methyl 4-O-methyl-β-D-glucopyranosyl-(1->4)-β-D-glucopyranoside | 112988-85-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-methyl-β-D-glucopyranosyl-(1->4)-β-D-glucopyranoside
• 英文别名: methyl 4'-O-methyl-β-D-cellobioside；Glc4Me(b1-4)b-Glc1Me；(2S,3R,4R,5S,6R)-2-[(2R,3S,4R,5R,6R)-4,5-dihydroxy-2-(hydroxymethyl)-6-methoxyoxan-3-yl]oxy-6-(hydroxymethyl)-5-methoxyoxane-3,4-diol
• CAS: 112988-85-9
• 化学式: C₁₄H₂₆O₁₁
• 分子量: 370.354
• InChiKey: PTHCMJGKKRQCBF-CGKOVJDHSA-N

物化性质

• 熔点：
  204-210 °C(Solv: methanol (67-56-1))
• 沸点：
  627.7±55.0 °C(Predicted)
• 密度：
  1.52±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -4.2
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  168
• 氢给体数：
  6
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  三苯基氯甲烷 、 methyl 4-O-methyl-β-D-glucopyranosyl-(1->4)-β-D-glucopyranoside 在 吡啶 作用下， 反应 4.0h， 以74%的产率得到methyl 4-O-methyl-6-O-triphenylmethyl-β-D-glucopyranosyl-(1->4)-6-O-triphenylmethyl-β-D-glucopyranoside
  参考文献：
  名称：

  氧化的甲基4-O-甲基-β-d-吡喃葡萄糖苷和甲基β-d-吡喃葡萄糖基-（1→4）-β-d-吡喃葡萄糖苷衍生物作为荧光标记反应的底物

  摘要：

  摘要合成纤维素模型合成了甲基4-O-甲基-β-d-吡喃葡萄糖苷和甲基4-O-甲基-β-d-吡喃葡萄糖苷-（1→4）-β-d-吡喃葡萄糖苷及相关的6-O-保护的化合物分别使用Swern条件或溴/双（三丁基锡）氧化物以高至中等收率氧化中间体，得到含有6-醛基，3-酮基和2,3-二酮基的化合物。然后，用羰基选择性荧光标记9-（7-氨基-1,4,7-三氧杂庚基）-9 H-咔唑羧酰胺（CCOA）标记纤维二糖和氧化的单糖。标记的衍生物用作模型化合物，用于测定纤维素多糖中的微量羰基。

  DOI：

  10.1016/s0008-6215(02)00048-4
• 作为产物：
  描述：

  methyl 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-glucopyranoside 在 palladium on activated charcoal 三乙基硅烷 、 三氟化硼乙醚 、 氢气 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 43.0h， 生成 methyl 4-O-methyl-β-D-glucopyranosyl-(1->4)-β-D-glucopyranoside
  参考文献：
  名称：

  由13C6-d-葡萄糖合成甲基4'-O-甲基-13C12-β-d-纤维二糖苷。第1部分：反应优化和合成

  摘要：

  建立了从d-葡萄糖开始的甲基4'-O-甲基-β-D-纤维二糖苷高产合成路线。使用未经标记的材料优化的反应条件用于合成甲基4'-O-甲基-13C12-β-D-纤维二糖苷，该化合物在十二个吡喃糖碳原子中的每一个上均具有超过99％的13C富集度。通过CPMAS NMR实验需要标记的化合物来研究纤维糊精和纤维素的氢键网络。

  DOI：

  10.1016/j.carres.2005.08.003

文献信息

• Inhibition of acid-catalyzed depolymerization of cellulose with boric acid in non-aqueous acidic media
  作者：Haruo Kawamoto、Shinya Saito、Shiro Saka

  DOI：10.1016/j.carres.2007.11.004

  日期：2008.2

  Boric acid inhibited the acid-catalyzed depolymerization of cellulose in sulfolane, a non-aqueous medium, at high temperature. Formation of the dehydration products such as levoglucosenone, furfural, and 5-hydroxymethyl furfural were also effectively inhibited. Similar inhibition was observed for cellooligosaccharides and starch, although the glucosidic bonds in methyl glucopyranosides and methyl cellobioside

  硼酸在高温下抑制环丁砜（一种非水介质）中纤维素的酸催化解聚。脱水产物如左旋葡萄糖醛酮，糠醛和5-羟甲基糠醛的形成也得到有效抑制。对于纤维寡糖和淀粉也观察到了相似的抑制作用，尽管甲基吡喃葡萄糖苷和甲基纤维二糖苷中的糖苷键被裂解形成了α-d-葡萄糖呋喃糖环状的1,2：3,5-双硼酸酯。
• β-Elimination as major side reaction in periodate-oxidation of cellulosic model mono- and disaccharides
  作者：Jumpei Sasaki、Paul Kosma

  DOI：10.1007/s00706-023-03146-4

  日期：——

  unit was released as non-oxidized methyl β-d-glucopyranoside. This data indicate that periodate oxidation of cellulosic model substrates might be accompanied by peeling reactions and formation of β-elimination products even under slightly acidic conditions. Graphical abstract

  为了表征高碘酸盐氧化的纤维素底物的结构，在 pH 4.8–5.0 下对甲基 4- O-甲基 β- d-吡喃葡萄糖苷和甲基 4'- O-甲基-纤维二糖苷进行高碘酸盐处理。使用两摩尔当量的氧化剂氧化单糖产生3-甲氧基-2,5-二氢-2-呋喃醇作为主要产物。为了确认其结构和形成模式，合成了6- O-双氘代甲基4 -O-甲基-β -d-吡喃葡萄糖苷和甲基4 -O-三氘代甲基-β- d-吡喃葡萄糖苷，并氧化生成3-甲氧基-5-前一种情况为氘代-2-氢-2-呋喃醇，后一种情况为3-三氘甲氧基-2,5-二氢-2-呋喃醇。使用一摩尔当量的高碘酸盐进行氧化导致优先形成半缩醛产物和( E )-4-羟基-2-甲氧基-2-丁烯醛。后一产物也是在甲基4'- O-甲基-纤维二糖苷的末端氧化时形成的，其中还原单元作为未氧化的甲基β- d-吡喃葡萄糖苷释放。该数据表明，即使在微酸性条件下，纤维素模型底物的高碘酸盐氧化也可能伴随剥离反应和β-消除产物的形成。
• Crystal and molecular structure of methyl 4-O-methyl-β-d-glucopyranosyl-(1→4)-β-d-glucopyranoside
  作者：Iain D. Mackie、Jürgen Röhrling、Robert O. Gould、Jutta Pauli、Christian Jäger、Malcolm Walkinshaw、Antje Potthast、Thomas Rosenau、Paul Kosma

  DOI：10.1016/s0008-6215(01)00299-3

  日期：2002.2

  The cellulose model compound methyl 4-O-inethyl-beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranoside (6) was synthesised in high overall yield from methyl beta-D-cellobioside. The compound was crystallised from methanol to give colourless prisms, and the crystal structure was determined. The monoclinic space group is P2(1) with Z = 2 and unit cell parameters a = 6.6060 (13), b = 14.074 (3), c = 9.3180 (19) Angstrom, beta = 108.95(3)degrees. The structure was solved by direct methods and refined to R = 0.0286 for 2528 reflections. Both glucopyranoses occur in the C-4(1) chair conformation with endocyclic bond angles in the range of standard values. The relative orientation of both units described by the interglycosidic torsional angles [phi (O-5-C-1'-O-4-C-4:) -89.1degrees, phi (C-1'-O-4-C-4-C-5) - 152.0degrees] is responsible for the very flat shape of the molecule and is similar to those found in other cellodextrins. Different rotamers at the exocyclic hydroxymethyl group for both units are present. The hydroxymethyl group of the terminal glucose moiety displays a gauche-trans orientation, whereas the side chain of the reducing unit occurs in a gauche-gauche conformation. The solid state C-13 NMR spectrum of compound 6 exhibits all 14 carbon resonances. By using different cross polarisation times, the resonances of the two methyl groups and C-6 carbons can easily be distinguished. Distinct differences of the C-1 and C-4 chemical shifts in the solid and liquid states are found. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis of methyl 4′-O-methyl-13C12-β-d-cellobioside from 13C6-d-glucose. Part 1: Reaction optimization and synthesis
  作者：Yuko Yoneda、Toshinari Kawada、Thomas Rosenau、Paul Kosma

  DOI：10.1016/j.carres.2005.08.003

  日期：2005.10

  A high yielding synthetic route for methyl 4'-O-methyl-beta-D-cellobioside starting from d-glucose was established. The reaction conditions optimized with nonlabeled materials were used for the synthesis of methyl 4'-O-methyl-13C12-beta-D-cellobioside, a compound having more than 99% 13C enrichment at each of the twelve pyranose carbon atoms. The labeled compound is required to study the hydrogen bond

  建立了从d-葡萄糖开始的甲基4'-O-甲基-β-D-纤维二糖苷高产合成路线。使用未经标记的材料优化的反应条件用于合成甲基4'-O-甲基-13C12-β-D-纤维二糖苷，该化合物在十二个吡喃糖碳原子中的每一个上均具有超过99％的13C富集度。通过CPMAS NMR实验需要标记的化合物来研究纤维糊精和纤维素的氢键网络。
• Synthesis of oxidized methyl 4-O-methyl-β-d-glucopyranoside and methyl β-d-glucopyranosyl-(1→4)-β-d-glucopyranoside derivatives as substrates for fluorescence labeling reactions
  作者：Jürgen Röhrling、Antje Potthast、Thomas Lange、Thomas Rosenau、Immanuel Adorjan、Andreas Hofinger、Paul Kosma

  DOI：10.1016/s0008-6215(02)00048-4

  日期：2002.4

  3-diketo groups. Cellobiose and oxidized monosaccharides were then labeled with the carbonyl-selective fluorescence marker 9-(7-amino-1,4,7-trioxaheptyl)-9 H -carbazolecarboxamide (CCOA). The labeled derivatives serve as model compounds for the determination of minute amounts of carbonyl groups in cellulosic polysaccharides.

  摘要合成纤维素模型合成了甲基4-O-甲基-β-d-吡喃葡萄糖苷和甲基4-O-甲基-β-d-吡喃葡萄糖苷-（1→4）-β-d-吡喃葡萄糖苷及相关的6-O-保护的化合物分别使用Swern条件或溴/双（三丁基锡）氧化物以高至中等收率氧化中间体，得到含有6-醛基，3-酮基和2,3-二酮基的化合物。然后，用羰基选择性荧光标记9-（7-氨基-1,4,7-三氧杂庚基）-9 H-咔唑羧酰胺（CCOA）标记纤维二糖和氧化的单糖。标记的衍生物用作模型化合物，用于测定纤维素多糖中的微量羰基。