anti-6,13-diamino-6,13-dimethyl-1,4,8,11-tetra-azacyclotetradecane-hexahydrochloride dihydrate | 122075-15-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂卓
• 英文名称: anti-6,13-diamino-6,13-dimethyl-1,4,8,11-tetra-azacyclotetradecane-hexahydrochloride dihydrate
• 英文别名: trans-6,13-Dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine hexahydrochloride；trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine
• CAS: 122075-15-4；140925-26-4；140925-27-5
• 化学式: C₁₂H₃₆N₆*6Cl
• 分子量: 477.176
• InChiKey: SHGCZHYQVIDBOV-GJTSMBTKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.78
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  100.16
• 氢给体数：
  6.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  anti-6,13-diamino-6,13-dimethyl-1,4,8,11-tetra-azacyclotetradecane-hexahydrochloride dihydrate 、 9-蒽甲醛 在 三乙胺 、 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 17.0h， 生成 6-((anthracen-9-yl-methyl)amino)-trans-6,13-dimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane
  参考文献：
  名称：

  Metal-centred versus ligand-centred luminescence quenching of a macrocyclic copper(II) complex †

  摘要：

  我们合成了新的大环配体反式-6-（9-蒽基甲基氨基）-6,13-二甲基-1,4,8,11-四氮杂环十四烷-13-胺，并确定了其铜（II）络合物的晶体结构。大环蒽基的荧光在其游离碱形式和与 CuII 复合物结合时被淬灭。当在配体溶液中加入路易斯酸（如 H+ 和 ZnII）时，荧光又会恢复，这表明在自由碱形式下，由胺孤对光诱导的电子转移是导致荧光淬灭的原因。相比之下，复合物的荧光是通过分子内电子能量转移淬灭的。

  DOI：

  10.1039/a902881a
• 作为产物：
  描述：

  (6,13-diamino-6,13-dinitro-1,4,8,11-tetra-azacyclotetradecane)copper(II) perchlorate 在 盐酸 、 锌 作用下， 反应 2.0h， 以75%的产率得到anti-6,13-diamino-6,13-dimethyl-1,4,8,11-tetra-azacyclotetradecane-hexahydrochloride dihydrate
  参考文献：
  名称：

  Bernhardt, Paul V.; Lawrance, Geoffrey A.; Hambley, Trevor W., Journal of the Chemical Society, Dalton Transactions, 1989, p. 1059 - 1066

  摘要：

  DOI：

文献信息

• Immobilisation of electroactive macrocyclic complexes within titania films
  作者：Paul V. Bernhardt、Nathan L. Kilah、Andrew P. Meacham、Paul Meredith、Robert Vogel

  DOI：10.1039/b505917h

  日期：——

  (HL10) has been synthesised and complexed with CoIII. The mononuclear complexes [Co(HL10)(CN)]2+ and [CoL10(OH)]+ have been prepared and the crystal structures of their perchlorate salts are presented, where the ligand is bound in a pentadentate mode in each case while the 4-carboxybenzyl-substituted pendent amine remains free from the metal. The cyano-bridged dinuclear complex [CoL10-µ-NC-Fe(CN)5]2− was

  4-羧基苯基附加的大环 配体 已经合成了反式-6,13-​​二甲基-6-（（（4-羧基苄基）氨基）-1,4,8,11-四氮杂环十四烷-6-胺（HL 10）并与Co III络合。已经制备了单核络合物[Co（HL 10）（CN）] 2+和[CoL 10（OH）] +，并给出了其高氯酸盐的晶体结构，其中配体 在每种情况下均以五齿模式结合，而被4-羧基苄基取代的五键结合 胺保持不含金属。这氰基还制备了桥联的双核络合物[CoL 10 - μ -NC-Fe（CN）5 ] 2-并化学吸附在涂有二氧化钛的ITO导电玻璃上。吸附的络合物具有电化学活性，并且循环伏安法 改性ITO 工作电极 同时 水 MeCN解决方案采用了同步光学 光谱学。该实验证明可逆电化学氧化作用Fe II中心的原子吸收与薄膜光吸收率的快速变化有关。
• N-methylation of diamino-substituted macrocyclic complexes: intermolecular reactions
  作者：Paul V. Bernhardt

  DOI：10.1039/dt9960004319

  日期：——

  Two N-based isomeric copper(II) complexes of the macrocycle trans-6,13-dimethyl-6,13-bis(dimethylamino)-1,4,8,11-tetraazacyclotetradecane (L3) have been synthesized and characterised spectroscopically and structurally: α-[CuL3(OH2)2]Cl2, monoclinic, space group C2/m, a= 12.908(4), b= 12.433(2), c= 7.330(2)Å, β= 105.87(2)°, Z= 2; β-[CuL3(OClO3)2]·2H2O, monoclinic, space group P21/c, a= 9.708(3), b= 9.686(3), c= 14.202(4)Å, β= 106.17(1)°, Z= 2. The two isomers exhibit very similar co-ordination spheres but significantly different visible electronic maxima. This difference is attributed to an intramolecular N ⋯ H contact between the pendant dimethylamino group and an adjacent secondary amine H atom.

  合成了大环反式-6,13-二甲基-6,13-双(二甲基氨基)-1,4,8,11-四氮杂环十四烷(L3)的两种 N 基异构铜(II)配合物，并从光谱和结构上对其进行了表征：α-[CuL3(OH2)2]Cl2，单斜，空间群 C2/m，a= 12.908(4)，b= 12.433(2)，c= 7.330(2)埃，β= 105.87(2)°，Z= 2；β-[CuL3(OClO3)2]-2H2O，单斜，空间群 P21/c，a= 9.708(3)，b= 9.686(3)，c= 14.202(4)埃，β= 106.17(1)°，Z= 2。这两种异构体显示出非常相似的配位层，但可见电子最大值却明显不同。这种差异归因于悬挂的二甲基氨基与邻近的仲胺 H 原子之间的分子内 N ⋯ H 接触。
• N-methylation of diamino-substituted macrocyclic complexes: intramolecular cyclisation
  作者：Paul V. Bernhardt、Josephine C. Hetherington、Lathe A. Jones

  DOI：10.1039/dt9960004325

  日期：——

  Two new macropolycyclic hexaamines L2 and L4 as their copper(II) complexes have been isolated as products from the condensation of the diamino-substituted macrocyclic complex trans-(6,13-dimethyl-1,4,8,11-tetraazacyclo-tetradecane-6,13-diamine)copper(II)[CuL1]2+ with aqueous formaldehyde. Both of the complexes exhibit methylene bridges between the pendant amine and the adjacent co-ordinated macrocyclic N-donors. Their crystal structures have been determined: [CuL2(NCS)][SCN], triclinic, space group P, a= 7.133(2), b= 9.813(2), c= 16.745(3)Å, α= 101.05(2), β= 99.36(2), γ= 99.77(2)°, Z= 2; [CuL4Cl][ClO4]·H2O, triclinic, space group P, a= 9.3327(8), b= 10.8989(6), c= 12.672(1)Å, α= 68.591(6), β= 78.899(6), γ= 87.384(6)°, Z= 2. The complexes exhibit square-pyramidal geometries, and significantly lower-energy electronic maxima relative to their parent complex [CuL1]2+. Electrochemistry of [CuL2]2+ revealed a reversible CuII-CuI redox couple, by contrast to those of macromonocyclic analogues.

  从二氨基取代的大环络合物反式-(6,13-二甲基-1,4,8,11-四氮杂环-十四烷-6,13-二胺)铜(II)[CuL1]2+ 与甲醛水溶液的缩合产物中分离出了两种新的大环六胺 L2 和 L4 及其铜(II)络合物。这两种配合物在悬挂胺和相邻共配位大环 N-载体之间都显示出亚甲基桥。它们的晶体结构已经确定：[CuL2(NCS)][SCN]，三linic，空间群 P，a= 7.133(2)，b= 9.813(2)，c= 16.745(3)埃，α= 101.05(2)，β= 99.36(2)，γ= 99.77(2)°，Z= 2；[CuL4Cl][ClO4]-H2O，三菱形，空间群 P，a= 9.3327(8)，b= 10.8989(6)，c= 12.672(1)埃，α= 68.591(6)，β= 78.899(6)，γ= 87.384(6)°，Z= 2。与母体复合物[CuL1]2+相比，这些复合物显示出方阵几何结构和明显较低的电子能量最大值。与大单环类似物相比，[CuL2]2+ 的电化学过程显示出一种可逆的 CuII-CuI 氧化还原耦合。
• Crown Ether Appended Cyclam Receptors for Cationic Guests
  作者：Paul V. Bernhardt、Elizabeth J. Hayes

  DOI：10.1021/ic011232h

  日期：2002.6.1

  A series of crown ether appended macrocyclic amines has been prepared comprising benzo-12-crown-4, benzo-15-crown-5, or benzo-18-crown-6 attached to a diamino-substituted cyclam. The Co(III) complexes of these three receptors have been prepared and characterized spectroscopically and structurally. Crystal structures of each receptor in complex with an alkali metal ion and structures of the benzo-12-crown-4

  已经制备了一系列附接有冠醚的大环胺，所述胺包括与二氨基取代的环蛋白连接的苯并-12-冠-4，苯并-15-冠-5或苯并-18-冠-6。已经制备了这三种受体的Co（III）配合物，并在光谱和结构上进行了表征。报道了与碱金属离子复合的每种受体的晶体结构以及不含客体离子的苯并-12-冠-4和苯并-15-冠-5受体的结构。2D NMR和分子力学建模已用于检查客体离子络合后的构象变化。将阳离子添加到这些受体会导致Co（III / II）氧化还原电势发生明显的阳极移位，即使在水溶液中也是如此，但是观察到的阳离子选择性很小。
• Isolation and complexation of the cis isomer of the pendant arm macrocycle 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine
  作者：Paul V. Bernhardt、Peter Comba、Trevor W. Hambley、Geoffrey A. Lawrance、Katalin Várnagy

  DOI：10.1039/dt9920000355

  日期：——

  The cis isomer of the pendant arm macrocyclic hexaamine 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L2) has been isolated for the first time. The ligand has been complexed with cadmium(II) and characterised structurally. The complex [CdL2][ClO4]2 crystallises in the monoclinic space group P2(1)/n, a = 10.238(1), b = 16.445(2), c = 13.106(2) angstrom, beta = 103.33(1)-degrees, and Z = 4. The Cd-N bond lengths are not unusual by comparison with those exhibited by typical CdN62+ complexes, compared with the generally short M-N bond lengths that have been observed in sexidentate co-ordinated complexes of the trans isomer L1. Reaction of L1 with cadmium(II) does not yield a hexaamine complex, instead the pendant primary amines are not co-ordinated and the four secondary amines encircle the metal centre.