Catalytic oxidative cleavage of olefins by RuO4 organic solvent-free under ultrasonic irradiation

Rup, Sandrine; Sindt, Michèle; Oget, Nicolas

doi:10.1016/j.tetlet.2010.04.040

Cited by 41 publications

(22 citation statements)

References 18 publications

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“…is also observed in earlier reports on the oxidation of aliphatic alkenes (entries 3-4). 47,39 The drop in conversion for erucic acid methyl ester (96% compared to 54%) is higher than that previously observed for cis-cyclooctene (99% compared to 90%). 47 On the other hand, the D/E ratio in the case of erucic acid methyl ester proved less sensitive to the presence of water (1.2 compared to 1.6) than in the case of cis-cyclooctene (0.6 compared to 3.6).…”

Section: Cis-dihydroxylation Of Unsaturated Fatty Acidsmentioning

confidence: 65%

“…While the use of [Fe(OTf) 2 (PyTACN)] (1) also resulted in a high diol/epoxide ratio under oxidant-limiting conditions, 51,52 the recently developed [Fe(OTf) 2 (6-Me-PyTACN)] (2) (6-MePyTACN = 1-[(6-methyl-2-pyridyl)methyl]-4,7-dimethyl-1,4,7triazacyclononane, 2) showed good chemoselectivity for the formation of diols also under substrate-limiting conditions. 47 1 is furthermore capable of converting diols into hydroxyl-ketones 39 and is known to oxidize the water molecule with NaIO 4 . 53 1 and 2 (Scheme 5) were therefore considered as catalyst candidates for the oxidative cleavage of unsaturated fatty acids into carboxylic acids.…”

Section: Introductionmentioning

confidence: 99%

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Fe(6-Me-PyTACN)-catalyzed, one-pot oxidative cleavage of methyl oleate and oleic acid into carboxylic acids with H2O2 and NaIO4

Spannring

Prat

Costas

et al. 2014

Catal. Sci. Technol.

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The first Fe-based catalytic system for the oxidative cleavage of unsaturated fatty acids and esters to carboxylic acids is reported. The system comprises [Fe(OTf) 2 (6-Me-PyTACN)] (2) (6-Me-PyTACN = 1-[(6-methyl-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, OTf = trifluoromethane sulfonate anion) as the catalyst (3 mol%) either with a combination of hydrogen peroxide and NaIO 4 or exclusively with NaIO 4 as the oxidant, and operates at 0°C or ambient temperature. Under these standard conditions (method A), methyl oleate is converted in a one-pot procedure into 50-55% of both nonanoic and azelaic acid, together with some epoxide and aldehyde intermediates as byproducts. These yields can be further improved by addition of sulfuric acid (method B) to hydrolyze the epoxide byproducts, by including a pH neutralization step and addition of more catalyst (1 mol%). Under the optimized conditions, both methyl oleate and oleic acid are converted into high yields of the corresponding carboxylic acids (80-85%). Overall, this catalytic system provides an alternative to the industrial ozonolysis of oleic acid and to catalytic Ru-and Os-based systems for the oxidative cleavage of unsaturated fatty acids and esters.

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Section: Cis-dihydroxylation Of Unsaturated Fatty Acidsmentioning

confidence: 65%

Section: Introductionmentioning

confidence: 99%

Fe(6-Me-PyTACN)-catalyzed, one-pot oxidative cleavage of methyl oleate and oleic acid into carboxylic acids with H2O2 and NaIO4

Spannring

Prat

Costas

et al. 2014

Catal. Sci. Technol.

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“…Many catalysts have been applied to this type of reaction [37][38][39][40]. For example, a niobium oxide catalyst has been recently used in the oxidative cleavage of methyl linoleate to obtain aldehydes as a major product.…”

Section: Catalystmentioning

confidence: 99%

Oxidative Cleavage of Fatty Acid Derivatives for Monomer Synthesis

et al. 2018

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Oxidative cleavage of fatty acids and fatty acid derivatives is a practical way to obtain bifunctional molecules that can be used in polycondensation reactions. Diacids, hydroxyacids, and amino acids can then be used to produce polyesters or polyamides and also a large range of other products, such as lubricants and plasticizers. Ozonolysis has long been the sole industrial process for oxidative cleavage, but recently, routes using hydrogen peroxide as a clean oxidant have regained interest. Hydrogen peroxide is easier to use, but the kinetics of the catalyzed reactions are still slow. Although several catalytic systems have been described in the literature, tungsten-based catalysts are still the preferred choices. Different catalysts can trigger different mechanisms, such as a radical mechanism instead of a catalytic reaction. In addition, some side products and co-products often disregarded in the literature, such as shorted cleavage products, indicate the presence of side reactions that affect the quality of the final products. The oxidative cleavages in continuous and batch processes have significant differences, which are discussed with an illustration of our understanding of the process used by Matrica S.p.A.

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“…Comparing the oxidative cleavage of OA using different oxidants and catalytic systems, it was observed that the yield or selectivity of PA and AA are almost similar, suggesting the stoichiometric oxidation of OA to PA and AA through the cleavage of an olefinic double bond. However, the yield of AA and PA differed considerably when oxidation was carried out using RuCl 3 /NaIO 4 under ultrasonic irradiation [17,18]. The difference in yield was mainly due to degradation of AA in the ultrasonic irradiation environment.…”

Section: Introductionmentioning

confidence: 99%

Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex

Hajra

Sultana

Guria

et al. 2017

J Americ Oil Chem Soc

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Industrially important di‐carboxylic acids are synthesized from mono‐carboxylic unsaturated and unsaturated fatty acids. In this study, the aim is to perform the simultaneous catalytic oxidative C=C cleavage of oleic acid (OA) to azelaic acid and pelargonic acid, and oxidation of the terminal methyl group in pelargonic acid to azelaic acid using cobalt‐ and manganese‐acetate as catalyst, hydrogen bromide as co‐catalyst and air in acetic acid at elevated pressure (2.8–5.8 barg) and temperature (353–383 K). Oxygen solubility is determined under varying pressure, temperature and OA loading. The effect of OA loading, pressure and temperature on OA conversion and azelaic acid selectivity is studied by varying one variable at a time; however, the presence of the synergistic effect of the catalyst and co‐catalyst is investigated by central composite design assisted response surface methodology. Oxidation of terminal methyl group in saturated fatty acid is also confirmed by the oxidation of stearic acid to octadecanedioic acid using identical oxidation conditions of OA. Oxidation products of fatty acids are quantified by gas chromatographic analysis. The innovation of the work is thus the ability of the catalytic system to perform a total oxidation of a terminal methyl group of the hydrocarbon chain. OA oxidation kinetics relating to catalyst and co‐catalyst concentration along with oxygen solubility at elevated temperature and pressure is established. The frequency factor and activation energy for OA oxidation is determined using the Arrhenius equation.

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Catalytic oxidative cleavage of olefins by RuO4 organic solvent-free under ultrasonic irradiation

Cited by 41 publications

References 18 publications

Fe(6-Me-PyTACN)-catalyzed, one-pot oxidative cleavage of methyl oleate and oleic acid into carboxylic acids with H2O2 and NaIO4

Fe(6-Me-PyTACN)-catalyzed, one-pot oxidative cleavage of methyl oleate and oleic acid into carboxylic acids with H2O2 and NaIO4

Oxidative Cleavage of Fatty Acid Derivatives for Monomer Synthesis

Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex

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