1,7-dimethoxyheptane | 137333-33-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,7-dimethoxyheptane
• 英文别名: 1,7-dimethoxy-heptane；1,7-Dimethoxy-heptan；α.η-Dimethoxy-heptan；1,7-Dimethoxyheptan；Dimethoxyheptan
• CAS: 137333-33-6
• 化学式: C₉H₂₀O₂
• 分子量: 160.257
• InChiKey: WMVXKWPJSLKYPS-UHFFFAOYSA-N

物化性质

• 沸点：
  182-190 °C
• 密度：
  0.844±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,7-dimethoxyheptane 在 氢碘酸 作用下， 生成 1,7-庚二醇
  参考文献：
  名称：

  Dionneau, Annales de Chimie (Cachan, France), 1915, vol. <9> 3, p. 201,220

  摘要：

  DOI：
• 作为产物：
  描述：

  1,7-庚二醇 在 吡啶 、 sodium methylate 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 生成 1,7-dimethoxyheptane
  参考文献：
  名称：

  Fingerprinting a transition-structure guest by a building-block approach with an incremental series of catalytic hosts. Structural requirements for glyme and .alpha.,.omega.-dimethoxyalkane catalyses in N-methylbutylaminolysis and butylaminolysis of 4-nitrophenyl acetate in chlorobenzene

  摘要：

  Glymes, H-(CH2OCH2)n-H, GLM(n), catalyze butylaminolysis of 4-nitrophenyl acetate in chlorobenzene. Values of k(cat)/Oxy, where Oxy is the number of oxygens in the catalyst, increase with oligomer length up to triglyme, GLM(4), and then plateau. Optimal catalysis on a per oxygen basis requires a -(CH2OCH2)4-fragment, which suggests a four-point recognition of the secondary ammonium ion of the zwitterionic tetrahedral intermediate (TI) (J. Org. Chem. 1991, 56, 2821-2826). Dissection of individual structural components and reassembly to the same structure of the complex verifies this model. The following kinetic studies of 4-nitrophenyl acetate in chlorobenzene have accomplished the task: (a) methylbutylaminolysis catalyzed by GLM(n), n = 2-4; (b) methylbutylaminolysis catalyzed by alpha,omega-dimethoxyalkanes, CH3O-(CH2)n-OCH3, DME(n), n = 2-10 and 12; and (c) butylaminolysis catalyzed by DME(n), n = 2-10 and 12. Experiment a has revealed that k(cat)/Oxy is the same for GLM(2)-GLM(4). Optimal catalysis for breakdown of a zwitterionic TI with one ammonium proton only requires a -(CH2OCH2)2- fragment. Experiment b has shown that k(cat)/Oxy is largest for DME(2) with the values for the remaining DMEs 2-2.5-fold lower. A -CH2CH2- is the best spacer between the two oxygens. Thus, bifurcated hydrogen-bond formation between the two oxygens and the one ammonium proton enhances catalysis. Experiment c has revealed that k(cat)/Oxy for DME(2) exceeds the remaining DMEs by 3-3.6-fold, except for DME(8) and DME(10), which have values of k(cat)/Oxy only 1.7-fold slower. DME(8), the carba analogue of GLM(4), likely binds to the two ammonium protons individually with the two oxygens. DME(10) behaves similarly. GLM(4) catalysis of butylaminolysis identifies -(CH2OCH2)4- as an optimal size. DME(8) catalysis confirms this size, although the two catalysts stabilize the two-proton ammonium ion differently. GLM(4) catalyzes butylaminolysis by forming two bifurcated hydrogen bonds. This suggested structure defines the size of the ammonium ion, which agrees with X-ray structural studies of polyether-ammonium complexes. Mechanistic proposals of butylaminolysis of aryl esters require such an ion. The results of this study confirm the structure of the ion in the rate-limiting step. This building-block approach is a method for ''fingerprinting'' ammonium ions in transition structures of ionogenic reactions.

  DOI：

  10.1021/jo00027a014

文献信息

• Thermodynamic stabilities of Cu+ and Li+ complexes of dimethoxyalkanes (MeO(CH2)nOMe,n = 2–9) in the gas phase: conformational requirements for binding interactions between metal ions and ligands
  作者：Masaaki Mishima、Hideyuki Maeda、Soe Than、Maki Irie、Kiyoshi Kikukawa

  DOI：10.1002/poc.1104

  日期：2006.8

  ML+ = M+ + L (M = Cu+ and Li+) were determined in the gas phase for a series of dimethoxyalkanes (MeO(CH2)nOMe, n = 2–9) by measuring the equilibrium constants of ligand-transfer reactions using a FT-ICR mass spectrometry. Stable 1:1 Cu+-complexes (CuL+) were observed when the chain is longer than n = 4 while the 1:2 complexes (CuL) were formed for smaller compounds as stable ions. The dissociation

  对于一系列二甲氧基烷烃（MeO（CH 2）n OMe，n  = 2–9），在气相中确定了反应ML +  = M +  + L（M = Cu +和Li +）的相对自由能变化。通过使用FT-ICR质谱仪测量配体转移反应的平衡常数来进行。当链长于n  = 4时，观察到稳定的1：1 Cu +-络合物（CuL +），而较小的化合物则以稳定离子形式形成1：2络合物（CuL + ）。CuL +的解离自由能随着链长的增加而显着增加，增加了10 kcal mol-1从n  = 4到9。这种增加归因于与Cu +-络合物的环状构象有关的约束的释放。这与在B3LYP / 6-311G理论水平上通过DFT计算获得的配合物的几何和能量特征一致。相反， 尽管1∶1 Li +-络合物的结构也被认为是环状的，但LiL +的相应解离自由能仅从n = 2增加至9，增加了3 kcal mol -1。从这些结果可以得出结论，Cu [MeO（CH
• Lenne,H.-U. et al., Justus Liebigs Annalen der Chemie, 1970, vol. 732, p. 70 - 96
  作者：Lenne,H.-U. et al.

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  日期：——
• Dionneau, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1907, vol. 145, p. 129
  作者：Dionneau

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• Lespieau, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1928, vol. 187, p. 606
  作者：Lespieau

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  日期：——
• Dionneau, Bulletin de la Societe Chimique de France, 1910, vol. <4> 7, p. 330
  作者：Dionneau

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  日期：——