The Synthesis Of Helix Polymethacrylate With Bulky Group By Atrp

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.