13,26-dibenzyl-3,6,9,12,13,16,19,22,25,26-decaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene | 244217-92-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 13,26-dibenzyl-3,6,9,12,13,16,19,22,25,26-decaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene
• 英文别名: 13,26-dibenzyl-3,6,9,12,13,16,19,22,25,26-decaazatricyclo[22.2.1.1^11,14]octacosa-1(27),11,14(28),24-tetraene；13,26-dibenzyl-3,6,9,12,13,16,19,22,25,26-decaazatricyclo[22.2.1.1(11,14)]octacosa-1(27),11,14(28),24-tetraene；13,26-Dibenzyl-3,6,9,12,13,16,19,22,25,26-decazatricyclo[22.2.1.111,14]octacosa-1(27),11,14(28),24-tetraene
• CAS: 244217-92-3
• 化学式: C₃₂H₄₆N₁₀
• 分子量: 570.784
• InChiKey: CSXJEYXZBSEEOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  42
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  108
• 氢给体数：
  6
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  13,26-dibenzyl-3,6,9,12,13,16,19,22,25,26-decaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene 在 盐酸 作用下， 以 水 为溶剂， 反应 12.0h， 以85%的产率得到13,26-dibenzyl-3,6,9,12,13,16,19,22,25,26-decaazatricyclo[22.2.1.1(11,14)]octacosa-1(27),11,14(28),24-tetraene hexahydrochloride
  参考文献：
  名称：

  In Vitro and in Vivo Trypanosomicidal Activity of Pyrazole-Containing Macrocyclic and Macrobicyclic Polyamines: Their Action on Acute and Chronic Phases of Chagas Disease

  摘要：

  The in vitro and in vivo anti-Trypanosoma cruzi activity of the pyrazole-containing macrobicyclic polyamine 1 and N-methyl- and N-benzyl-substituted monocyclic polyamines 2 and 3 was studied. Activity against both the acute and chronic phases of Chagas disease was considered. The compounds were more active against the parasite and less toxic against Vero cells than the reference drug benznidazole, but 1 and 2 were especially effective, where cryptand 1 was the most active, particularly in the chronic phase. The activity results found for these compounds were complemented and discussed by considering their inhibitory effect on the iron superoxide dismutase enzyme of the parasite, the nature of the metabolites excreted after treatment, and the ultrastructural alterations produced. A complementary histopathological analysis confirmed that the compounds tested were significantly less toxic to mammals than the reference drug and that 1 and 2 exhibited lower levels of damage than 3.

  DOI：

  10.1021/jm2017144
• 作为产物：
  描述：

  diethyl 1-benzyl-3,5-pyrazoledicarboxylate 在 manganese(IV) oxide 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醇 、 乙腈 为溶剂， 反应 4.0h， 生成 13,26-dibenzyl-3,6,9,12,13,16,19,22,25,26-decaazatricyclo-[22.2.1.1^11,14]-octacosa-1(27),11,14(28),24-tetraene
  参考文献：
  名称：

  Synthesis and Protonation Behavior of 26-Membered Oxaaza and Polyaza Macrocycles Containing Two Heteroaromatic Units of 3,5-Disubstituted Pyrazole or 1-Benzylpyrazole. A Potentiometric and ¹H and ¹³C NMR Study

  摘要：

  The synthesis and acid-base behavior of two series of 26-membered dioxatetraamine and hexaamine heterocyclophanes containing two nuclei of either pyrazole (4a and 6a) or 1-benzylpyrazole (4b and 6b), respectively, are reported. Dipodal (2 + 2) condensations of 3,5-pyrazoledicarbaldehyde 2a or its 1-benzyl derivative 2b with 1,5-diamino-3-oxapentane afford in both cases the stable Schiff bases 3a,b in 90% yield, which after reduction with NaBH4 gave 4a;b in 75% and 84% yield, respectively. Condensation of 2a with diethylenetriamine leads to a complex mixture containing imidazolidine isomers, which was reduced in situ to afford 6a in 30% yield. Condensation of 2b with the same amine gave the stable diimidazolidine derivative 5b, which after crystallization was isolated as a pure compound in 80% yield and fully identified from analytical and H-1 and C-13 NMR data as a constitutional isomer with both imidazolidine rings located at the side of the pyrazole closer to the benzylic substituents. Reduction of 5b with NaBH4 afforded the polyamine 6b in 86% yield. Protonation constants of 4a,b and 6a,b have been determined by potentiometric methods in the pH 2-11 range, and their protonation sequences were established by a H-1 and C-13 NMR study in D2O at variable pH. For each compound, the number of protonation constants equals the number of nitrogens in the side chains. In the pH range studied, the pyrazole rings are not involved in protonation or deprotonation processes.

  DOI：

  10.1021/jo981699i

文献信息

• Dopamine Interaction in the Absence and in the Presence of Cu²⁺ Ions with Macrocyclic and Macrobicyclic Polyamines Containing Pyrazole Units. Crystal Structures of [Cu₂(<b>L</b>₁)(H₂O)₂](ClO₄)₄ and [Cu₂(H_-1<b>L</b>₃)](ClO₄)₃·2H₂O
  作者：Laurent Lamarque、Pilar Navarro、Carlos Miranda、Vicente J. Arán、Carmen Ochoa、Francisco Escartí、Enrique García-España、Julio Latorre、Santiago V. Luis、Juan F. Miravet

  DOI：10.1021/ja010956p

  日期：2001.10.31

  The solution studies reveal a ready deprotonation of the pyrazole units induced by coordination to Cu2+. In the case of L2 (L2 = 3,6,9,12,13,16,19,22,25,26-decaazatricyclo[22.2.1.1(11,14)]octacosa-1(27),11,14(28),24-tetraene), deprotonation of both pyrazole subunits is already observed at pH ca. 4 for 2:1 Cu2+:L2 molar ratios. All three free receptors interact with dopamine in aqueous solution. L3

  描述了含有吡唑片段作为间隔物的三种聚氮杂环芳烃与 Cu2+ 和多巴胺的相互作用。混合配合物 Cu2+-大环-多巴胺的形成已通过电位法在水溶液中进行了研究。配合物 [Cu2(L1)(H2O)2](ClO4)4*2 (4) (L1 = 13,26-dibenzyl-3,6,9,12,13,16,19,22, 25,26-十氮杂三环[22.2.1.1(11,14)]octacosa-1(27),11,14(28),24-四烯)和[Cu2(H-1L3)](H )( )2* 2 (6) (L3 = 1,4,7,8,11,14,17,20,21,24,29,32,33,36-十四碳氮杂五环[12.12.12.1(6,9).1(19, 22).1(31,34)]hentetraconta-6,9(41),19(40),21,31,34(39)-己烯)。在第一个 (4) 中，每个 Cu2+
• Electrochemistry of copper complexes with macrocyclic polyamines containing pyrazole units
  作者：Antonio Doménech、Enrique García-España、Pilar Navarro、Carlos Miranda

  DOI：10.1039/b607296h

  日期：——

  The voltammetric behaviour of bi- and mono-nuclear complexes formed in solution by Cu2+ with three polyazacyclophanes containing pyrazole units in aqueous solution is described. Cyclic and square wave voltammetric responses at glassy carbon electrodes indicate that the reduction of copper–macrocycle complexes in solution takes place in two successive one-electron per Cu transfer processes coupled with preorganization and protonation reactions that mimic the behaviour of superoxide dismutase. The electrochemistry of ternary Cu2+–receptor–dopamine complexes exhibits significant differences with respect to the protection of the neurotransmitter from post-electron transfer cyclization reactions.

  描述了Cu²⁺与三种含有吡唑单元的聚氮环的溶液中形成的双核和单核配合物的伏安行为。玻碳电极上的循环伏安和方波伏安响应表明，溶液中铜-大环配合物的还原过程发生在两个连续的每个Cu转移一个电子的过程中，这些过程与预组装和质子化反应相耦合，模拟了超氧化物歧化酶的行为。三元Cu²⁺-受体-多巴胺配合物的电化学特征在保护神经递质免受电子转移后的环化反应方面显示出显著差异。
• Cu ^II and Zn ^II Coordination Chemistry of Pyrazole‐Containing Polyamine Receptors − Influence of the Hydrocarbon Side Chain Length on the Metal Coordination
  作者：Carlos Miranda、Francisco Escartí、Laurent Lamarque、Enrique García‐España、Pilar Navarro、Julio Latorre、Francisco Lloret、Hermás R. Jiménez、María J. R. Yunta

  DOI：10.1002/ejic.200400671

  日期：2005.1

  pH values than in the complexes of the analogous ligand containing diethylenetriamine bridges (L 1 ). The crystal structures of [Cu 2 (H - 2 L 4 )](ClO 4 ) 2 and [Zn 2 (H - 2 L 4 )](ClO 4 ) 2 obtained by treatment of Na 2 [H - 2 L 4 ) with either Cu(ClO 4 ) 2 .6H 2 O or Zn(ClO 4 ) 2 .6H 2 O in methanol followed by recrystallisation from water/methanol also show the deprotonation of the pyrazole moieties

  首次报道了一种新的大环受体（L 4 ）的合成，该受体含有两个通过二丙三胺桥连接的3,5-二甲基吡唑单元；pH 计量滴定表明 L 4 在 pH 范围 2-11 中显示出六个质子化步骤。在没有金属离子的情况下，吡唑部分不参与该 pH 范围内的酸碱过程。Cu II 和Zn II 的添加导致作为双(单齿) η 1 :η 1 配体的吡唑部分的去质子化。这种诱导的去质子化发生在比含有二亚乙基三胺桥 (L 1 ) 的类似配体的复合物更高的 pH 值下。[Cu 2 (H - 2 L 4 )](ClO 4 ) 2 和[Zn 2 (H - 2 L 4 )](ClO 4 ) 2 的晶体结构由Na 2 [H - 2 L 4 )处理得到Cu(ClO 4 ) 2 .6H 2 O 或 Zn(ClO 4 ) 2 。在甲醇中的 6H 2 O 随后从水/甲醇中重结晶也显示出吡唑部分的去质子化。每个金属离子周围的配位几何是方锥体，涉及大环的所有氮原子。[Zn