Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Department of Chemistry and Biotechnology, Faculty of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
ChemSusChem. 2020 Apr 7;13(7):1775-1784. doi: 10.1002/cssc.202000090. Epub 2020 Mar 9.
Fluorinated dialkyl carbonates (DACs), which serve as environmentally benign phosgene substitutes, were produced successfully from carbon dioxide either directly or indirectly. Nucleophilic addition of 2,2,2-trifluoroethanol to carbon dioxide and subsequent reaction with 2,2,2-trifluoroethyltriflate (3 a) afforded bis(2,2,2-trifluoroethyl) carbonate (1) in up to 79 % yield. Additionally, carbonate 1 was obtained through the stoichiometric reaction of 3 a and cesium carbonate. Although bis(1,1,1,3,3,3-hexafluoro-2-propyl) carbonate (4) was difficult to obtain by either of the above two methods, it could be synthesized through the transesterification of carbonate 1.
氟化二烷基碳酸酯（DACs）是一种环境友好的光气替代品，可通过二氧化碳直接或间接成功合成。2,2,2-三氟乙醇的亲核加成到二氧化碳上，然后与 2,2,2-三氟乙基三氟甲磺酸酯（3a）反应，以高达 79%的收率得到双（2,2,2-三氟乙基）碳酸酯（1）。此外，碳酸酯 1 还可以通过 3a 和碳酸铯的计量反应得到。尽管通过上述两种方法都难以得到双（1,1,1,3,3,3-六氟-2-丙基）碳酸酯（4），但它可以通过碳酸 1 的酯交换反应合成。
