Nylon Intermediates from Bio-Based Levulinic Acid
Annemarie Marckwordt
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorFatima El Ouahabi
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorDr. Hadis Amani
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorDr. Sergey Tin
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorCorresponding Author
Dr. Narayana V. Kalevaru
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorProf. Dr. Paul C. J. Kamer
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorDr. Sebastian Wohlrab
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Johannes G. de Vries
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorAnnemarie Marckwordt
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorFatima El Ouahabi
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorDr. Hadis Amani
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorDr. Sergey Tin
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorCorresponding Author
Dr. Narayana V. Kalevaru
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorProf. Dr. Paul C. J. Kamer
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorDr. Sebastian Wohlrab
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Johannes G. de Vries
Leibniz Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Search for more papers by this authorGraphical Abstract
Green nylon: Use of 25 % ZrO2/SiO2 as catalyst allows the gas-phase ring-opening of bio-based γ-valerolactone with methanol to a mixture of methyl pentenoates containing 81 % of the 4-isomer, which could be selectively hydroformylated from the mixture to methyl 5-formyl-valerate, an intermediate for ϵ-caprolactam. The remaining isomers were converted into dimethyl adipate.
Abstract
Use of ZrO2/SiO2 as a solid acid catalyst in the ring-opening of biobased γ-valerolactone with methanol in the gas phase leads to mixtures of methyl 2-, 3-, and 4-pentenoate (MP) in over 95 % selectivity, containing a surprising 81 % of M4P. This process allows the application of a selective hydroformylation to this mixture to convert M4P into methyl 5-formyl-valerate (M5FV) with 90 % selectivity. The other isomers remain unreacted. Reductive amination of M5FV and ring-closure to ϵ-caprolactam in excellent yield had been reported before. The remaining mixture of 2- and 3-MP was subjected to an isomerising methoxycarbonylation to dimethyl adipate in 91 % yield.
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