1,6-anhydro-β-D-glucopyranose | 498-07-7

• 物质功能分类: 生物化工 - 糖类化合物 - 单糖
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 1,6-anhydro-β-D-glucopyranose
• 英文别名: 1,6 anhydro-glucopyranose；levoglucosan；(2S,3S,4R)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol
• CAS: 498-07-7；644-76-8；10339-41-0；10339-42-1；13051-71-3；14059-68-8；14059-73-5；14168-65-1；14274-90-9；22224-56-2；22658-88-4；42744-19-4；60619-47-8；67999-95-5；107795-40-4；129097-81-0
• 化学式: C₆H₁₀O₅
• 分子量: 162.142
• InChiKey: TWNIBLMWSKIRAT-UWWPDOAWSA-N

物化性质

• 熔点：
  182-184 °C(lit.)
• 比旋光度：
  -66 º (C=1 IN H2O)
• 沸点：
  208.81°C (rough estimate)
• 密度：
  1.2132 (rough estimate)
• 溶解度：
  少量溶于甲醇和水
• LogP：
  -1.694 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.1
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  79.2
• 氢给体数：
  3
• 氢受体数：
  5

安全信息

• 危险品标志：
  Xn
• 安全说明：
  S22,S24/25
• 危险类别码：
  R20/21/22
• WGK Germany：
  3
• 海关编码：
  29400000
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335

制备方法与用途

生物活性方面，levoglucosan（LG、LEV、Leucoglucosan、Glucosan或1,6-烷基-β-D-葡萄糖）是一种内源性代谢产物。

反应信息

• 作为反应物：
  描述：

  1,6-anhydro-β-D-glucopyranose 在 palladium on activated charcoal 、 1,1-二氯甲醚 、 4 A molecular sieve 、 硫酸 、 四乙基氯化铵 、 sodium methylate 、 氰化汞 、 N,N-二异丙基乙胺 、 mercury dibromide 、 zinc(II) chloride 、 barium(II) oxide 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， -70.0~60.0 ℃ 、482.63 kPa 条件下， 反应 173.0h， 生成 8-methoxycarbonyloctyl 3,6-di-O-<3,6-dideoxy-α-L-xylohexopyranosyl>-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of the colitose determinant of Escherichiacoli O111 and 3,6-di-O-(α-D-galactopyranosyl)-α-D-glucopyranoside

  摘要：

  本文描述了两种分枝三糖的合成方法，它们是肠杆菌脂多糖的重要组成部分。每个三糖的共同结构特征是α-D-葡萄糖苷，在其中分支发生在O-3和O-6位置。通过对1,6-脱水-β-D-葡萄糖苷（1）进行苯甲基化，实现了对该己糖在O-2和O-4处的选择性阻断。产物2的醋解反应得到了异构三乙酸酯3的混合物，从中制备了相应的3,6-二-O-乙酰基-2,4-O-苯甲基-α-D-葡萄糖苷氯化物（4）。当4与8-甲氧羰基辛醇反应时，α和β 8-甲氧羰基辛基糖苷5和6的比例为约2:1。对α-糖苷5进行转酯化反应，得到了无糖基的中间体7，从中可以通过一步反应获得每个三糖。因此，将7与四-O-苯甲基-α-D-半乳糖苷氯化物（8）或2,4-二-O-苯甲基-3,6-二脱氧-α-L-木糖己糖苷氯化物（10）进行糖基化反应，可以得到三糖11和13。在两种情况下，阻断基的去除都可以通过单一的氢解反应实现。三糖12代表了沙门氏菌脂多糖核心糖的三糖序列，而含有科利酮的三糖14是大肠杆菌O111 O抗原的重要组成部分。

  DOI：

  10.1139/v82-045
• 作为产物：
  描述：

  protonated cycloheptaamylose 280.0 ℃ 、266.64 Pa 条件下， 反应 2.0h， 生成 甲酸 、 1,6-anhydro-β-D-glucopyranose 、 溶剂黄146 、 羟乙醛 、 羟基丙酮
  参考文献：
  名称：

  Cycloheptaamylose as a model for starch in the pyrolysis of polysaccharides

  摘要：

  The pyrolysis of cycloheptaamylose has been studied as a model for starch. 1,6-Anhydro-beta-D-glucopyranose (levoglucosan, LG, 7) and its furanose isomer are major products from vacuum pyrolysis at 280, 300, and 320-degrees, with combined yields ranging from 38 to 50% of the substrate dependent on temperature. Pyrolysis in methyl sulfoxide at 150-degrees produced LG and glucose as well as gluco-oligosaccharides of d.p. up to 7, with both reducing and 1,6-anhydro end-groups. A mechanism is postulated in which the first step is the heterolytic scission of a glucosidic linkage to form a linear, seven-membered oligosaccharide having a glucosyl cation in place of the reducing end-group. The cation is stabilized either by intramolecular attack of O-6 on the C-1 cation or by intermolecular transglycosylation. The former product subsequently yields LG upon scission of a terminal glucosidic linkage.

  DOI：

  10.1016/0008-6215(91)84094-u

文献信息

• Cycloheptaamylose as a model for starch in the pyrolysis of polysaccharides
  作者：Todd L. Lowary、Geoffrey N. Richards

  DOI：10.1016/0008-6215(91)84094-u

  日期：1991.9

  The pyrolysis of cycloheptaamylose has been studied as a model for starch. 1,6-Anhydro-beta-D-glucopyranose (levoglucosan, LG, 7) and its furanose isomer are major products from vacuum pyrolysis at 280, 300, and 320-degrees, with combined yields ranging from 38 to 50% of the substrate dependent on temperature. Pyrolysis in methyl sulfoxide at 150-degrees produced LG and glucose as well as gluco-oligosaccharides of d.p. up to 7, with both reducing and 1,6-anhydro end-groups. A mechanism is postulated in which the first step is the heterolytic scission of a glucosidic linkage to form a linear, seven-membered oligosaccharide having a glucosyl cation in place of the reducing end-group. The cation is stabilized either by intramolecular attack of O-6 on the C-1 cation or by intermolecular transglycosylation. The former product subsequently yields LG upon scission of a terminal glucosidic linkage.
• Synthesis of the colitose determinant of <i>Escherichia</i><i>coli</i> O111 and 3,6-di-<i>O</i>-(α-<scp>D</scp>-galactopyranosyl)-α-<scp>D</scp>-glucopyranoside
  作者：Tommy Iversen、David R. Bundle

  DOI：10.1139/v82-045

  日期：1982.2.1

  The syntheses of two branched trisaccharides, which constitute important elements of enterobacterial lipopolysaccharides are described. The common structural feature of each trisaccharide is α-D-glucopyranoside, upon which branching occurs at the O-3 and O-6 positions. Selective blocking of this hexoside at O-2 and O-4 by persistent blocking groups was accomplished by benzylation of 1,6-anhydro-β-D-glucopyranoside (1). Acetolysis of the product 2 afforded a mixture of anomeric triacetates 3 from which the corresponding 3,6-di-O-acetyl-2,4-O-benzyl-α-D-glucopyranosyl chloride (4) was prepared. The α and β 8-methoxycarbonyloctyl glycosides 5 and 6 were obtained in the ratio ~2:1, when 4 was reacted with 8-methoxycarbonyloctanol. Transesterification of the α-glycoside 5 gave the aglyconic intermediate 7 from which each trisaccharide could be obtained in a one step reaction. Thus glycosylation of 7 with tetra-O-benzyl-α-D-galactopyranosyl chloride (8) or 2,4-di-O-benzyl-3,6-dideoxy-α-L-xylo-hexopyranosyl chloride (10) gave the trisaccharides 11 and 13. In both cases removal of blocking groups was achieved in a single hydrogenolysis step. Trisaccharide 12 represents a trisaccharide sequence present in the core saccharide of Salmonella lipopolysaccharides, while the colitose containing trisaccharide 14 is an essential element of the E. coli O111 O-antigen.

  本文描述了两种分枝三糖的合成方法，它们是肠杆菌脂多糖的重要组成部分。每个三糖的共同结构特征是α-D-葡萄糖苷，在其中分支发生在O-3和O-6位置。通过对1,6-脱水-β-D-葡萄糖苷（1）进行苯甲基化，实现了对该己糖在O-2和O-4处的选择性阻断。产物2的醋解反应得到了异构三乙酸酯3的混合物，从中制备了相应的3,6-二-O-乙酰基-2,4-O-苯甲基-α-D-葡萄糖苷氯化物（4）。当4与8-甲氧羰基辛醇反应时，α和β 8-甲氧羰基辛基糖苷5和6的比例为约2:1。对α-糖苷5进行转酯化反应，得到了无糖基的中间体7，从中可以通过一步反应获得每个三糖。因此，将7与四-O-苯甲基-α-D-半乳糖苷氯化物（8）或2,4-二-O-苯甲基-3,6-二脱氧-α-L-木糖己糖苷氯化物（10）进行糖基化反应，可以得到三糖11和13。在两种情况下，阻断基的去除都可以通过单一的氢解反应实现。三糖12代表了沙门氏菌脂多糖核心糖的三糖序列，而含有科利酮的三糖14是大肠杆菌O111 O抗原的重要组成部分。