methyl-3,4-O-(2,2,2-trichlorethylidene)-α-D-altropyranoside | 159573-13-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-3,4-O-(2,2,2-trichlorethylidene)-α-D-altropyranoside
• CAS: 159573-13-4
• 化学式: C₉H₁₃Cl₃O₆
• 分子量: 323.558
• InChiKey: OUJJVNLNLPPOOU-KNRMECKQSA-N

物化性质

• 沸点：
  462.0±45.0 °C(predicted)
• 密度：
  1.62±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.19
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  77.38
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  methyl-3,4-O-(2,2,2-trichlorethylidene)-α-D-altropyranoside 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 生成 (2R,3aR,4R,6S,7S,7aS)-4-Hydroxymethyl-6-methoxy-2-methyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-ol
  参考文献：
  名称：

  Chloral/DCC - reagent for stereospecific rearrangements and new protecting group techniques in carbohydrate chemistry

  摘要：

  DOI：

  10.1002/prac.19953370191
• 作为产物：
  描述：

  Methyl 2-O-(Cyclohexylcarbamoyl)-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 methyl-3,4-O-(2,2,2-trichlorethylidene)-α-D-altropyranoside
  参考文献：
  名称：

  Chloral/DCC - reagent for stereospecific rearrangements and new protecting group techniques in carbohydrate chemistry

  摘要：

  DOI：

  10.1002/prac.19953370191

文献信息

• Organofluorverbindungen und Fluorierungsagenzien 12¹. Von<i>manno</i>-Pyranosiden zu 3,4-<i>O</i>-(2,2,2-Trichlorethyliden)altropyranosylfluoriden in nur zwei Reaktionsschritten
  作者：Ralf Miethchen、Daniel Rentsch

  DOI：10.1055/s-1994-25583

  日期：——

  Organofluorine Compounds and Fluorinating Agents 12.1 From manno-Pyranosides to 3,4-O-(2,2,2-Trichloroethylidene) altropyranosyl Fluorides in Only Two Reaction Steps Methyl α-D-mannopyranoside (1) and methyl α-L-rhamnopyrano-side (9) react with chloral and dicyclohexylcarbodiimide (DCC) in an one-pot reaction selectively to form the α-D-altropyranoside 2 and α-L-altropyranoside 10, respectively, in good yield. The glycosyl donor 3 was prepared from 2 by treatment with hydrogen fluoride/nitromethane/acetic anhydride. Compound 2 can be deprotected stepwise by treatment with methanol/sodium methanolate at r.t. to 4, and heating under reflux to methyl 3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside (5). Treatment of the dihydroxy derivative 5 with hydrogen fluoride/nitromethane/acetic anhydride gave an anomeric mixture of the α/β-D-altropyranosyl fluorides 6. Acylation of 5 with benzoyl or pivaloyl chloride gave the corresponding 2,6-diacyl derivatives 7 and 8, respectively. Finally, the α-L-altro-pyranoside 10 was deprotected in boiling methanol/sodium methanolate to afford the α-L-altropyranoside 11 and fluorinated in hydrogenfluoride/nitromethane/acetic anhydride to α-L-altropyranosyl fluoride 12. The various functionalized altropyranoses differ partially in their conformations. The ratio of the endo-H to exo-H diastereomers of the chloral acetals was determined.

  有机氟化合物和氟化剂 12.1 从甘露吡喃糖苷到 3,4-O-(2,2、甲基δ-D-吡喃甘露糖苷 (1) 和甲基δ-L-吡喃鼠李糖苷 (9) 与氯醛和二环己基碳二亚胺 (DCC) 发生选择性反应，分别生成δ-D-吡喃金刚烷糖苷 2 和δ-L-吡喃金刚烷糖苷 10，产率良好。用氟化氢/硝基甲烷/乙酸酐处理 2，制备出糖基供体 3。将化合物 2 用甲醇/甲醇钠在恒温条件下处理至 4，然后在回流条件下加热，可逐步脱保护，制得甲基 3,4-O-(2,2,2-三氯亚乙基)-δ±-D-酰基吡喃糖苷 (5)。 用氟化氢/硝基甲烷/乙酸酐处理二羟基衍生物 5，得到δ/δ-D-altropyranosyl 氟化物 6 的同分异构体混合物。用苯甲酰氯或特戊酰氯对 5 进行酰化，分别得到相应的 2,6-二乙酰基衍生物 7 和 8。最后，δ-L-酰基吡喃糖苷 10 在沸腾的甲醇/甲醇钠中脱保护，得到δ-L-酰基吡喃糖苷 11，在氟化氢/硝基甲烷/乙酸酐中氟化，得到δ-L-酰基吡喃糖基氟化物 12。各种官能化的altropyranoses在构象上存在部分差异。测定了氯醛缩醛的内-H 非对映异构体和外-H 非对映异构体的比例。