Single-Pot Reductive Rearrangement of Furfural to Cyclopentanone over Silica-Supported Pd Catalysts.

Autor: Date NS; Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune 411008, India.; M.E.S. Department of Chemistry, Abasaheb Garware College of Arts and Science, Karve Road, Pune 411004, India., Kondawar SE; Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune 411008, India., Chikate RC; M.E.S. Department of Chemistry, Abasaheb Garware College of Arts and Science, Karve Road, Pune 411004, India., Rode CV; Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune 411008, India.
Jazyk: angličtina
Zdroj: ACS omega [ACS Omega] 2018 Aug 24; Vol. 3 (8), pp. 9860-9871. Date of Electronic Publication: 2018 Aug 24 (Print Publication: 2018).
DOI: 10.1021/acsomega.8b00980
Abstrakt: Direct one-pot hydrogenation of furfural (FFR) to cyclopentanone (CPO) was investigated over different silica-supported Pd catalysts. Among these, 4% Pd on fumed silica (4%Pd/f-SiO 2 ) showed remarkable results, achieving almost 98% furfural (FFR) conversion with ∼89% selectivity and 87% yield to cyclopentanone at 165 °C and 500 psig H 2 pressure. More interestingly, the fumed-silica-supported catalyst tuned the selectivity toward the rearrangement product, i.e., cyclopentanone, whereas all of the other supports were found to give ring hydrogenation as well as side chain hydrogenation products due to their parent Brönsted acidity and specific support properties. X-ray diffraction data revealed the presence of different phases of the face-centered cubic lattice of metallic Pd along with lowest crystallite size of 15.6 nm in the case of the silica-supported Pd catalyst. However, Pd particle size was found to be in the range of 5-13 nm with even dispersion over the silica support, confirmed by high-resolution transmission electron microscopy analysis. While studying the effect of reaction parameters, it was observed that lower temperature gave low furfural conversion of 58% with only 51% CPO selectivity. Similarly, higher H 2 pressure lowered CPO selectivity with subsequent increase in 2-methyl furan and ring hydrogenation product 2-methyl furan and 2-methyl tetrahydrofuran. Thus, as per the requirement, the product selectivity can be tuned by varying the type of support and/or the reaction parameters suitably. With the help of several control experiments and the characterization data, a plausible reaction pathway was proposed for the selective formation of cyclopentanone.
Competing Interests: The authors declare no competing financial interest.
Databáze: MEDLINE
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