N,N'-bis(4-carbomethoxybenzyl)-p-xylenediamine | 180397-81-3

• 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: N,N'-bis(4-carbomethoxybenzyl)-p-xylenediamine
• CAS: 180397-81-3
• 化学式: C₂₆H₂₈N₂O₄
• 分子量: 432.519
• InChiKey: HWYSDKUESIKZPL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  32.0
• 可旋转键数：
  10.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  76.66
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  N,N'-bis(4-carbomethoxybenzyl)-p-xylenediamine 在 4-二甲氨基吡啶 、 N-氯代丁二酰亚胺 、 lithium aluminium tetrahydride 、 sodium azide 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 丙酮 为溶剂， 生成 N,N'-bis(4-azidomethylbenzyl)-p-xylylenediamine
  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：

  Methyl 4-[[4-[[(4-methoxycarbonylphenyl)methylideneamino]methyl]phenyl]methyliminomethyl]benzoate 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 N,N'-bis(4-carbomethoxybenzyl)-p-xylenediamine
  参考文献：
  名称：

  Ashton, Peter R.; Glink, Peter T.; Stoddart, J. Fraser, Chemistry - A European Journal, 1996, vol. 2, # 6, p. 729 - 736

  摘要：

  DOI：

文献信息

• Axle Length Does Not Affect Switching Dynamics in Degenerate Molecular Shuttles with Rigid Spacers
  作者：Philip G. Young、Keiji Hirose、Yoshito Tobe

  DOI：10.1021/ja412671k

  日期：2014.6.4

  For a series of [2]rotaxane molecular shuttles possessing linear rigid rod-like axles of varying lengths between degenerate recognition sites, the activation barrier for shuttling motion was clearly shown to be constant. Moreover, dynamic NMR studies have revealed that both the entropic and enthalpic contributions to the shuttling motion remain constant regardless of the actual length of the rigid

  对于在简并识别位点之间具有不同长度的线性刚性棒状轴的一系列 [2] 轮烷分子穿梭机，穿梭运动的激活障碍清楚地显示为恒定的。此外，动态 NMR 研究表明，无论本文采用的刚性杆状轴的实际长度如何，对穿梭运动的熵和焓的贡献都保持不变。
• A Shuttling Molecular Machine with Reversible Brake Function
  作者：Keiji Hirose、Yoshinobu Shiba、Kazuaki Ishibashi、Yasuko Doi、Yoshito Tobe

  DOI：10.1002/chem.200702001

  日期：2008.4.7

  reported. It is a photochemically and thermally reactive rotaxane composed of a dianthrylethane-based macrocycle as the ring component and a dumbbell shaped molecular unit with two, secondary ammonium stations separated by a phenylene spacer as the axle component. The rate of shuttling motion was shown to be reduced to less than 1 % (from 340 to <2.5 s(-1)) by reducing the size of the ring component from

  报告了具有可逆制动功能的穿梭分子机器原型的设计，合成和演示。它是一种光化学和热反应性轮烷，由基于二蒽乙烷的大环作为环组分和哑铃状分子单元组成，其中两个亚铵站被亚苯基间隔基隔开，作为轴组分。通过在光辐照下将环组分的大小从30冠8减少到24冠8大环，表明穿梭运动的速率降低到小于1％（从340降低到<2.5 s（-1））。 。通过热环打开，环组件会变回30-crown-8，从而建立可逆的制动功能，该功能可响应光化学和热刺激而发挥作用。