1,3-(N,N'-bis(1,5,9-triazacycododecane))propane | 112498-63-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,3-(N,N'-bis(1,5,9-triazacycododecane))propane
• 英文别名: 1,3-bis-N,N'-(1,5,9-triazacyclododecyl)propane；1,3-bis-N1-(1,5,9-triazacyclododecyl)propane；1,3-bis(1,5,9-triazacyclododecyl)propane；1-[3-(1,5,9-Triazacyclododec-1-yl)propyl]-1,5,9-triazacyclododecane
• CAS: 112498-63-2
• 化学式: C₂₁H₄₆N₆
• 分子量: 382.636
• InChiKey: FDDFUCIQHOEJRX-UHFFFAOYSA-N

物化性质

• 沸点：
  536.3±50.0 °C(Predicted)
• 密度：
  0.906±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  54.6
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  钠二苄基磷酸酯 、 copper(II) bis(trifluoromethanesulfonate) 、 1,3-(N,N'-bis(1,5,9-triazacycododecane))propane 在 NaOCH₃ 作用下， 以 甲醇 为溶剂， 生成 [(1,3-bis-N1-(1,5,9-triazacyclododecyl)propane)Cu2(OH)((PhCH2O)2PO2)](CF3SO3)2
  参考文献：
  名称：

  甲醇中双核铜 (II) 复合物促进 RNA 和 DNA 模型系统的快速三步裂解。催化功效的能量起源

  摘要：

  1,3-双-N(1)-(1,5,9-三氮杂环十二烷基)丙烷与相关甲醇盐 (2-Cu(II)(2):(-OCH(3) )) 制备，及其与 RNA 模型（2-羟丙基-对硝基苯基磷酸酯 (1, HPNPP)）和两个 DNA 模型（甲基对硝基苯基磷酸酯 (3) 和异丁基对氯苯基磷酸酯）的反应动力学(4)) 在 (s)(s) pH 7.2 +/- 0.2 的甲醇溶液中进行研究。2-Cu(II)(2):(-OH)(H(2)O)(CF(3)SO(3)-)(3):0.5CH(3)CH(2)的X射线衍射结构)OCH(2)CH(3) 和 2-Cu(II)(2):(-OH)((C(6)H(5)CH(2)O)(2)PO(2)-)( CF(3)SO(3)-)2 显示了第一个复合物中两个 Cu(II) 离子之间桥连 -OH 和 H(2)O 的配位模式，以及第二个复合物中桥连 -OH 和磷酸盐基团之间的配位模式。对 1

  DOI：

  10.1021/ja073780l
• 作为产物：
  描述：

  1,5,9-三氮杂环十二烷 在 sodium hydroxide 作用下， 反应 3.0h， 生成 1,3-(N,N'-bis(1,5,9-triazacycododecane))propane
  参考文献：
  名称：

  中环三胺的选择性N保护

  摘要：

  1,4,7-三氮杂环壬烷和1,5,9-三氮杂环十二烷的选择性N-保护以及相关双-冠冕的合成的有效方案是基于三环原酰胺的合成中间体。

  DOI：

  10.1039/c39870000886
• 作为试剂：
  描述：

  甲醇 、 sodium 4-nitrophenyl phenylphosphonate 在 sodium methylate 、 zinc trifluoromethanesulfonate 、 1,3-(N,N'-bis(1,5,9-triazacycododecane))propane 作用下， 生成 O-methyl phenylphosphonate
  参考文献：
  名称：

  关于甲醇中合成的双核Zn（ii）配合物促进的RNA模型的逐步与一致裂解问题：不可裂解的膦酸酯探针的实现†

  摘要：

  为了解决由双核Zn（II）络合物（4）在s s pH 9.8和25°C促进的2-羟丙基芳基和烷基RNA模型（1a-k）环化的协调反应和逐步反应机制的问题，不可裂解的O-羟丙基苯基膦酸酯类似物6a和6b在甲醇。这些膦酸酯未在研究中进行异构化，唯一可观察到的甲醇分解反应是释放出1,2-丙二醇并形成邻甲基苯基膦酸酯。用于甲醇分解通过促进所观察到的一级速率常数4是ķ OBS 6A =（1.47±0.09）×10 -4小号-1和ķ OBS 6B =（2.08±0.09）×10 -6小号-1，分别。在增加[ 4 ]的条件下，分析了一系列邻芳基苯基膦酸酯（8a–f）的甲醇分解速率，以提供结合常数K b和催化速率常数k cat max。，用于8  ：  4 Michaelis配合物的单分子分解。log（k cat max）对s s p K a苯酚（布环烷基中离去基团的共轭酸的酸度常数）的布朗斯台德图。甲醇）拟合为log

  DOI：

  10.1039/b918310h

文献信息

• Mono- and dinuclear metal complexes containing the 1,5,9-triazacyclododecane ([12]aneN₃) unit and their interaction with DNA
  作者：Alfredo Medina-Molner、Melanie Rohner、Devaraj Pandiarajan、Bernhard Spingler

  DOI：10.1039/c4dt02713b

  日期：——

  It takes two to tango: Only the dinuclear but not the mononuclear metal complexes of triazacyclododecane ([12]aneN₃) were able to induce the Z-DNA of poly d(GC).

  需要两个人才能跳探戈：只有三氮杂十二烷([12]aneN3)的二核金属配合物而非一核金属配合物能诱导聚d(GC)的Z-DNA形成。
• The Dinuclear Zn(II) Complex Catalyzed Cyclization of a Series of 2-Hydroxypropyl Aryl Phosphate RNA Models:  Progressive Change in Mechanism from Rate-Limiting P−O Bond Cleavage to Substrate Binding
  作者：Shannon E. Bunn、C. Tony Liu、Zhong-Lin Lu、Alexei A. Neverov、R. Stan Brown

  DOI：10.1021/ja076847d

  日期：2007.12.1

  substrates (4b,a) the rate-limiting step is binding. The catalysis of the cyclization of these substrates is extremely efficient. The kcat/KM values for the catalyzed reactions range from 2.75 x 10(5) to 2.3 x 10(4) M-1 s-1, providing an acceleration of 1 x 10(8) to 4 x 10(9) relative to the methoxide reaction (k2OCH3, which ranges from 2.6 x 10(-3) to 5.9 x 10(-6) M-1 s-1 for 4a-g). At a pH of 9.8 where the

  制备了 1,3-[N,N'-双(1,5,9-三氮杂环十二烷)]丙烷 (1-Zn(II)2:(-O )) 的甲醇桥连双核 Zn(II) 络合物，并通过停流分光光度法在甲醇中在 pH 9.8、T = 25°C 下研究了其对一系列 2-羟丙基磷酸芳基酯 (4a-g) 环化的催化作用。1-Zn(II)2:(-O ) 的氢氧化物类似物的 X 射线衍射结构，即 1-Zn(II)2:(-OH)，表明每个 Zn(II) 离子都是配位的由三氮杂环十二烷单元的三个 N 和一个桥连氢氧化物组成。底物 4a-g 的环化揭示了从 Michaelis-Menten 饱和动力学观察到的较差底物（4-O (4g); 4-H (4f); 3-O (4e); 4-Cl (4d); 3-NO2, (4c)) 到二级动力学（在 1-Zn(II)2:(-O ) 中线性）对于更好的底物（4- ，3-CH3
• Biomimetic Cleavage of RNA Models Promoted by a Dinuclear Zn(II) Complex in Ethanol. Greater than 30 kcal/mol Stabilization of the Transition State for Cleavage of a Phosphate Diester
  作者：C. Tony Liu、Alexei A. Neverov、R. Stan Brown

  DOI：10.1021/ja806462x

  日期：2008.12.10

  rate limiting step from cleavage of the phosphate to a conformational change where the binding of the phosphate changes from one P-O- ----Zn(II) interaction to a Zn(II)----O-P-O---Zn(II) double activation. An energetics calculation comparing the ethoxide promoted cleavage of 1a-g with the 3:Zn(ll)2:(-OEt) promoted reaction indicates that the complex, 3:Zn(II)2, stabilizes the ethoxide plus substrate transition

  在 pH 9.0 +/ 的乙醇中研究了由双核 Zn(II) 络合物 (3:Zn(II)2:(-OCH2CH3)) 促进的一系列七个取代的芳基 2-羟丙基磷酸酯 (1a-g) 的裂解- 0.2 和 25 摄氏度。对于所有底物，产物酚类的出现动力学遵循非常强的饱和行为，其中结合复合物的解离常数的上限为 Km = 3 x 10(-7) M 和 k( cat)(max corr.) 值（针对三氟甲磺酸盐抑制校正）范围从 168 到 3 s(-1)。部分 s(s)pH/log k(cat)(max corr)。3:Zn(II)2:(-OCH2CH3)-催化的 le（3-甲氧基苯基 2-羟丙基磷酸酯）反应的曲线是钟形的，从 7.9-10 趋于稳定，并且适合两个动力学上重要的电离，具有s(s)pKa 值为 7.22 和 10.9。log (k(cat)(max corr.)) 与 酚类的 s(s)pKa
• A Simple DNase Model System Comprising a Dinuclear Zn(II) Complex in Methanol Accelerates the Cleavage of a Series of Methyl Aryl Phosphate Diesters by 10¹¹−10¹³
  作者：Alexei A. Neverov、C. Tony Liu、Shannon E. Bunn、David Edwards、Christopher J. White、Stephanie A. Melnychuk、R. Stan Brown

  DOI：10.1021/ja8006963

  日期：2008.5.1

  The di-Zn(II) complex of 1,3-bis[N-1,N-1'-(1,5,9-triazacyclododecyl)] propane with an associated methoxide (3:Zn(II)(2):-OCH3) was prepared and its catalysis of the methanolysis of a series of fourteen methyl aryl phosphate diesters (6) was studied at (s)(s)pH 9.8 in methanol at 25.0 +/- 0.1 degrees C. Plots of k(obs) VS [3:Zn(II)(2):-OCH3](free) for all members of 6 show saturation behavior from which K-M and k(cat)(max) were determined. The second order rate constants for the catalyzed reactions (k(cat)(max)/K-M) for each substrate are larger than the corresponding methoxide catalyzed reaction (k(2)(-OMe)) by 1.4 x 10(8) to 3 x 10(9)-fold. The values of kcatmax for all members of 6 are between 4 x 10(11) and 3 x 10(13) times larger than the solution reaction at (s)(s)pH 9.8, with the largest accelerations being given for substrates where the departing aryloxy unit contains ortho-NO2 or C(= O)OCH3 groups. Based on the linear Bronsted plots of k(cat)(max) VS (s)(s)pK(a)of the phenol, beta(Ig) values of -0.57 and -0.34 are determined respectively for the catalyzed methanolysis of "regular' substrates that do not contain the ortho-NO2 or C(= O)OCH3 groups, and those substrates that do. The data are consistent with a two step mechanism for the catalyzed reaction with rate limiting formation of a catalyst-coordinated phosphorane intermediate, followed by fast loss of the aryloxy leaving group. A detailed energetics calculation indicates that the catalyst binds the transition state comprising [CH3O-:6]double dagger, giving a hypothetical [3:Zn(II)(2):CH3O-:6]double dagger complex, by -21.4 to -24.5 kcal/mol, with the strongest binding being for those substrates having the ortho-NO2 or C(= O)OCH3 groups.
• Effective and reversible DNA condensation induced by bifunctional molecules containing macrocyclic polyamines and naphthyl moieties
  作者：Hao Yan、Zhi-Fen Li、Zhi-Fo Guo、Zhong-Lin Lu、Feng Wang、Li-Zhu Wu

  DOI：10.1016/j.bmc.2011.11.069

  日期：2012.1

  A series of bifunctional molecules containing macrocyclic polyamines [12]aneN(3) and naphthyl moieties 1-3(a, b) have been designed and synthesized through efficient N-alkylation and copper-mediated alkyne-azide click reactions. Experiments on gel electrophoresis, dynamic light scattering and atomic force microscopy confirmed that 2b and 3b with two [12]aneN(3) units efficiently induced the DNA condensation at the concentration of 120 mu M in less than 5 min. The condensation mechanism was studied by EB displacement fluorescence spectra, viscosity titration, and ionic strength effects. The condensation process was found to be reversible, and the presence of both naphthyl and [12]aneN(3) units in the molecules was proved to be necessary for the effective DNA condensation inductions. Cytotoxicity assay showed that the presence of triazole moieties can result in lower toxicity. (C) 2011 Elsevier Ltd. All rights reserved.