- Renewable bio-based routes to γ-valerolactone in the presence of hafnium nanocrystalline or hierarchical microcrystalline zeotype catalysts
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Different renewable bio-based routes leading to the versatile bioproduct γ-valerolactone (GVL) were studied in integrated fashions, starting from furfural (Fur), α-angelica lactone (AnL) and levulinic acid (LA), in the presence of multifunctional hafnium-
- Antunes, Margarida M.,Fernandes, Auguste,Pillinger, Martyn,Ribeiro, Filipa,Silva, Andreia F.,Valente, Anabela A.
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- Synthesis of renewable alkylated naphthalenes with benzaldehyde and angelica lactone
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Herein, we report a new route for the synthesis of renewable alkylated naphthalenes (ANs) with benzaldehyde and angelica lactone, two platform compounds that can be derived from lignocellulose.
- Cong, Yu,Li, Guangyi,Li, Ning,Wang, Aiqin,Wang, Ran,Wang, Xiaodong,Xu, Jilei,Zhang, Tao
-
supporting information
p. 5474 - 5480
(2021/08/16)
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- Construction of Enantioenriched γ,γ-Disubstituted Butenolides Enabled by Chiral Amine and Lewis Acid Cascade Cocatalysis
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Herein we report a cascade cocatalysis strategy for the facile construction of chiral γ,γ-disubstituted butenolides. The synthetic manifold employs simple alkynoic acids instead of the preformed silyloxy furans or 5-substituted furan-2(3H)-ones. In situ formed 5-substituted furan-2(3H)-ones by AgNO3 or Ph3PAuCl/AgOTf catalyzed cyclization of alkynoic acids can smoothly engage in the subsequent chiral diphenylprolinol TMS-ether catalyzed Michael and Michael-aldol reactions. The cascade process serves as a general approach to chiral quaternary γ,γ-disubstituted butenolides.
- Yu, Chenguang,Ji, Peng,Zhang, Yueteng,Meng, Xiang,Wang, Wei
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supporting information
p. 7656 - 7660
(2021/10/12)
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- Esterification of levulinic acid over Sn(II) exchanged Keggin heteropolyacid salts: An efficient route to obtain bioaditives
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In this paper, we describe a process to add value to the biomass derivatives (i.e., levulinic acid), converting it to bioadditives over solid Sn(II) exchanged Keggin heteropolyacid salts. These solid catalysts are an attractive alternative to the traditional soluble and corrosive Br?nsted acid catalysts. Among Sn(II) heteropoly salts, the Sn1.5PW12O40 was the most active and selective catalyst, achieving high conversions (ca. 90 %) and selectivity (90–97 %) for alkyl esters and angelica lactone, the main reaction products. The impacts of the main reaction parameters (i.e., catalyst load, temperature, and the molar ratio of alcohol to acid) were investigated. The use of renewable raw material, and an efficient and recyclable catalyst are the main positive features of this process. The Sn1.5PW12O40 catalyst was easily recovered and reused without loss activity.
- Da Silva, Márcio José,Chaves, Diego Morais,Teixeira, Milena Galdino,Oliveira Bruziquesi, Carlos Giovani
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- Regioselective β-Arylation of α-Angelica Lactone through Isomerization/Addition under Mild Conditions
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The conversion of biomass-based platform molecules into various high-value chemicals greatly promotes the utilization of renewable biomass resources. Herein, an example of Rh-catalyzed β-arylation of levulinic-acid-derived α-angelica lactone was reported, providing the γ-lactone-structure products with high regioselectivity. Both arylboronic and alkenylboronic acids could be applied in this transformation. This reaction tolerated a variety of synthetically important functional groups. Moreover, the obtained γ-lactone products could be readily converted to high-value products such as 1,4-diols and γ-methoxy-carboxylates.
- Zhuo, Kai-Feng,Yu, Shang-Hai,Gong, Tian-Jun,Fu, Yao
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p. 693 - 697
(2020/02/04)
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- Lewis-Pair-Mediated Selective Dimerization and Polymerization of Lignocellulose-Based β-Angelica Lactone into Biofuel and Acrylic Bioplastic
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This contribution reports an unprecedentedly efficient dimerization and the first successful polymerization of lignocellulose-based β-angelica lactone (β-AL) by utilizing a selective Lewis pair (LP) catalytic system, thereby establishing a versatile bio-refinery platform wherein two products, including a dimer for high-quality gasoline-like biofuel (C8–C9 branched alkanes, yield=87 %) and a heat- and solvent-resistant acrylic bioplastic (Mn up to 26.0 kg mol?1), can be synthesized from one feedstock by one catalytic system. The underlying reason for exquisite selectivity of the LP catalytic system toward dimerization and polymerization was explored mechanistically.
- Hong, Miao,Wang, Xiao-Jun
-
supporting information
p. 2664 - 2668
(2020/01/24)
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- Efficient synthesis of niobium pentoxide nanowires and application in ethanolysis of furfuryl alcohol
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Nb2O5 nanowires with high specific surface area and crystallinity were prepared by using ammonium oxalate and an acetic acid solvent system. The nanomaterial was applied in ethanolysis of furfuryl alcohol (FA), and the yield of the product, 2-(ethoxymethyl)furan (FEE), achieved was up to 79.6%. Compared to mesoporous Nb2O5 materials and other porous materials, the residence time of FEE on the surface of the catalyst is shorter, and the yield of ethyl levulinate (EL) is lower. Furthermore, a high temperature calcination treatment can change the acid sites and acidity type distribution on the nanowire surface. By XRD, NH3-TPD, IR, and TG-DTA determination methods, it was found that the weak and medium-strong acid sites on the surface of Nb2O5 nanowires were reduced after a 300 °C treatment, and the amount of strong acid was relatively higher. According to the catalytic performance test data and acidity determination, it was concluded that more weak acid and medium-strong acid sites improve the conversion of furfuryl alcohol to FEE, and the strong acid sites promote further conversion of FEE to EL.
- Zhang, Zhenwei,Wang, Peng,Wu, Zeying,Yue, Chuanjun,Wei, Xuejiao,Zheng, Jiwei,Xiang, Mei,Liu, Baoliang
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p. 5690 - 5696
(2020/02/26)
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- CATALYST FOR PRODUCING GAMMA-VALEROLACTONE, METHOD FOR PREPARING THE SAME AND METHOD FOR MANUFACTURING GAMMA-VALEROLACTONE USING THE SAME
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Disclosed are a heteropolyacid catalyst for producing gamma-valerolactone, which is supported on M-Beta zeolite (M=Sn, Ti, Zr or Hf), and a method for preparing the same and a method for manufacturing gamma-valerolactone using the catalyst. The catalyst has an effect of producing gamma-valerolactone from biomass-derived furfural at a high yield through a one-pot process.
- -
-
Paragraph 0076; 0079
(2019/05/18)
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- Butenolide Derivatives of Biobased Furans: Sustainable Synthetic Dyes
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The dye and pigment manufacturing industry is one of the most polluting in the world. Each year, over one million tons of petrochemical colorants are produced globally, the synthesis of which generates a large amount of waste. Naturally occurring, plant-based dyes, on the other hand, are resource intensive to produce (land, water, energy), and are generally less effective as colorants. Between these two extremes would be synthetic dyes that are fully sourced from biomass-derived intermediates. The present work describes the synthesis of such compounds, containing strong chromophores that lead to bright colors in the yellow to red region of the visible spectrum. The study was originally motivated by an early report of an unidentified halomethylfurfural derivative which resulted from hydrolysis in the presence of barium carbonate, now characterized as a butenolide of 5-(hydroxymethyl)furfural (HMF). The method has been generalized for the synthesis of dyes from other biobased platform molecules, and a mechanism is proposed.
- Saska, Jan,Li, Zheng,Otsuki, Andrew L.,Wei, Jiahui,Fettinger, James C.,Mascal, Mark
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p. 17293 - 17296
(2019/11/11)
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- An electrocatalytic route for transformation of biomass-derived furfural into 5-hydroxy-2(5H)-furanone
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Development of efficient strategies for biomass valorization is a highly attractive topic. Herein, we conducted the first work on electrocatalytic oxidation of renewable furfural to produce the key bioactive intermediate 5-hydroxy-2(5H)-furanone (HFO). It was demonstrated that using H2O as the oxygen source and metal chalcogenides (CuS, ZnS, PbS, etc.) as electrocatalysts, the reaction could proceed efficiently, and the CuS nanosheets prepared in this work showed the best performance and provided high HFO selectivity (83.6%) and high conversion (70.2%) of furfural. In addition, the CuS electrocatalyst showed long-term stability. Mechanism investigation showed that furfural was oxidized to HFO via multistep reactions, including C-C cleavage, subsequent ring opening and oxidation, and intramolecular isomerization.
- Wu, Haoran,Song, Jinliang,Liu, Huizhen,Xie, Zhenbing,Xie, Chao,Hu, Yue,Huang, Xin,Hua, Manli,Han, Buxing
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p. 4692 - 4698
(2019/05/14)
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- Role of group V elements on the hydrogenation activity of Ni/TiO2 catalyst for the vapour phase conversion of levulinic acid to Γ-valerolactone
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Influence of group V elements such as Ta, Nb and V on the product distribution in the vapour phase hydrogenation of levulinic acid (LA) over Ni/TiO2 catalyst was examined at ambient pressure. The Nb promoted Ni/TiO2 demonstrated a high selectivity towards γ-valerolactone (GVL) compared to other catalysts at 275 °C. The TPR results showed a lower H2 uptake over Ta and V modified Ni/TiO2 which was explained due to a strong interaction between these oxide species with nickel. Presence of a high ratio of ionic nickel (Ni2+) on Ta and V modified catalyst could be a possible reason for the formation of valeric acid (VA) through the ring opening of GVL. The high GVL selectivity over the Ni-Nb/TiO2 catalyst attributed to the presence of a high proportion of Lewis acid sites in conjunction with finely dispersed Ni species on the catalyst surface. This however, is accomplished by the pyridine adsorbed diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and CO-chemisorption results.
- Peddakasu, Ganga Bhavani,Velisoju, Vijay Kumar,Kandula, Manasa,Gutta, Naresh,VR Chary, Komandur,Akula, Venugopal
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- The phosphinoboration of 2-diphenylphosphino benzaldehyde and related aldimines
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We have investigated the addition of a simple phosphinoboronate ester, Ph2PBpin (pin = 1,2-O2C2Me4), to 2-diphenylphosphinobenzaldehyde (2-Ph2PC6H4C(O)H) and related aldimine derivatives (2-Ph2PC6H4C(NR)H) as a simple and effective strategy for generating unique diphosphine ligands bearing a pendant Lewis-acid Bpin group. These reactions proceed selectively to give one new product where the phosphide fragment has added to the aldehyde (or imine) carbon atom and the electron-deficient boron group has added to the electron-rich heteroatom. Preliminary studies show these new compounds can ligate to Pd(II) and Pt(II) metal centres. These novel metal complexes, as well as the organic soluble [MCl2(coe)]2 (M = Pd, Pt, coe = cis-cyclooctene) compounds, have been shown to be effective precatalysts in the cyclisation of alkynoic acids to give the corresponding exo-dig cyclic lactones. Reactions employing these metal complexes also generated unusual endo-dig cyclic lactones not traditionally observed in these cyclisation reactions. For instance, reactions of 4-pentynoic acid also afforded significant amounts of α-angelica lactone, a biologically-important compound traditionally prepared via the catalytic dehydration and cyclisation of levulinic acid.
- Kindervater, Meagan B.,Binder, Justin F.,Baird, Samuel R.,Vogels, Christopher M.,Geier, Stephen J.,Macdonald, Charles L.B.,Westcott, Stephen A.
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supporting information
p. 378 - 385
(2018/12/14)
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- Levulinic acid upgrade to succinic acid with hydrogen peroxide
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Levulinic acid is produced from the acidic aqueous degradation of 5-hydroxymethylfurfural, with potential applications in bio-value added chemicals synthesis. Here, we report for the first time, the Baeyer-Villiger oxidation of levulinic acid to succinic acid, with hydrogen peroxide and tungstic acid at mild conditions and without any organic solvent. We investigated the effects of time, amount of reagent-to-catalyst molar ratio and H2O2-to-levulinic acid molar ratio. The maximum succinic acid selectivity was 75% with a levulinic acid conversion as high as 48%, after 6 h at 90 °C. We propose a reaction mechanism based on results obtained from the reactivity of the intermediates. The catalyst interacts with the substrate, forming a cyclic species that enhances the formation of succinic acid versus 3-hydroxypropanoic acid.
- Carnevali, Davide,Rigamonti, Marco G.,Tabanelli, Tommaso,Patience, Gregory S.,Cavani, Fabrizio
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- Selective Levulinic Acid Hydrogenation in the Presence of Hybrid Dendrimer-Based Catalysts. Part I: Monometallic
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Hybrid Ru-containing catalysts, based on poly(propylene imine) (PPI) dendrimers, immobilized in silica pores, were synthesized and characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The synthesized Ru catalysts proved their efficiency in the selective hydrogenation of levulinic acid and its esters at 80 °C, 30 bar of H2, and 50 % volume substrate concentration in water. Quantitative yields of γ-valerolactone were obtained for both micro- and mesoporous Ru catalysts within 2 h with catalytic activity as high as 1610 h?1. The reaction rate and selectivity on γ-valerolactone were found to depend on several factors such as carrier structure, temperature, presence of water, and substrate/Ru ratio. The novelty of these hybrid materials is the presence of both weak acid (SiO2) and organic base centers (dendrimer amino groups), enhancing the dispersion of Ru nanoparticles. The presence of amino groups in the catalyst stabilizes the Ru nanoparticles during the synthesis and promotes the adsorption of levulinic acid on the surface of Ru nanoparticles during the reaction. Synthesized hybrid Ru catalysts can be reused several times without significant loss of activity.
- Maximov, Anton L.,Zolotukhina, Anna V.,Mamedli, Adila A.,Kulikov, Leonid A.,Karakhanov, Edward A.
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p. 222 - 233
(2017/11/27)
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- Preparation of valeric acid and valerate esters from biomass-derived levulinic acid using metal triflates + Pd/C
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Recently, great attention has been paid to the study of the conversion of biomass-derived compounds to value-Added chemicals. Levulinic acid (LA) is a versatile and valuable chemical and its various applications have been described. The selective conversion of biomass-derived LA to produce valeric acid and valerate esters was successfully performed in the presence of H2, in which metal triflates and Pd/C were used as the catalysts. Under optimal conditions, a 99% conversion of LA and a 92% selectivity of valeric acid was obtained with Hf(OTf)4 and Pd/C as the catalysts at a relatively low temperature of 150 °C. Moreover, the metal center of the catalyst, the solvent, the reaction temperature and other reaction conditions were studied. In addition, the results of the recycling experiment exhibited that the catalysts continued to have a satisfactory activity after being reused 5 times.
- Zhou, Jian,Zhu, Rui,Deng, Jin,Fu, Yao
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p. 3974 - 3980
(2018/09/11)
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- Influence of W on the reduction behaviour and Br?nsted acidity of Ni/TiO2catalyst in the hydrogenation of levulinic acid to valeric acid: Pyridine adsorbed DRIFTS study
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Effect of W on 20 wt%Ni/TiO2catalyst is examined in the hydrogenation of levulinic acid (LA) to valeric acid at ambient H2pressure. The interaction between W and Ni had a significant influence on the hydrogenation activity and product selectivity. The H2-TPR (temperature programmed reduction) results emphasized a shift in Tmaxto very high temperatures due to W species which are in close proximity to Ni particles. The N2O decomposition measurements showed a decrease in N2O uptake with the increase in ‘W’ loadings due to a high ratio of Ni2+/Ni0species at higher tungsten content. X-ray photoelectron spectra (XPS) demonstrated a shift in binding energy to higher owing to a strong interaction between W and Ni particles by the presence of ionic Ni at the near surface region. The ionic Ni species seems to be involved in the conversion of γ-valerolactone (GVL) to valeric acid (VA). Pyridine adsorbed infrared (IR) spectra revealed an enormous increase in surface Br?nsted acidity originated from tungsten interacted Ni/TiO2are the sites responsible for ring opening of GVL to form VA.
- Kumar, V. Vijay,Naresh,Deepa,Bhavani, P. Ganga,Nagaraju,Sudhakar,Chary,Venugopal,Tardio,Bhargava
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p. 169 - 176
(2016/12/27)
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- Metal-exchanged magnetic β-zeolites: Valorization of lignocellulosic biomass-derived compounds to platform chemicals
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An array of magnetically recoverable β-zeolites exchanged with late transition metals (Pd, Fe and Ir) have been synthesized and fully characterized and had their catalytic activity evaluated on the conversion of several bio-derived compounds to other value-added platform chemicals. The nature of the transition metals exchanged in the zeolite matrix and the significant effect of reaction conditions such as temperature, time and solvent usage on both the conversion and selectivity of the process are delineated.
- Jorge, Erlen Y. C.,Lima, Thiago De M.,Lima, Carolina G. S.,Marchini, Lucas,Castelblanco, William N.,Rivera, Daniel G.,Urquieta-González, Ernesto A.,Varma, Rajender S.,Paix?o, Márcio W.
-
supporting information
p. 3856 - 3868
(2017/08/22)
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- Catalytic upgrading of furfuryl alcohol to bio-products: Catalysts screening and kinetic analysis
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The conversion of furfuryl alcohol, a highly versatile biomass-derived platform molecule, into a large variety of bio-products, including ethers, lactones and levulinates, has been evaluated in alcohol media using different solid acid catalysts, such as commercial zeolites, sulfonic acid-functionalized materials, and sulfated zirconia. Reaction pathways and mechanisms have been correlated to the particular type of catalyst used, aiming to establish the influence of the main physico-chemical properties of the materials on the extent of furfuryl alcohol conversion, as well as on the predominant reaction pathway followed. Mechanistic and kinetics modelling studies for each type of catalyst have been developed and compared, providing an useful tool for the selection of the most suitable solid acid catalyst for the production of each of the reaction intermediates in the cascade from furfuryl alcohol to alkyl levulinate.
- Paniagua,Melero,Iglesias,Morales,Hernández,López-Aguado
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- Gold Functionalized Platinum M12L24-Nanospheres and Their Application in Cyclization Reactions
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Nanospheres can be formed by combining 24 bispyridinyl building blocks with a palladium or platinum precursor. These spheres can be functionalized on the inside with a gold(I) chloride complex leading to a high local concentration of gold(I) complexes. The high local concentration makes the neutral gold species an active catalyst. Furthermore, the platinum-gold spheres can be post-modified with a silver(I) salt to form cationic gold(I) catalysts. The platinum assemblies are demonstrated to be stable in the presence of various substrates and as a result several cyclization reactions have been carried out using these new spheres as catalysts. Higher conversions in a [4+2] cycloaddition are observed for the sphere catalyst compared to the mono-nuclear analogues. Also the cyclization of 1,6-enynes can be facilitated by the confined gold catalyst and high activity is observed in the activation of allenes. For the lactonization of alkynoic acids, a different selectivity is observed compared to a standard gold(I) complex, demonstrating that the high local concentration due to a confined space can induce other selectivity in catalysis.
- Leenders, Stefan H. A. M.,Dürr, Maximillian,Ivanovic-Burmazovic, Ivana,Reek, Joost N. H.
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supporting information
p. 1509 - 1518
(2016/05/19)
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- Efficient formation of angelica lactones in a vapor-phase conversion of levulinic acid
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Vapor-phase lactonization of levulinic acid to produce angelica lactones, which include α-, β- and γ-form isomers, was performed in fixed-bed down-flow glass reactors over various oxide catalysts. SiO2 and SiO2-Al2O3 showed relatively high catalytic activity. The lactonization of levulinic acid to angelica lactones was found to be an endothermic equilibrium reaction, and the pressure equilibrium constant was calculated to be 0.2?atm at 275?°C. High temperatures and reduced pressures were effective for shifting the equilibrium from levulinic acid to angelica lactones, while the suitable reaction temperature was estimated to be 275?°C because temperatures higher than 275?°C decreased the selectivity to angelica lactones. The highest angelica lactones yield of 87.5% was achieved at a levulinic acid conversion of 95.3% over SiO2 under reduced pressure conditions of ca. 5?kPa at 275?°C. IR, NH3-TPD and TG analyses were performed for characterizing the catalysts used after the reactions together with a silylated SiO2 prepared for studying the active species on SiO2. The silanol groups of SiO2 with weak acidity were proposed to be the active species.
- Sun, Daolai,Takahashi, Yuta,Yamada, Yasuhiro,Sato, Satoshi
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- Obtaining a high value branched bio-alkane from biomass-derived levulinic acid using RANEY as hydrodeoxygenation catalyst
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Compared to 5-HMF (C6H6O3), angelica lactone (C5H6O2) is a platform compound that has more potential for biomass-derived high performance bio-alkane fuel production due to a CC bond in the molecular structure, leading to a C-C coupling intermediate (C10 self-aggregation dimer) and higher C:O ratio (2.5), resulting in lower hydrogen consumption for the subsequent hydrodeoxygenation process. Biomass-derived levulinic acid was used as the only starting raw material to produce C10 branched alkanes. First, carboxyl and carbonyl functional groups of levulinic acid under catalysis via intramolecular esterification and dehydration yielded angelica lactone, which included two isomers of angelica lactone (α-angelica lactone and β-angelica lactone). Secondly, angelica lactone di/trimers would be obtained by angelica lactone self-aggregation: α-angelica lactone and β-angelica lactone connecting via C-C bond coupling. Finally, these intermediate products are selectively hydrodeoxygenated over a RANEY catalyst to obtain C7-C10 branched alkanes. Nearly a 90% yield can be achieved under 483 K and 5 MPa H2 and the C10 branched alkane product, 3-ethyl-4-methyl heptane, accounts for 75% of the same.
- Lu, Boqiong,Li, Jinlong,Lv, Guangqiang,Qi, Yongqin,Wang, Yingxiong,Deng, Tiansheng,Hou, Xianglin,Yang, Yongxing
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p. 93956 - 93962
(2016/10/21)
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- Synthesis of renewable diesel with 2-methylfuran and angelica lactone derived from carbohydrates
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Diesel and jet fuel range branched alkanes were first synthesized by the combination of hydroxyalkylation/alkylation (HAA) of 2-methylfuran with angelica lactone and subsequent hydrodeoxygenation. Compared with the previous ethyl levulinate route, the angelica lactone route exhibited evident advantages at higher HAA reactivity.
- Wang, Wei,Li, Ning,Li, Shanshan,Li, Guangyi,Chen, Fang,Sheng, Xueru,Wang, Aiqin,Wang, Xiaodong,Cong, Yu,Zhang, Tao
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supporting information
p. 1218 - 1223
(2016/03/09)
-
- Palladium NNC Pincer Complex as an Efficient Catalyst for the Cycloisomerization of Alkynoic Acids
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A two-step (nucleophilic substitution/palladation by oxidative addition) sequence provides a high-yielding access to a non-symmetrical palladium NNC pincer complex. A number of terminal and internal alkynoic acids with different substitution patterns at the α- and β-positions are regio- and diastereoselectively cycloisomerized to the corresponding exocyclic enol lactones in the presence of exceedingly low amounts of the latter palladium complex, so that unprecedented turnover numbers and frequencies ranging from 1,000,000 to 700,000 and from 41,667 to 9722 h?1, respectively, are achieved. The optimized protocol, based on the use of a catalytic amount of triethylamine as base, allows an easy real-time monitoring of the reaction by NMR spectroscopy. Several pieces of evidence in favor of the direct participation of the above pincer complex as the catalyst of the reaction have been gathered from kinetic and poisoning experiments. (Figure presented.).
- Conde, Nerea,SanMartin, Raul,Herrero, María Teresa,Domínguez, Esther
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p. 3283 - 3292
(2016/10/21)
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- Catalytic oxidative C-C bond cleavage route of levulinic acid and methyl levulinate
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Recently, obtaining value-added chemicals from biomass resources has attracted considerable attention. Levulinic acid is one of the most important biomass platform compounds, which could be obtained from carbohydrate biomass. In this work, levulinic acid was selectively converted into C4 product, including succinic anhydride, via catalytic oxidation with a manganese catalyst in acetic anhydride. Moreover, an unexpected product of maleic anhydride was obtained, which greatly differs from that of levulinate ester. The pathway for formation of maleic anhydride was studied by monitoring and confirming intermediates α-angelica lactone and its derivative 2-methyl-5-oxotetrahydro-2-furanyl acetate. Based on the obtained mechanistic information, the different behaviour between the oxidative cleavage of levulinic acid and levulinate ester was further discussed.
- Xia, Fei,Du, Zhongtian,Liu, Junxia,Ma, Yangyang,Xu, Jie
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p. 72744 - 72749
(2016/08/09)
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- Tandem thionation of biomass derived levulinic acid with Lawesson's reagent
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Herein we report a tandem thionation of biomass derived levulinic acid (LA) to generate thiophenic compounds. LA is initially converted to several thiophenones and then an aromatic di-thionated product, 5-methylthiophene-2-thiol, is obtained with the highest yield of 78%. An overall synthesis of thiophenic products from cellulose is also developed.
- Li, Zheng,Tang, Xing,Jiang, Yetao,Zuo, Miao,Wang, Yangjun,Chen, Wei,Zeng, Xianhai,Sun, Yong,Lin, Lu
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p. 2971 - 2975
(2016/06/06)
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- An investigation on the influence of support type for Ni catalysed vapour phase hydrogenation of aqueous levulinic acid to γ-valerolactone
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Ni (20 wt%) supported on SiO2, γ-Al2O3 and ZrO2 catalysts was examined for hydrogenation of aqueous levulinic acid (LA) to γ-valerolactone (GVL) at 270°C and ambient pressure. The band intensities of Br?nsted (BAS: 1540 cm-1) and Lewis acid sites (LAS: 1450 cm-1) estimated by pyridine adsorbed DRIFT spectra revealed a lower ratio of BAS/LAS over the Ni/SiO2 catalyst than over the Ni/ZrO2 and Ni/γ-Al2O3 catalysts. The rate of angelica lactone (AL) formation was lower than the rate of AL hydrogenation over the Ni/SiO2 catalyst. The poisoning and regeneration of the Ni/SiO2 catalyst using pyridine and 2,6-dimethylpyridine demonstrated that Lewis acid sites influenced the conversion of LA to AL and subsequent hydrogenation of AL to GVL occurred on surface Ni sites. In contrast, Br?nsted acid sites were responsible for the ring opening of GVL to valeric acid (VA). Kinetic data emphasized that the hydrogenation activity and product distribution were dependent on the type of acid site, and the Ni sites in close proximity to Br?nsted acid sites are prone to hydrogenolysis of GVL to valeric acid and hydrocarbons.
- Kumar, Velisoju Vijay,Naresh, Gutta,Sudhakar, Medak,Anjaneyulu, Chatla,Bhargava, Suresh Kumar,Tardio, James,Reddy, Vanga Karnakar,Padmasri, Aytam Hari,Venugopal, Akula
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p. 9872 - 9879
(2016/02/05)
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- Pd/C catalyzed conversion of levulinic acid to γ-valerolactone using alcohol as a hydrogen donor under microwave conditions
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Levulinic acid can be converted to γ-valerolactone in 83-86% yield under microwave heating with 10 mg of 5% Pd/C per mmol levulinic acid as the catalyst and 2.0 equivalents of KOH in ethanol or iso-propanol. The alcohol is used as the hydrogen source as well as the solvent. Pd/C catalyst could be reused for five catalytic cycles without appreciable loss in activity.
- Amarasekara, Ananda S.,Hasan, Muhammad A.
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- GASOLINE PREPARED FROM BIOMASS-DERIVED LEVULINIC ACID
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The present invention provides methods for preparing a C6-C10 alkane, and mixture thereof. The methods include forming a reaction mixture containing an angelica lactone dimer, a catalyst, and a hydrogen source under conditions sufficient to reduce the angelica lactone dimer, thereby preparing the alkane. The methods can be used to prepare branched alkanes useful for fuels. Methods for preparing an angelica lactone, methods for preparing an angelica lactone dimer, and methods for reducing a lactone to an alkane are also described.
- -
-
Paragraph 0076
(2015/06/03)
-
- Silica-Supported Cationic Gold(I) Complexes as Heterogeneous Catalysts for Regio- and Enantioselective Lactonization Reactions
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An efficient method for the synthesis of heterogeneous gold catalysts has been developed. These catalysts were easily assembled from readily available silica materials and gold complexes. The heterogeneous catalysts exhibited superior reactivity in various reactions where protodeauration is the rate-limiting step. Dramatic enhancement in regio- and enantioselectivity was observed when compared to the homogeneous unsupported gold catalyst. The catalysts are easily recovered and recycled up to 11 times without loss of enantioselectivity.
- Shu, Xing-Zhong,Nguyen, Son C.,He, Ying,Oba, Fadekemi,Zhang, Qiao,Canlas, Christian,Somorjai, Gabor A.,Alivisatos, A. Paul,Toste, F. Dean
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supporting information
p. 7083 - 7086
(2015/06/25)
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- Nickel-promoted copper-silica nanocomposite catalysts for hydrogenation of levulinic acid to lactones using formic acid as a hydrogen feeder
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Highly active, thermally stable nickel-promoted copper-silica nanocomposite catalysts were prepared via a deposition-precipitation method and used for hydrogenation of levulinic acid (LA) using formic acid (FA) as H2 feeder. Ni(20)Cu(60)-SiO2 (3:1 weight ratio of Cu to Ni, 80 wt% metal content) showed better activity for vapor-phase formation of γ-valerolactone (GVL) from LA with FA as a hydrogen source. The catalyst selectively converts 99% of LA into 96% of GVL; the remaining 4% is angelica-lactone (AL). The effect of different concentrations of Ni promoted on Cu-silica and different LA to FA molar ratios on the catalyst activity affecting the hydrogen-free hydrogenation of LA was studied. The catalyst Ni(20)Cu(60)-SiO2 exhibited long-term stability (200 h) without loss in activity. Characterization using TEM, XPS, TPR, XRD and N2O titration was performed to find the most active phase for LA hydrogenation to GVL and the reason for the long-term stability. It was found that Ni-promoted well-dispersed metallic Cu species were the most active phases in hydrogenation, and the nanocomposite nature of the catalyst helped in providing long-term stability to the active phase.
- Upare, Pravin P.,Jeong, Myung-Geun,Hwang, Young Kyu,Kim, Dae Han,Kim, Young Dok,Hwang, Dong Won,Lee, U.-Hwang,Chang, Jong-San
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p. 127 - 135
(2015/05/06)
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- Formation of C-C bonds for the production of bio-alkanes under mild conditions
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It is of crucial importance to form C-C bonds between biomass-derived compounds for the production of bio-alkanes from biomass. In this study, it was found that C-C bonds can be formed between angelica lactones, key intermediates derived from biomass, through free radical reactions under mild conditions without using a noble catalyst or solvent, which gave elongated carbon chains of di/trimers with 10 or 15 carbons, with complete conversion and 100% selectivity. The di/trimers produced serve as a novel feedstock for the carbon backbones of bio-alkanes. Hydrogenation of the di/trimers produced C6-C13 hydrocarbons suitable for use as transportation fuels. This journal is the Partner Organisations 2014.
- Xin, Jiayu,Zhang, Suojiang,Yan, Dongxia,Ayodele, Olubunmi,Lu, Xingmei,Wang, Jianji
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p. 3589 - 3595
(2014/07/08)
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- Hydrodeoxygenation of the angelica lactone dimer, a cellulose-based feedstock: Simple, high-yield synthesis of branched C7-C10 gasoline-like hydrocarbons
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Dehydration of biomass-derived levulinic acid under solid acid catalysis and treatment of the resulting angelica lactone with catalytic K 2CO3 produces the angelica lactone dimer in excellent yield. This dimer serves as a novel feedstock for hydrodeoxygenation, which proceeds under relatively mild conditions with a combination of oxophilic metal and noble metal catalysts to yield branched C7-C10 hydrocarbons in the gasoline volatility range. Considering that levulinic acid is available in >80 % conversion from raw biomass, a field-to-tank yield of drop-in, cellulosic gasoline of >60 % is possible. Fuel for thought: Biomass-derived levulinic acid can be converted in three simple steps via the angelica lactone dimer into branched, gasoline-range hydrocarbons in high yield by using a combination of oxophilic metal and noble metal catalysts (see scheme). Copyright
- Mascal, Mark,Dutta, Saikat,Gandarias, Inaki
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supporting information
p. 1854 - 1857
(2014/03/21)
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- Continuous flow nanocatalysis: Reaction pathways in the conversion of levulinic acid to valuable chemicals
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The selective production of 2-methyltetrahydrofuran from levulinic acid has been effectively conducted using designed Cu based catalysts and compared with a commercial Pd/C system under microwave irradiation. Optimised conditions for the most active catalysts Cu-MINT (>90% conversion, 75% selectivity to MTHF) and Pd/C (78% conversion, 92% selectivity to MTHF) were further translated into a continuous flow process using the proposed catalysts to find out the deactivation of Cu-MINT under flow conditions (79 vs. 13% conversion with a switch in selectivity to products after 30 min in flow), the high stability of Pd/C (73 vs. 70% conversion at stable selectivity under analogous conditions to those of Cu-MINT) but, most importantly, different relevant pathways to valuable products from levulinic acid depending on the type of catalyst employed.
- Bermudez, Jose M.,Menendez, J. Angel,Romero, Antonio A.,Serrano, Elena,Garcia-Martinez, Javier,Luque, Rafael
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p. 2786 - 2792
(2013/10/08)
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- Metal-ligand cooperation in the cycloisomerization of alkynoic acids with indenediide palladium pincer complexes
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Indenediide Pd complexes 1a-c are shown to very efficiently catalyze the cycloisomerization of alkynoic acids into alkylidene lactones via metal-ligand cooperation (TON up to 2000). Complexes 1a-c are competent toward a broad range of alkynoic acids, including functionalized and internal ones, and give access to 5- as well as 6- and 7-membered lactones in excellent yields and with very high selectivities.
- Nebra, Noel,Monot, Julien,Shaw, Rosie,Martin-Vaca, Blanca,Bourissou, Didier
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p. 2930 - 2934
(2014/01/06)
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- Intramolecular cyclization of γ-acetylenic acids using dendrimer-encapsulated Pd2+ catalysts
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Polyamine dendrimer-encapsulated Pd2+ catalysts were prepared by complexation of PdCl2 with internal tertiary amino groups of the dendrimer. The fifth-generation Pd2+ dendrimer catalyst showed cooperative catalysis between Pd2+ species and the internal nanocavity consisting of regularly arranged tertiary amino groups to promote the intramolecular cyclization of γ-acetylenic acids efficiently.
- Maeno, Zen,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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p. 947 - 954
(2013/08/15)
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- Production of methyl-vinyl ketone from levulinic acid
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A method for converting levulinic acid to methyl vinyl ketone is described. The method includes the steps of reacting an aqueous solution of levulinic acid, over an acid catalyst, at a temperature of from room temperature to about 1100 K. Methyl vinyl ketone is thereby formed.
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Page/Page column 10-12
(2011/06/25)
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- METHODS FOR CONVERSION OF CARBOHYDRATES IN IONIC LIQUIDS TO VALUE-ADDED CHEMICALS
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Methods are described for converting carbohydrates including, e.g., monosaccharides, disaccharides, and polysaccharides in ionic liquids to value-added chemicals including furans, useful as chemical intermediates and/or feedstocks. Fructose is converted to 5-hydroxylmethylfurfural (HMF) in the presence of metal halide and acid catalysts. Glucose is effectively converted to HMF in the presence of chromium chloride catalysts. Yields of up to about 70% are achieved with low levels of impurities such as levulinic acid.
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Page/Page column 6; 8
(2008/06/13)
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- Catalytic activation of the leaving group in the SN2 reaction
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A novel catalytic activation of the leaving group in the SN2 reaction is achieved as an extension of our mercuric triflate-catalyzed reactions. Derivatives of anilinoethyl 4-pentynoate reacted smoothly with catalytic amounts of Hg(OTf)2 to give indoline derivatives in excellent yield with efficient catalytic turnovers under very mild conditions. The reaction of optically pure secondary alcohol derivatives resulted in inversion of stereochemistry, which is a definitive feature of the S N2 reaction. The procedure is applicable for benzoazepine synthesis.
- Yamamoto, Hirofumi,Pandey, Ghanshyam,Asai, Yumiko,Nakano, Mayo,Kinoshita, Atsushi,Namba, Kosuke,Imagawa, Hiroshi,Nishizawa, Mugio
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p. 4029 - 4032
(2008/02/10)
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- Mercuric triflate·3TMU catalyzed cyclization of ω-alkynoic acids and synthesis of a naturally occurring γ-methylene-γ-lactone
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Hg(OTf)2·3TMU showed efficient catalytic activity for the cyclization of ω-alkynoic acid to give ω-methylene-ω-lactone in excellent yield, and the procedure was efficiently applied for the synthesis of naturally occurring γ-methylene-γ-lactone.
- Imagawa, Hiroshi,Fujikawa, Yukari,Tsuchihiro, Atsushi,Kinoshita, Atsushi,Yoshinaga, Takayuki,Takao, Hiroko,Nishizawa, Mugio
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p. 639 - 641
(2007/10/03)
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- Stepwise cross-couplings of a dibromo-γ-methylenebutenolide as an access to Z-configured α-alkenyl-γ-alkylidenebutenolides. Straightforward synthesis of the antibiotic lissoclinolide
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The Z-isomer of α-bromo-γ-(bromomethylene)butenolide was prepared from α-angelica lactone or levulinic acid in three and four steps, respectively. Successive Stille-couplings with an unsaturated stannane, with the potential to use a different second unsaturated stannane, involved the a?-substituent first and the a?-substituent thereafter. Thereby, α-alkenyl-γ-alkylidenebutenolides and their arene analogs were obtained Z-selectively.
- Sorg, Achim,Blank, Frederik,Bruckner, Reinhard
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p. 1286 - 1290
(2007/10/03)
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- Microwave assisted Suzuki reactions for the preparation of the antifungal 3-aryl-5-methyl-2,5-dihydrofuran-2-ones
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The Suzuki cross-coupling reaction of arylboronic acids with a bromo-furanone has been developed to prepare a series of substituted 2,5-dihydrofuran-2-ones related to the fungal metabolite, incrustoporin. A protocol of microwave heating was introduced to improve synthesis throughput. Georg Thieme Verlag Stuttgart.
- Mathews, Christopher J.,Taylor, John,Tyte, Melloney J.,Worthington, Paul A.
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p. 538 - 540
(2007/10/03)
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- Production of 5-methyl-dihydro-furan-2-one from levulinic acid in supercritical media
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This invention relates to a process for producing 5-methyl-dihydro-furan-2-one from levulinic acid in presence of a supercritical fluid, and in presence of optionally-supported metal catalyst.
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- Interconversion and decomposition of furanones
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The interconversion and decomposition of furan-2(3H)- and -2(5H)-one and their methylated derivatives were studied by following the changes in their photoelectron spectra during pyrolysis. Interconversion occurred at 300-400°C and decomposition at around 600°C giving CO and acrolein as the only products for the unsubstituted furanones. The experimental results suggest that decarbonylation takes place through the 2(3H) form as the common precursor.
- Xu, Zhi Ping,Mok, Chup Yew,Chin, Wee Shong,Huang, Hsing Hua,Li, Sheng,Huang, Wei
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p. 725 - 729
(2007/10/03)
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- Polymer pyrolysis and oxidation studies in a continuous feed and flow reactor: Cellulose and polystyrene
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A dual-zone, continuous feed tubular reactor is developed to assess the potential for formation of products from incomplete combustion in thermal oxidation of common polymers. Solid polymer (cellulose or polystyrene) is fed continuously into a volatilization oven where it fragments and vaporizes. The gas-phase polymer fragments flow directly into a second, main flow reactor to undergo further reaction. Temperatures in the main flow reactor are varied independently to observe conditions needed to convert the initial polymer fragments to CO2 and H2O. Combustion products are monitored at main reactor temperatures from 400 to 850 °C and at 2.0-s total residence time with four on-line GC/FIDs; polymer reaction products and intermediates are further identified by GC/MS analysis. Analysis of polymer decomposition fragments at 400 °C encompasses complex oxygenated and aromatic hydrocarbon species, which range from high-molecular-weight intermediates of ca. 300 amu, through intermediate mass ranges down to C1 and C2 hydrocarbons, CO, and CO2. Approximately 41 of these species are positively identified for cellulose and 52 for polystyrene. Products from thermal oxidation of cellulose and polystyrene are shown to achieve complete combustion to CO2 and H2O at a main reactor temperature of 850 °C under fuel-lean equivalence ratio and 2.0-s reaction time. A dual-zone, continuous feed tubular reactor is developed to assess the potential for formation of products from incomplete combustion in thermal oxidation of common polymers. Solid polymer (cellulose or polystyrene) is fed continuously into a volatilization oven where it fragments and vaporizes. The gas-phase polymer fragments flow directly into a second, main flow reactor to undergo further reaction. Temperatures in the main flow reactor are varied independently to observe conditions needed to convert the initial polymer fragments to CO2 and H2O. Combustion products are monitored at main reactor temperatures from 400 to 850°C and at 2.0-s total residence time with four on-line GC/FIDs; polymer reaction products and intermediates are further identified by GC/MS analysis. Analysis of polymer decomposition fragments at 400°C encompasses complex oxygenated and aromatic hydrocarbon species, which range from high-molecular-weight intermediates of ca. 300 amu, through intermediate mass ranges down to C1 and C2 hydrocarbons, CO, and CO2. Approximately 41 of these species are positively identified for cellulose and 52 for polystyrene. Products from thermal oxidation of cellulose and polystyrene are shown to achieve complete combustion to CO2 and H2O at a main reactor temperature of 850°C under fuel-lean equivalence ratio and 2.0-s reaction time.
- Park, Byung-Ik,Bozzelli, Joseph W.,Booty, Michael R.,Bernhard, Mary J.,Mesuere, Karel,Pettigrew, Charles A.,Shi, Ji-Chun,Simonich, Staci L.
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p. 2584 - 2592
(2007/10/03)
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- Relative thermodynamic stabilities of γ-methylene-γ-butyrolactone and α-angelicalactone
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The relative thermodynamic stabilities of the title compounds have been determined by chemical equilibration in cyclohexane and dipentyl ether solutions at several temperatures. In each solvent, α-angelicalactone is favored thermodynamically, the values of ΔH(θ) and ΔS(θ) being ca. -8.0 kJ mol-1 and 2 J K-1 mol-1, respectively, for the γ-methylene-γ- butyrolactone → α-angelicalactone isomerization.
- Taskinen, Esko
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p. 1885 - 1888
(2007/10/02)
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- Hydrothermal formation of 1,2,4-benzenetriol from 5-hydroxymethyl-2-furaldehyde and D-fructose
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Thermolysis of 0.05 M aqueous 5-hydroxymethyl-2-furaldehyde (HMF) at 27.5 MPa and 290 to 400°C led to the formation of 1,2,4-benzenetriol in yields of up to 46% at 50% HMP conversion. The reaction temperature and water density have a significant effect on the product composition. Pseudo-first-order reaction rate constants for HMF conversion under these conditions range from 0.107 to 0.308 min-1. For the region 290 to 350°C, the activation energy for HMF conversion was found to be 47.7 kJ.mol-1. When subjecting D-fructose to hydrothermolysis, the main products are HMF, 1,2,4-benzenetriol, and furfural. Thermolysis of 0.05 M aqueous 5-hydroxymethyl-2-furaldehyde (HMF) at 27.5 MPa and 290 to 400°C led to the formation of 1,2,4-benzenetriol in yields of up to 46% at 50% HMF conversion. The reaction temperature and water density have a significant effect on the product composition. Pseudo-first-order reaction rate constants for HMF conversion under these conditions range from 0.107 to 0.308 min-1. For the region 290 to 350°C, the activation energy for HMF conversion was found to be 47.7 kJ.mol-1. When subjecting D-fructose to hydrothermolysis, the main products are HMF, 1,2,4-benzenetriol, and furfural.
- Luijkx,Van Rantwijk,Van Bekkum
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p. 131 - 139
(2007/10/02)
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- FRIEDEL-CRAFTS ALKYLATIONS OF FERROCENE WITH UNSATURATED LACTONES, SOME UNUSUAL REACTIONS CAUSED BY THE Β-FERROCENYLCARBENIUM ION
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Friedel-Crafts alkylations of ferrocene with 5- and 6-membered unsaturated lactones have been studied.The expected alkylation products were isolated in the case of 5-membered lactones, while several products such as unsaturated ferrocenyllactones, ferrocenyldiketones as well as ferrocenylhydroxylactones were isolated in the case of 6-membered lactones. β-Ferrocenylcarbenium ion was suggested to be the key intermediate in this case.
- Salisova, M.,Toma, S.,Solcaniova, E.
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- Synthesis of 2-Penten-4-olides, 3-Penten-4-olides, and 4,4-Dialkyl-1,3-cyclopentanediones by Acid- and Base-Induced Isomerization of 4-Penten-4-olides (γ-Methylene-γ-butyrolactones)
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3-Penten-4-olides, 2-penten-4-olides, and 4,4-dialkyl-1,3-cyclopentanediones may by obtained selectively by isomerization of 4-penten-4-olides (γ-methylene-γ-butyrolactones).
- Guntrum, Eberhard,Kuhn, Walter,Spoenlein, Wolfgang,Jaeger, Volker
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p. 921 - 925
(2007/10/02)
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- PALLADIUM(II) CATALYZED CYCLIZATION OF ALKYNOIC ACIDS
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Under the catalytic action of palladium(II) in the presence of triethylamine, 3-, 4-, and 5-alkynoic acids afford 3-buten-4-olides, 4-penten-4-olides,and 5-hexen-5-olide, respectively, in good to excellent yields.
- Lambert, Claude,Utimoto, Kiitiro,Nozaki, Hitosi
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p. 5323 - 5326
(2007/10/02)
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- Synthesis and photooxidation of furylthymines; chemiexcitation model studies
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A method for the synthesis of 1-(5-methyl-2-furoyl)thymine (7) and 1-(5-methyl-2-furyl)thymine (8) is described.Trimethylsilyliodide catalysed addition of 5-methyl-2,4-bis(trimethylsilyloxy)pyrimidine (9) to 2-methyl-2,5-dihydro-2,5-dimethoxyfuran yielded the new thymine derivative 13.Photooxidations of 7 and 8 gave not the excepted addition products but furan endoperoxides and hydroperoxides and the novel rearrangement product 1-(3-keto-1-butenyl)-thymine.
- Feringa, Ben L.,Dannenberg, W.
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p. 192 - 196
(2007/10/02)
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