100-79-8Relevant articles and documents
Acetalisation of bio-glycerol with acetone to produce solketal over sulfonic mesostructured silicas
Vicente, Gemma,Melero, Juan A.,Morales, Gabriel,Paniagua, Marta,Martin, Eric
, p. 899 - 907 (2010)
Sulfonic acid-functionalized mesostructured silicas have demonstrated excellent catalytic behaviour in the acetalisation of glycerol with acetone to yield 2,2-dimethyl-1,3-dioxolane-4-methanol, also known as solketal. This molecule constitutes an excellent compound for the formulation of gasoline, diesel and biodiesel fuels. The activity achieved with arenesulfonic acid-functionalized silica is comparable to that displayed by Amberlyst-15. Optimal production of solketal over arenesulfonic acid mesostructured silica has been established for a reaction system consisting of three consecutive 2-step batches (30 min under reflux and an evaporation step under vacuum), and using a 6/1 acetone/glycerol molar ratio. The use of lower grades of glycerol, such as technical (purity of 91.6 wt%) and crude (85.8 wt%) glycerol, has also provided high conversions of glycerol over sulfonic acid-modified heterogeneous catalysts (84% and 81%, respectively). For refined and technical glycerol the catalysts have been reused, without any regeneration treatment, up to three times, keeping the high initial activity. However, the high sodium content in crude glycerol deactivates the sulfonic acid sites by cation exchange. This deactivation is readily reversed by simple acidification of the catalyst after reaction.
Selective glycerol transformations to high value-added products catalysed by aluminosilicate-supported iron oxide nanoparticles
Gonzalez-Arellano, Camino,De, Sudipta,Luque, Rafael
, p. 4242 - 4249 (2014)
Conversion of glycerol to cyclic acetals (with paraformaldehyde, benzaldehyde, furfural and acetone) and to mono-, di- and triacetylglycerides (with levulinic acid) was investigated using a supported iron oxide nanoparticle system of a mesoporous aluminosilicate heterogeneous catalyst (Fe/Al-SBA-15). The effect of various parameters on the reaction, temperature, mol% of catalyst or ratio of glycerol:substrate were studied. An optimization of the reaction conditions carried out with glycerol by means of experimental design methodology showed that a very high glycerol conversion (99%) and high combined selectivity toward di- and triacetylglycerides could be obtained under optimized conditions. All of the acetalisation reactions carried out at 100 °C also gave good to excellent conversions and selectivities to target products, illustrating the potential of Fe/Al-SBA-15 as a highly active, stable and reusable heterogeneous catalyst in glycerol acid-catalysed transformations.
Intramolecular Chirality Transfer [2 + 2] Cycloadditions of Allenoates and Alkenes
Xu, Yao,Hong, Young J.,Tantillo, Dean J.,Brown, M. Kevin
, p. 3703 - 3706 (2017)
Intramolecular chirality transfer [2 + 2] cycloaddition of enantiomerically enriched allenoates and alkenes is presented. The use of a chiral catalyst was found to be critical to achieve high levels of diastereoselectivity compared to use of an achiral catalyst. The method developed leads to highly substituted cyclobutanes that would be difficult to prepare by alternative methods.
Solventless acetalization of glycerol with acetone to fuel oxygenates over Ni-Zr supported on mesoporous activated carbon catalyst
Khayoon,Hameed
, p. 191 - 199 (2013)
Glycerol was selectively converted to branched oxygenated compounds (five membered ring solketal, 5, and six membered ring acetal, 6) through a solventless acetalization process with acetone catalyzed by mesoporous 5%Ni-1%Zr/AC catalyst. The reaction was carried out under nitrogen flow conditions using 0.20 g of catalyst at 45 C. The conversion of glycerol was almost complete with corresponding selectivity of 26% and 74% toward 5 and 6 components, respectively. The catalytic activity was mainly attributed to the intercalated NiO and ZrO2 species into the AC structure and to the surface characteristics as well. Zirconium species are essential co-catalysts with Ni species. The prepared catalysts were characterized for their intrinsic physicochemical and textural properties using BET surface area, XRD, XPS, TPR, FTIR, and EDX. The effect of different operational parameters such as reaction temperature, molar ratio of glycerol/acetone, catalyst weight and reaction time was investigated. The stability of the catalytic activity was examined through leaching and reusability tests.
Toward sustainable and eco-efficient novel catalytic distillation process for production of solketal using seepage catalytic packing internal
Cong, Haifeng,Gao, Xin,Lai, Jianing,Li, Hong,Li, Xingang,Shu, Chang,Wang, Yiwei,Zhao, Runnan
, (2020)
The initial aim of this paper is to dramatically improve the post-treatment stage of biodiesel production, which converts problematic glycerol to solketal (SK), by introduction of an eco-efficient integrated reactive and dividing wall distillation process. To overcome the chemical equilibrium limitations and the long post-treatment process with the high energy consumption and waste water emission, this study provides the potentially, sustainable and novel reactive distillation (RD) process for cleanly catalytic synthesis of SK, taking into account costs and environmental impact. The ketalization kinetics experiments were carried out to provide a basis for subsequent experiments and simulations. A reliable model was established for further RD technological design and validated by the pilot-scale experiments. Through sensitivity analysis, the effects of multiplex parameters in RD process were determined. The advanced intensification of SK production by reactive dividing wall column (RDWC) achieves reduction in energy, total annual cost (TAC) and CO2 emissions of 13.9 %, 18.2 % and 16.4 % (as oil resources), respectively, compared to the optimal SK production by RD process. This proposed technology is also compared with the conventional industrial route of ketalization with 18.7 % energy saving.
Selective cleavage of ethers using silica-alumina gel catalysts prepared by the sol-gel method
Matsumoto, Yoshihiko,Mita, Keisuke,Hashimoto, Keiji,Iio, Hideo,Tokoroyama, Takashi
, p. 9387 - 9398 (1996)
The selective cleavage of tetrahydropyranyl (THP), methoxymethyl (MOM), 1-ethoxyethyl (EE), 1-methyl-1-methoxyethyl (MME) and trimethylsilyl (TMS) ether groups with silica-alumina gels prepared by the sol-gel method has been investigated. The deprotection rate follows the order: TMS > MME >>, EE > THP >> MOM. The selective deprotection of diol derivatives with mixed protecting groups was achieved efficiently. Bis-THP and bis-MOM ether derivatives of a substrate which contained a primary and a tertiary hydroxyl groups were mono- deprotected with moderate selectivity. The selective deprotection of glycerol ethers was also examined. The silica-alumina gels prepared by the sol-gel method are thus shown to be a good catalyst for selective cleavage of ether protecting groups giving the product in a simple manner under mild conditions.
Choice of a catalyst and technological scheme for synthesis of solketal
Dmitriev,Terekhov,Zanaveskin,Khadzhiev,Zanaveskin,Maksimov
, p. 1619 - 1624 (2016)
Results are presented obtained in tests of various homogeneous and heterogeneous catalysts in a synthesis of solketal (2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane). It is shown that, all other conditions being the same, the highest catalytic activity is observed for sulfuric acid and beta zeolite. Data are presented on how the equilibrium constant of the reaction of glycerol ketalization depends on temperature. A technological scheme of the process for synthesis of solketal is suggested and its description is presented.
Investigations on heterogeneously catalysed condensations of glycerol to cyclic acetals
Deutsch,Martin,Lieske
, p. 428 - 435 (2007)
The acid-catalysed condensation of glycerol, a chemical from renewable materials, with benzaldehyde, formaldehyde, acetone (acetalisation), and their dimethyl acetals (transacetalisation) to mixtures of [1,3]dioxan-5-ols and [1,3]dioxolan-4-yl-methanols was investigated. Various solid acids were evaluated as heterogeneous catalysts for the desired glycerol conversion into these potential novel platform chemicals. [1,3]dioxan-5-ols are of particular interest as precursors for 1,3-propanediol derivatives. Therefore, the reported investigations were focused on the identification of reaction conditions that promote the formation of [1,3]dioxan-5-ols and suppress the formation of [1,3]dioxolan-4-yl-methanols.
Synthesis of glycerol-derived 4-alkyl-substituted 1,2,3-triazoles and evaluation of their fungicidal, phytotoxic, and antiproliferative activities
Costa, Adilson V.,Moreira, Luiza C.,Pinto, Roberta T.,Alves, Thammyres A.,Schwan, Vitor V.,de Queiroz, Vagner T.,Pra?a-Fontes, Milene M.,Teixeira, Róbson Ricardo,Morais, Pedro A.B.,de Jesus, Waldir C.
, p. 821 - 832 (2020)
Herein, the synthesis of nine novel glycerol-derived 4-alkyl-substituted 1,2,3-triazoles, using the CuI-catalyzed alkyne-azide cycloaddition reaction as the key step, is reported. The triazoles were characterized by infrared and nuclear magnetic resonance (NMR 1H and 13C) spectroscopy and mass spectrometry. The nine prepared compounds were evaluated with regard to their phytotoxic, antiproliferative, and fungicidal activities. The fungicidal activity was assessed on Colletotrichum gloeosporioides, the causative agent of papaya anthracnose. All compounds presented high efficiency (comparable to the commercial fungicide tebuconazole) in inhibiting C. gloeosporioides sporulation. The phytotoxicity of the triazoles was assessed against Lactuca sativa. Germination was the less-affected parameter, whereas the most pronounced effects of the triazoles were on the germination speed index and root growth of the L. sativa seedlings. As indicators of antiproliferative activity, the mitotic index was evaluated along with chromosomal and nuclear alterations, all of which were influenced to different degrees by the triazoles. In addition, all derivatives demonstrated aneugenic and clastogenic actions in meristematic cells of L. sativa roots. Therefore, these 4-alkyl-substituted triazoles may represent a scaffold to be explored for the development of new fungicidal agents.
Surface-functionalized mesoporous gallosilicate catalysts for the efficient and sustainable upgrading of glycerol to solketal
Vivian, Alvise,Soumoy, Loraine,Fusaro, Luca,Fiorilli, Sonia,Debecker, Damien P.,Aprile, Carmela
, p. 354 - 366 (2021)
Two series of functionalized mesoporous Ga silicates were prepared in a straightforward and sustainable one-pot procedure using different alkyl silanes. The efficacy of the adopted co-synthetic approach based on aerosol processing has been proved by 29Si solid-state NMR experiments revealing a degree of functionalization close to the theoretical value. The successful incorporation of gallium as single sites within the silica framework was confirmed via71Ga solid-state magic-angle-spinning NMR measurements. These materials were tested as catalysts for the synthesis of solketal from glycerol at low temperature and under solventless conditions. A systematic study evidenced the importance of a careful tuning of surface polarity, achievable with surface functionalization as well as with different thermal treatments. The solids functionalized with a low degree of methyl groups (5%) displayed enhanced performances compared to the non-functionalized analogues, highlighting the highly beneficial role of surface hydrophobicity as well as the importance of the careful tuning of the hydrophilic/hydrophobic balance. The best functionalized catalysts proved to be easily reusable for multiple catalytic runs. With such a high-performance catalyst in hand, we propose a process which shows a favorable E-factor, indicating that the production of solketal can be envisaged in a sustainable way.
