2025-03-21 カリフォルニア大学サンディエゴ校 (UCSD)
＜関連情報＞
- https://today.ucsd.edu/story/a-less-toxic-way-to-manufacture
- https://onlinelibrary.wiley.com/doi/10.1002/anie.202421540
ガラクトースからの再生可能なテレフタレートと芳香族ジイソシアネート Renewable Terephthalates and Aromatic Diisocyanates from Galactose
Matthew W. Halloran, Roxanne Naumann, Aanchal Jaisingh, Nathan A. Romero, Michael D. Burkart
Angewandte Chemie International Edition Published: 17 February 2025
DOI:https://doi.org/10.1002/anie.202421540
Graphical Abstract
Preparation of renewable terephthalates and aromatic diisocyanates is presented using a transition metal-free route through a mild electrochemical decarboxylative aromatization on gram scale. Terephthalates were readily converted into aromatic diisocyanates in flow and used to synthesize 100 % renewable thermoplastic polyurethanes.
Abstract
Aromatic diisocyanates, invaluable commodity chemicals for polymer manufacturing, are produced annually on megaton scales from petroleum-derived diamines via phosgenation. Existing routes toward renewable alternatives are sparse and limited by access to functionalized aromatic starting materials, such as terephthalates. Herein, we report the development of a robust route to renewable terephthalates and aromatic diisocyanates from D-galactose via Eastwood olefination and Diels–Alder cycloaddition, followed by a mild electrochemical decarboxylative aromatization. This process was developed and applied on gram-scale to synthesize terephthalates, which were transformed into aromatic diisocyanates via Curtius rearrangement in flow. We demonstrate gram-scale preparation of 1,4-phenylene diisocyanate and 2,5-toluene diisocyanate and formulation of these monomers to prepare fully renewable thermoplastic polyurethanes. Preparation of these renewable aromatic diisocyanates proceeds without the use of high-pressure gases or costly transition-metals and represents a novel route to fully renewable aromatic diisocyanates.
