N,N'-bis(tert-butoxycarbonyl)-N,N'-bis(4-hydroxymethylbenzyl)-1,6-hexanediamine | 264191-34-6

• 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(tert-butoxycarbonyl)-N,N'-bis(4-hydroxymethylbenzyl)-1,6-hexanediamine
• 英文别名: 1,6-Bis(4-hydroxymethylbenzylamino-N,N'-tert-butoxycarbonyl)hexane；tert-butyl N-[[4-(hydroxymethyl)phenyl]methyl]-N-[6-[[4-(hydroxymethyl)phenyl]methyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]hexyl]carbamate
• CAS: 264191-34-6
• 化学式: C₃₂H₄₈N₂O₆
• 分子量: 556.743
• InChiKey: DURPEFJPXRMNFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  40
• 可旋转键数：
  17
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  99.5
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N,N'-bis(tert-butoxycarbonyl)-N,N'-bis(4-hydroxymethylbenzyl)-1,6-hexanediamine 在 4-二甲氨基吡啶 、 N-氯代丁二酰亚胺 、 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， 反应 64.0h， 生成 (4-Azidomethyl-benzyl)-[6-(4-azidomethyl-benzylamino)-hexyl]-carbamic acid tert-butyl ester
  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：

  N,N'-bis(tert-butoxycarbonyl)-N,N'-bis(4-methoxycarbonylbenzyl)-1,6-hexanediamine 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 N,N'-bis(tert-butoxycarbonyl)-N,N'-bis(4-hydroxymethylbenzyl)-1,6-hexanediamine
  参考文献：
  名称：

  由一个“穿线加塞-随后逐削波”的方式杂[4]轮烷的有效合成†

  摘要：

  “杂物切断”技术被用于杂[4]轮烷的合成，其中一种 葫芦[6]尿 （CB [6]）和两个杂冠醚大环被旋接到一个哑铃形分子上。该过程涉及三个步骤：（1）将CB [6]大环穿线到包含两个二烷基铵位点的线程上以形成基于CB [6]的线程假[2]轮烷; （2）封堵的形式假[2]轮烷通过亚胺缩合反应，然后还原/质子化得到具有两个新的二烷基铵位点的基于CB [6]的[2]轮烷。（3）将两个杂冠醚大环选择性剪切到新形成的铵盐 位和随后还原每个冠醚中的亚胺键以提供最终 杂[4]轮烷产量高。整个过程通过NMR光谱法进行，并且通过NMR光谱法，元素分析和质谱法确认了杂[4]轮烷的结构。

  DOI：

  10.1039/c001343a

文献信息

• Dual-Mode “Co-Conformational” Switching in Catenanes Incorporating Bipyridinium and Dialkylammonium Recognition Sites Molecular Meccano, Part 63. For Part 62, see: R. Ashton, C. L. Brown, J. Cao, Y. Lee, P. Newton, M. Raymo, F. Stoddart, P. White, D. J. Williams, Eur. J. Org. Chem. 2001, 957–965.
  作者：Peter R. Ashton、Virna Baldoni、Vincenzo Balzani、Alberto Credi、H. D. Andreas Hoffmann、Maria-Victoria Martínez-Díaz、Françisco M. Raymo、J. Fraser Stoddart、Margherita Venturi

  DOI：10.1002/1521-3765(20010817)7:16<3482::aid-chem3482>3.0.co;2-g

  日期：2001.8.17

  Three [2]catenanes and three [3]catenanes incorporating one or two pi -electron-rich macrocyclic polyethers and one pi -electron-deficient polycationic cyclophane have been synthesized in yields ranging from 4 to 38 %. The pi -electron-rich macrocyclic components possess either two 1,4-dioxybenzene or two 1,5-dioxynaphthalene recognition sites. The pi -electron-deficient cyclophane components incorporate two bipyridinium and either one or two dialkylammonium recognition sites. The template-directed syntheses of these catenanes rely on i) pi . . . pi stacking interactions between the dioxyarene and bipyridinium recognition sites, ii) C-H . . .O hydrogen bonds between some of the bipyridinium hydrogen atoms and some of the polyether oxygen atoms, and iii) C-H . . . pi interactions between some of the dioxyarene hydrogen atoms and the aromatic spacers separating the bipyridinium units. The six catenanes were characterized by mass spectrometry and by both IH and C-13 NMR spectroscopy. The absorption spectra and the electrochemical properties of the catenanes have been investigated and compared with those exhibited by the component macrocycles and by related known catenanes. Broad and weak absorption bands in the visible region, originating from charge-transfer (CT) interactions between electron-donor and electron-acceptor units, have been observed. Such charge-transfer interactions are responsible for the quenching of the potentially fluorescent excited states of the aromatic units of the macrocyclic polyether components. The redox behavior of these novel compounds has been investigated and correlations among the observed redox potentials are illustrated and discussed. The catenanes undergo co-conformational switching upon one-electron reduction of the two bipyridinium units. One of them-in its reduced form-can be also switched by acid/base inputs and exhibits AND logic behavior. The co-conformational rearrangements induced by the redox and acid/base stimulations lend themselves to exploitation in the development of molecular-level machines and logic gates.
• Synthesis of [<i>n</i>]Rotaxanes by Template-Directed Clipping: The Role of the Dialkylammonium Recognition Sites
  作者：Jun Yin、Suvankar Dasgupta、Jishan Wu

  DOI：10.1021/ol100256w

  日期：2010.4.16

  Linear and rectangular [n]rotaxanes were synthesized by template-directed clipping of heterocrown ether components onto the dumbbell-shaped molecules containing different dialkylammonium recognition sites. The effect of the structure of the dialkylammonium sites on the clipping efficiency was investigated, and selective clipping led to formation of a rectangular [4]rotaxane.
• Efficient synthesis of a hetero[4]rotaxane by a “threading-stoppering-followed-by-clipping” approach
  作者：Jun Yin、Chunyan Chi、Jishan Wu

  DOI：10.1039/c001343a

  日期：——

  the synthesis of a hetero[4]rotaxane, in which one cucurbit[6]uril (CB[6]) and two hetero crown ether macrocycles are threaded onto one dumbbell-shaped molecule. The process involves three steps: (1) threading of a CB[6] macrocycle onto a thread containing two dialkylammonium sites to form a CB[6]-based pseudo[2]rotaxane; (2) stoppering of the as-formed pseudo[2]rotaxane by imine condensation reaction

  “杂物切断”技术被用于杂[4]轮烷的合成，其中一种 葫芦[6]尿 （CB [6]）和两个杂冠醚大环被旋接到一个哑铃形分子上。该过程涉及三个步骤：（1）将CB [6]大环穿线到包含两个二烷基铵位点的线程上以形成基于CB [6]的线程假[2]轮烷; （2）封堵的形式假[2]轮烷通过亚胺缩合反应，然后还原/质子化得到具有两个新的二烷基铵位点的基于CB [6]的[2]轮烷。（3）将两个杂冠醚大环选择性剪切到新形成的铵盐 位和随后还原每个冠醚中的亚胺键以提供最终 杂[4]轮烷产量高。整个过程通过NMR光谱法进行，并且通过NMR光谱法，元素分析和质谱法确认了杂[4]轮烷的结构。
• Molecular Shuttles by the Protecting Group Approach
  作者：Jianguo Cao、Matthew C. T. Fyfe、J. Fraser Stoddart、Graham R. L. Cousins、Peter T. Glink

  DOI：10.1021/jo991397w

  日期：2000.4.1

  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.