过渡金属催化的焦油酚底物的直接选择性烷基化反应及其机理研究

The development of downstream products is of importance to realize coal grading conversion utilization and high value-added utilization of coal tar. As important components of coal tar, the functionalization of phenolic compounds especially their alkylation reaction is very significant for the downstream products development of crude phenols. Herein we put forward new processes for the selective alkylation of phenol tar. In this project, we will mainly concentrate on exploring reaction conditions of transition metal catalyzed C-H bond functionalization and developing catalytic systems for the selective direct alkylation of phenolic compounds. According to the phenomena and experimental data observed during the research, an appropriate model will be proposed to investigate the reaction mechanism. Furthermore, it will also reveal the effects on reactivity by using different reaction conditions and the influence among different phenolic compounds on their reactivity and selectivity. This work will contribute to the establishment of the new method and theoretical basis for the conversion of coal tar into important chemical raw materials and intermediates.

煤焦油下游产品的开发是煤分级分质利用和煤焦油高附加值利用的重要途径。酚类化合物作为煤焦油的重要组分，其官能化特别是烷基化对于煤焦油的高附加值利用十分重要。本项目提出了焦油酚选择性烷基化的新工艺，拟探索过渡金属催化的酚类化合物的C-H键直接选择性烷基化的催化体系，根据实验现象和采集到的数据提出合适的模型探讨反应的机理，揭示烷基化反应选择性的催化调控机理，阐明混合酚化合物组分对反应活性和选择性的影响机制，形成焦油酚向下游重要化工原料或中间体转化的方法体系和理论基础。

煤焦油下游产品的开发是煤分级分质利用和煤焦油高附加值利用的重要途径。酚类化合物作为煤焦油的重要组分，其官能化特别是烷基化对于煤焦油的高附加值利用十分重要。本项目从苯酚及其衍生物出发，研究了过渡金属在酚类化合物的C-H键直接选择性烷基化的中的催化活性，筛选并优化了Rh系和Co系金属催化剂，考察了底物在最优条件下的适用性，并将反应体系拓展至离子液体中，实现目标分子的绿色高效，此外，本项目还通过实验设计揭示了反应的过渡态和机理，为苯酚类化合物的官能化和高附加值转化提供了理论指导。