2104-19-0Relevant articles and documents
METAL-FREE METHOD FOR OXIDATIVE CLEAVAGE OF VIC-DIOLS TO CARBOXYLIC ACIDS
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Page/Page column 7-8; 9, (2021/11/13)
The invention relates to a simple and efficient metal-free method for oxidative cleavage of vic-diols, in particular those derived from fatty esters, to the corresponding carboxylic acids, using a cheap, safe and environmentally friendly oxidant under mild conditions wherein oxone? is used as an oxidant and a halide as a catalyst in presence of the accurate organic solvent.
Biobased Aldehydes from Fatty Epoxides through Thermal Cleavage of β-Hydroxy Hydroperoxides**
De Dios Miguel, Thomas,Duc Vu, Nam,Lemaire, Marc,Duguet, Nicolas
, p. 379 - 386 (2020/11/30)
The ring-opening of epoxidized methyl oleate by aqueous H2O2 has been studied using tungsten and molybdenum catalysts to form the corresponding fatty β-hydroxy hydroperoxides. It was found that tungstic acid and phosphotungstic acid gave the highest selectivities (92–93 %) towards the formation of the desired products, thus limiting the formation of the corresponding fatty 1,2-diols. The optimized conditions were applied to a range of fatty epoxides to give the corresponding fatty β-hydroxy hydroperoxides with 30–80 % isolated yields (8 examples). These species were fully characterized by 1H and 13C NMR spectroscopy and HPLC-HRMS, and their stability was studied by differential scanning calorimetry. The thermal cleavage of the β-hydroxy hydroperoxide derived from methyl oleate was studied both in batch and flow conditions. It was found that the thermal cleavage in flow conditions gave the highest selectivity towards the formation of aldehydes with limited amounts of byproducts. The aldehydes were both formed with 68 % GC yield, and nonanal and methyl 9-oxononanoate were isolated with 57 and 55 % yield, respectively. Advantageously, the overall process does not require large excess of H2O2 and only generates water as a byproduct.
Synthesis of Branched Biolubricant Base Oil from Oleic Acid
Chen, Shuang,Wu, Tingting,Zhao, Chen
, p. 5516 - 5522 (2020/09/07)
The mature manufacturing of synthetic lubricants (poly-α-olefins, PAO) proceeds through oligomerization, polymerization, and hydrogenation reactions of petrochemical ethylene. In this work, we utilize the inexpensive bio-derived oleic acid as raw material to synthesize a crotch-type C45 biolubricant base oil via a full-carbon chain synthesis without carbon loss. It contains several cascade chemical processes: oxidation of oleic acid to azelaic acid (further esterification to dimethyl azelate) and nonanoic acid (both C9 chains). The latter is then selectively hydrogenated to nonanol and brominated to the bromo-Grignard reagent. In a next step, a C45 biolubricant base oil is formed by nucleophilic addition (NPA) of excessive C9 bromo-Grignard reagent with dimethyl azelate, followed by subsequent hydrodeoxygenation. The specific properties of the prepared biolubricant base oil are almost equivalent to those of the commercial lubricant PAO6 (ExxonMobil). This process provides a new promising route for the production of value-added biolubricant base oils.
Method for synthesizing azelaic acid monomethyl ester by catalyzing epoxy methyl oleate through ionic liquid
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Paragraph 0033-0044, (2020/12/30)
The invention relates to a method for synthesizing azelaic acid monomethyl ester by catalyzing epoxy methyl oleate with ionic liquid, which comprises the following steps: dissolving 1-(3-sulfonic acid) propyl piperidine dodecaphosphomolybdic acid ionic liquid and a certain amount of hydrogen peroxide by using a derivative epoxy methyl oleate of biodiesel as a raw material, dropwisely adding epoxymethyl oleate and a hydrogen peroxide solution, controlling the temperature, and fully stirring, after the reaction is finished, and arranging an oil layer on an upper surface, wherein an aqueous solution is dark green, obvious in layering and easy to separate; and drying the separated oily substance, carrying out high-vacuum rectification, and collecting the distillate at the temperature of 210-220 DEG C and the vacuum degree of 6-10mmHg to obtain a azelaic acid monomethyl ester finished product with the mass fraction of more than 99.0%. The method has the characteristics of simple process, no addition of other solvents and phase transfer catalysts, environment-friendly oxidation mode, no pollution and high added value of the product. The method has high reaction yield, can obtain a largeamount of high-purity azelaic acid monomethyl ester, and is easy for industrial application.
A Two-Step Oxidative Cleavage of 1,2-Diol Fatty Esters into Acids or Nitriles by a Dehydrogenation–Oxidative Cleavage Sequence
Guicheret, Boris,Bertholo, Yann,Blach, Philippe,Raoul, Yann,Métay, Estelle,Lemaire, Marc
, p. 3431 - 3437 (2018/09/06)
Dehydrogenative oxidation of vicinal alcohols catalyzed by a commercially 64 wt.% Ni/SiO2 catalyst leads to the formation of α-hydroxyketone. This first step was developed without additional solvent according to two protocols: “under vacuum” or “with an olefin scavenger”. The synthesis of ketols was carried out with good conversions and selectivities. The recyclability of the supported nickel was also studied. Acyloin was then cleaved with oxidative reagent “formic acid/hydrogen peroxide”, which is cheap and can be used on a large scale for industrial oxidation processes. The global yield of this sequential system was up to 80 % to pelargonic acid and azelaic acid monomethyl ester without intermediate purification. By treating the acyloin intermediate with hydroxylamine, nitriles were obtained with a good selectivity.
Amphiphilic dipyridinium-phosphotungstate as an efficient and recyclable catalyst for triphasic fatty ester epoxidation and oxidative cleavage with hydrogen peroxide
De La Garza, Luis Carlos,De Oliveira Vigier, Karine,Chatel, Gregory,Moores, Audrey
, p. 2855 - 2862 (2017/07/24)
A novel amphiphilic dipyridinium peroxophosphotungstate ion pair was developed as a selective and recyclable catalyst for the triphasic epoxidation of fatty acids and esters with hydrogen peroxide. The synthesis of the catalyst was studied extensively by solid and liquid phase 31P nuclear magnetic resonance (NMR). The oxidation of vegetable oils is of prime importance for the production of lubricants, plasticizers, polymer stabilizers and other olefinic compounds. Based on the oxidizing activity of peroxophosphotungstates, we designed a lipophilic phase transfer agent that renders the active complex insoluble in the reaction media, without having to support it on a matrix. This affords a catalyst combining the activity of homogeneous catalysts and the recyclability of heterogeneous systems. We show that this catalyst is able to fully epoxidize methyl oleate with excellent selectivity, with a turnover frequency of 149 at 60 °C, and can be easily recycled, to reach a record turn over number of 1868. A larger scale experiment on 13 grams and a scope including linoleic and ricinoleic acids were also demonstrated. The catalyst also shows excellent activity and selectivity for the oxidative cleavage of methyl oleate and the oxidation of small olefins.
Selective monomethyl esterification of linear dicarboxylic acids with bifunctional alumina catalysts
Santacroce, Veronica,Bigi, Franca,Casnati, Alessandra,Maggi, Raimondo,Storaro, Loretta,Moretti, Elisa,Vaccaro, Luigi,Maestri, Giovanni
supporting information, p. 5764 - 5768 (2016/11/06)
An environmentally friendly protocol for the selective protection of dicarboxylic acids is reported using methanol as a cheap esterifying agent and alumina as a heterogeneous catalyst; the selectivity of the process has been ascribed to a balanced acidity/basicity of the bifunctional alumina catalyst.
Synthesis of ceramides NS and NP with perdeuterated and specifically ω deuterated N-acyl residues
Sonnenberger, Stefan,Lange, Stefan,Langner, Andreas,Neubert, Reinhard H.H.,Dobner, Bodo
, p. 531 - 542 (2016/11/06)
The synthesis of 12 deuterated ceramides with either a deuteration at the last carbon atom of the amide bound fatty acid or a perdeuterated fatty acid chain is described. The ceramides were prepared starting from sphingosine or phytosphingosine and ω deuterated or perdeuterated fatty acids with PyBOP as activating agent in high yields. For the synthesis of the specifically deuterated fatty acids, dicarboxylic acids were transformed into ω deuterated alkyl bromide, which was chain elongated with blocked ω bromo alcohols by copper catalyzed Grignard coupling. Oxidation of regenerated alcohol function yields the ω deuterated fatty acids.
Ozonolysis of methyl oleate monolayers at the air-water interface: Oxidation kinetics, reaction products and atmospheric implications
Pfrang, Christian,Sebastiani, Federica,Lucas, Claire O. M.,King, Martin D.,Hoare, Ioan D.,Chang, Debby,Campbell, Richard A.
, p. 13220 - 13228 (2014/06/24)
Ozonolysis of methyl oleate monolayers at the air-water interface results in surprisingly rapid loss of material through cleavage of the CC bond and evaporation/dissolution of reaction products. We determine using neutron reflectometry a rate coefficient of (5.7 ± 0.9) × 10-10 cm2 molecule-1 s-1 and an uptake coefficient of ～3 × 10-5 for the oxidation of a methyl ester monolayer: the atmospheric lifetime is ～10 min. We obtained direct experimental evidence that a minor change to the structure of the molecule (fatty acid vs. its methyl ester) considerably impacts on reactivity and fate of the organic film.
Efficient ruthenium-catalysed oxidative cleavage of methyl oleate with hydrogen peroxide as oxidant
Behr, Arno,Tenhumberg, Nils,Wintzer, Andreas
, p. 172 - 180 (2013/04/23)
The oxidative cleavage of alkenes leads to the formation of carboxylic acids. One of the few technical processes using this reaction is the production of azelaic acid via the ozonolysis of oleic acid. Because of the need for stoichiometric amounts of the expensive oxidant ozone, together with safety hazards, there is still a requirement for a catalytic process using a cheap and environmentally friendly oxidant. In the present work, the oxidative cleavage of methyl oleate by hydrogen peroxide was catalysed by an easily available ruthenium precursor with dipicolinic acid as ligand. The systematic optimisation of the reaction led to the formation of azelaic acid monomethyl ester in high yields amounting to 86%. The investigation of the reaction pathway showed that the reaction proceeds via a tandem reaction of epoxidation and hydrolysis of the epoxide and oxidative cleavage of the vic-diol. The Royal Society of Chemistry.
