652-67-5Relevant articles and documents
Heterogeneous cyclization of sorbitol to isosorbide catalyzed by a novel basic porous polymer-supported ionic liquid
Wang, Yao-Feng,Xu, Bao-Hua,Du, Yi-Ran,Zhang, Suo-Jiang
, p. 59 - 66 (2018)
In this study, heterogeneous cyclization of sorbitol to isosorbide under basic condition was realized for the first time with a novel porous polymer-supported ionic liquid as catalyst. These polymer-supported ILs were synthesized through the suspension polymerization of 4-vinylbenzyl chloride and divinylbenzene, followed by a quaternization reaction. As compared to those of non-porous, the porous polymers had high specific surface area and large number of active sites. Consequently, they exhibited excellent catalytic activity in the cyclization of sorbitol with dimethylcarbonate (DMC) to isosorbide. As a result, a high conversion of sorbitol (99%) was achieved with 83% yield of isosorbide under optimized conditions. Importantly, the catalysts could be easily separated by decantation and reused for five times without obvious loss of catalytic activity.
Aqueous-phase hydrodeoxygenation of sorbitol with Pt/SiO2-Al2O3: Identification of reaction intermediates
Li, Ning,Huber, George W.
, p. 48 - 59 (2010)
Aqueous-phase hydrodeoxygenation of sugar and sugar-derived molecules can be used to produce a range of alkanes and oxygenates. In this paper, we have identified the reaction intermediates and reaction chemistry for the aqueous-phase hydrodeoxygenation of sorbitol over a bifunctional catalyst (Pt/SiO2-Al2O3) that contains both metal (Pt) and acid (SiO2-Al2O3) sites. A wide variety of reactions occur in this process including C{single bond}C bond cleavage, C{single bond}O bond cleavage, and hydrogenation reactions. The key C{single bond}C bond cleavage reactions include: retro-aldol condensation and decarbonylation, which both occur on metal catalytic sites. Dehydration is the key C{single bond}O bond cleavage reaction and occurs on acid catalytic sites. Sorbitol initially undergoes dehydration and ring closure to produce cyclic C6 molecules or retro-aldol condensation reactions to produce primarily C3 polyols. Isosorbide is the major final product from sorbitol dehydration. Isosorbide then undergoes ring opening hydrogenation reactions and a dehydration/hydrogenation step to form 1,2,6-hexanetriol. The hexanetriol is then converted into hexanol and hexane by dehydration/hydrogenation. Smaller oxygenates are produced by C{single bond}C bond cleavage. These smaller oxygenates undergo dehydration/hydrogenation reactions to produce alkanes from C1-C5. The results from this paper suggest that hydrodeoxygenation chemistry can be tuned to make a wide variety of products from biomass-derived oxygenates.
METHOD FOR PURIFICATION OF ISOSORBIDE
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Page/Page column 14; 15, (2021/02/26)
The invention relates to a process for purifying a crude isosorbide, in which the crude isosorbide is melted and converted, by cooling, into a crude isosorbide melt suspension consisting of isosorbide crystals and residual melt, the amount by weight of impurities in the isosorbide crystals being less than the amount by weight of impurities in the residual melt, optionally a part of the residual melt is separated off mechanically from the crude isosorbide suspension, further the isosorbide crystals in the melt isosorbide suspension are purified from residual melt by washing with a washing isosorbide melt, the amount by weight of impurities in the washing isosorbide melt being less than the amount by weight of impurities in the residual melt.
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.
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.
Direct Amination of Isohexides via Borrowing Hydrogen Methodology: Regio- and Stereoselective Issues
Bahé, Florian,Grand, Lucie,Cartier, Elise,Jacolot, Ma?wenn,Moebs-Sanchez, Sylvie,Portinha, Daniel,Fleury, Etienne,Popowycz, Florence
supporting information, p. 599 - 608 (2020/02/04)
The regio and diastereoselective direct mono or diamination of bio-based isohexides (isosorbide and isomannide) has been developed through borrowing hydrogen (BH) methodology using a cooperative catalysis between an iridium complex and a Br?nsted acid. The access to chiral amino-alcohol (NH2-OH) and diamine (NH2-NH2), interesting optically pure bio-based monomers, was also proposed using BH strategy as a sustainable route for their obtention.
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
Biological upgrading of 3,6-anhydro-l-galactose from agarose to a new platform chemical
Kim, Dong Hyun,Liu, Jing-Jing,Lee, Jae Won,Pelton, Jeffrey G.,Yun, Eun Ju,Yu, Sora,Jin, Yong-Su,Kim, Kyoung Heon
, p. 1776 - 1785 (2020/03/26)
Recently, the utilization of renewable biomass instead of fossil fuels for producing fuels and chemicals has received much attention due to the global climate change. Among renewable biomass, marine algae are gaining importance as third generation biomass feedstocks owing to their advantages over lignocellulose. Particularly, red macroalgae have higher carbohydrate contents and simpler carbohydrate compositions than other marine algae. In red macroalgal carbohydrates, 3,6-anhydro-l-galactose (AHG) is the main sugar composing agarose along with d-galactose. However, AHG is not a common sugar and is chemically unstable. Thus, not only AHG but also red macroalgal biomass itself cannot be efficiently converted or utilized. Here, we biologically upgraded AHG to a new platform chemical, its sugar alcohol form, 3,6-anhydro-l-galactitol (AHGol), an anhydrohexitol. To accomplish this, we devised an integrated process encompassing a chemical hydrolysis process for producing agarobiose (AB) from agarose and a biological process for converting AB to AHGol using metabolically engineered Saccharomyces cerevisiae to efficiently produce AHGol from agarose with high titers and yields. AHGol was also converted to an intermediate chemical for plastics, isosorbide. To our knowledge, this is the first demonstration of upgrading a red macroalgal biomass component to a platform chemical via a new biological route, by using an engineered microorganism.
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.
