53648-56-9Relevant articles and documents
Sequential dehydration of sorbitol to isosorbide over acidified niobium oxides
Guo, Jiaxing,Huang, Long,Li, Cuiqing,Liu, Shanshan,Song, Yongji,Wang, Xincheng
, p. 4226 - 4234 (2021/06/30)
Isosorbide is a bio-based functional diol, which is prepared by sequential dehydration of sorbitol and widely used in plasticizers, monomers, solvents or pharmaceuticals. In this study, a variety of acidified Nb2O5catalysts were prepared and used for the sequential dehydration of sorbitol to isosorbide. Acidification can effectively regulate the surface acidity of catalysts, which was measured by pyridine infrared spectroscopy and NH3-TPD analysis. The catalytic performance was related to the surface acidity, including the reaction temperature and the amount of catalysts. After optimization of reaction conditions, the yield of isosorbide reached 84.1% with complete sorbitol conversion during reaction at 150 °C for 3 h over 2 M sulfuric acid modified Nb2O5. Finally, the reaction mechanism regarding the role of Lewis acid sites was discussed. This study is of great significance for further development of an efficient catalytic system for the dehydration of carbohydrates to isosorbide.
Efficient and selective aqueous photocatalytic mono-dehydration of sugar alcohols using functionalized yttrium oxide nanocatalysts
Cheng, Yu,Fan, Chao,Guo, Lina,Huang, Benhua,Li, Xiaoyong,Luque, Rafael,Ma, Xiaomo,Meng, Xu,Pan, Cheng,Sun, Yang,Yang, Juncheng,Zhang, Junjie,Zhang, Weining,Zheng, Aqun
, p. 5333 - 5344 (2020/09/17)
The mono-dehydration of sugar alcohols such as d-sorbitol and d-mannitol generates 1,4-sorbitan and 1,4-mannitan, respectively, which are relevant platform molecules for the synthesis of detergents and pharmaceuticals. Most reported catalytic systems provided access to di-dehydrated products, while mono-dehydration required special efforts, particularly regarding selectivity and reaction temperature. A series of functionalized yttrium oxides were prepared via sol-gel synthesis in this work, which not only showed an interesting micropipe-like morphology, but also contained functional components. These materials were investigated as photocatalysts in the dehydration of d-sorbitol and d-mannitol, exhibiting high selectivity to mono-dehydration. The effects of solvent, temperature and catalyst were fully discussed. A catalytic mechanism was proposed based on the experimental results and calculations.
METHOD FOR PREPARATION OF 1,4-SORBITAN IN AQUEOUS MEDIUM
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Page/Page column 11, (2020/07/31)
The invention discloses a method for preparation of 1,4-sorbitan by dehydration of D-sorbitol in aqueous medium, wherein one equivalent of water is removed and a cyclization occurs, followed by a treatment with ethanol and isopropanol.
Direct conversion of cellulose into isosorbide over Ni doped NbOPO4catalysts in water
Guo, Jiaxing,He, Minyao,Li, Cuiqing,Liu, ShanShan,Song, Yongji,Wang, Hong,Wang, Xincheng
supporting information, p. 10292 - 10299 (2020/07/14)
Isosorbide is a versatile chemical intermediate for the production of a variety of drugs, chemicals, and polymers, and its efficient production from natural cellulose is of great significance. In this study, bifunctional catalysts based on niobium phosphates were prepared by a facile hydrothermal method and used for the direct conversion of cellulose to isosorbide under aqueous conditions. NH3-TPD analysis showed that a high acid content existed on the catalyst surface, and pyridine infrared spectroscopic analysis confirmed the presence of both Lewis acid and Br?nsted acid sites, both of which played an important role in the process of carbohydrate conversion. XRD and H2-TPR characterization determined the composition and the hydrogenation centers of the catalyst. An isosorbide yield of 47% could be obtained at 200 °C for 24 h under 3 MPa H2 pressure. The Ni/NbOPO4 bifunctional catalyst retains most of its activity after five consecutive runs with slightly decreased isosorbide yield of 44%. In addition, a possible reaction mechanism was proposed that the synergistic effect of surface acid sites and hydrogenation sites was favorable to enhancing the cascade dehydration and hydrogenation reactions during the conversion of cellulose to isosorbide. This study provides as an efficient strategy for the development of novel multifunctional heterogeneous catalysts for the one-pot valorisation of cellulose. This journal is
Kinetic analyses of intramolecular dehydration of hexitols in high-temperature water
Yamaguchi, Aritomo,Mimura, Naoki,Shirai, Masayuki,Sato, Osamu
, (2019/11/29)
Intramolecular dehydration of the biomass-derived hexitols D-sorbitol, D-mannitol, and galactitol was investigated. These reactions were performed in high-temperature water at 523–573 K without added acid catalyst. The rate constants for the dehydration steps in the reaction networks were determined at various reaction temperatures, and the activation energies and pre-exponential factors were calculated from Arrhenius plots. The yield of each product was estimated as a function of reaction time and temperature using the calculated rate constants and activation energies. The maximum yield of each product from the dehydration reactions was predicted over a range of reaction time and temperature, allowing the selective production of these important platform chemicals.
Catalytic dehydration of sorbitol to isosorbide in the presence of metal tosylate salts and metallized sulfonic resins
Dussenne, Corentin,Wyart, Hervé,Wiatz, Vincent,Suisse, Isabelle,Sauthier, Mathieu
, p. 61 - 66 (2018/12/11)
Homogeneous catalytic dehydration of sorbitol to isosorbide has been performed with a series of metal tosylates as catalysts. Conversions up to 100 % and selectivities into isosorbide up to 67% were obtained with Bi(OTs)3. The metals were exchanged with acidic sites of sulfonic resins and the resulting materials were evaluated as heterogeneous catalysts. On the contrary to their homogeneous counter parts, the heterogenized metal sites are non-active. The catalytic activity of the modified resins was systematically diminished in comparison to the native resins. The inhibition is greatly dependent on the nature of the metal and, on a larger extent, of the used resin for the cation exchange.
Confinement of Br?nsted acidic ionic liquids into covalent organic frameworks as a catalyst for dehydrative formation of isosorbide from sorbitol
Du, Yi-Ran,Xu, Bao-Hua,Pan, Jia-Sheng,Wu, Yi-Wei,Peng, Xiao-Ming,Wang, Yao-Feng,Zhang, Suo-Jiang
supporting information, p. 4792 - 4799 (2019/09/09)
The confinement of Br?nsted acidic 1-methyl-3-(3-sulfopropyl)-1H-imidazol-3-ium hydrosulfate ([PSMIm][HSO4]) into the channel walls of two-dimensional (2D) COFs using a one-pot self-assembly strategy was achieved by incorporating an imine-linked TPB-DMTP-COF (TPB, triphenylbenzene; DMTP, dimethoxyterephthaldehyde) as the host. An appropriate loading of [PSMIm][HSO4] is crucial for the BIL-COF hybrids to maintain proper geometry in the channel and sufficient acidic sites for the sorbitol substrate and sorbitan intermediate to enter and react. The best yield of isosorbide (97%) from sorbitol to date was obtained in the presence of BIL-COF-30 as the catalyst under optimized conditions. Besides, BIL-COF-30 can be recycled for at least five runs without activity loss.
Effect of carbon chain length on catalytic C–O bond cleavage of polyols over Rh-ReOx/ZrO2 in aqueous phase
Besson, Michèle,Da Silva Perez, Denilson,Perret, Noémie,Pinel, Catherine,Sadier, Achraf
, (2019/08/30)
Production of linear deoxygenated C4 (butanetriols, -diols, and butanols), C5 (pentanetetraols, -triols, -diols, and pentanols), and C6 products (hexanepentaols, -tetraols, -triols, -diols, and hexanols) is achievable by hydrogenolysis of erythritol, xylitol, and sorbitol over supported-bimetallic Rh-ReOx (Re/Rh molar ratio 0.5) catalyst, respectively. After validation of the analytical methodology, the effect of some reaction parameters was studied. In addition to C–O bond cleavage by hydrogenolysis, these polyols can undergo parallel reactions such as epimerization, cyclic dehydration, and C–C bond cleavage. The time courses of each family of linear deoxygenated C4, C5, and C6 products confirmed that the sequence of appearance of the different categories of deoxygenated products followed a multiple sequential deoxygenation pathway. The highest selectivity to a mixture of linear deoxygenated C4, C5, and C6 products at 80percent conversion was favoured under high pressure in the presence of 3.7wt.percentRh-3.5wt.percentReOx/ZrO2 catalysts (54–71percent under 80 bar) at 200 °C.
Harnessing the reactivity of poly(methylhydrosiloxane) for the reduction and cyclization of biomass to high-value products
Hein, Nicholas M.,Seo, Youngran,Lee, Stephen J.,Gagné, Michel R.
supporting information, p. 2662 - 2669 (2019/06/13)
Poly(methylhydrosiloxane) (PMHS) has been examined for its ability to reduce and subsequently cyclize carbohydrate substrates using catalytic tris(pentafluorophenyl)borane (BCF). The work herein is the first reported example of the direct conversion of monosaccharides to 1,4-anhydro and 2,5-anhydro products utilizing a hydrosiloxane reducing agent. PMHS is produced from waste products of the silicone industry, making it a green alternative to traditional hydrosilane reducing agents. This work thus contributes to the goal of utilizing renewable feedstocks in the production of fine-chemicals.
A strategy of ketalization for the catalytic selective dehydration of biomass-based polyols over H-beta zeolite
Che, Penghua,Lu, Fang,Si, Xiaoqin,Ma, Hong,Nie, Xin,Xu, Jie
supporting information, p. 634 - 640 (2018/02/14)
Biomass contains plentiful hydroxyl groups that lead to an oxygen-rich structure compared to petroleum-based chemicals. Dehydration is the most energy-efficient technique to remove oxygen; however, multiple similar vicinal hydroxyl groups in sugar alcohols impose significant challenges for their selective dehydration. Here, we present a novel strategy to control the etherification site in sugar alcohols by the ketalization of the vicinal-diol group for the highly selective formation of tetrahydrofuran derivatives. A ketone firstly reacts with terminal vicinal hydroxyl groups to form the 1,3-dioxolane structure. This structure of the constrained 1,3-dioxolane ring would improve the accessibility of reactive groups to facilitate intramolecular etherification. As a better leaving group than water, the ketone can also promote intramolecular etherification. Consequently, a range of tetrahydrofuran derivatives are produced in excellent yields with the H-beta zeolite catalyst under mild reaction conditions. This strategy opens up new opportunities for the efficient upgrading of biomass via the modification or protection of hydroxyl groups.
