New Insights into the Reactivity of Biomass with Butenes for the Synthesis of Butyl Levulinates

• Published in: ChemSusChem 2017-06, Vol.10 (12), p.2612-2617
• Main Authors: Démolis, Alexandre, Eternot, Marion, Essayem, Nadine, Rataboul, Franck
• Format: Article
• Language: English
• Subjects: Alkenes - chemistry; Biomass; butene; Butenes; butyl levulinates; Butyrolactone; Catalysis; Catalysts; Cellulose; Cellulose - chemistry; Chemical Sciences; Chemistry Techniques, Synthetic; Environment and Society; Environmental Sciences; Esterification; Levulinic acid; Levulinic Acids - chemical synthesis; Levulinic Acids - chemistry; Solvents; Solvents - chemistry; Sustainability; sustainable chemistry; Synthesis
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201700416

This article reports a detailed study on the reactivity of levulinic acid and cellulose with 1‐butene and iso‐butene for the catalytic formation of sec‐ and tert‐butyl levulinates. The influence of catalyst type and various solvent conditions have been investigated to assess the potential of a sustainable transformation. A very simple and efficient procedure was discovered by using reusable Amberlyst‐15 in the absence of solvent to form, from levulinic acid and iso‐butene, tert‐butyl levulinate (70 % yield), a compound very difficult to prepare by other means. sec‐Butyl levulinate (66 % yield) was obtained by using Amberlyst‐15 in γ‐butyrolactone as a biosourced solvent. The original procedure was also extended notably by directly using cellulose as a reactant. In the presence of a catalytic amount of H2SO4, it was possible to form sec‐butyl levulinate (19 % yield) from 1‐butene in a more efficient way than by using the alcohol as an esterifying agent. Levulinates from olefins: An in‐depth study on the transformation of biomass reactants into butyl levulinates through the reaction with butene isomers is presented. In particular, the possibility of using sustainable solvents in the presence of a reusable solid catalyst is demonstrated.