Efficient Synthesis of Novel Plasticizers by Direct Palladium‐Catalyzed Di‐ or Multi‐carbonylations

• Published in: Angewandte Chemie International Edition Vol. 62; no. 6; pp. e202214706 - n/a
• Main Authors: Hu, Yuya, Sang, Rui, Vroemans, Robby, Mollaert, Guillaume, Razzaq, Rauf, Neumann, Helfried, Junge, Henrik, Franke, Robert, Jackstell, Ralf, Maes, Bert U. W., Beller, Matthias
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 01.02.2023; Wiley Subscription Services, Inc; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Alcohols; Alkenes; Calorimetry; Carbonylation; Carbonyls; Catalysts; Chemical industry; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Diesters; Differential scanning calorimetry; Esterification; Glass transition temperature; Lubricants; Olefins; Palladium; Physical Sciences; Plasticizers; Polyols; Science & Technology; Surfactants; Sustainability; Transition temperatures; Plasticizers; ALKOXYCARBONYLATION; Olefins; POLY(VINYLIDENE FLUORIDE); Palladium; DESIGNING GREEN PLASTICIZERS; HIGHLY SELECTIVE FORMATION; HYDROESTERIFICATION; ALKENES; Carbonylation; BIODIESEL PRODUCTION; Sustainability; ESTERS; ENGINE PERFORMANCE; PHTHALATE DEHP
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202214706

Diesters are of fundamental importance in the chemical industry and are used for many applications, e.g. as plasticizers, surfactants, emulsifiers, and lubricants. Herein, we present a straightforward and efficient method for the selective synthesis of diesters via palladium‐catalyzed direct carbonylation of di‐ or polyols with readily available alkenes. Key‐to‐success is the use of a specific palladium catalyst with the “built‐in‐base” ligand L16 providing esterification of all alcohols and a high n/iso ratio. The synthesized diesters were evaluated as potential plasticizers in PVC films by measuring the glass transition temperature (Tg) via differential scanning calorimetry (DSC). The first di‐ and multi‐carbonylations of olefins with di‐ or polyols provide a general and straightforward access to a variety of di‐ or multiesters with high efficiency and selectivity. Representative diesters show potential performance (Tg) as novel plasticizers.