2-((2,5,8,11,14,17,20-heptaoxadocosan-22-yl)oxy)tetrahydro-2H-pyran | 1134159-70-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 2-((2,5,8,11,14,17,20-heptaoxadocosan-22-yl)oxy)tetrahydro-2H-pyran
• CAS: 1134159-70-8
• 化学式: C₂₀H₄₀O₉
• 分子量: 424.532
• InChiKey: BGTIYTLJIYILBN-UHFFFAOYSA-N

物化性质

• 沸点：
  487.6±45.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.28
• 重原子数：
  29.0
• 可旋转键数：
  22.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  83.07
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  2-((2,5,8,11,14,17,20-heptaoxadocosan-22-yl)oxy)tetrahydro-2H-pyran 在 盐酸 、 氯化亚砜 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 26.0h， 生成 2-(2'-(2''-(2'''-(2''''-(2'''''-(2''''''-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethoxy)ethyl 1-naphthaleneacetate
  参考文献：
  名称：

  Doubly Activated Supramolecular Reaction: Transesterification of Acyclic Oligoether Esters with Metal Alkoxides

  摘要：

  Transesterification reactions of acyclic oligoether esters E3-E10 with metal alkoxides were accelerated upon noncovalent complexation of the esters with metal ions. In the reaction of monovalent alkaline metal alkoxides, CH3ONa and CH3OK, plots of the observed rate constants k(obs) with respect to the chain length of E3-E10 showed selective acceleration of the transesterification. Compared with the shortest E3, which can hardly bind metal ion, 4.3- and 6.6-fold accelerations in the Maxima were achieved in the combinations of E5/CH3ONa and E6/CH3OK, respectively. Supramolecular intermediate complex could be spectrometrically visualized by ESI-FT-ICR-MS in the course of reaction. Kinetic experiments, together with structural analyses by means of NMR, mass spectrometry, and DFT calculations of the intermediate complexes, indicate that a size-fit complex of host substitute with alkali metal ion allows strong electron withdrawing due to the close contact of the carbonyl oxygen to the metal ion, resulting in the selective rate enhancement of the reaction, while in the reaction of E3-E10 with a divalent alkaline earth metal alkoxide, (CH3-CH2O)(2)Ba, the k(obs) values increased stepwise with elongation of the side arm to attain an dramatic large acceleration. In comparison with the k(obs) of E3, 4610-fold acceleration was achieved in the reaction of E10. The double activation of the host substrate and guest counter nucleophile at once brings about this extraordinary rate acceleration. The strong wrapping complexation of long oligoether ester with barium ethoxide allows for the effective electron withdrawal from the ester carbonyl group (host activation) as well as separation of the accompanying guest alkoxide anions (guest activation).

  DOI：

  10.1021/jo102106g
• 作为产物：
  描述：

  2-氯乙氧基-2-乙氧基二乙醇 在 盐酸 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 2-((2,5,8,11,14,17,20-heptaoxadocosan-22-yl)oxy)tetrahydro-2H-pyran
  参考文献：
  名称：

  Doubly Activated Supramolecular Reaction: Transesterification of Acyclic Oligoether Esters with Metal Alkoxides

  摘要：

  Transesterification reactions of acyclic oligoether esters E3-E10 with metal alkoxides were accelerated upon noncovalent complexation of the esters with metal ions. In the reaction of monovalent alkaline metal alkoxides, CH3ONa and CH3OK, plots of the observed rate constants k(obs) with respect to the chain length of E3-E10 showed selective acceleration of the transesterification. Compared with the shortest E3, which can hardly bind metal ion, 4.3- and 6.6-fold accelerations in the Maxima were achieved in the combinations of E5/CH3ONa and E6/CH3OK, respectively. Supramolecular intermediate complex could be spectrometrically visualized by ESI-FT-ICR-MS in the course of reaction. Kinetic experiments, together with structural analyses by means of NMR, mass spectrometry, and DFT calculations of the intermediate complexes, indicate that a size-fit complex of host substitute with alkali metal ion allows strong electron withdrawing due to the close contact of the carbonyl oxygen to the metal ion, resulting in the selective rate enhancement of the reaction, while in the reaction of E3-E10 with a divalent alkaline earth metal alkoxide, (CH3-CH2O)(2)Ba, the k(obs) values increased stepwise with elongation of the side arm to attain an dramatic large acceleration. In comparison with the k(obs) of E3, 4610-fold acceleration was achieved in the reaction of E10. The double activation of the host substrate and guest counter nucleophile at once brings about this extraordinary rate acceleration. The strong wrapping complexation of long oligoether ester with barium ethoxide allows for the effective electron withdrawal from the ester carbonyl group (host activation) as well as separation of the accompanying guest alkoxide anions (guest activation).

  DOI：

  10.1021/jo102106g