Jan C. van der Waal

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources

Renewable Resources Robert-Jan van Putten,†,‡ Jan C. van der Waal,† Ed de Jong,*,† Carolus B. Rasrendra,‡,⊥ Hero J. Heeres,*,‡ and Johannes G. de Vries* †Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam, the Netherlands ‡Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands DSM Innovative Synthesis BV, P.O. Box 18, 6160 MD Geleen, the Netherlands Department of Chemical Engineering, Institut Teknologi Bandung, Ganesha 10, Bandung 40132, Indonesia

Application of zeolite titanium Beta in the rearrangement of α-pinene oxide to campholenic aldehyde

Zeolite titanium Beta is found to be an effective catalyst for the industrially relevant rearrangement of α-pinene oxide to campholenic aldehyde, giving selectivities of up to 89% in the liquid phase. In the gas phase, up to 94% selectivity is obtained at conversions above 95%, which exceeds the best values obtained with homogeneous Lewis acid catalysts. The selectivity obtained is profoundly influenced by the solvent or co‐adsorbate applied.

Biomass‐Derived Porous Carbon Materials: Synthesis and Catalytic Applications

Novel biomass‐derived porous carbons are attractive candidates for the preparation of carbon‐supported catalysts with a wide range of catalytic applications. Such carbonaceous catalysts are environmentally benign and could provide a cost‐competitive advantage as compared to existing heterogeneous catalysts. Tunable surface properties of carbon materials and excellent physical properties (e.g., hydrophobicity, chemically inert nature, etc.) are compatible with diverse catalysis reactions including organic transformations, as well as electro‐ and photochemical processes in aqueous solutions. This contribution provides an overview on the utilization of different biomass feedstocks and/or biomass‐derived precursors for the synthesis of carbonaceous materials to design advanced catalytic systems and their emerging applications in catalysis.

Zeolite titanium beta : A versatile epoxidation catalyst. Solvent effects

The essentially aluminum-free titanium containing analogue of zeolite beta was synthesized using di(cyclohexylmethyl)dimethylammonium (DCDMA) as the template. The titanium zeolite beta was found to exhibit Bronsted acidic properties when alcohols were employed as the solvent, which is explained by the Lewis acid character of the titanium site, which on coordination of an alcohol yields a mild Bronsted acid site. The use of alcohol/acetonitrile mixtures as the solvent showed a clear maximum in activity in 1-octene epoxidation, depending on the type and amount of alcohol used. A catalytic species is proposed in which an alcohol as well as a hydroperoxo group is coordinated to a framework connected titanium atom.

The hydration and isomerization of α-pinene over zeolite beta. A new coupling reaction between α-pinene and ketones

Abstract The catalytic potential of zeolite H-beta in the hydration and isomerization of α-pinene was investigated. In the presence of water the main product is the monocyclic alcohol α-terpineol (48%) though selectivity towards bicyclic terpenes is higher than observed for sulphuric acid (26% vs. 5.5%). When the isomerization is performed in pure acetone, a new compound forms by a novel C C coupling reaction between α-pinene and acetone. The product is identified as α-terpinyl acetone. This coupling seems to be a general reaction between α-pinene and ketones and is catalyzed exclusively by zeolite beta.

Zeolite titanium beta: a selective and water resistant catalyst in Meerwein-Ponndorf-Verley-Oppenauer reactions

Aluminium-free zeolite titanium beta was found to be a selective and water stable catalyst in the Meerwein-Ponndorf-Verley reduction of alkylcyclohexanones and the Oppenauer oxidation of alkylcyclohexanol. 4-t-butyl- and 4-methylcyclohexanone were reduced with > 98% selectivity to the cis-alcohol. The high stereoselectivity is explained by transition-state selectivity.

Dehydration of Different Ketoses and Aldoses to 5‐Hydroxymethylfurfural

5-Hydroxymethylfurfural (HMF) is considered an important building block for future bio-based chemicals. Here, we present an experimental study using different ketoses (fructose, sorbose, tagatose) and aldoses (glucose, mannose, galactose) under aqueous acidic conditions (65 g L(-1) substrate, 100-160 °C, 33-300 mM H2 SO4 ) to gain insights into reaction pathways for hexose dehydration to HMF. Both reaction rates and HMF selectivities were significantly higher for ketoses than for aldoses, which is in line with literature. Screening and kinetic experiments showed that the reactivity of the different ketoses is a function of the hydroxyl group orientation at the C3 and C4 positions. These results, in combination with DFT calculations, point to a dehydration mechanism involving cyclic intermediates. For aldoses, no influence of the hydroxyl group orientation was observed, indicating a different rate-determining step. The combination of the knowledge from the literature and the findings in this work indicates that aldoses require an isomerization to ketose prior to dehydration to obtain high HMF yields.

A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics

Abstract Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid‐phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H‐Y was found to perform the best and can be easily reused after calcination.

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Ruthenium supported on activated carbon, on which acidic groups were introduced by pre-treatment with (NH4)2S2O8, is a highly active and selective catalyst for the synthesis of benzylamine via the reductive amination of benzaldehyde.

Substituted Phthalic Anhydrides from Biobased Furanics: A New Approach to Renewable Aromatics

A novel route for the production of renewable aromatic chemicals, particularly substituted phthalic acid anhydrides, is presented. The classical two-step approach to furanics-derived aromatics via Diels-Alder (DA) aromatization has been modified into a three-step procedure to address the general issue of the reversible nature of the intermediate DA addition step. The new sequence involves DA addition, followed by a mild hydrogenation step to obtain a stable oxanorbornane intermediate in high yield and purity. Subsequent one-pot, liquid-phase dehydration and dehydrogenation of the hydrogenated adduct using a physical mixture of acidic zeolites or resins in combination with metal on a carbon support then allows aromatization with yields as high as 84 % of total aromatics under relatively mild conditions. The mechanism of the final aromatization reaction step unexpectedly involves a lactone as primary intermediate.