623-39-2Relevant articles and documents
Regioselective Ring-Opening of Glycidol to Monoalkyl Glyceryl Ethers Promoted by an [OSSO]-FeIII Triflate Complex
Monica, Francesco Della,Ricciardi, Maria,Proto, Antonio,Cucciniello, Raffaele,Capacchione, Carmine
, p. 3448 - 3452 (2019/08/01)
A FeIII-triflate complex, bearing a bis-thioether-di-phenolate [OSSO]-type ligand, was discovered to promote the ring-opening of glycidol with alcohols under mild reaction conditions (0.05 mol % catalyst and 80 °C). The reaction proceeded with high activity (initial turnover frequency of 1680 h?1 for EtOH) and selectivity (>95 %) toward the formation of twelve monoalkyl glyceryl ethers (MAGEs) in a regioselective fashion (84–96 % yield of the non-symmetric regioisomer). This synthetic approach allows the conversion of a glycerol-derived platform molecule (i.e., glycidol) to high-value-added products by using an Earth-crust abundant metal-based catalyst.
Hydrogenation of CO2-Derived Carbonates and Polycarbonates to Methanol and Diols by Metal–Ligand Cooperative Manganese Catalysis
Zubar, Viktoriia,Lebedev, Yury,Azofra, Luis Miguel,Cavallo, Luigi,El-Sepelgy, Osama,Rueping, Magnus
supporting information, p. 13439 - 13443 (2018/09/21)
The first base-metal-catalysed hydrogenation of CO2-derived carbonates to alcohols is presented. The reaction proceeds under mild conditions in the presence of a well-defined manganese complex with a loading as low as 0.25 mol %. The non-precious-metal homogenous catalytic system provides an indirect route for the conversion of CO2 into methanol with the co-production of value-added (vicinal) diols in yields of up to 99 %. Experimental and computational studies indicate a metal–ligand cooperative catalysis mechanism.
Optimization of the synthesis of glycerol derived monoethers from glycidol by means of heterogeneous acid catalysis
Pires, Elisabet,García, José Ignacio,Leal-Duaso, Alejandro,Mayoral, José Antonio,García-Peiro, José Ignacio,Velázquez, David
, (2018/11/24)
We present an efficient and green methodology for the synthesis of glycerol monoethers, starting from glycidol and different alcohols, by means of heterogeneous acid catalysis. A scope of Br?nsted and Lewis acid catalysts were applied to the benchmark reaction of glycidol and methanol. The selected catalysts were cationic exchangers, such as Nafion NR50, Dowex 50WX2, Amberlyst 15 and K10-Montmorillonite, both in their protonic form and exchanged with Al(III), Zn(II) and Fe(III). Thus, total conversions were reached in short times by using 1 and 5% mol catalyst loading and room temperature, without the need for excess glycidol or the presence of a solvent. Finally, these conditions and the best catalysts were successfully applied to the reaction of glycidol with several alcohols such as butanol or isopropanol.
A Kinetic Model for the Epoxidation of Allyl Alcohol with Hydrogen Peroxide on Titanium Silicate TS-1
Sulimov,Danov,Ovcharova,Flid,Bruk
, p. 673 - 678 (2018/03/08)
The kinetic regularities of the oxidation of allyl alcohol into glycidol in the presence of titanium silicate are studied at varied initial concentrations of the reagents, products, and temperature. The probable mechanism is used as the basis to develop a substantial kinetic model, which adequately describes the obtained experimental data.
Synthesis of 3-alkoxypropan-1,2-diols from glycidol: Experimental and theoretical studies for the optimization of the synthesis of glycerol derived solvents
Leal-Duaso,Caballero,Urriolabeitia,Mayoral,García,Pires
, p. 4176 - 4185 (2017/09/07)
A straightforward synthetic methodology has been derived for the synthesis of glycerol monoethers from glycidol and alcohols. Several homogeneous and heterogeneous basic catalysts have been tested, the best results being obtained with readily available and inexpensive alkaline metal hydroxides. In the best case, good yield of the desired monoether is obtained under smooth reaction conditions, always with total conversion of glycidol. The selectivity of the reactions mainly depends on the alcohol used, due to the concurrence of undesired side reactions. A mechanistic study carried out through computational DFT calculations, in which solvent effects are taken into account, also complemented the experiments, has allowed to identify the main reaction paths taking place under reaction conditions, giving insights into the main causes affecting the reaction selectivity and also into how it could be improved.
Glycerol as a source of designer solvents: Physicochemical properties of low melting mixtures containing glycerol ethers and ammonium salts
Leal-Duaso, Alejandro,Pérez, Pascual,Mayoral, José A.,Pires, Elisabet,García, José I.
, p. 28302 - 28312 (2017/11/06)
In this work we report the preparation of mixtures of several alkyl glyceryl ethers, as hydrogen bond donor compounds, with two ammonium salts, choline chloride and N,N,N-triethyl-2,3-dihydroxypropan-1-aminium chloride. The stability of the mixtures at different molar ratios and temperatures has been evaluated in order to determine the formation of low melting mixtures. Liquid and stable mixtures have been characterized and their physico-chemical properties such as density, viscosity, refractive index, conductivity and surface tension have been measured in the temperature range of 293.15 K to 343.15 K. Comparison of the mixtures prepared herein with the ones containing glycerol and choline chloride evidences the possibility of tuning the physico-chemical properties by changing the substitution pattern in the hydrogen bond donor compound or in the ammonium salt, thus broadening the scope of application of these mixtures.
Synthesis of Monoalkyl Glyceryl Ethers by Ring Opening of Glycidol with Alcohols in the Presence of Lewis Acids
Cucciniello, Raffaele,Ricciardi, Maria,Vitiello, Rosa,Di Serio, Martino,Proto, Antonio,Capacchione, Carmine
, p. 3272 - 3275 (2016/12/16)
The present work deals with the production of monoalkyl glyceryl ethers (MAGEs) through a new reaction pathway based on the reaction of glycidol and alcohols catalyzed by Lewis acid-based catalysts. Glycidol is quantitatively converted with high selectivity (99 %) into MAGEs under very mild reaction conditions (80 °C and 0.01 mol % catalyst loading) in only 1 h using Al(OTf)3 or Bi(OTf)3 as catalyst. The proposed method enhances the choice of possible green synthetic approaches for the production of value-added products such as MAGEs.
Cyclic sulfates as useful tools in the asymmetric synthesis of 1-aminocyclopropane-1-carboxylic acid derivatives
Jakubowska, Anna,Zuchowski, Grzegorz,Kulig, Katarzyna
, p. 1261 - 1267 (2015/11/09)
The enantiomers of 4-(2-methoxyethyl)-1,3,2-dioxathiolane-2,2-dioxide and 4-(methoxymethyl)-1,3,2-dioxathiolane-2,2-dioxide have been used as 'epoxide-like' synthons during the asymmetric alkylation of oxazinone-derived glycine equivalents. Using a fully stereoselective synthesis, eight stereoisomers of the spiro derivatives of the glycine equivalents were obtained. The relative configurations of the spiro compounds obtained were easily determined using nuclear magnetic resonance spectroscopy and two dimensional nuclear Overhauser effect experiments. Additionally, one of the spiro derivatives obtained was hydrolyzed to its corresponding amino acid, which was a derivative of 1-aminocyclopropano-1-carboxylic acid, a very important building block that is present in many compounds, which have interesting biological activity.
Ecotoxicity studies of glycerol ethers in Vibrio fischeri: checking the environmental impact of glycerol-derived solvents
Garca,Pires,Aldea,Lomba,Perales,Giner
supporting information, p. 4326 - 4333 (2015/08/11)
The toxicities of a series of glycerol mono-, di-, and trialkyl ethers against Vibrio fischeri bacteria have been determined. A systematic study has been carried out and the possible structure-toxicity relationships have been discussed using different QSAR models. Inhibition of bioluminescence after 30 minutes of exposure shows relatively low toxicity of many of the glycerol derived chemicals studied. Results indicate that, as a general rule, the ecotoxicity increases with the length and number of substituents. However, if the size of the molecule increases, an extra substituent at position 2 makes the toxicity lower than that of the corresponding analogues.
Carbohydrate and polyol ethers as renewable oils, greases, and liquid fuels
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Page/Page column 7, (2014/05/20)
Alkyl ethers are produced directly from polyols or their salts in a single step reaction, or alternatively, the polyols are first converted to a ketal or acetal derivative which comprises at least one free hydroxyl moiety and one or more ketal or acetal moieties. In either embodiment, the polyol, its salt, or its ketal or acetal derivative is reacted with an alkylating agent to produce a first alkoxy polyol ether comprising one or more alkoxy moieties formed at the sites of the free hydroxyl moieties. Ethers prepared from the polyol ketal or acetal derivatives retain their ketal or acetal moieties, which may be hydrolyzed to additional free hydroxyls and reacted with alkylating agent to produce a second alkoxy polyol ether. Alkyl tosylates are preferred alkylating agents. The spent alkylating agents may also be recovered and regenerated. Recovered alkoxy polyol ethers may be used as renewable fuels, solvents and lubricants.
