金属卟啉仿生催化环烷烃选择氧化过程规律及机理研究

项目名称： 金属卟啉仿生催化环烷烃选择氧化过程规律及机理研究

项目编号： No.21476270

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 有机化学

项目作者： 佘远斌

作者单位： 浙江工业大学

项目金额： 92万元

中文摘要： 针对目前环烷烃选择氧化合成环烷醇、酮、二元酸等重要精细化学品或中间体的方法存在选择性差、收率低、机理不清、污染重、能耗高等诸多问题，围绕不同环烷烃环内张力及结构差异及其对环上C-H氧化和/或C-C断裂开环的影响，以及不同催化剂与不同底物间作用机理及规律等关键科学问题，采用化学计量学方法高精度定量表征理论化学计算与实验结果之间的特征相关性，建立环烷烃选择氧化反应的多因素、多层次、多水平、多变量整体研究模式，挖掘和阐释环烷烃选择氧化过程中多水平下多层次因素的各种变量和参数与其催化氧化活性或选择性真正相关的特征描述符和参数（环烷烃结构参数、金属卟啉结构参数、传递过程和反应条件参数等），构建高精度的QSAR/QSSR模型，定量描述和表征环烷烃氧化反应中影响原料转化率和产物选择性的系列本质因素，实现对金属卟啉催化选择氧化环烷烃反应活性及选择性的精确调控，实现整个过程节能减排，丰富和发展仿生催化理论。

中文关键词： 金属卟啉；仿生催化氧化；环烷烃；规律；机理研究

英文摘要： Contraposing the problems such as poor selectivity , low yield , undefined mechanism, serious environment pollution and high energy consumption existed in the various selective oxidation of cycloalkanes to cycloalkanols, cycloalkanones, dicarboxylic acid and other important fine chemical intermediates, and surrounding the key scientific issues such as the different ring strain of cycloalkanes, and the effect of the ring strain on C-H oxidation and/or C-C broken to open ring, the reaction mechanism and laws between different catalysts and substrates, the objectives of this project will aim to precisely quantitatively characterize the results between theory chemical calculations and experiments by using chemometrics methods, establish the overall research mode for simultaneous analysis of multi-factor and multivariate at various different level in the selective oxidation process of cycloalkanes, deeply excavate and interpret the truly relevant feature values and parameters (cycloalkane structure parameters, metalloporphyrin structure parameters, transfer process and reaction conditions, etc.),then effectively quantitatively characterize for characteristic relation between truly relevant feature values and parameters and catalytic activity or selectivity in selective oxidation process of cycloalkanes, hereby exactly construct the high-precision QSAR/QSSR models for quantitative describing the nature factors affecting the feedstock conversion and product selectivity in the oxidation of cycloalkanes.Based on the above research,the activity and selectiveity for the oxidation of cycloalkanes to different products with metalloporphyrins as the catalysts can be precisely adjusted by controlling a serious of influenced factors and condtions, and energy saving as well as emission reduction also will be achieved throughout the reaction process. Therefore, the theory of biomimetic catalysis will be further enriched and developed.

英文关键词： metalloporphyrin;biomimetic catalytic oxidation;cycloalkane;rule;mechanism