112-05-0Relevant articles and documents
Activation of Reducing Agents.Sodium Hydride Containing Complex Reducing Agents.16. FeCRACO, a new Reagent for Carbonylation of Primary, Secondary, and Tertiary Alkyl Halides at Atmospheric Pressure
Brunet, Jean-Jacques,Sidot, Christian,Caubere, Paul
, p. 3147 - 3149 (1981)
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v.Rudloff
, p. 1413,1414 (1956)
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.
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.
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.
Ozonolysis in flow using capillary reactors
Roydhouse, M. D.,Motherwell, W. B.,Ghaini, A.,Constantinou, A.,Cantu-Perez, A.,Gavriilidis, A.
, p. 989 - 996 (2011)
Reactions of n-decene with ozone and subsequent quenching of the formed ozonides were carried out under flow conditions using the standard Vapourtec flow system equipped with a cooled flow cell. The reactions were performed continuously and in the annular flow regime within the circular cross-section channels. Typical flow rates were 0.25-1 mL min-1 for liquid and 25-100 mL min-1 for gas, reactor volumes were 0.07-10 mL formed of 1 mm ID PFA tubing. The reaction temperature was -10 °C. The flow was not always smooth, while waves in the liquid film and droplets in the gas core were observed. Liquid residence times were found to be independent of gas flow rates and increasing with decreasing liquid flow rates. Substrate residence times in the ozonolysis reactor ranged between 1 and 80 s, and complete conversion could be achieved at ～1 s residence time. Two common reductants, triethylphosphite and triphenylphosphine, were examined as to their suitability under flow conditions. Triphenylphosphine achieved faster reduction of the intermediate ozonides, resulting in a greater than 10:1 selectivity for the aldehyde over the corresponding acid. The cooling system provided a safe and efficient control of the highly exothermic reaction system. The configuration of the system allowed the production of chemically significant amounts (1.8 g h-1 at 1.3 ozone equivalents), with minimal amounts of ozonides present at any time.
New environmentally friendly oxidative scission of oleic acid into azelaic acid and pelargonic acid
Godard, Anais,De Caro, Pascale,Thiebaud-Roux, Sophie,Vedrenne, Emeline,Mouloungui, Zephirin
, p. 133 - 140 (2013)
Oleic acid (OA) is a renewable monounsaturated fatty acid obtained from high oleic sunflower oil. This work was focused on the oxidative scission of OA, which yields a mono-acid (pelargonic acid, PA) and a di-acid (azelaic acid, AA) through an emulsifying system. The conventional method for producing AA and PA consists of the ozonolysis of oleic acid, a process which presents numerous drawbacks. Therefore, we proposed to study a new alternative process using a green oxidant and a solvent-free system. OA was oxidized in a batch reactor with a biphasic organic-aqueous system consisting of hydrogen peroxide (H 2O2, 30 %) as an oxidant and a peroxo-tungsten complex Q3{PO4[WO(O2)2]4} as a phase-transfer catalyst/co-oxidant. Several phase-transfer catalysts were prepared in situ from tungstophosphoric acid, H2O2 and different quaternary ammonium salts (Q+, Cl-). The catalyst [C5H5N(n-C16H33)] 3{PO4[WO(O2)2]4} was found to give the best results and was chosen for the optimization of the other parameters of the process. This optimization led to a complete conversion of OA into AA and PA with high yields (>80 %) using the system OA/H 2O2/[C5H5N(n-C16H 33)]3{PO4[WO(O2)2] 4} (1/5/0.02 molar ratio) at 85 C for 5 h. In addition, a new treatment was developed in order to recover the catalyst.
Engineering the nucleotide coenzyme specificity and sulfhydryl redox sensitivity of two stress-responsive aldehyde dehydrogenase isoenzymes of Arabidopsis thaliana
Stiti, Naim,Adewale, Isaac O.,Petersen, Jan,Bartels, Dorothea,Kirch, Hans-Hubert
, p. 459 - 471 (2011)
Lipid peroxidation is one of the consequences of environmental stress in plants and leads to the accumulation of highly toxic, reactive aldehydes. One of the processes to detoxify these aldehydes is their oxidation into carboxylic acids catalyzed by NAD(P)+-dependent ALDHs (aldehyde dehydrogenases). We investigated kinetic parameters of two Arabidopsis thaliana family 3 ALDHs, the cytosolic ALDH3H1 and the chloroplastic isoform ALDH3I1. Both enzymes had similar substrate specificity and oxidized saturated aliphatic aldehydes. Catalytic efficiencies improved with the increase of carbon chain length. Both enzymes were also able to oxidize α,β-unsaturated aldehydes, but not aromatic aldehydes. Activity of ALDH3H1 was NAD+-dependent, whereas ALDH3I1 was able to use NAD+ and NADP+. An unusual isoleucine residue within the coenzyme-binding cleft was responsible for the NAD +-dependence of ALDH3H1. Engineering the coenzyme-binding environment of ALDH3I1 elucidated the influence of the surrounding amino acids. Enzyme activities of both ALDHs were redox-sensitive. Inhibitionwas correlatedwith oxidation of both catalytic and noncatalytic cysteine residues in addition to homodimer formation. Dimerization and inactivation could be reversed by reducing agents. Mutant analysis showed that cysteine residues mediating homodimerization are located in the N-terminal region. Modelling of the protein structures revealed that the redox-sensitive cysteine residues are located at the surfaces of the subunits. The Authors Journal compilation
Carbon-Carbon Double Bond Cleavage Using Solid-Supported Potassium Permanganate on Silica Gel
Ferreira, J. Tercio B.,Cruz, W. O.,Vieira, P. C.,Yonashiro, M.
, p. 3698 - 3699 (1987)
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Liquid-phase catalytic oxidation of unsaturated fatty acids
Noureddini,Kanabur
, p. 305 - 312 (1999)
Liquid-phase catalytic oxidation of oleic acid with hydrogen peroxide in the presence of various transition metal/metal oxide catalysts was studied in a batch autoclave reactor. Azelaic and pelargonic acids are the major reaction products. Tungsten and tantalum and their oxides in supported and unsupported forms were used as catalysts. Alumina pellets and Kieselguhr powder were used as supports for the catalysts. Tungsten, tantalum, molybdenum, zirconium, and niobium were also examined as catalysts. Tertiary butanol was used as solvent. Experimental results concluded that tungsten and tungstic oxide are more suitable catalysts in terms of their activity and selectivity. The rate of reaction observed in the case of supported catalysts appears to be comparable or superior to that of unsupported catalysts. In pure form, tungsten, tantalum, and molybdenum showed strong catalytic activity in the oxidation reaction; however, except for tantalum the other two were determined to be economically unfeasible. Zirconium and niobium showed very little catalytic activity. Based on the experimental observations, tungstic oxide supported on silica is the most suitable catalyst for the oxidation of oleic acid with 85% of the starting oleic acid converted to the oxidation products in 60 min of reaction with high selectivity for azelaic acid.
Product recovery from ionic liquids by solvent-resistant nanofiltration: Application to ozonation of acetals and methyl oleate
Van Doorslaer, Charlie,Glas, Daan,Peeters, Annelies,Cano Odena, Angels,Vankelecom, Ivo,Binnemans, Koen,Mertens, Pascal,De Vos, Dirk
, p. 1726 - 1733 (2010)
In this work we tackle the problematic separation of reaction products from ionic liquid media. Solvent-resistant nanofiltration proves to be an attractive technique for the separation of non-volatile polar products from ionic liquids. In view of the high compatibility between ozone and ionic liquids, two ozone-mediated model reactions were chosen: firstly the oxidation of acetals to esters in the presence of ozone and secondly the ozonation of methyl oleate to monomethyl azelate and pelargonic acid. The objective was to retain the ionic liquid phase by means of a solvent-resistant nanofiltration membrane, while the organic reaction products permeate through the polymeric membrane. First, the ozonations were studied in order to know the characteristic product compositions. Next, a screening of membranes was performed on synthetic product mixtures. The second generation polyimide-based DuraMem membranes showed the highest rejection, up to 96%, for the evaluated ionic liquids. These DuraMem membranes also proved suitable for the separation of the products on real reaction mixtures, even in a single filtration step.
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Allen,J.C. et al.
, p. 1918 - 1932 (1965)
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Novel regioselective hydrogenation of alkadienoic acids caused by the addition of water
Okano, Temon,Kaji, Mitsunari,Isotani, Satoru,Kiji, Jitsuo
, p. 5547 - 5550 (1992)
The regioselective hydrogenation of 3,8-nonadienoic acid to 8-nonenoic acid was realized by the addition of water with RhCl[P(p-tolyl)3]3 in benzene at 1 atm hydrogen, whereas in the absence of water the reaction mostly gave 3-nonenoic acid. The novel selectivity is caused by both an accelerating effect of water on the hydrogenation of the 3-position and a retarding effect on that of the 8-position.
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Litvinov,V.P.,Gol'dfarb,Ya.L.
, (1963)
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Products and mechanisms of ozone reactions with oleic acid for aerosol particles having core-shell morphologies
Katrib, Yasmine,Martin, Scot T.,Hung, Hui-Ming,Rudich, Yinon,Zhang, Haizheng,Slowik, Jay G.,Davidovits, Paul,Jayne, John T.,Worsnop, Douglas R.
, p. 6686 - 6695 (2004)
Heterogeneous reactions of oleic acid aerosol particles with ozone are studied below 1% relative humidity. The particles have inert polystyrene latex cores (101-nm diameter) coated by oleic acid layers of 2 to 30 nm. The chemical content of the organic layer is monitored with increasing ozone exposure by using an aerosol mass spectrometer. The carbon-normalized percent yields of particle-phase reaction products are 20-35% 9-oxononanoic acid, 1-3% azelaic acid, 1-3% nonanoic acid, and 35-50% other organic molecules (designated as CHOT). There is approximately 25% evaporation, presumably as 1-nonanal. To explain the formation of CHOT molecules and the low yields of azelaic and nonanoic acids, we suggest a chemical mechanism in which the Criegee biradical precursors to azelaic acid and nonanoic acid are scavenged by oleic acid to form CHOT molecules. These chemical reactions increase the carbon-normalized oxygen content (z/x) of the CxH yOz layer from 0.1 for unreacted oleic acid to 0.25 after high ozone exposure. Under the assumption that oxygen content is a predictor of hygroscopicity, our results suggest an increased cloud condensation nuclei activity of atmospherically aged organic particles that initially have alkene functionalities.
METHOD FOR MANUFACTURING PELARGONIC ACID AND AZELAIC ACID
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Paragraph 0055-0083, (2021/07/27)
The present invention relates to a method for producing pelargonic acid and azelaic acid, and more specifically, provides a method for producing pelargonic acid and azelaic acid, which comprises the following steps of: a) reacting an unsaturated carboxylic acid compound under a tungstic acid catalyst to obtain an intermediate product comprising vicinal diol; and b) reacting the intermediate product under a transition metal hydroxide catalyst to obtain the pelargonic acid and azelaic acid. The production method is capable of producing the pelargonic acid and azelaic acid in a high yield from the unsaturated carboxylic acid compound.
An efficient and ultrastable single-Rh-site catalyst on a porous organic polymer for heterogeneous hydrocarboxylation of olefins
Yuan, Qiao,Song, Xiangen,Feng, Siquan,Jiang, Miao,Yan, Li,Li, Jingwei,Ding, Yunjie
supporting information, p. 472 - 475 (2021/01/25)
A heterogeneous hydrocarboxylation process of olefins to obtain carboxylic acids with one more carbon was first realized using a single-Rh-site catalyst formed on porous organic polymer (Rh1/POPs). The in situ formation of hydrophilic porous ionic polymer from hydrophobic POPs with the help of CH3I led to high activity and superb stability.
