13980-07-9Relevant academic research and scientific papers
Epoxidation of soybean oil using a homogeneous catalytic system based on a molybdenum (VI) complex
Farias, Maritana,Martinelli, Márcia,Bottega, Diana Pagliocchi
, p. 213 - 219 (2010)
The ability of bis(acetyl-acetonato)dioxo-molybdenum (VI) [MoO 2(acac)2] to catalyse the epoxidation of soybean oil in the presence of tert-butyl hydroperoxide as oxidizing agent has been investigated. The influence of reaction time and temperature in the course of the epoxidation reaction was evaluated by quantitative 1H NMR. When epoxidation was carried out in refluxing toluene at 110 °C for 2 h, a 70.1% conversion of substrate was obtained, producing 54.1% epoxidation with a selectivity of 77.2%. The 1H NMR spectroscopic method selected for the purpose of this work allowed a simple and rapid evaluation of the mono- and diepoxides obtained following the epoxidation of soybean oil.
Strategies for synthesis of epoxy resins from oleic acid derived from food wastes
Hayes, Theodore,Hu, Yingxue,Sanchez-Vazquez, Sandra A.,Hailes, Helen C.,Aliev, Abil E.,Evans, Julian R. G.
, p. 3159 - 3170 (2016)
The use of biomass-sourced chemical feedstocks creates a conflict over land use between food and fuel/chemical production. Such conflict could be reduced by making use of the annual 1.3 Pg food waste resource. Oleic acid is available from seed oils such as pumpkin, grape, avocado and mango. Its esterification with diols 1,3-propanediol, resorcinol and orcinol was used to form diesters and the naturally occurring norspermidine was used to prepare a diamide, all under ambient conditions. These compounds were then epoxidized and polymerized. When esterification was followed by epoxidation and subsequent curing at elevated temperature with p-phenylenediamine or diethylenetriamine, hard insoluble resins were formed. When the sequence was changed such that the epoxidized oleic acid was first reacted with cis-1,2-cyclohexanedicarboxylic anhydride and then esterified with orcinol and resorcinol, insoluble crosslinked polymers were also obtained.
Direct epoxidation of unprotected olefinic carboxylic acids using HOF-CH3CN
Rozen, Shlomo,Bareket, Yifat,Dayan, Sharon
, p. 531 - 534 (1996)
The reaction of HOF·CH3CN complex, made directly by passing fluorine through aqueous acetonitrile, with double bond containing unprotected carboxylic acids and alcohols results in fast and almost quantitative epoxidation.
A fluorescence-based activity assay for immobilized lipases in non-native media
Ingenbosch, Kim N.,Rousek, Anna,Wunschik, Dennis S.,Hoffmann-Jacobsen, Kerstin
, p. 22 - 27 (2019)
A new method for the analysis of lipase activity in the immobilized state is developed. The fluorescence assay aims to quantify the potential of lipases for the application in organic solvents. As lipases are universally immobilized on polymeric carriers for the use in bioorganic synthesis, the assay includes an immobilization step on the walls of polymeric cuvettes. The activity of the immobilized lipase is probed by 4-methylumbelliferyl ester hydrolysis. The activity retention as a function of solvent concentration is used as a measure for the solvent resistance of the enzyme variant. The method is applied to two different lipases, Candida antarctica lipase B (CalB) and Bacillus subtilis lipase A (BSLA) in the presence of the solvents acetonitrile and ethanol. By comparison of the assay results with a commercial biocatalyst consisting of CalB on polymeric carrier (Novozyme 435) it is demonstrated that the assay allows a good prediction of the activity of the respective lipase as immobilisate on polymeric carriers. The assay surpasses the respective analysis in solution in terms of accuracy and precision.
Immobilized oxo-vanadium Schiff base on graphene oxide as an efficient and recyclable catalyst for the epoxidation of fatty acids and esters
Verma, Sanny,Aila, Mounika,Kaul, Savita,Jain, Suman L.
, p. 30598 - 30604 (2014)
Oxo-vanadium Schiff base was covalently immobilized onto chemically functionalized graphene oxide (GO) using 3-aminopropyltriethoxysilane as a coupler. The loading of vanadyl Schiff base onto GO nanosheets was confirmed by FTIR, XRD, TGA, and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The synthesized heterogeneous catalyst was found to be efficient and selective for the epoxidation of fatty acids and esters using t-butyl hydroperoxide (TBHP) as an oxidant. Interestingly, the immobilized catalyst showed a higher catalytic efficiency than the homogeneous vanadyl acetylacetonate. The recycling experiment results indicated that the catalyst was highly stable and maintained very high activity, and selectivity even after being used for six cycles. This journal is the Partner Organisations 2014.
Selective Epoxidation of Fatty Acids and Fatty Acid Methyl Esters by Fungal Peroxygenases
Aranda, Carmen,Olmedo, Andrés,Kiebist, Jan,Scheibner, Katrin,del Río, José C.,Martínez, Angel T.,Gutiérrez, Ana
, p. 3964 - 3968 (2018)
Recently discovered fungal unspecific peroxygenases from Marasmius rotula and Chaetomium globosum catalyze the epoxidation of unsaturated fatty acids (FA) and FA methyl esters (FAME), unlike the well-known peroxygenases from Agrocybe aegerita and Coprinopsis cinerea. Reactions of a series of unsaturated FA and FAME with cis-configuration revealed high (up to 100 %) substrate conversion and selectivity towards epoxidation, although some significant differences were observed between enzymes and substrates with the best results being obtained with the C. globosum enzyme. This and the M. rotula peroxygenase appear as promising biocatalysts for the environmentally-friendly production of reactive FA epoxides given their self-sufficient monooxygenase activity and the high conversion rate and epoxidation selectivity.
Highly efficient epoxidation of vegetable oils catalyzed by a manganese complex with hydrogen peroxide and acetic acid
Chen, Jianming,De Liedekerke Beaufort, Marc,Gyurik, Lucas,Dorresteijn, Joren,Otte, Matthias,Klein Gebbink, Robertus J. M.
, p. 2436 - 2447 (2019)
Epoxidized vegetable oils (EVOs) are versatile building blocks for lubricants, plasticizers, polyvinyl chloride (PVC) stabilizers, and surface coating formulations. In this paper, a catalytic protocol for the efficient epoxidation of vegetable oils is presented that is based on a combination of a manganese catalyst, H2O2 as an oxidant, and acetic acid as an additive. This protocol relies on the use of a homogeneous catalyst based on the non-noble metal manganese in combination with a racemic mixture of the N,N′-bis(2-picolyl)-2,2′-bispyrrolidine ligand (rac-BPBP). The optimized reaction conditions entail only 0.03 mol% of the manganese catalyst with respect to the number of double bonds (ca. 0.1 wt% with respect to the oil) and ambient temperature. This epoxidation protocol is highly efficient, since it allows most of the investigated vegetable oils, including cheap waste cooking oil, to be fully epoxidized to EVOs in more than 90% yield with excellent epoxide selectivities (>90%) within 2 h of reaction time. In addition, the protocol takes place in a biphasic reaction medium constituted by the vegetable oil itself and an aqueous acetic acid phase, from which the epoxidized product can be easily separated via simple extraction. In terms of efficiency and reaction conditions, the current epoxidation protocol outperforms previously reported catalytic protocols for plant oil epoxidation, representing a promising alternative method for EVO production.
A novel vegetable oil-lactate hybrid monomer for synthesis of high-T g polyurethanes
Miao, Shida,Zhang, Songping,Zhiguo, Su,Wang, Ping
, p. 243 - 250 (2010)
A study was conducted to introduce a vegetable oil-lactate hybrid monomer for synthesis of high Tg polyurethanes (PU). The conjugation of epoxidized soybean oil (ESO) was investigated, which was prepared by epoxidation of soybean oil using lipase as catalyst, with lactic acid (LA) through ring-opening reaction. It was demonstrated that 1000 mg of ESO and 600 mg of LA were charged in a reactor that contained a stirrer bar. The reactor was purged with nitrogen for around 15 minutes to remove the air and it was sealed. The reaction was allowed to continue for 6 hours and the final reaction mixture was washed with water to remove unreacted chemicals till the pH value of the washing solution turned to 7.0 and the desired product, lactic acid-epoxidized soybean oil (LA-ESO) was recovered by evaporating the water off under reduced pressure.
Lipase catalysed oxidations in a sugar-derived natural deep eutectic solvent
Vagnoni, Martina,Samorì, Chiara,Pirini, Daniele,Vasquez De Paz, Maria Katrina,Gidey, Dawit Gebremichael,Galletti, Paola
, (2021/05/06)
Chemoenzymatic oxidations involving the CAL-B/H2O2 system was developed in a sugar derived Natural Deep Eutectic Solvent (NaDES) composed by a mixture of glucose, fructose and sucrose. Good to excellent conversions of substrates like cyclooctene, limonene, oleic acid and stilbene to their corresponding epoxides, cyclohexanone to its corresponding lactone and 2-phenylacetophenone to its corresponding ester, demonstrate the viability of the sugar NaDES as a reaction medium for epoxidation and Baeyer-Villiger oxidation.
Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H2O2over Tungsten Oxide Catalysts
Yun, Danim,Ayla, E. Zeynep,Bregante, Daniel T.,Flaherty, David W.
, p. 3137 - 3152 (2021/04/06)
Oxidative cleavage of carbon-carbon double bonds (C-C) in alkenes and fatty acids produces aldehydes and acids valued as chemical intermediates. Solid tungsten oxide catalysts are low cost, nontoxic, and selective for the oxidative cleavage of C-C bonds with hydrogen peroxide (H2O2) and are, therefore, a promising option for continuous processes. Despite the relevance of these materials, the elementary steps involved and their sensitivity to the form of W sites present on surfaces have not been described. Here, we combine in situ spectroscopy and rate measurements to identify significant steps in the reaction and the reactive species present on the catalysts and examine differences between the kinetics of this reaction on isolated W atoms grafted to alumina and on those exposed on crystalline WO3 nanoparticles. Raman spectroscopy shows that W-peroxo complexes (W-(η2-O2)) formed from H2O2 react with alkenes in a kinetically relevant step to produce epoxides, which undergo hydrolysis at protic surface sites. Subsequently, the CH3CN solvent deprotonates diols to form alpha-hydroxy ketones that react to form aldehydes and water following nucleophilic attack of H2O2. Turnover rates for oxidative cleavage, determined by in situ site titrations, on WOx-Al2O3 are 75% greater than those on WO3 at standard conditions. These differences reflect the activation enthalpies (ΔH?) for the oxidative cleavage of 4-octene that are much lower than those for the isolated WOx sites (36 ± 3 and 60 ± 6 kJ·mol-1 for WOx-Al2O3 and WO3, respectively) and correlate strongly with the difference between the enthalpies of adsorption for epoxyoctane (ΔHads,epox), which resembles the transition state for epoxidation. The WOx-Al2O3 catalysts mediate oxidative cleavage of oleic acid with H2O2 following a mechanism comparable to that for the oxidative cleavage of 4-octene. The WO3 materials, however, form only the epoxide and do not cleave the C-C bond or produce aldehydes and acids. These differences reflect the distinct site requirements for these reaction pathways and indicate that acid sites required for diol formation are strongly inhibited by oleic acids and epoxides on WO3 whereas the Al2O3 support provides sites competent for this reaction and increase the yield of the oxidative cleavage products.
