화학공학소재연구정보센터
Applied Catalysis A: General, Vol.569, 170-174, 2019
Pd-catalysed formation of ester products from cascade reaction of 5-hydroxymethylfurfural with 1-hexene
A cascade reaction involving decarbonylation of 5-hydroxymethylfurfural (HMF) followed by methoxycarbonylation of 1-hexene produces methyl heptanoate (MH) using a catalytic system composed of a Pdphosphine complex and methanesulfonic acid (MSA) co-catalyst at moderate reaction temperature. Concomitant hydration of HMF followed by hydrogenation of methyl levulinate (ML) to gamma-valerolactone (GVL) occurs with the catalytic system under the same reaction conditions using HMF and methanol as the source of CO and H-2, respectively. Under optimized reaction conditions, about 50% of MH along with 12% ML and 35% GVL is obtained from HMF using Pd-(1,2-bis(di-tert-butylphosphinomethyl)benzene) (DTBPMB), MSA and 1-hexene in methanol at 120 degrees C. Interestingly, sugars, such as glucose, fructose and xylose, are able to be converted to MH, ML and GVL as well. Isotopic labeling studies with C-13(1)-fructose in methanol-d(4) and C-13-methanol-d(4) confirm that H-2 originates from methanol, while CO generates predominantly from the formyl group of the HMF formed by fructose dehydration.