From tandem to catalysis – organic solvent nanofiltration for catalyst separation in the homogeneously W-catalyzed oxidative cleavage of renewable methyl 9,10-dihydroxystearate

Vondran, Johanna; Peters, M.; Schnettger, Alexander; Sichelschmidt, Christian; Seidensticker, Thomas

doi:10.1039/d1cy02317a

Cited by 7 publications

(7 citation statements)

References 38 publications

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“…Thereby, a higher acid concentration is expected to result in a faster reaction but might also influence selectivity, as we have shown in our previous work. [ 8 ] In addition, hydrolysis of the methyl ester function can occur at high acid concentrations, which also leads to lower selectivity. The isolated diol 3 should be present in high purity and without acid residues.…”

Section: Resultsmentioning

confidence: 99%

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Catalytic Synthesis of Methyl 9,10‐dihydroxystearate from Technical Feedstocks in Continuous Flow via Epoxidation and Hydrolysis

Vondran

Benninghoff

Emminghaus

et al. 2022

Euro J Lipid Sci & Tech

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The sequence of the homogeneously Ru-catalyzed epoxidation of methyl oleate and acid-catalyzed hydrolysis of the corresponding epoxide methyl 9,10-epoxy stearate is successfully transferred from batch into flow mode, allowing for the continuous production of methyl 9,10-dihydroxystearate. Thereby, methyl oleate is first converted up to 97% within 14 min at excellent selectivity in the epoxidation using aqueous hydrogen peroxide as the sole oxidant. In the subsequent hydrolysis, a residence time of 10 min is sufficient for quantitative conversion of the epoxide. The desired, pure vicinal diol is isolated upon crystallization from the crude reaction mixture in an integrated process starting from technical grade (91.5%) substrate. The isolated yield is increased upon the addition of water as a green antisolvent from 75% up to 97%. Finally, the concept is transferred to methyl oleate of even lower purity (76%), still obtaining an isolated yield of 66% of the vicinal diol. Thus, the integration of sequential epoxidation and hydrolysis into continuous flow and subsequent crystallization allows for high conversion and selectivities within a total residence time of 27 min, corresponding to a space-time yield of 190 g h −1 L −1 in the epoxidation and 164 g h −1 L −1 in the hydrolysis, respectively. Practical applications: The modular flow setup enables the targeted functionalization toward the epoxide intermediate or the vicinal diol. Both offer versatile applications for the production of polymers, surfactants, or toward further conversion as in oxidative cleavage starting from methyl oleate. The application of flow chemistry offers advantages for the safe handling of hydrogen peroxide even at high temperatures. With fats and oils being natural substances, oleochemicals such as fatty acid methyl esters are typically available in technical purity so that efficient strategies for the isolation of pure products are of need. Crystallization of the product is promising, as additional organic solvents are not required. Thus, using the difference in melting point and solubility behavior of the desired product compared to other compounds is a promising method for the applicability of renewable resource-based substrate mixtures.

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Section: Resultsmentioning

confidence: 99%

“…[ 7 ] Additionally, the vicinal diol can function as a stable intermediate toward oxidative cleavage. [ 8 ] The model reaction of two‐step epoxidation of methyl oleate and subsequent hydrolysis is shown in Figure .…”

Section: Introductionmentioning

confidence: 99%

Catalytic Synthesis of Methyl 9,10‐dihydroxystearate from Technical Feedstocks in Continuous Flow via Epoxidation and Hydrolysis

Vondran

Benninghoff

Emminghaus

et al. 2022

Euro J Lipid Sci & Tech

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“…Besides the Pd, Rh and Ru catalysts, some other homogeneous catalysts such as gold-based, − platinum-based, tungsten-based, − magnesium triflate, , Co-Jacobsen catalyst, and quinidine-based organocatalyst − have been explored for recovery/recycling. For example, gold N-heterocyclic carbene complexes in the hydration of diphenylacetylene (Scheme ) were first recovered by Bayrakdar et al The Borsig oNF-1 membrane was selected due to its high rejection toward the catalyst (98.5%) and moderate rejection toward the product (53%) in the mixture of THF/water.…”

Section: Pharmaceutical Applicationsmentioning

confidence: 99%

Organic Solvent Nanofiltration in Pharmaceutical Applications

Xiao,

Feng,

Goundry

et al. 2024

Org. Process Res. Dev.

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Separation and purification in organic solvents are indispensable procedures in pharmaceutical manufacturing. However, they still heavily rely on the conventional separation technologies of distillation and chromatography, resulting in high energy and massive solvent consumption. As an alternative, organic solvent nanofiltration (OSN) offers the benefits of low energy consumption, low solid waste generation, and easy scale-up and incorporation into continuous processes. Thus, there is a growing interest in employing membrane technology in the pharmaceutical area to improve process sustainability and energy efficiency. This Review comprehensively summarizes the recent progress (especially the last 10 years) of organic solvent nanofiltration and its applications in the pharmaceutical industry, including the concentration and purification of active pharmaceutical ingredients, homogeneous catalyst recovery, solvent exchange and recovery, and OSN-assisted peptide/oligonucleotide synthesis. Furthermore, the challenges and future perspectives of membrane technology in pharmaceutical applications are discussed in detail.

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“…[10,11] So far, oxidative cleavage of UFAs is mainly performed by ozonolysis (high energy demanding) or with homogenous catalysts which are not reusable and are polluting. [12][13][14][15] Moreover, current heterogeneous catalysts display a poor activity as a result of the poor contact amid the UFA and the active phase. In addition, bad performances of heterogeneous catalysts are related as well to loss of activity because of leaching issues.…”

Section: Introductionmentioning

confidence: 99%

“…For instance, oleic acid can be transformed into pelargonic (PA) and azelaic (AA) acids which are valuable as herbicides and skin cancer treatment respectively [10,11] . So far, oxidative cleavage of UFAs is mainly performed by ozonolysis (high energy demanding) or with homogenous catalysts which are not reusable and are polluting [12–15] . Moreover, current heterogeneous catalysts display a poor activity as a result of the poor contact amid the UFA and the active phase.…”

Section: Introductionmentioning

confidence: 99%

Ru on Modified Carbon Submicrometric Spheres as Novel Catalysts for the Oxidative Cleavage of Oleic Acid with N‐Methylmorpholine‐N‐Oxide as Green Oxidizing Agent

2022

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Oxidative cleavage of unsaturated fatty acids involves the rupture of carbon‐carbon double bonds to produce carbonyl compounds of high added value. This reaction is mainly performed using homogenous catalysts which are pollutant and cannot be recovered while current heterogeneous catalysts display poor activity. To solve this issue, an active catalyst was prepared by impregnating Ru ions on carbon spheres synthesized by hydrothermal carbonization of a glucose solution. Carbon spheres were calcined under air atmosphere to create porosity and functionalized with polydopamine to improve their ability to complex Ru ions. The catalyst was fully characterized and completed the oxidative cleavage of oleic acid within 7 h of stirring at room temperature using NaIO4 as oxidizing agent. The addition of N‐methylmorpholine N‐oxide, a green oxidizing agent, allowed >99 % conversion in only 5 h. Therefore, it was possible to conceive an eco‐friendly carbon catalyst for the valorization of oleic acid under mild conditions.

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From tandem to catalysis – organic solvent nanofiltration for catalyst separation in the homogeneously W-catalyzed oxidative cleavage of renewable methyl 9,10-dihydroxystearate

Abstract: Feasibility of oxidative cleavage of methyl oleate in a homogeneous reaction, facilitating the subsequent recovery of the catalyst from a single phase, is a challenge. Using the high molecular catalyst...

Cited by 7 publications

References 38 publications

Catalytic Synthesis of Methyl 9,10‐dihydroxystearate from Technical Feedstocks in Continuous Flow via Epoxidation and Hydrolysis

Catalytic Synthesis of Methyl 9,10‐dihydroxystearate from Technical Feedstocks in Continuous Flow via Epoxidation and Hydrolysis

Organic Solvent Nanofiltration in Pharmaceutical Applications

Ru on Modified Carbon Submicrometric Spheres as Novel Catalysts for the Oxidative Cleavage of Oleic Acid with N‐Methylmorpholine‐N‐Oxide as Green Oxidizing Agent

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