Reaction of oxiranes with cyclodextrins under high-energy ball-milling conditions

Jicsinszky, László; Calsolaro, Federica; Martina, Katia; Bucciol, Fabio; Manzoli, Maela; Cravotto, Giancarlo

doi:10.3762/bjoc.15.145

Cited by 11 publications

(20 citation statements)

References 30 publications

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“…The article mentions that a small amount of water can be used to knead the mixture to prepare a paste solution, which has potential in the treatment of biologically active phenolic compounds, the purification of wastewater or the reuse of agricultural waste. Giancarlo Cravotto et al [ 41 ] used low-boiling epoxy reagents in high-energy ball mills (HEBM) to simplify the preparation and purification of low-substitution (2-hydroxy) propylated β-and γ-cyclodextrins (β/γ-CDs). Compared with traditional methods, the properties of mechanically synthesized pCD, such as the degree of complexation, are different, and most of them are better.…”

Section: Synthesis Of Pcdsmentioning

confidence: 99%

Research Progress on Synthesis and Application of Cyclodextrin Polymers

et al. 2021

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Cyclodextrins (CDs) are a series of cyclic oligosaccharides formed by amylose under the action of CD glucosyltransferase that is produced by Bacillus. After being modified by polymerization, substitution and grafting, high molecular weight cyclodextrin polymers (pCDs) containing multiple CD units can be obtained. pCDs retain the internal hydrophobic-external hydrophilic cavity structure characteristic of CDs, while also possessing the stability of polymer. They are a class of functional polymer materials with strong development potential and have been applied in many fields. This review introduces the research progress of pCDs, including the synthesis of pCDs and their applications in analytical separation science, materials science, and biomedicine.

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Section: Synthesis Of Pcdsmentioning

confidence: 99%

Research Progress on Synthesis and Application of Cyclodextrin Polymers

et al. 2021

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“…BM reactions are suitable for the synthesis of SiO 2 /CD composites [91] and chemically stable CD polymers [85,92]. The water and pH more sensitive CD-nanosponge preparations are also an excellent target of the mechanochemical syntheses.…”

Section: Mechanochemical Transformation In Millsmentioning

confidence: 99%

Toward a Greener World—Cyclodextrin Derivatization by Mechanochemistry

Jicsinszky

Cravotto

2021

Molecules

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Cyclodextrin (CD) derivatives are a challenge, mainly due to solubility problems. In many cases, the synthesis of CD derivatives requires high-boiling solvents, whereas the product isolation from the aqueous methods often requires energy-intensive processes. Complex formation faces similar challenges in that it involves interacting materials with conflicting properties. However, many authors also refer to the formation of non-covalent bonds, such as the formation of inclusion complexes or metal–organic networks, as reactions or synthesis, which makes it difficult to classify the technical papers. In many cases, the solubility of both the starting material and the product in the same solvent differs significantly. The sweetest point of mechanochemistry is the reduced demand or complete elimination of solvents from the synthesis. The lack of solvents can make syntheses more economical and greener. The limited molecular movements in solid-state allow the preparation of CD derivatives, which are difficult to produce under solvent reaction conditions. A mechanochemical reaction generally has a higher reagent utilization rate. When the reaction yields a good guest co-product, solvent-free conditions can be slower than in solution conditions. Regioselective syntheses of per-6-amino and alkylthio-CD derivatives or insoluble cyclodextrin polymers and nanosponges are good examples of what a greener technology can offer through solvent-free reaction conditions. In the case of thiolated CD derivatives, the absence of solvents results in significant suppression of the thiol group oxidation, too. The insoluble polymer synthesis is also more efficient when using the same molar ratio of the reagents as the solution reaction. Solid reactants not only reduce the chance of hydrolysis of multifunctional reactants or side reactions, but the spatial proximity of macrocycles also reduces the length of the spacing formed by the crosslinker. The structure of insoluble polymers of the mechanochemical reactions generally is more compact, with fewer and shorter hydrophilic arms than the products of the solution reactions.

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“…Finally, we attempted the ring opening of epoxide using ball milling, a mecanosynthesis technique widely used in green chemistry [12,13]. Very recently, Cravotto et al [14] described ring opening of low-boiling epoxides by CDs under high-energy ball milling conditions and in the presence of NaOH, leading to well-known HP-β-CD, HP-γ-CD and epichlorhydrin cross-linked CD-polymers. We tried to initiate the opening reaction of methyl oleate epoxide by β-CD with various bases and acids in the absence of solvent.…”

Section: Scheme 1 Epoxidation Reaction Of Methyl Oleatementioning

confidence: 99%

“…Indeed, activation modes such as ultrasound [8,9], microwaves [10,11], or mechanochemistry [12] are considered as useful green tools for the chemical modification of cyclodextrins. Cravotto et al reported some works where ball milling is used to obtain well-known CD derivatives but under green and solventless conditions and with better yields [13,14]. Very few examples of more specific regioselectivity induced by mechanochemistry are reported.…”

Section: Introductionmentioning

confidence: 99%

New Lipidyl-Cyclodextrins Obtained by Ring Opening of Methyl Oleate Epoxide Using Ball Milling

et al. 2020

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Bearing grafts based on fatty esters derivatives, lipidyl-cyclodextrins (L-CDs) are compounds able to form water-soluble nano-objects. In this context, bicatenary biobased lipidic-cyclodextrins of low DS were easily synthesized from a fatty ester epoxide by means of alternative methods (ball-milling conditions, use of enzymes). The ring opening reaction of methyl oleate epoxide needs ball-milling and is highly specific of cyclodextrins in solventless conditions. L-CDs are thus composed of complex mixtures that were deciphered by an extensive structural analysis using mainly mass spectrometry and NMR spectroscopy. In addition, as part of their potential use as vectors of active drugs, these products were submitted to an integrity study on in vitro model of the blood-brain-barrier (BBB) and the intestinal epithelium. No toxicity has been observed, suggesting that applications for the vectorization of active ingredients can be expected.

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Reaction of oxiranes with cyclodextrins under high-energy ball-milling conditions

Cited by 11 publications

References 30 publications

Research Progress on Synthesis and Application of Cyclodextrin Polymers

Research Progress on Synthesis and Application of Cyclodextrin Polymers

Toward a Greener World—Cyclodextrin Derivatization by Mechanochemistry

New Lipidyl-Cyclodextrins Obtained by Ring Opening of Methyl Oleate Epoxide Using Ball Milling

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