Α-angelica Lactone Research Articles

The effect of modulator in the synthesis of UiO-66(Zr) and UiO-67(Zr) and their performances in catalytic transfer hydrogenation reaction of α-angelica lactone to γ-valerolactone

The effect of modulator in the synthesis of UiO-66(Zr) and UiO-67(Zr) and their performances in catalytic transfer hydrogenation reaction of α-angelica lactone to γ-valerolactone

Synthesis of Alkyl Levulinates from α-Angelica Lactone Using Methanesulfonic Acid as a Catalyst: A Sustainable and Solvent-Free Route

Synthesis of Alkyl Levulinates from α-Angelica Lactone Using Methanesulfonic Acid as a Catalyst: A Sustainable and Solvent-Free Route

Organocatalyzed Synthesis of γ-Alkenyl Butenolides via Asymmetric Direct Vinylogous Conjugate Addition-Elimination of Substituted Furanone Derivatives to β-Phenylsulfonylenones.

A diaminomethylenemalononitrile organocatalyst efficiently promoted the asymmetric direct vinylogous conjugate addition of α-angelica lactone derivatives to β-phenylsulfonylenones, affording the corresponding γ-alkenyl γ-butenolides in high yields with excellent enantioselectivities (up to 97% ee) after the elimination of the phenylsulfonyl group. This study reports the first successful example of a stereoselective reaction using β-phenylsulfonylenone as the direct alkenyl donor.

Catalytic transfer hydrogenation of α-angelica lactone over Nickel(II) modified UiO-66 metal organic framework under mild conditions

In the realm of biomass valorization, catalysts play a pivotal role, and UiO-66(Zr), a type of metal organic framework (MOF), emerges as a promising heterogeneous catalyst. This study focuses on incorporating Ni2+ into UiO-66(Zr) for application in catalytic transfer hydrogenation (CTH) of bio-derived α-angelica lactone (a-AL) to ɣ-valerolactone (GVL). The synthesis of UiO-66(Zr) occurs through a solvothermal process at 120 °C for 24 h. Ni(II) modification, achieved through wet impregnation with loadings of 2.5 and 5.0 wt%, results in no observable diffraction peaks associated with Ni particles in XRD analysis. FTIR analysis indicates significant shifts, suggesting deprotonation of the carboxylic moiety from the ligand and coordination with Zr4+ metal ion. Nitrogen sorption isotherms show a reduction in surface area and pore volume upon Ni(II) incorporation. FESEM analysis reveals particle agglomeration and increased size with Ni(II) introduction. EDX and HRTEM confirm the presence of 0.9 and 1.8 wt% Ni(II) on UiO-66(Zr). TG/DTA analysis affirms that Ni(II) does not affect the thermal stability of UiO-66(Zr). Ultimately, the introduction of Ni(II) enhances the catalytic performance of UiO-66(Zr), increasing the conversion and selectivity towards ɣ-valerolactone from 67 to 83.3 % and 71.6 % to 97.4 %, respectively, under mild reaction conditions.

Evaluation of antibacterial and antiviral efficacy of volatile organic compounds.

This study searched for volatile organic compounds (VOCs）having antibacterial and antiviral efficacy. The antibacterial efficacy of volatilized components was evaluated and (2E,4E）-2,4-hexadienal, α- angelica lactone, 2-cyclohexen-1-one and 2-cyclopenten-1-one were found to inhibit the formation of colonies of Staphylococcus aureus and Escherichia coli. Evaluating the antimicrobial efficacy of the surfaces to which each VOC adhered to, these four compounds were revealed to have antibacterial efficacy (antibacterial activity value (A-value）against S. aureus; ≧2.63, A-value against Klebsiella pneumoniae; >5.07, A-value against E. coli; ≧2.17）. Furthermore, (2E,4E）-2,4-hexadienal and α-angelica lactone were found to have antiviral efficacy against Influenza A virus (H1N1）and Feline calicivirus on the cotton cloths to which it adheres to (antiviral activity value (R-value）against Influenza A virus; >2.94, R-value against Feline calicivirus; ≧2.31）. Using these components, it might be possible to develop antimicrobial products that exhibit antibacterial and antiviral efficacy.

Cellulosic protic ionic liquid hydrogel confined Pd nanoparticles for selective hydrogenation of α-angelica lactone and alkenes

A cellulosic protic ILs hydrogel with confining ability to Pd NPs was synthesized through a cyclic anhydride cross-linking reaction in TMG/DMSO/CO2 solvent system, presenting good catalytic activity for the hydrogenation of α-AL and common alkenes.

Production of Alkyl Levulinates from Carbohydrate-Derived Chemical Intermediates Using Phosphotungstic Acid Supported on Humin-Derived Activated Carbon (PTA/HAC) as a Recyclable Heterogeneous Acid Catalyst

This work reports a straightforward and high-yielding synthesis of alkyl levulinates (ALs), a class of promising biofuel, renewable solvent, and chemical feedstock of renewable origin. ALs were prepared by the acid-catalyzed esterification of levulinic acid (LA) and by the alcoholysis of carbohydrate-derived chemical platforms, such as furfuryl alcohol (FAL) and α-angelica lactone (α-AGL). Phosphotungstic acid (PTA) was chosen as the solid acid catalyst for the transformation, which was heterogenized on humin-derived activated carbon (HAC) for superior recyclability. Using HAC as catalyst support expands the scope of valorizing humin, a complex furanic resin produced inevitably as a side product (often considered waste) during the acid-catalyzed hydrolysis/dehydration of sugars and polymeric carbohydrates. Under optimized conditions (150 °C, 7 h, 25 wt.% of 20%PTA/HAC-600 catalyst), ethyl levulinate (EL) was obtained in an 85% isolated yield starting from FAL. Using the general synthetic protocol, EL was isolated in 88% and 84% yields from LA and α-AGL, respectively. The 20%PTA/HAC-600 catalyst was successfully recovered from the reaction mixture and recycled for five cycles. A marginal loss in the yield of ALs was observed in consecutive catalytic cycles due to partial leaching of PTA from the HAC support.

Stereodivergent Biocatalytic Formal Reduction of α-Angelica Lactone to (R)- and (S)-γ-Valerolactone in a One-Pot Cascade.

The formal asymmetric and stereodivergent enzymatic reduction of α-angelica lactone to both enantiomers of γ-valerolactone was achieved in a one-pot cascade by uniting the promiscuous stereoselective isomerization activity of Old Yellow Enzymes with their native reductase activity. In addition to running the cascade with one enzyme for each catalytic step, a bifunctional isomerase-reductase biocatalyst was designed by fusing two Old Yellow Enzymes, thereby generating an unprecedented case of an artificial enzyme catalyzing the reduction of nonactivated C=C bonds to access (R)-valerolactone in overall 41 % conversion and up to 91 % ee. The enzyme BfOYE4 could be used as single biocatalyst for both steps and delivered (S)-valerolactone in up to 84 % ee and 41 % overall conversion. The reducing equivalents were provided by a nicotinamide recycling system based on formate and formate dehydrogenase, added in a second step. This enzymatic system provides an asymmetric route to valuable chiral building blocks from an abundant bio-based chemical.

WOx/ZrO2 catalysts for the conversion of α-angelica lactone with butanol to butyl levulinates

WOx/ZrO2 catalysts for the conversion of α-angelica lactone with butanol to butyl levulinates

Hydrogenation of levulinic acid to γ-valerolactone over single-atom Pt confined in Sn-modified MIL-101(Fe).

We synthesize a Sn-modified MIL-101(Fe), which can confine Pt to the single-atom scale. This novel Pt@MIL(FeSn) catalyst efficiently hydrogenates levulinic acid to γ-valerolactone (TOF: 1386 h-1, yield: >99%) at only 100 °C and 1 MPa of H2via α-angelica lactone as an intermediate. This could be the first report on switching the reaction path from 4-hydroxypentanoic acid to α-angelica lactone under very mild conditions. Incorporating Sn into MIL-101(Fe) enables the creation of abundant micro-pores less than 1 nm and Lewis acidic sites that stabilize Pt0 atoms. The ensemble of active Pt atoms and a Lewis acid can synergistically enhance adsorption of the CO bond and facilitate dehydrative cyclization of levulinic acid.

Effective synthesis of ethyl levulinate via alcoholysis of furfuryl alcohol over simple nickel-titanium dioxide

A series of non-noble metals based titanium dioxide catalysts were synthesized following a facile sol-gel route. The catalytic performance for direct furfuryl alcohol (FAL) conversion to ethyl levulinate (EL) was investigated. Successful performance was confirmed by N2 physisorption analysis, XRD, XPS, SEM, EDS, TEM, ICP-OES, NH3-TPD, Pyridine-IR spectroscopy. 5 % Ni-TiO2 with the highest surface area, enhanced physical and textural characteristics exhibited better catalytic performance than other candidates. The strong Brönsted/Lewis acidity strength showed a pivotal role in defining product range. Ethoxymethylfuran (EMF), α-angelica lactone (AAL), 5-methyl-2(5 H)-furanone (β-angelica lactone, BAL) and other important intermediates were obtained, as well as the two routes mechanism was proposed. The ever reported highest EL productivity and TOF value (652.0 molFAL/molNih and 1018.1 molEL/molNih) achieved under the optimum condition. The differential charge density diagram demonstrated the loss of electrons promoted by Ni doping, and the route mainly transferred from the O and Ni to Ti.

Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics.

The biomass-derived platform chemicals furfural and 5-(hydroxymethyl)furfural (HMF) may be converted to α-angelica lactone (AnL) and levulinic acid (LA). Presently, LA (synthesized from carbohydrates) has several multinational market players. Attractive biobased oxygenated fuel additives, solvents, etc., may be produced from AnL and LA via acid and reduction chemistry, namely alkyl levulinates and γ-valerolactone (GVL). In this work, hierarchical hafnium-containing multifunctional Linde type L (LTL) related zeotypes were prepared via top-down strategies, for the chemical valorization of LA, AnL and HMF via integrated catalytic transfer hydrogenation (CTH) and acid reactions in alcohol medium. This is the first report of CTH applications (in general) of LTL related materials. The influence of the post-synthesis treatments/conditions (desilication, dealumination, solid-state impregnation of Hf or Zr) on the material properties and catalytic performances was studied. AnL and LA were converted to 2-butyl levulinate (2BL) and GVL in high total yields of up to ca. 100%, at 200°C, and GVL/2BL molar ratios up to 10. HMF conversion gave mainly the furanic ethers 5-(sec-butoxymethyl)furfural and 2,5-bis(sec-butoxymethyl)furan (up to 63% total yield, in 2-butanol at 200°C/24 h). Mechanistic, reaction kinetics and material characterization studies indicated that the catalytic results depend on a complex interplay of different factors (material properties, type of substrate). The recovered-reused solids performed steadily.

Experimental critical temperatures, pressures, heat capacities, and thermal diffusivities of triacetin and α-angelica lactone

The critical temperatures, critical pressures, heat capacities, and thermal diffusivities of α-angelica lactone and triacetin have been measured. The compounds under study are involved in the production of fuels and fuel additives from lignocellulose. The critical properties of the compounds have also been calculated by the group contribution methods of Wilson and Jasperson (WJ), Nannoolal et al. (NRR), Marrero and Gani, Hukkerikar et al. in two variants (H-sw and H-s). The NRR method provides the best estimation of the critical temperature and pressure of α-angelica lactone: the differences between experimental and estimated values are about 1.6 and 3.0 %, respectively. For triacetin, all the methods used give approximately the same discrepancy between the experimental and estimated critical temperature in the range from 1.2 to 2.0 % which is less than the uncertainty of the measurement. However, the H-s and H-sw techniques slightly overestimate the critical temperature, while the rest of the methods underestimate it. All the methods overestimate the critical pressure of triacetin; the H-s method provides the minimum difference between the measured and calculated values of the critical pressure (1.3 %).The heat capacities of liquid α-angelica lactone and triacetin have been measured at atmospheric pressure in the temperature range from 298.6 to 440.6 K (α-angelica lactone) and from 298.4 to 530.2 K (triacetin). The data obtained have been fitted with first-order polynomials. The heat capacities of the compound under study have also been estimated using the group-contribution method of Kolska et al. This method has been recommended to estimate the heat capacities of α-angelica lactone and triacetin.The thermal diffusivities of liquid α-angelica lactone and triacetin have been measured at atmospheric pressure in the temperature range from 303.15 to 373.15 K. The thermal conductivities have been calculated from the results of the experiment. The experimental data on thermal diffusivity and thermal conductivity have been approximated with linear polynomials. The thermal conductivities of α-angelica lactone and triacetin have been calculated by the methods of Govender et al. and Sastri. In general, the method of Govender et al. gives thermal conductivity values of the compounds under study that are closer to the experimental values than those obtained using the Sastri method.

Conversion of Biomass-Derived Methyl Levulinate to Methyl Vinyl Ketone

A high-throughput screening exercise testing 60 different catalysts resulted in 5 wt % Pt on sulfided carbon as the best catalyst in the conversion of bio-based methyl levulinate (ML) to methyl vinyl ketone (MVK) in a gas-phase continuous process. Up to 18% yield of MVK was obtained, but fast catalyst deactivation was observed. For a better understanding of the reaction mechanism, the potential reaction intermediates [α-angelica lactone (α-AL), γ-valerolactone, methyl ethyl ketone (MEK), and levulinic acid (LA)] were also fed as starting materials under the same reaction conditions as those used for ML. Of the different pathways possible, the route via AL seems to be the most likely route. Since the side product methanol led to the hydrogenation of MVK to MEK, LA is a better substrate in this reaction toward MVK at a medium reaction temperature. Herein, we report the highest yield of MVK (>50%) from LA at 350 °C. However, this knowledge of the reaction pathway via AL also opened up the possibility of a high-temperature conversion process of ML to MVK. It was found that ML could be converted to MVK in 71% selectivity at 600 °C using 40% CaO on γ-Al2O3 as the catalyst. Here, the catalyst merely serves to accelerate the ring closure of ML to AL, which undergoes an electrocyclic reaction under extrusion of CO to form MVK.

Renewable bio-based routes to γ-valerolactone in the presence of hafnium nanocrystalline or hierarchical microcrystalline zeotype catalysts

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-containing catalysts, in alcohol media. These routes involved acid and reduction reactions for which multifunctional catalysts were prepared via top-down strategies, namely the nanocatalyst Hf-deAlBeta-n and the hierarchical (intracrystalline micro/mesopores) microcrystalline material Hf-WdeSAlBeta-m. Mechanistic and kinetic modelling studies, molecular-level investigations by solid-state spectroscopic characterization, and catalyst stability studies led to assessments about the catalytic roles and potentialities of the prepared materials for GVL production. The influences of the catalytic reaction conditions and type of transition metal in the catalysts were studied. The best-performing catalyst was the hierarchical zeotype Hf-WdeSAlBeta-m (GVL yields of up to 99% from LA, 91% from AnL, and 73% from Fur, at 180 °C), which correlated with its enhanced acidity and mesoporosity. To the best of our knowledge, this is the first reported hafnium-containing BEA zeotype possessing an intracrystalline hierarchical pore system, and the results highlighted the catalytic potentialities of these types of materials for the integrated production of GVL.

γ-Valerolactone synthesis from α-angelica lactone and levulinic acid over biobased multifunctional nanohybrid catalysts

The selective chemical conversion of biomass components to useful bioproducts may contribute to a renewable resource-based economy. The selective production of target bioproducts may be accomplished using heterogeneous catalysts operating under relatively moderate reaction conditions. In this work, carbohydrate biomass derived α-angelica lactone (AnL) and levulinic acid (LA) were converted to the versatile bioproduct γ-valerolactone (GVL), in the presence of nanohybrid catalysts (M-FDCA) and the microcrystalline metal-organic framework CAU-28, all of which were synthesized from bio-based 2,5-furandicarboxylic acid (FDCA) and a metal (M=Zr or Hf) precursor. The nanohybrids were prepared in a simple fast (FT) fashion, and, for comparison, via a conventional solvothermal (S) procedure. The M-FDCA catalysts stood on a higher footing than CAU-28 in the conversion of AnL and LA to GVL. The superior results for the M-FDCA catalysts may be partly due to their higher ratio Sext:SBET and nano-features, which may advantageously enhance active sites accessibility. In particular, the Hf-FDCA catalysts were stable and performed superiorly to the Zr-FDCA ones. Experimental mechanistic studies shed light on the multifunctional behavior of the hybrid catalysts in the one-pot conversion of AnL-to-GVL, which involved acid and reduction chemistry.

Mechanistic Investigations into the Catalytic Levulinic Acid Hydrogenation, Insight in H/D Exchange Pathways, and a Synthetic Route to d8-γ-Valerolactone

γ-Valerolactone (GVL) is readily accessible by catalytic hydrogenation of carbohydrate-derived levulinic acid (LA) and is an attractive biobased chemical with a wide range of applications in both the chemical (e.g., as biomass-derived solvent) and the transportation fuel sector. In this study, we used isotopic labeling experiments to provide insights into the catalytic hydrogenation pathways involved in the conversion of LA to GVL under different reaction conditions using water as an environmentally benign solvent and Ru/C as a readily available catalyst. 2H NMR experiments combined with quantum chemical calculations revealed that deuterium atoms can be incorporated at different positions as well as the involvement of the different intermediates 4-hydroxypentanoic acid and α-angelica lactone (α-AL). The insight provided by these studies revealed an as of yet unexploited sequential deuteration route to synthesize fully deuterated LA and GVL. The route starts by the conversion of LA to α-AL followed by a selective deuteration of the acidic protons of α-AL by H/D exchange with D2O. Subsequent ring-opening in D2O (d2-AL to d3-LA) and exchange of the remaining protons of d3-LA via a keto-enol tautomerization by heating in D2O under acidic conditions gives d8-LA. Finally, the d8-LA is catalytically reduced at low temperature using Ru/C with D2 in D2O to d8-GVL.

From Waste to Value—Direct Utilization of α-Angelica Lactone as a Nonconventional Irreversible Acylating Agent in a Chromatography-Free Lipase-Catalyzed KR Approach toward sec-Alcohols

From Waste to Value—Direct Utilization of α-Angelica Lactone as a Nonconventional Irreversible Acylating Agent in a Chromatography-Free Lipase-Catalyzed KR Approach toward <i>sec</i>-Alcohols

Ozonolysis of α-angelica lactone: a renewable route to malonates

α-Angelica lactone, derived from the platform chemical Levulinic acid, can be efficiently converted into malonic acid derivatives and 3-oxopropionate acetals by ozonolysis.

Asymmetric Direct Vinylogous Conjugate Addition of Substituted Furanone Derivatives to Benzoyl Acrylonitrile: Stereoselective Synthesis Toward Bicyclic γ-Lactams.

A diaminomethylenemalononitrile organocatalyst efficiently promotes the asymmetric direct vinylogous conjugate additions of α-angelica lactones to benzoyl acrylonitrile derivatives, resulting in the corresponding addition products bearing vicinal tertiary and quaternary stereogenic centers with excellent enantioselectivities (up to 99% ee). This report is the first successful example of the asymmetric conjugate additions of α-angelica lactone to benzoyl acrylonitriles. The chiral γ,γ-disubstituted γ-butenolides obtained can be readily transformed to the bicyclic γ-lactam derivative as a valuable synthetic intermediate.