2500-56-3Relevant academic research and scientific papers
Epoxide yield determination of oils and fatty acid methyl esters using 1H NMR
Aerts, Hans A. J.,Jacobs, Pierre A.
, p. 841 - 846 (2004)
Product mixtures of epoxidized fatty compounds can be analyzed by using 1H NMR. Conversion of double bonds and selectivities to different products can easily be calculated. Moreover, if diunsaturated substrates are used in epoxidation reactions, yields to mono- and diepoxidized products can be determined. The effectiveness of this method is proven by comparing some NMR results with those found by GC analysis.
Synthesis of carbonated fatty methyl esters using supercritical carbon dioxide
Doll, Kenneth M.,Erhan, Sevim Z.
, p. 9608 - 9614 (2005)
The two-step syntheses of the cyclic carbonates carbonated methyl oleate (CMO) and carbonated methyl linoleate (CML) are reported. First, synthesis of epoxides through well-precedented chemical reactions of unsaturated fatty methyl esters with hydrogen peroxide and formic acid was accomplished. Next, a carbonation reaction with a simple tetrabutylammonium bromide catalyst was performed, allowing the direct incorporation of carbon dioxide into the oleochemical. These syntheses avoid the use of the environmentally unfriendly phosgene. The carbonated products are characterized by IR, 1H NMR, and 13C NMR spectroscopy and studied by thermogravimetric analysis (TGA). Also reported is the synthesis of a similar cyclic carbonate from the commercially available 2-ethylhexyl epoxy soyate. These carbonates show properties that may make them useful as petrochemical replacements or as biobased industrial product precursors.
Azide derivatives of soybean oil and fatty esters
Biswas, Atanu,Sharma, Brajendra K.,Willett,Advaryu, Atanu,Erhan,Cheng
, p. 5611 - 5616 (2008)
An environmentally friendly water-based pathway to form the azide derivatives of soybean oil and fatty esters is reported. This entails first the formation of epoxides and then the azidization of the epoxides. The azidization reaction is carried out at high yields in water with only a small amount of an ionic liquid as a catalyst. The distribution of azide and alcohol functionalities on the fatty acid moiety is approximately random. This reaction has been applied to methyl oleate, methyl linoleate, soybean oil, and methyl soyate. The resulting structures have been studied by NMR.
A silicododecamolybdate/pyridinium-tetrazole hybrid molecular salt as a catalyst for the epoxidation of bio-derived olefins
Nunes, Martinique S.,Neves, Patrícia,Gomes, Ana C.,Cunha-Silva, Luís,Lopes, André D.,Valente, Anabela A.,Pillinger, Martyn,Gon?alves, Isabel S.
, (2020/11/27)
The hybrid polyoxometalate (POM) salt (Hptz)4[SiMo12O40]?nH2O (1) (ptz = 5-(2-pyridyl)tetrazole) has been prepared, characterized by X-ray crystallography, and examined as a catalyst for the epoxidation of cis-cyclooctene (Cy) and bio-derived olefins, namely dl-limonene (Lim; a naturally occurring monoterpene found in the rinds of citrus fruits), methyl oleate and methyl linoleate (fatty acid methyl esters (FAMEs) obtained by transesterification of vegetable oils). The crystal structure of 1 consists of α-Keggin-type heteropolyanions, [SiMo12O40]4-, surrounded by space-filling and charge-balancing 2-(tetrazol-5-yl)pyridinium (Hptz+) cations, as well as by a large number of water molecules of crystallization (n = 9). The water molecules mediate an extensive three-dimensional (3D) hydrogen-bonding network involving the inorganic anions and organic cations. For the epoxidation of the model substrate Cy in a nonaqueous system (tert-butylhydroperoxide as oxidant), the catalytic performance of 1 (100% epoxide yield at 24 h, 70 °C) was superior to that of the tetrabutylammonium salt (Bu4N)4[SiMo12O40] (2) (63% epoxide yield at 24 h), illustrating the role of the counterion Hptz+ in enhancing catalytic activity. The hybrid salt 1 was effective for the epoxidation of Lim (69%/85% conversion at 6 h/24 h) and the FAMEs (87–88%/100% conversion at 6 h/24 h), leading to useful bio-based products (epoxides, diepoxides and diol products).
Heterogeneous catalysis with an organic-inorganic hybrid based on MoO3chains decorated with 2,2′-biimidazole ligands
Amarante, Tatiana R.,Neves, Patrícia,Almeida Paz, Filipe A.,Gomes, Ana C.,Pillinger, Martyn,Valente, Anabela A.,Gon?alves, Isabel S.
, p. 2214 - 2228 (2021/04/12)
The discovery of selective heterogeneous catalytic systems for industrial oxidation processes remains a challenge. Molybdenum oxide-based polymeric hybrid materials have been shown to be oxidation catalysts under mild reaction conditions, although difficulties remain with catalyst recovery/reuse since most perform as homogeneous catalysts or possess low activity. The present study shows that the hybrid material [MoO3(2,2′-biimidazole)]·H2O (1) is a superior catalyst regarding these issues. The structure of1was confirmed (by single crystal and synchrotron X-ray powder diffraction) to comprise one-dimensional chains of corner-sharing {MoO4N2} octahedra. Strong MoO?H-N hydrogen bonds separate adjacent chains to afford parallel channels that are occupied by disordered water molecules. Hybrid1was additionally characterised by FT-IR spectroscopy,1H and13C MAS NMR, scanning electron microscopy and thermogravimetric analysis. The catalytic studies highlighted the versatility of1for oxidation reactions withtert-butylhydroperoxide as oxidant. By complementing with characterisation studies, it was verified that the reaction occurs in the heterogeneous phase, the catalyst has good stability and is recoverableviasimple procedures. The chemical reaction scope covered epoxidation and sulfoxidation, and the substrate scope included biomass-deriveddl-limonene and fatty acid methyl esters to give renewable bio-products, as well as thiophene and thioanisole substrates.
Ionic ammonium and anilinium based polymolybdate hybrid catalysts for olefin epoxidation
Bo?ek, Barbara,Neves, Patrícia,?asocha, Wies?aw,Valente, Anabela A.
, p. 13 - 25 (2018/07/29)
Ionic polymolybdate hybrids (IPH) are interesting catalysts for liquid phase olefin epoxidation with tert-butylhydroperoxide; (tbhp), e.g. conversion of terpenic and fatty acid methyl ester (FAME) components of biomass to useful bio-products. IPHs may be easily prepared, under clean, mild, aqueous phase conditions. The type of organic precursor and the synthesis conditions influence the structural features of the IPHs. In this work, IPH epoxidation catalysts possessing one- (1-D) or two-dimensional (2-D) structures were investigated, which included the new materials 1-D methylammonium ammonium trimolybdate [Mo3O10?CH3NH3·NH4] (1) and 2-D bis(2,5-dimethylanilinium) pentamolybdate [Mo5O16?2(NH3C6H3(CH3)2)] (4) with solved structures, and 1-D bis(3,5-dimethylanilinium) trimolybdate [Mo3O10·2(NH3C6H3(CH3)2)] (2), bis(4-methylanilinium) trimolybdate [Mo3O10·2(NH3C6H4CH3)] (3), 2-D bis(anilinium) pentamolybdate [Mo5O16?2(NH3C6H5)] (5), bis(4-methylanilinium) pentamolybdate [Mo5O16?2(NH3C6H4CH3)] (6) and bis(4-ethylanilinium) pentamolybdate [Mo5O16?2(NH3C6H4C2H5)] (7). Systematic characterisation and catalytic studies helped gain insights into structure-activity relationships. The best-performing catalyst (2) was effective for the epoxidation of the FAMEs such as, methyl oleate which gave 92% methyl 9,10-epoxyoctadecanoate yield, at 99% conversion, at 70 °C. The reaction conditions (temperature, type of cosolvent and oxidant) influenced the catalytic reaction. Catalytic performance in consecutive batch runs was steady, and the structural features were essentially preserved.
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 (2018/08/11)
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.
Chemistry and Catalytic Performance of Pyridyl-Benzimidazole Oxidomolybdenum(VI) Compounds in (Bio)Olefin Epoxidation
Neves, Patrícia,Nogueira, Lucie S.,Gomes, Ana C.,Oliveira, Tania S. M.,Lopes, André D.,Valente, Anabela A.,Gon?alves, Isabel S.,Pillinger, Martyn
, p. 2617 - 2627 (2017/05/29)
The chemistry and catalytic performance of the dichlorido complex [MoO2Cl2(pbim)] (1) [pbim = 2-(2-pyridyl)-benzimidazole] in the epoxidation of olefins is reported. Complex 1 acts as a precatalyst and is more effective with tert-butylhydroperoxide (TBHP) as the oxidant than with aq. hydrogen peroxide: the cis-cyclooctene (Cy) reaction with TBHP gave 98 % epoxide yield at 70 °C/24 h. Catalyst characterization showed that 1 is transformed in situ to the oxidodiperoxido complex [MoO(O2)2(pbim)] (2), with H2O2 and a hybrid molybdenum(VI) oxide solid formulated as [MoO3(pbim)] (3) with TBHP. The hybrid material 3 was prepared on a larger scale and explored for the epoxidation of the biorenewable olefins methyl oleate, methyl linoleate, and (R)-(+)-limonene. With TBHP as the oxidant, 3 acts as a source of soluble active species of the type 2. A practical method for recycling oxidodiperoxidomolybdenum(VI) catalysts for the Cy/TBHP reaction is demonstrated by using an ionic liquid as the solvent for the molecular catalyst 2.
Triazolyl, Imidazolyl, and Carboxylic Acid Moieties in the Design of Molybdenum Trioxide Hybrids: Photophysical and Catalytic Behavior
Lysenko, Andrey B.,Senchyk, Ganna A.,Domasevitch, Konstantin V.,Kobalz, Merten,Krautscheid, Harald,Cichos, Jakub,Karbowiak, Miroslaw,Neves, Patrícia,Valente, Anabela A.,Gon?alves, Isabel S.
, p. 4380 - 4394 (2017/04/26)
Three organic ligands bearing 1,2,4-triazolyl donor moieties, (S)-4-(1-phenylpropyl)-1,2,4-triazole (trethbz), 4-(1,2,4-triazol-4-yl)benzoic acid (trPhCO2H), and 3-(1H-imidazol-4-yl)-2-(1,2,4-triazol-4-yl)propionic acid (trhis), were prepared to evaluate their coordination behavior in the development of molybdenum(VI) oxide organic hybrids. Four compounds, [Mo2O6(trethbz)2]·H2O (1), [Mo4O12(trPhCO2H)2]·0.5H2O (2a), [Mo4O12(trPhCO2H)2]·H2O (2b), and [Mo8O25(trhis)2(trhisH)2]·2H2O (3), were synthesized and characterized. The monofunctional tr-ligand resulted in the formation of a zigzag chain [Mo2O6(trethbz)2] built up from cis-{MoO4N2} octahedra united through common μ2-O vertices. Employing the heterodonor ligand with tr/-CO2H functions afforded either layer or ribbon structures of corner- or edge-sharing {MoO5N} polyhedra (2a or 2b) stapled by tr-links in axial positions, whereas -CO2H groups remained uncoordinated. The presence of the im-heterocycle as an extra function in trhis facilitated formation of zwitterionic molecules with a protonated imidazolium group (imH+) and a negatively charged -CO2- group, whereas the tr-fragment was left neutral. Under the acidic hydrothermal conditions used, the organic ligand binds to molybdenum atoms either through [N-N]-tr or through both [N-N]-tr and μ2-CO2- units, which occur in protonated bidentate or zwitterionic tetradentate forms (trhisH+ and trhis, respectively). This leads to a new zigzag subtopological motif (3) of negatively charged polyoxomolybdate {Mo8O25}n2n- consisting of corner- and edge-sharing cis-{MoO4N2} and {MoO6} octahedra, while the tetradentate zwitterrionic trhis species connect these chains into a 2D net. Electronic spectra of the compounds showed optical gaps consistent with semiconducting behavior. The compounds were investigated as epoxidation catalysts via the model reactions of achiral and prochiral olefins (cis-cyclooctene and trans-β-methylstyrene) with tert-butylhydroperoxide. The best-performing catalyst (1) was explored for the epoxidation of other olefins, including biomass-derived methyl oleate, methyl linoleate, and prochiral dl-limonene.
Mild catalytic oxidations of unsaturated fatty acid methyl esters (FAMEs) by oxovanadium complexes
Cecchini, Martina Maya,De Angelis, Francesco,Iacobucci, Claudio,Reale, Samantha,Crucianelli, Marcello
, p. 120 - 128 (2016/03/22)
A selection of unsaturated fatty acid methyl esters, namely methyl oleate (C18:1), methyl linoleate (C18:2) and methyl linolenate (C18:3) has been oxidized under mild homogeneous catalytic conditions, using a series of oxovanadium(IV) complexes containing 4-acyl-5-pyrazolone donor ligands with different substituents on acyl residue. The main goal was to evaluate the catalytic role exerted by oxovanadium(IV) metal center, as precursor complex, in the selective oxyfunctionalization of carbon-carbon double bonds of these bio-renewable resources, as a greener alternative to more drastic processes currently used at the industrial level. The three substrates, oxidized using tert-butylhydroperoxide as main oxidant, with or without solvents, showed high conversions of starting materials and high selectivities in the formation of corresponding mono- di- and tri-epoxides, especially under solvent-less conditions. Investigations on a probable catalytic cycle mechanism operative in the tert-butylhydroperoxide oxidation of a simple FAME model substrate, have been performed by means of ESI-MS.
