Sustainable Synthesis of BTX-Derived Chemicals

在这个由化学系化学合成计划资助的项目中，密歇根州立大学化学系的John W.Frost教授将把微生物催化和化学催化相结合，将可再生的、无毒的糖原料转化为目前从石油和天然气精炼的苯-甲苯-二甲苯(BTX)流中提取的化学品。双烯将被微生物合成，并与亲双烯化合物发生化学反应，生成环加成产品，旨在提供获得新一代单体和增塑剂的途径，其中所有的碳原子都来自可再生糖。环加成产物催化脱氢得到取代对苯二甲酸酯。其他环加成产品将提供获得取代的环己烯三羧酸盐和环己烷三羧酸盐的途径。取代对苯二甲酸作为添加剂或单体用于电子和医疗应用的液晶聚合物中，以及用于服装纤维和瓶装树脂的聚乙烯对苯二甲酸乙二醇酯中，可以赋予独特的性能。取代对苯二甲酸酯赋予工程和消费聚合物的新性能可以打开新的应用和新的市场，从而在创造就业的同时提供重要的经济倍增。同样，各种环取代环己烯和环己烷三羧酸盐也瞄准了非芳香族增塑剂市场。通过将微生物合成与化学合成相结合，可以获得一定程度的结构多样性，最终可能使识别不与雌激素受体结合的新的高性能增塑剂成为可能。随之而来的健康、安全和环境效益将是相当可观的。最后，这项研究计划将为预科、本科生、研究生和博士后学生提供独特的培训机会，包括那些来自历史上在科学界代表性不足的群体的学生。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor John W. Frost of the Department of Chemistry at Michigan State University will interface microbial catalysis with chemical catalysis to convert renewable, nontoxic sugar starting materials into chemicals currently derived from the benzene-toluene-xylene (BTX) stream of petroleum and gas refining. Dienes will be microbe synthesized and chemically reacted with dienophiles to yield cycloaddition products designed to provide access to a new generation of monomers and plasticizers where all carbon atoms are derived from renewable sugars. Catalytic dehydrogenation of the cycloaddition products is to afford substituted terephthalates. Other cycloaddition products will provide access to substituted cyclohexene tricarboxylates and cyclohexane tricarboxylates. Substituted terephthalic acids can impart unique properties when employed as additives or monomers in liquid crystalline polymers used in electronic and medical applications as well as in polyethyleneterephthalate used in clothing fiber and bottle resin. The novel properties that substituted terephthalates impart to engineering and consumer polymers could open new applications and new markets thereby providing an important economic multiplier along with job creation. Similarly, the wide array of ring-substituted cyclohexene and cyclohexane tricarboxylates are targeted towards nonaromatic plasticizer markets. By interfacing microbial synthesis with chemical synthesis, a level of structural diversity is accessed that may ultimately enable the identification of new high-performance plasticizers that do not bind to estrogen receptors. The attendant health safety and environmental benefits would be considerable. Finally, this research program will provide a unique training opportunity for pre-undergraduate, undergraduate, graduate and post-doctoral students, including those from groups historically underrepresented in the sciences.