1-N,3-N-bis[4-(N-(4-bromophenyl)-4-butoxyanilino)phenyl]-1-N,3-N-bis(4-butoxyphenyl)benzene-1,3-diamine | 1428046-05-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-N,3-N-bis[4-(N-(4-bromophenyl)-4-butoxyanilino)phenyl]-1-N,3-N-bis(4-butoxyphenyl)benzene-1,3-diamine
• CAS: 1428046-05-2
• 化学式: C₇₀H₇₂Br₂N₄O₄
• 分子量: 1193.17
• InChiKey: CJJGEIHMBQVVDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.1
• 重原子数：
  80
• 可旋转键数：
  28
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  49.9
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-N,3-N-bis[4-(N-(4-bromophenyl)-4-butoxyanilino)phenyl]-1-N,3-N-bis(4-butoxyphenyl)benzene-1,3-diamine 、 1-N,3-N-bis[4-(4-butoxyanilino)phenyl]-1-N,3-N-bis(4-butoxyphenyl)benzene-1,3-diamine 在 1,2,3,4,5-五苯基-1′-(二叔丁基膦)二茂铁 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 36.0h， 以26%的产率得到2,7,12,18,23,28,33,39-Octakis(4-butoxyphenyl)-2,7,12,18,23,28,33,39-octazanonacyclo[38.2.2.23,6.28,11.219,22.224,27.229,32.113,17.134,38]hexapentaconta-1(42),3(56),4,6(55),8(54),9,11(53),13(52),14,16,19(51),20,22(50),24,26,29,31,34,36,38(45),40,43,46,48-tetracosaene
  参考文献：
  名称：

  Meta–Para-Linked Octaaza[1₈]cyclophanes and Their Polycationic States

  摘要：

  Octaazacyclophanes, octaaza[1(8)]m,p,m,p,m,p,m,p-cyclophane (2) and octaaza[1(8)]m,p,p,p,m,p,p,p-cyclophane (3), as ring-size extended congeners of tetraaza[1(4)]m,p,m,p-cyclophane were synthesized, and the electronic states of their polycationic species were investigated by quantum chemical calculations, electrochemical measurements (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)), UV-vis-NIR spectroelectrochemical measurements, and pulsed electron spin resonance (ESR) spectroscopy. These octaazacyclophanes exhibited multiredox activities depending on different linkage patterns along the macrocyclic molecular skeletons, and both molecules were oxidizable up to their respective octacations. Spectroelectrochemical measurements demonstrated that p-phenylenediamine (PD) moieties in 2 could be converted from the semiquinoidal structure to the quinoidal sturcture with increasing oxidation number, whereas higher oxidation states of 3 did not show definite quinoidal deformation of PD moieties. A pulsed ESR spectrum gave evidence about formation of the almost pure spin-triplet state for 3(2+), whereas the high-spin states of 2(2+) and 2(4+) are virtually degenerate with the competing low-spin states even at low temperatures, probably due to the fragility of spin-coupling pathway caused by facile conformational changes.

  DOI：

  10.1021/jo3026884
• 作为产物：
  描述：

  1,4-二溴苯 、 1-N,3-N-bis[4-(4-butoxyanilino)phenyl]-1-N,3-N-bis(4-butoxyphenyl)benzene-1,3-diamine 在 1,1'-双(二苯基膦)二茂铁 、 palladium diacetate 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 36.0h， 以82.8%的产率得到1-N,3-N-bis[4-(N-(4-bromophenyl)-4-butoxyanilino)phenyl]-1-N,3-N-bis(4-butoxyphenyl)benzene-1,3-diamine
  参考文献：
  名称：

  Meta–Para-Linked Octaaza[1₈]cyclophanes and Their Polycationic States

  摘要：

  Octaazacyclophanes, octaaza[1(8)]m,p,m,p,m,p,m,p-cyclophane (2) and octaaza[1(8)]m,p,p,p,m,p,p,p-cyclophane (3), as ring-size extended congeners of tetraaza[1(4)]m,p,m,p-cyclophane were synthesized, and the electronic states of their polycationic species were investigated by quantum chemical calculations, electrochemical measurements (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)), UV-vis-NIR spectroelectrochemical measurements, and pulsed electron spin resonance (ESR) spectroscopy. These octaazacyclophanes exhibited multiredox activities depending on different linkage patterns along the macrocyclic molecular skeletons, and both molecules were oxidizable up to their respective octacations. Spectroelectrochemical measurements demonstrated that p-phenylenediamine (PD) moieties in 2 could be converted from the semiquinoidal structure to the quinoidal sturcture with increasing oxidation number, whereas higher oxidation states of 3 did not show definite quinoidal deformation of PD moieties. A pulsed ESR spectrum gave evidence about formation of the almost pure spin-triplet state for 3(2+), whereas the high-spin states of 2(2+) and 2(4+) are virtually degenerate with the competing low-spin states even at low temperatures, probably due to the fragility of spin-coupling pathway caused by facile conformational changes.

  DOI：

  10.1021/jo3026884

文献信息

• <i>Meta</i>–<i>Para</i>-Linked Octaaza[1₈]cyclophanes and Their Polycationic States
  作者：Daisuke Sakamaki、Akihiro Ito、Ko Furukawa、Tatsuhisa Kato、Kazuyoshi Tanaka

  DOI：10.1021/jo3026884

  日期：2013.4.5

  Octaazacyclophanes, octaaza[1(8)]m,p,m,p,m,p,m,p-cyclophane (2) and octaaza[1(8)]m,p,p,p,m,p,p,p-cyclophane (3), as ring-size extended congeners of tetraaza[1(4)]m,p,m,p-cyclophane were synthesized, and the electronic states of their polycationic species were investigated by quantum chemical calculations, electrochemical measurements (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)), UV-vis-NIR spectroelectrochemical measurements, and pulsed electron spin resonance (ESR) spectroscopy. These octaazacyclophanes exhibited multiredox activities depending on different linkage patterns along the macrocyclic molecular skeletons, and both molecules were oxidizable up to their respective octacations. Spectroelectrochemical measurements demonstrated that p-phenylenediamine (PD) moieties in 2 could be converted from the semiquinoidal structure to the quinoidal sturcture with increasing oxidation number, whereas higher oxidation states of 3 did not show definite quinoidal deformation of PD moieties. A pulsed ESR spectrum gave evidence about formation of the almost pure spin-triplet state for 3(2+), whereas the high-spin states of 2(2+) and 2(4+) are virtually degenerate with the competing low-spin states even at low temperatures, probably due to the fragility of spin-coupling pathway caused by facile conformational changes.