冰片烯衍生物的单体 13