Synthesis of ketones from biomass-derived feedstock

Abstract

Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in H2O/CH2Cl2 can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory. Detailed study shows that the Pd, bromide salt and H2O/CH2Cl2 work cooperatively to promote the desired reaction and inhibit the side reaction. Thus high yields of desired products can be obtained. This work opens the way for production of ketones from aromatic ethers that can be derived from biomass.

Low temperature hydrogenation and hydrodeoxygenation of oxygen-substituted aromatics over Rh/silica: part 1: phenol, anisole and 4-methoxyphenol

“…The most recent studies of anisole hydrogenation over supported Rh nanoparticles in the literature reported no evidence of hydrogenolysis even at high hydrogen pressure, with 100% yield of methoxycyclohexane [16,23]. However other studies have shown the formation of cyclohexanol [24] in moderate yield (~ 16%). In contrast our results show that although hydrogenation is the primary process occurring there was also significant hydrogenolysis (Scheme 1).…”

Electrocatalytic Upgrading of Lignin‐Derived Bio‐Oil Based on Surface‐Engineered PtNiB Nanostructure

“…Therefore, the large‐scale application of bio‐oil upgrading requires the development of powerful ECH electrocatalysts. Several groups have reported the ECH of biomass‐based phenolic compounds to cyclohexanone and cyclohexanol using Pt/C, Rh/C, Pd/C, Ru/C, and Raney nickel catalysts. Nevertheless, the performance of ECH remains poor to fulfill specific requirements and the metal nanoparticles (NPs) are prone to dissolution or aggregation during ECH, affecting the electrochemical stability.…”

A New Route to Cyclohexanone using H2CO3 as a Molecular Catalytic Ligand to Boost the Thorough Hydrogenation of Nitroarenes over Pd Nanocatalysts

“…Heterogeneous Pd catalysts, especially Pd carbon supported (Pd/C) catalysts (The characterizations of Pd/C were presented as Figure S1 and S2), are currently preferred in industry for cyclohexanone production due to their excellent universality for hydrogenation of nitrobenzene with aniline as the main product (Figure a–b) . In the absence of CO 2 , we found that only 6 % of nitrobenzene was transformed into cyclohexanone (Figure b), with aniline being the main product.…”