4-O-beta-D-吡喃葡萄糖基-D-山梨糖醇 | 535-94-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 4-O-beta-D-吡喃葡萄糖基-D-山梨糖醇
• 英文名称: cellobiitol
• 英文别名: cellobitol；Cellobiotol；(2S,3R,4R,5R)-4-[(2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhexane-1,2,3,5,6-pentol
• CAS: 535-94-4
• 化学式: C₁₂H₂₄O₁₁
• 分子量: 344.316
• InChiKey: VQHSOMBJVWLPSR-WELRSGGNSA-N

物化性质

• 碰撞截面：
  174.3 Ų [M+Na]+ [CCS Type: TW, Method: calibrated with polyalanine and drug standards]

计算性质

• 辛醇/水分配系数(LogP)：
  -5.2
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  201
• 氢给体数：
  9
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  4-O-beta-D-吡喃葡萄糖基-D-山梨糖醇 在 水 、 氢气 作用下， 184.84 ℃ 、5.0 MPa 条件下， 生成 甘露醇 、 山梨醇
  参考文献：
  名称：

  Conversion of cellobiose into sorbitol in neutral water medium over carbon nanotube-supported ruthenium catalysts

  摘要：

  Carbon nanotube (CNT)-supported ruthenium catalysts were studied for the hydrogenation of cellobiose in neutral water medium. The acidity of catalysts and the size of Ru particles played key roles in the conversion of cellobiose to sorbitol. A higher concentration of nitric acid used for CNT pretreatment provided a better sorbitol yield, suggesting an important role of catalyst acidity. The catalysts with larger mean sizes of Ru particles and abundant acidic sites exhibited better sorbitol yields, while those with smaller Ru particles and less acidic sites favored the formation of 3-beta-D-glucopyranosyl-D-glucitol. We elucidated that cellobiose was first converted to 3-beta-D-glucopyranosyl-D-glucitol via the hydrogenolysis, and then sorbitol was formed through the cleavage of beta-1,4-glycosidic bond in 3-beta-D-glucopyranosyl-D-glucitol over the catalysts. The catalyst with smaller Ru particles favored the first step but was disadvantageous to the second step due to the less acidity. Smaller Ru particles also accelerated the degradation of sorbitol. (C) 2010 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jcat.2010.01.024
• 作为产物：
  描述：

  纤维素二糖 在 1-甲基吡咯烷 、 Ru-MACHO-BH 、 氢气 作用下， 以 乙醇 为溶剂， 150.0 ℃ 、5.0 MPa 条件下， 反应 6.0h， 生成 4-O-beta-D-吡喃葡萄糖基-D-山梨糖醇
  参考文献：
  名称：

  Ru-MACHO-BH 催化的糖的高效选择性加氢：糖醇的实用合成

  摘要：

  通过使用均相催化剂的选择性氢化实现了糖醇的高效合成。PN H P-钌催化剂Ru-MACHO-BH以极高的反应性和选择性促进氢化。该反应可应用于各种单糖和双糖，并已成功在几十克的规模上运行。

  DOI：

  10.1021/acs.oprd.2c00047

文献信息

• A One-Step Synthesis of C6 Sugar Alcohols from Levoglucosan and Disaccharides Using a Ru/CMK-3 Catalyst
  作者：Wang Yin、Zhenchen Tang、Robertus Hendrikus Venderbosch、Zheng Zhang、Catia Cannilla、Giuseppe Bonura、Francesco Frusteri、Hero Jan Heeres

  DOI：10.1021/acscatal.6b00296

  日期：2016.7.1

  Sorbitol is an important commercially available chemical with a broad application range and is typically made by the catalytic hydrogenation of glucose. Here we report a high-yield synthesis of sorbitol from levoglucosan (1,6-anhydro-β-d-glucopyranose) and cellobiose, two sugars present in pyrolysis liquids, using a mesoporous carbon-supported Ru catalyst (Ru/CMK-3). The hydrogenation reactions were

  山梨糖醇是一种重要的可商购获得的化学品，具有广泛的应用范围，通常是通过葡萄糖的催化加氢制得的。在这里我们报道了从左旋葡聚糖（1,6-anhydro-β- d-吡喃葡萄糖和纤维二糖，这两种糖存在于热解液体中，使用介孔碳负载的Ru催化剂（Ru / CMK-3）。氢化反应在间歇高压釜中在50 bar的氢气压力和120至180°C的水中温度下进行。左旋葡聚糖的氢化基本上得到定量的糖醇，其由96.2重量％的山梨糖醇和3.8重量％的甘露糖醇组成（180℃，5小时）。与商业化的Ru / C催化剂相比，Ru / CMK-3表现出优异的催化性能。提出了一种反应途径，其涉及葡萄糖作为所需山梨糖醇的中间和随后的（氢解）反应。进行与葡萄糖和山梨糖醇的反应以定义反应路径并突出Ru / C和Ru / CMK-3之间的差异。还测试了包括纤维二糖和蔗糖在内的二糖，两种底物在180°C下于5小时内产生高达95 wt％的C6
• Mechanisms of pyrolysis of polysaccharides: Cellobiitol as a model for cellulose
  作者：Todd L. Lowary、Geoffrey N. Richards

  DOI：10.1016/0008-6215(90)84278-3

  日期：1990.4

  The pyrolysis of cellobiitol has been studied as a model for cellulose. The products were determined from pyrolysis at 350° in vacuo and at 350° and at 171° at atmospheric pressure. In vacuo , a 32% yield of 1,6-anhydro-β- d -glucopyranose (levoglucosan, 5 ) and a 70% yield of d -glucitol and its anhydrides were obtained, but under atmospheric pressure these yields were much lower. A mechanism is postulated

  摘要研究了纤维二糖醇的热解作为纤维素的模型。由在真空中在350°，在大气压下在350°和在171°下的热解确定产物。在真空中，获得32％的1，6-脱水-β-d-吡喃葡萄糖（左旋葡聚糖，5）和70％的d-葡萄糖醇及其酸酐的产率，但是在大气压下，这些产率要低得多。假定一种机制，其中热解的第一步是糖苷键的杂合断裂以产生葡糖基阳离子和葡糖醇阴离子。前者通过O-6对C-1阳离子的分子内攻击而产生挥发性左旋葡聚糖，该反应在真空中较为有利，因为可以有效地除去5。谷甾醇主要以酸酐的形式获得，其在真空热解中是挥发性的。较低的温度（171°）热解未得到5。据信在这样的条件下，葡糖基阳离子被未反应的起始原料和葡糖醇的羟基进行分子间亲核取代，从而产生寡糖。
• Ru/P-Containing Porous Biochar-Efficiently Catalyzed Cascade Conversion of Cellulose to Sorbitol in Water under Medium-Pressure H₂ Atmosphere
  作者：Feng Mao、Shuainan Chen、Qiao Zhang、Long Yang、Feifei Wan、Dabo Jiang、Manman Xiong、Chao Zhang、Yachun Liu、Zaihui Fu

  DOI：10.1246/bcsj.20200095

  日期：2020.8.15

  This paper discloses a simple and productive strategy for the preparation of biochar-based bifunctional catalysts. In this strategy, very cheap bamboo powder is thermally carbonized to yield P-containing porous biochars (PBCs) by the activation of concentrated phosphoric acid (H3PO4), and the latter can be transformed into the target catalysts via loading Ru nanometer particles (NPs) on them (marked as Ru/PBCs). A series of characterizations and measurements support that PBCs have stable and rich micro-meso pores and small strong acidic protons (0.10–0.28 mmol·g−1) attributable to the grafted and/or skeleton phosphorus groups, as well as a strong affinity to β-1,4-glycosidic bonds, thus exhibiting a good acid catalytic activity for the hydrolysis of cellulose to glucose. More importantly, they are excellent acidic supports for the loading of Ru NPs owing to high BET surface area, which can give the loaded Ru NPs uniform and narrow distribution (1–6 nm). The resulting bifunctional Ru/PBCs catalysts possess excellent hydrolytic hydrogenating activity for the one-pot cascade conversion of cellulose and the optimized conditions can achieve ca. 89% hexitol yield with 98% sorbitol selectivity under relatively mild conditions. This work provides a good example for the preparation of biomass-derived bifunctional catalysts and their applications in biorefinery.

  本文披露了一种简单而高效的制备生物炭基双功能催化剂的策略。在该策略中，廉价的竹粉经过热碳化，利用浓磷酸（H3PO4）的活化生成含磷的多孔生物炭（PBCs），随后可以通过在其上负载钌纳米颗粒（NPs）将其转化为目标催化剂（标记为Ru/PBCs）。一系列表征和测量表明，PBCs具有稳定且丰富的微孔和中孔，以及由接枝和/或骨架磷基团引起的小而强酸性质子（0.10–0.28 mmol·g−1），同时对β-1,4-糖苷键具有强亲和力，因此展现出良好的酸催化活性，能够将纤维素水解为葡萄糖。更重要的是，由于高比表面积，它们是负载钌纳米颗粒的优良酸性载体，能够使负载的钌纳米颗粒均匀且窄的分布（1–6 nm）。所得到的双功能Ru/PBCs催化剂在纤维素的一锅级联转化过程中表现出优异的水解氢化活性，在相对温和的条件下，优化条件下可实现约89%的六醇产率和98%的山梨醇选择性。这项工作为制备生物质来源的双功能催化剂及其在生物炼制中的应用提供了良好的示范。
• Interaction of (1→4)- and (1→6)-linked disaccharides with the fenton reagent under physiological conditions
  作者：Koji Uchida、Shunro Kawakishi

  DOI：10.1016/s0008-6215(00)90805-x

  日期：1988.2

  (1→4)-linked disaccharides. About 35–40% of (1→6)-and 15–20% of (1→4)-linked disaccharides were oxidatively degraded to smaller molecules after incubation for 24 h. Of the four disaccharides examined, namely, maltose, isomaltose, cellobiose, and gentiobiose, the α-(1→6)-linked disaccharide isomaltose exhibited the highest reactivity, whereas the β-(1→4)-linked disaccharide cellobiose showed the lowest

  摘要研究了在生理条件下，以麦芽糖和异麦芽糖为主的（1→4）-和（1→6）连接的二糖与Fenton试剂的反应。通过glc和glc-ms的三甲基甲硅烷基衍生物对氧化产物进行化学表征，结果表明（1→6）连接的二糖与芬顿试剂产生的羟基自由基（·OH）的反应性大于（1）。 →4）-连接的二糖。孵育24小时后，约35-40％（1→6）-和15-20％（1→4）连接的二糖被氧化降解成较小的分子。在所检查的四种二糖中，即麦芽糖，异麦芽糖，纤维二糖和龙胆二糖，α-（1→6）连接的二糖异麦芽糖表现出最高的反应性，而β-（1→4）连接的二糖纤维二糖表现出最低的反应性。 。
• CONTINUOUS PROCESS FOR HYDROGENATION OF MALTOSE TO MALTITOL
  申请人：Archer-Daniels-Midland Company

  公开号：US20190345185A1

  公开（公告）日：2019-11-14

  A process for preparing maltitol is described. The process enables greater control of the reaction to minimized generation of glucose and sorbitol side products that can arise from the over-hydrogenation of maltitol. The process involves reacting a medium containing maltose at a concentration of ≤30% with hydrogen in a continuous manner using a fixed-bed reactor at a reaction temperature and pressure sufficient to produce a final product containing a yield of maltitol of at least 90 mol. %, at a conversion rate in which no more than about 2 mol. % of said maltose concentration remains, and a sorbitol concentration of less than 1.0 mol. %.

  描述了一种制备麦芽醇的过程。该过程能够更好地控制反应，以最小化由于麦芽醇过度加氢而产生的葡萄糖和山梨醇副产物。该过程涉及在反应温度和压力足以产生至少90摩尔％的麦芽醇收率的最终产品的情况下，以连续方式使用固定床反应器反应含有≤30％麦芽糖浓度的介质与氢气反应，在转化率中，不超过约2摩尔％的麦芽糖浓度剩余，山梨醇浓度小于1.0摩尔％。