112-05-0Relevant articles and documents
Conversion of oleic acid into azelaic and pelargonic acid by a chemo-enzymatic route
Brenna, Elisabetta,Colombo, Danilo,Di Lecce, Giuseppe,Gatti, Francesco G.,Ghezzi, Maria Chiara,Tentori, Francesca,Tessaro, Davide,Viola, Mariacristina
, (2020)
A chemo-enzymatic approach for the conversion of oleic acid into azelaic and pelargonic acid is herein described. It represents a sustainable alternative to ozonolysis, currently employed at the industrial scale to perform the reaction. Azelaic acid is produced in high chemical purity in 44% isolation yield after three steps, avoiding column chromatography purifications. In the first step, the lipase-mediated generation of peroleic acid in the presence of 35% H2O2 is employed for the self-epoxidation of the unsaturated acid to the corresponding oxirane derivative. This intermediate is submitted to in situ acid-catalyzed opening, to afford 9,10-dihydroxystearic acid, which readily crystallizes from the reaction medium. The chemical oxidation of the diol derivative, using atmospheric oxygen as a stoichiometric oxidant with catalytic quantities of Fe(NO3)3·9·H2O, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and NaCl, affords 9,10-dioxostearic acid which is cleaved by the action of 35% H2O2 in mild conditions, without requiring any catalyst, to give pelargonic and azelaic acid.
REACTION OF CARBON DIOXIDE WITH A BIMETALLIC OCTADIENYL-BRIDGED PALLADIUM COMPLEX
Behr, Arno,Ilsemann, Godard von
, p. C77 - C88 (1984)
Reaction of equimolar amounts of μ-1-3-η:6-8-η-octadienatobis(1,1,1,5,5,5-hexafluoroacetylacetonatopalladium) and triisopropylphosphine gives a bimetalic octadienyl-bridged complex, in which one palladium atom is η1-bound to the terminal carbon of the octadienyl chain.Insertion of CO2 into this Pd-C bond gives a carboxylate complex; acidic decomposition and hydrogenation of the carboxylate complex gives pelargonic acid.The results are discussed in relation to the mechanism of the palladium-catalyzed reaction between butadiene and carbon dioxide.
Hydrocarboxylation of terminal alkenes in supercritical carbon dioxide using perfluorinated surfactants
Tortosa-Estorach, Clara,Ruiz, Nuria,Masdeu-Bulto, Anna M.
, p. 2789 - 2791 (2006)
High selectivity in acids is obtained in the first example of hydrocarboxylation of 1-octene in supercritical carbon dioxide using a Pd/P(4-C6H4-CF3)3 catalyst system and a perfluorinated surfactant. The Royal Society of Chemistry 2006.
Microwave-induced electrostatic etching: Generation of highly reactive magnesium for application in Grignard reagent formation
Van De Kruijs, Bastiaan H. P.,Dressen, Mark H. C. L.,Meuldijk, Jan,Vekemans, Jef A. J. M.,Hulshof, Lumbertus A.
, p. 1688 - 1694 (2010)
A detailed study regarding the influence of microwave irradiation on the formation of a series of Grignard reagents in terms of rates and selectivities has revealed that these heterogeneous reactions may display a beneficial microwave effect. The interaction between microwaves and magnesium turnings generates violent electrostatic discharges. These discharges on magnesium lead to melting of the magnesium surface, thus generating highly active magnesium particles. As compared to conventional operation the microwave-induced discharges on the magnesium surface lead to considerably shorter initiation times for the insertion of magnesium in selected substrates (i.e. halothiophenes, halopyridines, octyl halides, and halobenzenes). Thermographic imaging and surface characterization by scanning electron microscopy showed that neither selective heating nor a "specific" microwave effect was causing the reduction in initiation times. This novel and straightforward initiation method eliminates the use of toxic and environmentally adverse initiators. Thus, this initiation method limits the formation of by-products. We clearly demonstrated that microwave irradiation enables fast Grignard reagent formation. Therefore, microwave technology is promising for process intensification of Grignard based coupling reactions.
Long-chain alkanoic acid esters of lupeol from Dorstenia harmsiana Engl. (Moraceae)
Poumale, Herve Martial P.,Awoussong, Kenzo Patrice,Randrianasolo, Rivoarison,Simo, Christophe Colombe F.,Ngadjui, Bonaventure Tchaleu,Shiono, Yoshihito
, p. 749 - 755 (2012)
In addition to lupeol (1a), three long-chain alkanoic acid esters of lupeol, in which two were new, were isolated from the hexane and ethyl acetate twigs extract of Dorstenia harmsiana Engl. (Moraceae). The structures of the new compounds were elucidated
Scalable, sustainable and catalyst-free continuous flow ozonolysis of fatty acids
Atapalkar, Ranjit S.,Athawale, Paresh R.,Srinivasa Reddy,Kulkarni, Amol A.
, p. 2391 - 2396 (2021)
A simple and efficient catalyst-free protocol for continuous flow synthesis of azelaic acid is developed from the renewable feedstock oleic acid. An ozone and oxygen mixture was used as the reagent for oxidative cleavage of double bond without using any metal catalyst or terminal oxidant. The target product was scaled up to more than 100 g with 86% yield in a white powder form. Complete recycling and reuse of the solvent were established making it a green method. The approach is significantly energy efficient and also has a very small chemical footprint. The methodology has been successfully tested with four fatty acids making it a versatile platform that gives value addition from renewable resources.
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)
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.
The OsO4-mediated oxidative cleavage of olefins catalyzed by alternative osmium sources
Whitehead, Daniel C.,Travis, Benjamin R.,Borhan, Babak
, p. 3797 - 3800 (2006)
The OsO4-mediated oxidative cleavage of olefins is compatible with alternative, easier-to-handle osmium sources. Four different osmium sources were employed with favorable results.
Aliphatic organolithiums by fluorine-lithium exchange: n-octyllithium
Yus, Miguel,Herrera, Raquel P.,Guijarro, Albert
, p. 5025 - 5027 (2003)
The reaction of 1-fluorooctane (1) with an excess of lithium powder (4-10 equiv.) and DTBB (2-4 equiv.) in THP at 0°C for 5 min gives a solution of the corresponding 1-octyllithium (2), which reacts then with different electrophiles at 0°C (D2O, MeSiCl, ButCHO, Et2CO), or -78°C [ClCO2Me, (PhCH2S)2] or -40°C (CO2) to room temperature to give, after hydrolysis, the expected products (3). The same process applied to 2-fluorooctane gives mainly octane as reaction product, independently on the electrophile used, resulting from a proton abstraction by 2-lithiooctane formed from the reaction medium before addition of the electrophilic reagent.
Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid
Benessere, Vincenzo,Cucciolito, Maria E.,De Santis, Augusta,Di Serio, Martino,Esposito, Roberto,Ruffo, Francesco,Turco, Rosa
, p. 1701 - 1707 (2015)
This work describes two sustainable methods for production and purification of azelaic acid (AA) to replace the current process of ozonolysis of oleic acid (OA). The first proceeds in two steps, coupling smooth oxidation of OA to 9,10-dihydroxystearic acid (DSA) with subsequent oxidative cleavage by sodium hypochlorite. An alternative methodology is also proposed, using a chemocatalytic system consisting of H2O2/H2WO4 for direct oxidative cleavage of the double bond of OA at 373 K. A convenient technique for separation and purification of azelaic acid is also proposed.
