Lu Rui, Lu Fang, Si Xiaoqin, Jiang Huifang, Huang Qianqian, Yu Weiqiang, Kong Xiangtao, Xu Jie
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, 457 Zhongshan Road, Dalian, 116023, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
ChemSusChem. 2018 May 25;11(10):1621-1627. doi: 10.1002/cssc.201800646. Epub 2018 Apr 25.
Direct transformation of bio-based platform chemicals into aromatic dicarboxylic acids and their derivatives, which are widely used for the manufacture of polymers, is of significant importance for the sustainable development of the plastics industry. However, limited successful chemical processes have been reported. This study concerns a sustainable route for the production of phthalate and its hydrogenated derivative from bio-based malic acid and erythritol. The key Diels-Alder reaction is applied to build a substituted cyclohexene structure. The dehydration reaction of malic acid affords fumaric acid with 96.6 % yield, which could be used as the dienophile, and 1,3-butadiene generated in situ through erythritol deoxydehydration serves as the diene. Starting from erythritol and dibutyl fumarate, a 74.3 % yield of dibutyl trans-4-cyclohexene-1,2-dicarboxylate is obtained. The palladium-catalyzed dehydrogenation of the cycloadduct gives a 77.8 % yield of dibutyl phthalate. Dibutyl trans-cyclohexane-1,2-dicarboxylate could be formed in nearly 100 % yield under mild conditions by hydrogenation of the cycloadduct. Furthermore, fumaric acid and fumarate, with trans configurations, were found to be better dienophiles for this Diels-Alder reaction than maleic acid and maleate, with cis configuration, based on the experimental and computational results. This new route will pave the way for the production of environmental friendly plastic materials from plants.
将生物基平台化学品直接转化为广泛用于制造聚合物的芳族二羧酸及其衍生物，对塑料工业的可持续发展具有重要意义。然而，成功的化学过程报道有限。本研究涉及一条从生物基苹果酸和赤藓糖醇生产邻苯二甲酸酯及其氢化衍生物的可持续路线。关键的狄尔斯-阿尔德反应用于构建取代的环己烯结构。苹果酸脱水反应以96.6%的产率得到富马酸，其可作为亲双烯体，通过赤藓糖醇脱氧脱水原位生成的1,3-丁二烯作为双烯体。以赤藓糖醇和富马酸二丁酯为原料，得到反式-4-环己烯-1,2-二羧酸二丁酯的产率为74.3%。环加成产物的钯催化脱氢反应得到邻苯二甲酸二丁酯的产率为77.8%。在温和条件下，环加成产物氢化可几乎100%产率地形成反式环己烷-1,2-二羧酸二丁酯。此外，基于实验和计算结果，发现反式构型的富马酸和富马酸酯比顺式构型的马来酸和马来酸酯更适合作为该狄尔斯-阿尔德反应的亲双烯体。这条新路线将为从植物生产环境友好型塑料材料铺平道路。
