1,6-bis(4-methoxycarbonylbenzylidene)hexanediamine | 106872-64-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,6-bis(4-methoxycarbonylbenzylidene)hexanediamine
• CAS: 106872-64-4
• 化学式: C₂₄H₂₈N₂O₄
• 分子量: 408.497
• InChiKey: JFDMCYCAKBPJTD-UHFFFAOYSA-N

物化性质

• 熔点：
  111-112 °C(Solv: isopropanol (67-63-0))
• 沸点：
  553.4±45.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.36
• 重原子数：
  30.0
• 可旋转键数：
  11.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  77.32
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1,6-bis(4-methoxycarbonylbenzylidene)hexanediamine 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 N,N'-bis(tert-butoxycarbonyl)-N,N'-bis(4-methoxycarbonylbenzyl)-1,6-hexanediamine
  参考文献：
  名称：

  Molecular Shuttles by the Protecting Group Approach

  摘要：

  Two new [2]rotaxane-based molecular shuttles, in which a mechanically bound dibenzo[24]crown-8 (DB24C8) macroring shunts back and forth between two dialkylammonium recognition sites situated on a chemical dumbbell, have been constructed by a novel synthetic strategy that relies upon the use of the tert-butoxycarbonyl (Boc) protecting group. During the syntheses of both molecular shuttles, this protecting group masks a dialkylammonium recognition center which is liberated only after the [2]rotaxane constitution is established. In both cases, the molecular shuttles' other dialkylammonium center is essential for the rotaxane-forming reactions and it ensures that DB24C8 is interpenetrated by threadlike precursors, as a result of noncovalent bonding interactions, to produce [2]pseudorotaxanes which are stoppered subsequently through 1,3-dipolar cycloadditions between azides and bulky acetylenedicarboxylates. The new molecular shuttles have been examined by means of dynamic H-1 NMR spectroscopy, which reveals that the movements of the DB24C8 macroring are very highly dependent both on solvent properties and on the nature of the spacer unit linking the two dialkylammonium centers. Thus, DB24C8 shunts facilely between the dialkylammonium centers when the shuttles are dissolved in solvents that readily donate their nonbonding electrons into noncovalent bonds, e.g., DMF, and when spacer units that do not offer much steric resistance to shuttling, e.g., hexamethylene, are used. On the other hand, shuttling is difficult in solvents that are less inclined to donate their electrons into noncovalent bonds, e.g., (CDCl2)(2), and when relatively bulky benzenoid spacer units, e.g., p-xylylene, link the two dialkylammonium centers. It has been proposed that the DB24C8 might act as a "ferry" which carries a proton between dialkylammonium and dialkylamine moieties in a singly protonated [2]rotaxane by means of ion-dipole interactions.

  DOI：

  10.1021/jo991397w
• 作为产物：
  描述：

  1,6-己二胺 、 对甲酰基苯甲酸甲酯 以 甲苯 为溶剂， 反应 1.0h， 以100%的产率得到1,6-bis(4-methoxycarbonylbenzylidene)hexanediamine
  参考文献：
  名称：

  通过“轮烷效应”异常稳定的仲铵基团的中和：“游离”仲胺/冠醚型轮烷的合成，结构和动力学性质

  摘要：

  十五年的难题得以解决：冠醚/仲铵盐型轮烷已被中和，这是最流行的化学事件，并且已分离出完全非离子冠醚/仲胺型轮烷。通过将二苯并[24]冠-8醚（DB24C8）和具有末端羟基的六氟磷酸仲铵（PF 6）的混合物通过与3,5-二甲基苯甲酸封端制备了[2]轮烷烷作为典型底物在三丁基膦作为催化剂存在下，乙酸酐的收率为90％。研究了几种中和轮烷铵的方法，以分离游离仲仲胺。降低热力学和动力学稳定性的胺型轮烷。一种方法是在其中软抗衡PF抗衡交换法6 -通过用四丁基氟化铵混合，从而降低了铵部分的阳离子特征与氟阴离子置换。随后用碱进行简单洗涤，使我们能够定量地分离出游离的仲胺型轮烷。另一种方法是基于保护/解除保护协议的综合。用2,2,2-三氯乙基氯甲酸酯对仲铵基进行酰化，得到N-氨基甲酸酯化的轮烷，可以通过在乙酸中的锌处理将其脱保护，得到相应的游离基。仲胺型轮烷的定量收率。光谱和分析数据充分证实了游离仲胺型轮烷

  DOI：

  10.1002/chem.201000968