1004-29-1Relevant articles and documents
Tailor-made biofuel 2-butyltetrahydrofuran from the continuous flow hydrogenation and deoxygenation of furfuralacetone
Strohmann, Marc,Bordet, Alexis,Vorholt, Andreas J.,Leitner, Walter
, p. 6299 - 6306 (2019)
In this work, we present the first continuous flow process to produce the tailored biofuel 2-butyltetrahydrofuran from renewable resources. In a two-step approach lignocellulose-derived furfuralacetone is first hydrogenated and then deoxygenated over commercial catalysts to form the desired product. Both reactions were studied independently in batch conditions. The transition to a continuous flow system was done and various parameters were tested in the miniplant. Both reactions were performed in a two-reactor-concept approach to yield the desired 2-butyltetrahydrofuran in a high yield directly from furfuralacetone.
Direct cross-coupling between alkenes and tetrahydrofuran with a platinum-loaded titanium oxide photocatalyst
Tyagi, Akanksha,Yamamoto, Akira,Yamamoto, Muneaki,Yoshida, Tomoko,Yoshida, Hisao
, p. 2546 - 2556 (2018)
A Pt-loaded TiO2 photocatalyst successfully catalyzed the direct cross-coupling between various alkenes and tetrahydrofuran (THF) without any additional oxidizing agent. The reaction between cyclohexene and THF gave three cross-coupling products, namely, 2-cyclohexyltetrahydrofuran (A), 2-(cyclohex-2-en-1-yl)tetrahydrofuran (B) and 2-(cyclohex-1-en-1-yl)tetrahydrofuran (C), along with gaseous hydrogen. The mechanistic study revealed that these products were formed through different individual mechanisms: successive addition of two radical species, a 2-tetrahydrofuranyl radical and a hydrogen radical, to the double bond of cyclohexene for A, coupling of a 3-cyclohexenyl radical and a 2-tetrahydrofuranyl radical for B, and 2-tetrahydrofuranyl radical addition and hydrogen radical elimination at the double bond of cyclohexene for C. Among these three mechanisms, those for B and C are dehydrogenative. In this photocatalytic reaction system, since the cyclohexene molecule has enough reactivity, due to the localized π electron density, the Pt nanoparticles loaded on the TiO2 function not as a metal catalyst but as an electron receiver to enhance the charge separation, although the dehydrogenative cross-coupling of benzene with THF requires Pd metal catalysis.
Synthesis of 1-octanol and 1,1-dioctyl ether from biomass-derived platform chemicals
Julis, Jennifer,Leitner, Walter
, p. 8615 - 8619 (2012)
The happy medium: A new catalytic pathway for the synthesis of the linear primary C8?alcohol products 1-octanol and dioctyl ether from furfural and acetone has been developed using retrosynthetic analysis. This opens a general strategy for the synthesis of medium-chain-length alcohols from carbohydrate feedstock.
SELECTIVITY OF TETRAHYDROFURAN FORMATION FROM UNACTIVATED ALIPHATIC ALCOHOLS BY THE BROMINE-SILVER-SALT REACTION
Roscher, Nina Matheny,Shaffer, D. Kent
, p. 2643 - 2650 (1984)
Studies of the bromine-silver carbonate reaction with aliphatic alcohols in which intramolecular δ-H competition is possible are generally quite specific.Loss of a tertiary δ- hydrogen occurs preferentially from both tertiary and secondary aliphatic alcohols to yield the most highly substituted cyclic ether.For example, 2,5-dimethyl-2-octanol yields only 2,2,5-trimethyl-5-propyltetrahydrofuran as the cyclic ether product; 2-methyl-2-isopentyltetrahydrofuran is not detected.
Bifunctional nanoparticle-SILP catalysts (NPs@SILP) for the selective deoxygenation of biomass substrates
Luska, Kylie L.,Julis, Jennifer,Stavitski, Eli,Zakharov, Dmitri N.,Adams, Alina,Leitner, Walter
, p. 4895 - 4905 (2014)
Ruthenium nanoparticles were immobilized onto an acidic supported ionic liquid phase (RuNPs@SILP) in the development of bifunctional catalysts for the selective deoxygenation of biomass substrates. RuNPs@SILPs possessed high catalytic activities, selectivities and recyclabilities in the hydrogenolytic deoxygenation and ring opening of C8- and C9-substrates derived from furfural or 5-hydroxymethylfurfural and acetone. Tailoring the acidity of the SILP through the ionic liquid loading provided a molecular parameter by which the catalytic activity and selectivity of the RuNPs@SILPs were controlled to provide a flexible catalyst system toward the formation of different classes of value-added products: cyclic ethers, primary alcohols or aliphatic ethers. This journal is
Energy-efficient production of 1-octanol from biomass-derived furfural-acetone in water
Xia, Qineng,Xia, Yinjiang,Xi, Jinxu,Liu, Xiaohui,Wang, Yanqin
, p. 4411 - 4417 (2015)
An energy-efficient catalytic system for the one-pot production of 1-octanol from biomass-derived furfural-acetone (FFA) under mild conditions in water was developed, by sequential hydrogenation/hydrogenolysis over a hydrophilic Pd/NbOPO4 catalyst. A strategy of creating an intentional "phase problem" has been employed to prevent the over-hydrogenolysis of 1-octanol into n-octane and therefore increased the selectivity to 1-octanol. The effects of reaction conditions as well as a variety of noble-metal loaded bifunctional catalysts have been systematically investigated to maximize the yield of 1-octanol. Moreover, the addition of liquid acids to the catalytic system further enhanced the selectivity towards the formation of 1-octanol. There is a strong correlation between the acid strength of an acidic additive and the sum yield of 1-octanol and octane. With the addition of TfOH, the highest yield of 1-octanol (62.7%) was obtained from one-pot conversion of biomass-derived FFA over Pd/NbOPO4.
Potential Vegetable-Based Diesel Fuels from Perkin Condensation of Furfuraldehyde and Fatty Acid Anhydrides
Baldwin, Lawrence C.,Davis, Matthew C.,Hughes, Alicia M.,Lupton, David V.
, p. 571 - 583 (2019)
Domestically produced biofuels may help to reduce dependence on imported oil for powering transportation and infrastructure in the future. In this report, we reacted medium-chain and long-chain fatty anhydrides (capric, caprylic, lauric, and palmitic) with furfuraldehyde by the Perkin condensation to produce 2-n-alkenylfurans. In the second step, the 2-n-alkenylfurans were hydrogenated to form 2-n-alkyltetrahydrofurans. Basic fuel property testing (melting point, density, kinematic viscosity, derived cetane number, and calorific value) of the 2-n-alkyltetrahydrofurans indicates they are potentially useful as fuels for diesel engines. The mixture composed of 2-octyl- and 2-decyltetrahydrofuran had the best combination of fuel properties including a low melting point (?39 °C), high cetane number (63.1), high flash point (98.2 °C), and low viscosity (2.26 mm2 s?1, 40 °C), which compares favorably with specifications for diesel #2 and biodiesel.
Selective Hydrogenation and Hydrodeoxygenation of Aromatic Ketones to Cyclohexane Derivatives Using a Rh&at;SILP Catalyst
Bordet, Alexis,Emondts, Meike,Leitner, Walter,Moos, Gilles
supporting information, p. 11977 - 11983 (2020/06/02)
Rhodium nanoparticles immobilized on an acid-free triphenylphosphonium-based supported ionic liquid phase (Rh&at;SILP(Ph3-P-NTf2)) enabled the selective hydrogenation and hydrodeoxygenation of aromatic ketones. The flexible molecular approach used to assemble the individual catalyst components (SiO2, ionic liquid, nanoparticles) led to outstanding catalytic properties. In particular, intimate contact between the nanoparticles and the phosphonium ionic liquid is required for the deoxygenation reactivity. The Rh&at;SILP(Ph3-P-NTf2) catalyst was active for the hydrodeoxygenation of benzylic ketones under mild conditions, and the product distribution for non-benzylic ketones was controlled with high selectivity between the hydrogenated (alcohol) and hydrodeoxygenated (alkane) products by adjusting the reaction temperature. The versatile Rh&at;SILP(Ph3-P-NTf2) catalyst opens the way to the production of a wide range of high-value cyclohexane derivatives by the hydrogenation and/or hydrodeoxygenation of Friedel–Crafts acylation products and lignin-derived aromatic ketones.
Solvent effects in hydrodeoxygenation of furfural-acetone aldol condensation products over Pt/TiO2 catalyst
Ramos, Rubén,Ti?ler, Zdeněk,Kikhtyanin, Oleg,Kubi?ka, David
, p. 174 - 183 (2016/12/06)
The solvent effects on hydrodeoxygenation (HDO) of 4-(2-furyl)-3-buten-2-one (F-Ac) over Pt/TiO2 catalyst were investigated at T = 200 °C and P(H2) = 50 bar. The initial reactant is the main product of aldol condensation between furfural and acetone, which constitutes a promising route for the production of bio-based chemicals and fuels. A sequence of experiments was performed using a selection of polar solvents with different chemical natures: protic (methanol, ethanol, 1-propanol, 2-propanol, 1-pentanol) and aprotic (acetone, tetrahydrofuran (THF), n,n-dimethylformamide (DMF)). In case of protic solvents, a good correlation was found between the polarity parameters and conversion. Consequently, the highest hydrogenation rate was observed when 2-propanol was used as a solvent. In contrast, the hydrogenation activity in presence of aprotic solvents was related rather to solvent-catalyst interactions. Thus, the initial hydrogenation rate declined in order Acetone > THF > DMF, i.e. in accordance with the increase in the nucleophilic donor number and solvent desorption energy. Regarding the product distribution, a complex mixture of intermediates was obtained, owing to the successive hydrogenation (aliphatic C[dbnd]C, furanic C[dbnd]C and ketonic C[dbnd]O bonds), ring opening (via C[sbnd]O hydrogenolysis) and deoxygenation reactions. Based on the proposed reaction scheme for the conversion of F-Ac into octane, the influence of the studied solvents over the cascade catalytic conversion is discussed. A significant formation of cyclic saturated compounds such as 2-propyl-tetrahydropyran and 2-methyl-1,6-dioxaspiro[4,4]nonane took place via undesirable side reactions of cyclization and isomerization. The best catalytic performance was found when using acetone and 2-propanol as solvents, achieving significant yields of 4-(2-tetrahydrofuryl)-butan-2-ol (28.5–40.4%) and linear alcohols (6.3–10.4%). The better performance of these solvents may be associated with a lower activation energy barrier for key intermediate products, due to their moderate interaction with the reactant and the catalyst. In case of methanol and DMF, undesired reactions between the reactant and the solvent took place, leading to a lower selectivity towards the targeted hydrodeoxygenated products.
Bifunctional property of Pt nanoparticles deposited on TiO2 for the photocatalytic sp3C-sp3C cross-coupling reactions between THF and alkanes
Tyagi, Akanksha,Yamamoto, Akira,Kato, Tatsuhisa,Yoshida, Hisao
, p. 2616 - 2623 (2017/07/25)
The photocatalytic sp3C-sp3C cross-coupling between tetrahydrofuran (THF) and various alkanes was accomplished with Pt loaded titanium oxide (Pt/TiO2) photocatalysts. The cross-coupling between THF and cyclohexane was systematically studied, which revealed that the reaction followed two routes: the main course was the photooxidation of both substrates on a Pt/TiO2 photocatalyst to generate radical species followed by their successive coupling; meanwhile, the minor one was a hybrid of photocatalysis by Pt/TiO2 and thermocatalysis by Pt metal nanoparticles. The activity of the Pt catalysis was suggested to consist in the activation of an sp3C-H bond in THF or alkane molecules adsorbed on its surface and promote the reaction between the activated molecules and photogenerated radical species. Thus, the Pt nanoparticles on TiO2 were believed to play a bifunctional role of an electron receiver as well as a metal catalyst.
