Catalytic production of S-valerolactone (DVL) from biobased 2-hydroxyte-trahydropyran (HTHP) - Combined experimental and modeling study

S- Valerolactone (DVL) is a five-carbon (C5) cyclic ester that can undergo ring-opening polymerization to yield high-performance, biocompatible polyesters. But current market prices of C5 chemicals like DVL are very high due to poor availability of C5 feedstock in petroleum. Herein, we demonstrate a novel route to DVL synthesis via dehydrogenation of biomass-derived 2-hydroxytetrahydropyran (HTHP) over Cu/SiO2 2 without the use of toxic reagents. Since HTHP exists in thermal equilibrium with 3,4-dihydropyran (DHP) via dehydration, and with 2,2'oxybis(tetrahydropyran) and 5-(tetrahydropyran-2-yloxy)pentanal via acetalization, we have also determined the thermochemistry ( Delta H rxn and Delta G rxn ) of each competing reaction using density functional theory (DFT) calculations at the M06-2X/cc-pVTZ level. Lastly, by developing a kinetic model of all 8 reactions involved, we have achieved 84 % selectivity to DVL at 150 degrees C degrees C in a packed bed reactor for over 72 hours of time on stream.