【作者】 龚行；

【导师】 阳年发；

【作者基本信息】 湘潭大学 ， 有机化学， 2011， 博士

【摘要】 自然界中的高功能生物大分子,如蛋白质和DNA等具有高精确排列的立体结构,而螺旋结构是其中最常见的立体结构之一,并且螺旋结构常常在生命活动中扮演着重要的角色。本文综述了螺旋聚合物的研究历程以及螺旋聚合物的合成方法,开展了原子转移自由基聚合(ATRP)制备单手性螺旋过量聚合物的研究。主要研究内容有:1)改进了甲基丙烯酸1-苯基二苯并环庚醇酯(PDBSMA)的合成工艺,将其产率由文献报道的15 %提高到了80 %。该单体是研究螺旋聚合反应较为常用的单体之一。合成了系列含大取代基的不饱和酯类单体,并研究了其聚合反应。2)研究了以卤代烃为原子转移自由基聚合引发剂引发PDBSMA的聚合反应,讨论了引发剂结构对其引发效率的影响。研究结果表明:(a)引发剂位阻太大则不能引发含有大取代基的PDBSMA发生ATRP反应;(b)氯代烃的引发活性低于相应的溴代烃,论文所选用的几种氯代烃均不能引发PDBSMA发生ATRP反应;(c)苄位溴代烃的引发活性要高于α-位溴代酯的活性。前者作为引发剂时单体的转化率较高,并且得到的单手性螺旋过量聚合物的比旋光值也较高。3)以带大取代基的不饱和酯为单体,研究了手性引发剂及手性配体对原子转移自由基聚合过程的立体选择性的影响。研究结果表明,手性配体或手性引发剂均可对聚合过程产生手性诱导作用。PDBSMA可以在手性配体或手性引发剂的存在下,由ATRP的聚合方式得到单手性螺旋构象过量的聚合物,。4)发现了一种合成2-噁唑烷酮的新方法。本文在尝试合成一类含吖啶环的单体时,没有得到预期的产物,却意外的得到了2-噁唑烷酮的衍生物。该合成方法具有以下优点:(a)该方法合成条件温和,安全且无毒;(b)该反应环境污染小,原料利用率也很高,水是该反应唯一的副产物;(c)反应底物芳香胺价廉易得。一句话来概括该反应对环境友好,且具有较高的原子经济效率。论文对该方法进行了较深入的研究,制得了一系列2-噁唑烷酮类化合物。更多还原

【Abstract】 The high functionalities of naturally occurring macromolecules, such as proteins and DNAs, arranged in a highly accurate stereostructures. In such stereostructures, the helix is often found among the most fundamental structures of the polymer chain and plays important roles in realizing biological activities. The status of helical polymer and the synthesis methods are reviewed in this dissertation. The synthesis of optically active helical polymer by the atom transformation radical polymerization (ATRP) is carried out. The main contents are listed below:1) The method for the synthesis of 1-phenyldibenzosuberyl methacrylate (PDBSMA) was improved, and the yield was increased from the reported 15 % to 80 % in this dissertation. PDBSMA is one of the more commonly used monomers in the study of helical polymmer. A series of methacrylate with bulky group were synthesized, and the polymerizations of these methacrylates were studied.2) The ATRP of PDBSMA initiated by several halohydrocarbon was studied. The effect of the structure of initiators was discussed. The results show that: (a) the ATRP of PDBSMA cannot be initiated if the steric hindrance initiators were used; (b) the activation of alkyl chloride is lower than the corresponding alkyl bromide. Chlorinated hydrocarbons used in this dissertation cannot initiated the ATRP of PDBSMA; (c) the initiating activation of benzyl bromide is higher than that of theα-bromo ester; Both the conversion of the monomer and the specific rotation of polymermer are higher when the former is used as the initiator.3) The stereochemistry of the polymer of methacrylate with bulky group obtained from atom transformation radical polymerization initiated by chiral initiators or controlled by chiral ligands was studied in this dissertation. The results indicated that chiral ligand or chiral initiators produced chiral induction on the polymerization processes. PDBSMA can form one-handed-helix-sense excess polymer by ATRP in the presence of chiral ligand or chiral initiators.4) A new method for synthesis of 2-oxazolidinone was discovered unexpected. It is not the expected product but the 2-oxazolidinone derivatives were found by accident when attempting to synthesize a class of monomers containing acridine ring. This synthetic method has several advantages: (a) the 2-oxazolidinones were obtained under mild conditions that are neither dangerous nor noxious; (b) this reaction was wasteless and pollution-free, water was the sole co-product; (c) the readily available arylamines was used as substrate. So, this reaction process was environmentally benign and high atom economic. The synthesis of 2-oxazolidinones was studed in this dissertation, and a series of 2-oxazolidinones compounds were obtained.更多还原