中文摘要
近年来随着高效低毒药物研发需求，利用高分子酰化剂进行含氨基有机化合物的N-酰化反应在国际功能高分子界受到重视。本项目开展了下列首创性研究性工作：1.国内外首次提出一种由大分子引发剂制备新型微凝胶（介星形聚合物）负载酰化试剂的方法。所合成试剂具良好的酰基转移活性和选择性：在温和反应条件下对伯胺和仲胺的酰基转移反应产率95.6-100%，产品纯度94.1-96.0%；对二元胺酰化产率93.4-94.0%，但其中含双酰基化产物10.1-10.6%；对具p-π共轭效应的弱碱类胺如4-乙氧基苯胺、吡咯等则不反应。根据实验结果推断了反应机理。理论研究结果已被功能高分子领域国际一流刊物J.Comb.Chem.（IF>3.0）录用，并应邀在NMS-V&FCFP-XIX,2009.做邀请报告。2.首创采用“开环歧化聚合-悬浮成形-热致自由基聚合”联用法由三臂星形聚合物合成了一种珠状高分子酰化试剂。研究成果已申请中国发明专利, 公开号：CN101412792A。3.首创利用商品化氯甲基化聚苯乙烯树脂经ATRP制备高性能球状高分子酰化剂工艺,研究成果已申请中国发明专利,申请号：200910228034.5。
英文摘要
In recent years the synthesis and application of polymer-supported acylating reagents for N-acylation reaction of amines have attracted considerable attention in the field of international functional chemistry along with the urgent need of developing pharmaceuticals of high efficiency and low toxicity. The following original research work was conducted in this project: 1. a novel method for synthesis of functional microgel-supported acylating reagents, a kind of meso-star functional polymers, was developed for the first time. The microgel reagents showed excellent acyl (benzoyl, acetyl, phenylsolfonyl) transfer activity and selectivity under mild reaction condition: For primary and secondary amines the desired product yield and purity reached up to 95.6-100 % and 94.1-96.0 % respectively; for diamines (e.g. ethylene diamine) the products were contaminated with 10.1-10.6 % bis-acylated compounds, and no reaction was observed for weak base amines possessing p-π conjugation (p-phenetidine, pyrrole etc.). An article covering this work was accepted by the J. Comb. Chem. (IF>3.0) and an invited lecture was presented at IUPAC 5th International Symposium on Novel Materials and Their synthesis & 19th International Symposium on Fine Chemistry and Functional Polymers (Oct. 2009). 2. A new method on synthesizing bead-form polymer–supported acylating reagents by combination of ROMP-suspension shape formation-thermal radical polymerization via a three-arm star polymer was developed, a China Invention Patent was applied (CN101412792A，2009). 3. A new method for preparation of a high-performance polymeric acylating reagent by ATRP using the commercial available chloromethylated polystyrene was developed. The technique was applied for a China Invention Patent (Appl. No. 200910228034.5).
结题摘要
近年来随着高效低毒药物研发需求，利用高分子酰化剂进行含氨基有机化合物的N-酰化反应在国际功能高分子界受到重视。本项目开展了下列首创性研究性工作：1.国内外首次提出一种由大分子引发剂制备新型微凝胶（介星形聚合物）负载酰化试剂的方法。所合成试剂具良好的酰基转移活性和选择性：在温和反应条件下对伯胺和仲胺的酰基转移反应产率95.6-100%，产品纯度94.1-96.0%；对二元胺酰化产率93.4-94.0%，但其中含双酰基化产物10.1-10.6%；对具p-π共轭效应的弱碱类胺如4-乙氧基苯胺、吡咯等则不反应。根据实验结果推断了反应机理。理论研究结果已被功能高分子领域国际一流刊物J.Comb.Chem.（IF>3.0）录用，并应邀在NMS-V&FCFP-XIX,2009.做邀请报告。2.首创采用“开环歧化聚合-悬浮成形-热致自由基聚合”联用法由三臂星形聚合物合成了一种珠状高分子酰化试剂。研究成果已申请中国发明专利, 公开号：CN101412792A。3.首创利用商品化氯甲基化聚苯乙烯树脂经ATRP制备高性能球状高分子酰化剂工艺,研究成果已申请中国发明专利,申请号：200910228034.5。