110-13-4Relevant articles and documents
Synthesis of functionalized tetrahydrofuran derivatives from 2,5-dimethylfuran through cascade reactions
Li,Muller,Pera-Titus,Jér?me,De Oliveira Vigier
, p. 2601 - 2609 (2019)
A three-step strategy is proposed for the functionalization of the methyl group of 2,5-dimethylfuran, encompassing the ring opening of 2,5-dimethylfuran to 2,5-hexanedione, its further aldol condensation with aldehydes, and hydrogenation-cyclization of the condensation intermediate to generate alkylated tetrahydrofuran. Active and selective catalysts could be identified for the aldol condensation and hydrogenation-cyclization reactions.
UN ANION β-ACYLE MASQUE DANS LES REACTIONS D'ACYLATION: LE DERIVE LITHIE DU DIOXOLANNE DU LEVULATE DE TRIMETHYLSILYLE
Moreau, Jean-Louis,Couffignal, Renee
, p. 139 - 144 (1985)
An organolithium reagent derived form trimethylsilyl-4,4-ethylenedioxypentanoate reacts with mixed carboxylic-carbonic anhydrides as a homoenolate anion equivalent.Several monoethylene acetals of 1,4-diketones and the corresponding diketones are synthesized by this way.
A facile synthesis of 1,4-diketones
Bergman,Nilsson,Wickberg
, p. 2783 - 2786 (1990)
1,4-Diketones may conveniently be synthesized by the addition of 2-methylcyclopropenyllithium to N-methoxy-N-methylcarboxamides followed by hydrolysis of intermediate cyclopropyl ketone adducts on silica gel. The new method has been applied to the synthesis of cis-jasmone.
A two-step approach for the catalytic conversion of glucose to 2,5-dimethylfuran in ionic liquids
Chidambaram, Mandan,Bell, Alexis T.
, p. 1253 - 1262 (2010)
Lignocellulosic biomass is an attractive resource for producing transportation fuels, and consequently novel approaches are being sought for transforming the lignin and cellulosic constituents of biomass to fuels or fuel additives. Glucose, the monomer of cellulose, is a good starting material for exploring such chemistries. We report here the results of an investigation aimed at identifying catalysts for the dehydration of glucose to 5- hydroxymethylfurfural (HMF) dissolved in ionic liquids and the subsequent conversion of HMF to 2,5-dimethylfuran (DMF), a high-energy content product that could be used as a fuel or fuel additive. Heteropoly acids were found to be exceptionally active and selective catalysts for the dehydration of glucose. Nearly 100% yield of HMF could be achieved using 12-molybdophosphoric acid (12-MPA) in a solution of 1-ethyl-3-methylimidazolium chloride (EMIMCl) and acetonitrile. The addition of acetonitrile to EMIMCl suppressed the formation of humins from glucose. The high HMF selectivity achievable with heteropoly acid catalysts is ascribed to stabilization of 1,2-enediol and other intermediates involved in the dehydration of glucose and the avoidance of forming the 2,3-enediol intermediate leading to furylhydroxymethyl ketone (FHMK). Carbon-supported metals, and in particular Pd/C, were effective in promoting the hydrogenation of HMF dissolved in EMIMCl and acetonitrile to DMF. The following intermediates were observed in the hydrogenation of HMF to DMF: 5-methylfurfural (MF), 5-methylfurfyl alcohol (MFA), and 2,5- dihydroxymethylfuran (DHMF). The relative rate of formation and consumption of these compounds was explored by using each of them as a reactant in order to identify the reaction pathway from HMF to DMF. It was also observed that HMF produced via glucose dehydration could be converted to DMF without isolation, if the dehydration catalyst, 12 MPA, was replaced by the hydrogenation catalyst, Pd/C. This two-step catalytic approach provides the basis for completely converting glucose to HMF and further converting HMF to DMF. The Royal Society of Chemistry 2010.
Efficient desymmetrization of 1,2 and 1,3 diols by dimethyldioxirane
Bovicelli, Paolo
, p. 3031 - 3034 (1995)
Dimethyldioxirane was used to monooxide 1,2 and 1,3 sec,sec-diols to the corresponding ketoalcohols, exploiting the inhibiting effect of the formed carbonyl group on the course of the process.
Carbon-Carbon Bond Formation by Light-Assisted B12 Catalysis. Nucleophilic Acylation of Michael Olefins
Scheffold, Rolf,Orlinski, Ryszard
, p. 7200 - 7202 (1983)
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Catalytic dehydration of d-xylose to 2-furfuraldehyde in the presence of Zr-(W,Al) mixed oxides. Tracing by-products using two-dimensional gas chromatography-time-of-flight mass spectrometry
Antunes, Margarida M.,Lima, Sérgio,Fernandes, Auguste,Candeias, Joana,Pillinger, Martyn,Rocha, Sílvia M.,Ribeiro, Maria Filipa,Valente, Anabela A.
, p. 127 - 135 (2012)
Zirconium-tungsten mixed oxides (ZrW) are effective catalysts in the aqueous-phase dehydration of d-xylose to 2-furfuraldehyde (Fur), at 170 °C. The texture and acid properties of ZrW materials were modified to enhance Fur yields. The catalysts prepared by co-condensation without a templating agent (ZrW(X), X = NO3, Cl; X is related to the type of zirconium precursor) possess relatively low specific surface area and amounts of accessible acid sites, leading to a modest Fur yield of ca. 35% at 99% conversion. The use of a templating agent in the preparation of mesoporous ZrW (ZrW-MP) increased considerably the specific surface area and the amount of accessible acid sites, which resulted in enhanced Fur yields (42%) reached at comparable conversions. Further improvements in Fur yields at high conversions were accomplished by introducing aluminium in the catalyst preparation procedure to give ZrAlW-MP (51% yield at 98% conversion). Fairly good catalytic results were also obtained in the case of the ZrAlW-MP catalyst, using solely water as solvent (46% yield at 93% conversion). A study of the identification of the reaction by-products by two-dimensional gas chromatography (GC × GC) combined with time-of-flight mass spectrometry (ToFMS) was carried out.
Facile Synthesis of 1,4-Diketones via Palladium Complex Catalyzed Isomerization of Alkynediols
Lu, Xiyan,Ji, Jianguo,Ma, Dawei,Shen, Wei
, p. 5774 - 5778 (1991)
Alkynediols isomerized under the catalysis of Pd(dba)3*CHCl3 + 2n-Bu3P in acetonitrile at 80 deg C to give 1,4-diketones in high yields.This experimentally simple and economically synthetic method is illustrated with examples including substituents such as alkyl, alkenyl, and aryl groups.The order of reactivity of the substituents in this reaction is aryl >/= alkenyl > alkyl.Alkenyl-substituted alkynediols chemoselectively isomerized to the corresponding α,β-unsaturated 1,4-diketones.The usefulness of this novel method is examplified by the synthesis of dihydrojasmone.
Radical cyclisation of α,ω-dinitroalkanes
Russell Bowman,Jackson, Stuart W.
, p. 7313 - 7324 (1990)
2,6-Dinitroalkanes have been cyclised to yield vicinal dinitrocyclopentanes via stereoselective intramolecular addition of nitronate anions to α-nitroalkyl radicals. A "cyclohexane type" transition state is proposed for this radical anion cyclisation.
SYNTHESE DE MONODIOXOLANNES DE DICETONES-1,4 ET DE DICETONES-1,4 AU MOYEN DES ANHYDRIDES MIXTES CARBOXYLIQUES ET CARBONIQUES: APPLICATION A LA PREPARATION DE LA DIHYDROJASMONE, DE LA Z-JASMONE ET DE LA DEHYDROJASMONE
Moreau, J.-L.,Couffignal, R.,Arous-Chtara, R.
, p. 307 - 310 (1981)
Levulinic acid 1 is easily converted by two steps into mixed carboxylic and carbonic anhydride 3 which reacts with the organolithium reagent issued from trimethylsilyl esters.Monoethylene acetal of 1,4-diketones 4 can be prepared; it is also possible to obtain 1,4-diketones 5 in one step by hot acid hydrolysis.The preparation of the dihydrojasmone 6d, Z-jasmone 6e and dehydrojasmone 6f shows the efficiency of the process.
Self-oscillating reaction in the Furan series
Gubina,Pankratov,Labunskaya,Rogacheva
, p. 1396 - 1401 (2004)
It was found for the first time that the acid hydrolysis of 2,5-dimethylfuran in water-ethanol solutions has self-oscillating character. Oscillations in the concentrations of the two products 2,5-hexanedione and an unidentified compound X were detected by GLC. The ranges of hydrochloric acid and ethanol concentrations in which these oscillations appear were determined. It is suggested that the formation of compound X results from tautomeric transformations of 2,5-hexanedione under the reaction conditions. Quantum-chemical calculations showed that the possible tautomers are formed with equal probability.
Electrochemical reductive biomass conversion: Direct conversion of 5-hydroxymethylfurfural (HMF) to 2,5-hexanedione (HD): Via reductive ring-opening
Roylance, John J.,Choi, Kyoung-Shin
, p. 2956 - 2960 (2016)
2,5-Hexanedione (HD), which can be produced by reduction of 5-hydroxymethylfurfural (HMF), one of the most important biomass intermediates, can serve as a precursor to produce various biofuels and key building block chemicals. The conversion of HMF to HD requires reduction of both the alcohol and aldehyde groups to alkane groups as well as opening of the furan ring. In this study, a direct electrochemical conversion of HMF to HD at ambient pressure and temperature was demonstrated without using H2 or precious metal catalysts. Water was used as the hydrogen source and zinc was used as the catalytic electrode, which enabled hydrogenolysis and Clemmensen reduction coupled with furan ring opening. Optimum conditions to achieve high Faradaic efficiency (FE) and selectivity for HD production were investigated and plausible mechanisms were proposed. The environmentally benign one-step procedure to produce HD reported in this study will serve as a new route to valorize biomass intermediates.
Bromine-Hydrolysis Control in the Cerium Ion-Bromate Ion-Oxalic Acid-Acetone Belousov-Zhabotinskii Oscillator
Field, Richard J.,Boyd, Patrick M.
, p. 3707 - 3714 (1985)
Chemical oscillations in reacting systems containing BrO3(1-) have been interpreted as a switching phenomenon in which control of the overall reaction is passed back and forth between a set of radical reactions, whose major effect is the removal of Br(1-).Control switches to the radical reactions when is driven low enough.Oscillation occurs because Br(1-) is an indirect product of the radical reactions, causing control to be returned to the nonradical reactions.Bromide ion control of BrO3(1-)-driven oscillations has been challanged on the basis that in some systems the usual source of Br(1-) from the radical reactions is absent.It has been suggested that the oscillations are fact Br2 controlled.It is shown here that one of these puzzling oscillators can be simulated as Br(1-) controlled.By implication the others also can be.Bromine is an important intermediate in these systems as the controlling Br(1-) comes from Br2 hydrolysis and is in equilibrium with Br2 and HOBr.We call such an oscillator Br2-hydrolysis controlled.The simulation is based on 31 elementary reactions of which 9 are reversible.It was constructed on the basis of a large number of experiments on simpler, nonoscillatory reactions involving the same reactants and is much simpler than the mechanism of other BrO3(1-)-driven oscillators because of the relative simplicity in it of the reactions of oxalic acid and acetone.The rate constants thus determined were used without modification to obtain an essentially quantitative simulation of the oscillatory system.It is thus the most complete and quantitatively accurate simulation of a BrO3(1-)-driven oscillator with an organic substrate yet carried out.The complete mechanism can be reduced to a simple five-variable Oregonator-like model that contains no expendable stoichiometric factor and whose rate parameters all can be related directly to the concentration of a principal reactant.
Production of 2,5-hexanedione and 3-methyl-2-cyclopenten-1-one from 5-hydroxymethylfurfural
Ren, Dezhang,Song, Zhiyuan,Li, Lu,Liu, Yunjie,Jin, Fangming,Huo, Zhibao
, p. 3075 - 3081 (2016)
A novel approach for the production of 2,5-hexanedione (HDN) and 3-methyl-2-cyclopenten-1-one (3-MCO) from 5-hydroxymethylfurfural (HMF) by water splitting with Zn is reported for the first time. The use of high temperature water (HTW) conditions is the key for the efficient conversion of HMF to HDN and 3-MCO. Parameters regarding the Zn amount, temperature and reaction time are optimized and HDN and 3-MCO are produced in 27.3% and 30.5% yields, respectively. The roles of HTW and ZnO obtained by oxidation of Zn in water for the conversion of HMF, together with intermediate structures, are discussed to understand the mechanism of the reaction.
Synthesis of Renewable Triketones, Diketones, and Jet-Fuel Range Cycloalkanes with 5-Hydroxymethylfurfural and Ketones
Li, Shanshan,Chen, Fang,Li, Ning,Wang, Wentao,Sheng, Xueru,Wang, Aiqin,Cong, Yu,Wang, Xiaodong,Zhang, Tao
, p. 711 - 719 (2017)
A series of renewable C9–C12triketones with repeating [COCH2CH2] units were synthesized in high carbon yields (ca. 90 %) by the aqueous-phase hydrogenation of the aldol-condensation products of 5-hydroxylmethylfurfural (HMF) and ketones over an Au/TiO2catalyst. Compared with the reported routes, this new route has many advantages such as being environmentally friendly, having fewer steps, using a cheaper and reusable catalyst, etc. The triketones as obtained can be used as feedstocks in the production of conducting or semi-conducting polymers. Through a solvent-free intramolecular aldol condensation over solid-base catalysts, the triketones were selectively converted to diketones, which can be used as intermediates in the synthesis of useful chemicals or polymers. As another application, the tri- and diketones can also be utilized as precursors for the synthesis of jet-fuel range branched cycloalkanes with low freezing points (224–248 K) and high densities (ca. 0.81 g mL?1).
A Synthesis of 4-Oxo Carboxylic Acids, 4-Oxo Aldehydes, and 1,4-Diketones from γ-Lactones
Betancourt de Perez, Rosa M.,Fuentes, Lelia M.,Larson, Gerald L.,Barnes, Charles L.,Heeg, Mary Jane
, p. 2039 - 2043 (1986)
The α-methyldiphenylsilyl derivatives of γ-butyrolactone, γ-valerolactone, and the cis lactone of 2-hydroxycyclohexaneacetic acid have been reacted with Grignard reagents.The α-silylated lactones of γ-butyrolactone and γ-valerolactone react with a single equivalent of Grignard reagent to give a 2-substituted 4,5-dihydrofuran, which can be hydrolyzed and oxidized to 4-oxo carboxylic acids, 1,4-diketones, or 4-oxo aldehydes.The α-silylated fused lactone failed to react with ethylmagnesium bromide in refluxing tetrahydrofuran.An X-ray crystal structure of this silylated lactone indicated that this lack of reactivity is due to steric factors.
STUDY OF THE MECHANISM OF RECYCLIZATION OF FURANS INTO THIOPHENES AND SELENOPHENES IN CONDITIONS OF ACID CATALYSIS. 4. STUDY OF THE EFFECT OF THE SOLVENT AND DIRECTION OF REACTIONS OF HYDROLYSIS AND RECYCLIZATION OF 2,5-DIMETHYLFURAN
Gubina, T. I.,Labunskaya, V. I.,Kornienko, G. K.,Borodina, L. A.,Kharchenko, V. G.
, p. 548 - 552 (1995)
The kinetics of hydrolysis of 2,5-dimethylfuran and its recyclization into the corresponding thiophene were investigated in water-alcohol medium in 95, 80, and 50percent ethyl alcohol in the presence of HCl.It was found that the rates of these reactions are a function of both the initial concentration of the acid component and the concentration of water in the alcohol.The rate of hydrolysis is a function of the dilution of the alcohol to a greater degree than the rate of recyclization.
Hydrogenation/hydrolytic ring opening of 5-HMF by Cp-Iridium(III) half-sandwich complexes for bioketones synthesis
Xu, Zhanwei,Yan, Peifang,Xu, Wenjuan,Liu, Xiumei,Xia, Zhi,Chung, Benjamin,Jia, Songyan,Zhang, Z. Conrad
, p. 788 - 792 (2015)
A new method for one-step synthesis of ketones from biobased 5-hydroxymethylfurfural (5-HMF) and its derivatives is reported. Bipyridine coordinated Cp-Iridium(III) complexes (Cp, 1,2,3,4,5-pentamethylcyclopenta-1,3-diene) exhibit highly efficient catalytic performance for hydrogenation/hydrolytic ring opening of 5-HMF and derivatives to produce ketones. The catalytic mechanism is proposed to proceed via carbonyl hydrogenation, hydroxyl group promoted and directed hydrolytic furan ring opening, followed by hydrogenation of α,β-unsaturated carbonyl compound based on the experimental and independent events' statistical calculation results. (Chemical Equation Presented).
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Sauers et al.
, p. 4763 (1967)
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Ruthenium and Formic Acid Based Tandem Catalytic Transformation of Bioderived Furans to Levulinic Acid and Diketones in Water
Dwivedi, Ambikesh D.,Gupta, Kavita,Tyagi, Deepika,Rai, Rohit K.,Mobin, Shaikh M.,Singh, Sanjay K.
, p. 4050 - 4058 (2015)
Efficient tandem catalytic transformations of bioderived furans, such as furfural, 5-hydroxymethylfurfural (5-HMF), and 5-methylfurfural (5-MF), to levulinic acid (LA) and diketones, 1-hydroxyhexane-2,5-dione (1-HHD), 3-hydroxyhexane-2,5-dione (3-HHD), and hexane-2,5-dione (2,5-HD), was achieved by using water-soluble arene-RuII complexes, containing ethylenediamine-based ligands, as catalysts in the presence of formic acid. The catalytic conversion of furans depends on the catalyst, ligand, formic acid concentration, reaction temperature, and time. Experimental evidence, including time-resolved 1H NMR spectral studies, indicate that the catalytic reaction proceeds first with formyl hydrogenation followed by hydrolytic ring opening of furans. The ruthenium-formic acid tandem catalytic transformation of fructose to diketones and LA was also achieved. Finally, the molecular structures of the four representative arene-RuII catalysts were established by single-crystal X-ray diffraction studies.
Catalytic transformation of bio-derived furans to valuable ketoacids and diketones by water-soluble ruthenium catalysts
Gupta, Kavita,Tyagi, Deepika,Dwivedi, Ambikesh D.,Mobin, Shaikh M.,Singh, Sanjay K.
, p. 4618 - 4627 (2015)
Bio-derived furans such as 2-furfural (furfural), 5-hydroxymethyl-2-furfural (5-HMF) and 5-methyl-2-furfural (5-MF) were successfully transformed to a ketoacid, levulinic acid (LA), and diketones, 1-hydroxyhexane-2,5-dione (1-HHD), 3-hydroxyhexane-2,5-dione (3-HHD) and hexane-2,5-dione (HD), under moderate reaction conditions using water soluble and recyclable 8-aminoquinoline coordinated arene-ruthenium(ii) complexes. Under the optimized reaction conditions using 1 mol% catalyst in the presence of 12 equivalents of formic acid at 80-100 °C, complete conversion of furfural to LA with high selectivity was achieved. Several experiments along with 1H NMR spectral studies are described which provide more insights into the mechanism underlying the transformation of furans to open ring components. Experiments performed using structural analogues of the active catalyst inferred a structure-activity relationship for the observed superior catalytic activity of the 8-aminoquinoline coordinated arene-ruthenium(ii) complex. Furthermore, due to the high aqueous solubility of the studied complexes, high recyclability, up to 4 catalytic runs, was achieved without any significant loss of activity. Molecular identities of the studied 8-aminoquinoline coordinated arene-ruthenium(ii) complex were also confirmed using single-crystal X-ray diffraction studies.
Highly efficient and stereoselective biosynthesis of (2S,5S)-hexanediol with a dehydrogenase from Saccharomyces cerevisiae
Mueller, Marion,Katzberg, Michael,Bertau, Martin,Hummel, Werner
, p. 1540 - 1550 (2010)
The enantiopure (2S,5S)-hexanediol serves as a versatile building block for the production of various fine chemicals and pharmaceuticals. For industrial and commercial scale, the diol is currently obtained through bakers' yeast-mediated reduction of 2,5-hexanedione. However, this process suffers from its insufficient space-time yield of about 4 g L-1 d-1 (2S,5S)-hexanediol. Thus, a new synthesis route is required that allows for higher volumetric productivity. For this reason, the enzyme which is responsible for 2,5-hexanedione reduction in bakers' yeast was identified after purification to homogeneity and subsequent MALDI-TOF mass spectroscopy analysis. As a result, the dehydrogenase Gre2p was shown to be responsible for the majority of the diketone reduction, by comparison to a Gre2p deletion strain lacking activity towards 2,5-hexanedione. Bioreduction using the recombinant enzyme afforded the (2S,5S)-hexanediol with >99% conversion yield and in >99.9% de and ee. Moreover, the diol was obtained with an unsurpassed high volumetric productivity of 70 g L-1 d-1 (2S,5S)-hexanediol. Michaelis-Menten kinetic studies have shown that Gre2p is capable of catalysing both the reduction of 2,5-hexanedione as well as the oxidation of (2S,5S)-hexanediol, but the catalytic efficiency of the reduction is three times higher. Furthermore, the enzyme's ability to reduce other keto-compounds, including further diketones, was studied, revealing that the application can be extended to α-diketones and aldehydes.
Initiation and Abstraction Reaction in the Pyrolysis of Acetone
Mousavipour, S. Hosein,Pacey, Philip D.
, p. 3573 - 3579 (1996)
The rates of the reactions, (CH3)2CO -> CH3 + CH3CO (1) and CH3 + (CH3)2CO -> CH4 + CH2COCH3 (3) have been studied in the flow pyrolysis of acetone at 825-940 K and 10-180 Torr.Yields of products were mesured by gas chromatography.The rate constant, k1, for the initiation reaction, determined from the sum of the yields of the termination products, was observed to be pressure dependent at 928 K.The Arrhenius expression for this reaction at the high-pressure limit (obtained from a nonlinear least-squares fit to the experimental data using the Troe factorization procedure) was found to be k1infinite (s-1) = 1017.9+/-0.8 exp(-353 +/- 14 kJ mol-1/RT).The Troe method has also been used to find the high-pressure limits of the cross-combination ratio for CH3 and CH3COCH2 radicals (1.9 +/- 0.1) and of the qoutient k5/k32, where reaction 5 is 2CH3 -> C2H6.Calculated rate constants for reaction 3, when combined with values reported from photolysis experiments at lower temperatures, were found to exhibit a curved Arrhenius plot.A transition state theory model was fitted to the data for k3 to determine the average transitional vibrational term value in the transition state (279 +/- 8 cm-1), the effective activation barrier height (46 +/- 1 kJ mol-1), and the full width of the barrier at half its height (52 +/- 3 pm).
Method for preparing 2, 5-hexanedione
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Paragraph 0031-0053, (2021/06/22)
The invention discloses a method for preparing 2, 5-hexanedione, which is characterized in that a polyhydroxy compound and a derivative thereof are used as substrates, and the 2, 5-hexanedione is obtained through a carbon growth-wacker oxidation reaction under the action of a catalyst and an oxidizing agent. According to the method disclosed by the invention, a large amount of by-product glycerol generated in a biodiesel production process is used as a raw material, so that the production cost of 2, 5-hexanedione can be reduced, and a high-added-value conversion and utilization path is provided for glycerol.
Preparation of 1-Hydroxy-2,5-hexanedione from HMF by the Combination of Commercial Pd/C and Acetic Acid
Duan, Ying,Yang, Dexi,Yang, Yanliang,Zhang, Chi,Zheng, Min
, (2020/06/17)
The development of a simple and durable catalytic system for the production of chemicals from a high concentration of a substrate is important for biomass conversion. In this manuscript, 5-hydroxymethylfurfural (HMF) was converted to 1-hydroxy-2,5-hexanedione (HHD) using the combination of commercial Pd/C and acetic acid (AcOH) in water. The influence of temperature, H2 pressure, reaction time, catalyst amount and the concentration of AcOH and HMF on this transformation was investigated. A 68% yield of HHD was able to be obtained from HMF at a 13.6 wt% aqueous solution with a 98% conversion of HMF. The resinification of intermediates on the catalyst was characterized to be the main reason for the deactivation of Pd/C. The reusability of the used Pd/C was studied to find that most of the activity could be recovered by being washed in hot tetrahydrofuran.
