MeSesamol, a bio-based and versatile polar aprotic solvent for organic synthesis and depolymerization

Gyula, Dargó; Kis, Dávid; Gede, Martin; Kumar, Sushil; Kupai, József; Székely, György

doi:10.1016/j.cej.2023.144365

Cited by 7 publications

(3 citation statements)

References 66 publications

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“…Since homogeneous catalysts usually exhibit higher activity and selectivity than their heterogeneous counterparts [ 27 ], our aim was to carry out the catalytic reaction homogeneously. The solubility of the lipophilic catalyst 2 was investigated in ten solvents with low polarity, including a new, bio-based polar aprotic solvent, MeSesamol [ 33 ]. The catalyst’s precipitation – which is necessary for its recycling – was tested by adding a polar solvent, i.e., methanol, to its solution.…”

Section: Resultsmentioning

confidence: 99%

A novel recyclable organocatalyst for the gram-scale enantioselective synthesis of (S)-baclofen

Dargó,

Erdélyi,

Molnár

et al. 2023

Beilstein J. Org. Chem.

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Synthesizing organocatalysts is often a long and cost-intensive process, therefore, the recovery and reuse of the catalysts are particularly important to establish sustainable organocatalytic transformations. In this work, we demonstrate the synthesis, application, and recycling of a new lipophilic cinchona squaramide organocatalyst. The synthesized lipophilic organocatalyst was applied in Michael additions. The catalyst was utilized to promote the Michael addition of cyclohexyl Meldrum’s acid to 4-chloro-trans-β-nitrostyrene (quantitative yield, up to 96% ee). Moreover, 1 mol % of the catalyst was feasible to conduct the gram-scale preparation of baclofen precursor (89% yield, 96% ee). Finally, thanks to the lipophilic character of the catalyst, it was easily recycled after the reaction by replacing the non-polar reaction solvent with a polar solvent, acetonitrile, with 91–100% efficiency, and the catalyst was reused in five reaction cycles without the loss of activity and selectivity.

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Section: Resultsmentioning

confidence: 99%

A novel recyclable organocatalyst for the gram-scale enantioselective synthesis of (S)-baclofen

Dargó,

Erdélyi,

Molnár

et al. 2023

Beilstein J. Org. Chem.

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“…This demonstrated the feasibility and advantages of replacing toxic and hazardous solvents that have long been the standard solvents used in membrane fabrication with benign alternatives [130]. Regarding the preparation of the membrane support layer, several green solvents are gaining attraction in OSN membrane fabrication, such as methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (PolarClean) [131,132], decanoic acid [133], γ-valerolactone (GVL) [134], MeSesamol [135], TamiSolve (trade name for N,N-Dimethyl Ethanolamine, produced by Eastman) [136,137], eucalyptol [43], p-cymene [138], dihydrolevoglucosenone (Cyrene), [139] and dimethyl isosorbide (DMI) [140,141]. Figure 15 presents the pricing of common organic solvents alongside a guide to their sustainability.…”

Section: Greener Solventsmentioning

confidence: 99%

Hollow Fiber Membrane Modification by Interfacial Polymerization for Organic Solvent Nanofiltration

Alammar,

Choi,

Buonomenna

2024

Processes

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Hollow fiber (HF) organic solvent nanofiltration (OSN) membranes have recently attracted significant interest in the field of membrane technology. Their popularity stems from comparative advantages, such as high packing density, fouling resistance, and easier scalability for larger applications, unlike flat-sheet/spiral-wound OSN membranes, which may present challenges in these aspects. The combination of interfacial polymerization (IP) and HF configuration has opened up new opportunities for developing advanced membranes with enhanced separation performance that can be tailored for various OSN applications. The objective of this review is to discuss the latest advancements in developing thin film composite (TFC) HF membranes, with a focus on the IP method. Novel materials and processes are discussed in detail, emphasizing the fabrication of greener, interfacially polymerized HF OSN membranes. In addition, the commercial viability and limitations of TFC HF membranes are highlighted, providing perspectives on future research directions.

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“…When alcohols are used as the HBD solvent, cyclohexanone (CHN), cyclopentanone (CPN), many kinds of esters, GBL, GVL, eucalytol (water insoluble), or possibly MeSesamol (water insoluble) [305] or diformylxylose [306] are candidates. Furthermore, interesting HBA-HBA combinations, such as Cyrene-Cygnet 0.0, are being suggested for polymer syntheses [303] to replace hazardous dipolar aprotic solvents, and these types of HBA-HBA mixed solvents could have advantages in processing APIs.…”

Section: Kamlet-taft Parameter Windows For Apismentioning

confidence: 99%

Solvent Replacement Strategies for Processing Pharmaceuticals and Bio-Related Compounds—A Review

Lee,

Chong,

Ota

et al. 2024

Liquids

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An overview of solvent replacement strategies shows that there is great progress in green chemistry for replacing hazardous di-polar aprotic solvents, such as N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), and 1,4-dioxane (DI), used in processing active industrial ingredients (APIs). In synthetic chemistry, alcohols, carbonates, ethers, eucalyptol, glycols, furans, ketones, cycloalkanones, lactones, pyrrolidinone or solvent mixtures, 2-methyl tetrahydrofuran in methanol, HCl in cyclopentyl methyl ether, or trifluoroacetic acid in propylene carbonate or surfactant water (no organic solvents) are suggested replacement solvents. For the replacement of dichloromethane (DCM) used in chromatography, ethyl acetate ethanol or 2-propanol in heptanes, with or without acetic acid or ammonium hydroxide additives, are suggested, along with methanol acetic acid in ethyl acetate or methyl tert-butyl ether, ethyl acetate in ethanol in cyclohexane, CO2-ethyl acetate, CO2-methanol, CO2-acetone, and CO2-isopropanol. Supercritical CO2 (scCO2) can be used to replace many organic solvents used in processing materials from natural sources. Vegetable, drupe, legume, and seed oils used as co-extractants (mixed with substrate before extraction) can be used to replace the typical organic co-solvents (ethanol, acetone) used in scCO2 extraction. Mixed solvents consisting of a hydrogen bond donor (HBD) solvent and a hydrogen bond acceptor (HBA) are not addressed in GSK or CHEM21 solvent replacement guides. Published data for 100 water-soluble and water-insoluble APIs in mono-solvents show polarity ranges appropriate for the processing of APIs with mixed solvents. When water is used, possible HBA candidate solvents are acetone, acetic acid, acetonitrile, ethanol, methanol, 2-methyl tetrahydrofuran, 2,2,5,5-tetramethyloxolane, dimethylisosorbide, Cyrene, Cygnet 0.0, or diformylxylose. When alcohol is used, possible HBA candidates are cyclopentanone, esters, lactone, eucalytol, MeSesamol, or diformylxylose. HBA—HBA mixed solvents, such as Cyrene—Cygnet 0.0, could provide interesting new combinations. Solubility parameters, Reichardt polarity, Kamlet—Taft parameters, and linear solvation energy relationships provide practical ways for identifying mixed solvents applicable to API systems.

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MeSesamol, a bio-based and versatile polar aprotic solvent for organic synthesis and depolymerization

Cited by 7 publications

References 66 publications

A novel recyclable organocatalyst for the gram-scale enantioselective synthesis of (S)-baclofen

A novel recyclable organocatalyst for the gram-scale enantioselective synthesis of (S)-baclofen

Hollow Fiber Membrane Modification by Interfacial Polymerization for Organic Solvent Nanofiltration

Solvent Replacement Strategies for Processing Pharmaceuticals and Bio-Related Compounds—A Review

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