39,40,41-Trithia-1,4,11,14,17,24,29,36-octazapentacyclo[12.12.12.16,9.119,22.131,34]hentetraconta-6,8,19,21,31,33-hexaene | 181044-51-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 39,40,41-Trithia-1,4,11,14,17,24,29,36-octazapentacyclo[12.12.12.16,9.119,22.131,34]hentetraconta-6,8,19,21,31,33-hexaene
• CAS: 181044-51-9
• 化学式: C₃₀H₄₈N₈S₃
• 分子量: 616.963
• InChiKey: MANKGKJWKIAOBA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  41
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  163
• 氢给体数：
  6
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  39,40,41-Trithia-1,4,11,14,17,24,29,36-octazapentacyclo[12.12.12.16,9.119,22.131,34]hentetraconta-6,8,19,21,31,33-hexaene 在 水 、 氢溴酸 作用下， 以 甲醇 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  Self-assembly of ordered water tetramers in an encapsulated [Br(H2O)12]− complex

  摘要：

  在一个受体的空腔内，一个溴化物和三个高度有序的 "水四聚体 "组装成了一个意想不到的阴离子水簇，形成了一个完美的C3对称螺旋桨形溴水簇[Br(H2O)12]。

  DOI：

  10.1039/c2cc30767g
• 作为产物：
  描述：

  三(2-氨基乙基)胺 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 51.0h， 生成 39,40,41-Trithia-1,4,11,14,17,24,29,36-octazapentacyclo[12.12.12.16,9.119,22.131,34]hentetraconta-6,8,19,21,31,33-hexaene
  参考文献：
  名称：

  毛细管电泳在阴离子结合研究中的应用：氮杂密码配体络合和分离硝酸盐和亚硝酸盐

  摘要：

  采用毛细管电泳（CE）研究了氮杂密码配体与硝酸盐和亚硝酸盐在水溶液中的络合。使用 10 mM 乙酸盐缓冲液（pH 3.3）对硝酸盐和亚硝酸盐混合物进行 CE 分离，显示硝酸盐和亚硝酸盐的保留时间分别为 2.8 和 3.1 分钟，出现两个峰。然而，当配体 (2 mM) 添加到运行缓冲液中时，硝酸盐和亚硝酸盐的峰以相反的顺序出现，保留时间分别为 2.7 分钟和 2.5 分钟。与亚硝酸盐相比，硝酸盐的保留时间较长，表明配体和硝酸盐之间形成更强的络合物，与结合不太牢固的亚硝酸盐相比，这降低了硝酸盐的迁移速度。在 pH 3.3 下用这两种阴离子对L进行1 H NMR 滴定，得出亚硝酸盐和硝酸盐的结合常数 (log K ) 分别为 3.75 和 4.23，这与 CE 方法获得的结果一致。版权所有 © 2010 约翰威利父子有限公司

  DOI：

  10.1002/poc.1693

文献信息

• Modulation of the CO₂ fixation in dinickel azacryptands
  作者：F. Möller、L. Castañeda-Losada、J. R. C. Junqueira、R. G. Miller、M. L. Reback、B. Mallick、M. van Gastel、U.-P. Apfel

  DOI：10.1039/c6dt04527h

  日期：——

  Different linker molecules within the dinickel azacryptand moiety show strong influence towards their CO₂ coordination behaviour.

  在二核氮杂环戊醚分子中，不同的连接分子对其CO₂配位行为产生强烈影响。
• Thiophene-linked azacryptand sites for dicopper and disilver; thiophene sulfur as an inert spacer?
  作者：Michael G. B. Drew、Charles J. Harding、Oliver W. Howarth、Qin Lu、Debbie J. Marrs、Grace G. Morgan、Vickie McKee、Jane Nelson

  DOI：10.1039/dt9960003021

  日期：——

  Two disilver cryptates of the thiophene-spaced azacryptand hexa Schiff bases N[(CH2)nNCHRHCN(CH2)n]3N (n= 2 or 3, R = thiophene-2,5-diyl) and with the dicopper(I) cryptate where n= 2 have been structurally characterised. The dinuclear separation increases by 0.36 Å on going from the disilver complex of the n= 2 cryptand, to the n= 3 analogue, with that in the dicopper(I) cryptate intermediate, but little difference in cryptand conformation is observed in the three complexes. Proton NMR spectra show three-bond (H–CN–Ag) coupling of each imino CH proton to 109,107Ag, confirmed by an 109Ag insensitive nuclei enhanced by polarisation transfer experiment. No copper(II) cryptates were obtained with the hexa(Schiff-base) cryptands. The analogous octaamino compounds generate dicopper(II) cryptates which accommodate bridging anions in cascade fashion, with a bridging disposition collinear, Cu–NNN–Cu, in the µ-azido-, but non-linear, Cu–O(H)–Cu, in the µ-hydroxo-cryptate. Both the hexa(Schiff-base) and octaamino cryptates are very similar to inert-spacer azacryptates and give no evidence for hemico-ordination of thiophene sulfur.

  我们从结构上描述了噻吩间距的偶氮和六席夫碱基 N[(CH2)nNCHRHCN( )n]3N（n= 2 或 3，R = 噻吩-2,5-二基）的两种二银隐色体，以及 n= 2 的二铜（I）隐色体。从 n= 2 隐核苷酸的二银配合物到 n= 3 类似物，二核分离度增加了 0.36 Å，而二铜(I)隐核苷酸中间体的二核分离度也增加了 0.36 Å，但在这三种配合物中观察到的隐核苷酸构象差别不大。质子核磁共振光谱显示，每个亚氨基 CH 质子都与 109、107Ag 发生了三键（H-CN-Ag）耦合，并通过极化转移实验证实了 109Ag 不敏感的核增强。六（希夫碱）隐色剂没有得到铜（II）隐色酸盐。类似的八氨基化合物生成的二铜(II)隐晶酸盐以级联方式容纳桥接阴离子，在 µ- 叠氮基隐晶酸盐中，桥接配置为串联式 Cu-NNN-Cu，而在µ-羟基隐晶酸盐中，桥接配置为非串联式 Cu-O(H)-Cu。六（希夫碱）隐色酸盐和八氨基隐色酸盐都与惰性填料偶氮隐色酸盐非常相似，没有证据表明噻吩硫存在半配位。
• Unusual bridging of three nitrates with two bridgehead protons in an octaprotonated azacryptand
  作者：Musabbir A. Saeed、Frank R. Fronczek、Ming-Ju Huang、Md. Alamgir Hossain

  DOI：10.1039/b923013k

  日期：——

  Structural analysis of the nitrate complex of a thiophene-based azacryptand suggests that three nitrates are bridged with two bridgehead protons which play the topological role of two transition metal ions in a classical Werner type coordination complex bridging three anions.

  对噻吩基氮杂庚烷的硝酸盐络合物的结构分析表明，三个硝酸盐与两个桥头质子桥接，这两个桥头质子在桥接三个阴离子的经典维尔纳型配位络合物中扮演着两个过渡金属离子的拓扑角色。
• Encapsulated chloride coordinating with two in–in protons of bridgehead amines in an octaprotonated azacryptand
  作者：Musabbir A. Saeed、Frank R. Fronczek、Md. Alamgir Hossain

  DOI：10.1039/b916099j

  日期：——

  An encapsulated chloride in a thiophene-based cryptand is bridged by two in–in protons of tertiary amines with an N⋯Cl− distance of 3.048(3) Å, similar to that observed in Park and Simmons’ katapinand chloride complex.

  噻吩基穴状配体中封装的氯化物由叔胺的两个 in-in 质子桥接，N-Cl-距离为 3.048(3) ×，类似于 Park 和 Simmons 的 katapinand 氯化物络合物中观察到的情况。
• A di-copper(II) bis-tren cage with thiophene spacers as receptor for anions in aqueous solution
  作者：Valeria Amendola、Luigi Fabbrizzi、Carlo Mangano、Piersandro Pallavicini、Michele Zema

  DOI：10.1016/s0020-1693(02)01029-0

  日期：2002.9

  The system made of the bis-tren octaamino cage ligand with thiophene spacers (3) and Cu-II (1:2 molar ratio) has been studied in aqueous solution by means of potentiometric titrations. Both protonation and formation constants of the metal-containing species were determined, so that the system can be fully described at any pH value. 6.9 was chosen as the best pH value for the system to work as receptor for a series of bidentate anionic species: this is the lowest value at which only dimetallic complexes exist. In particular, [Cu-2(3)(OH)](3+) is the species prevailing by far at this pH, so that a displacement equilibria takes places on binding anions, [Cu-2(3)(OH)](3+) +A(-) = [Cu-2(3)(A)(3+) +OH-. The binding process was followed by means of spectrophotometric titrations and, for the anions bound by the system, a K-obs was determined, related to the constant of the displacement equilibrium by K = K-obs[OH-]. A 109 K-obs value of 6.75 (+/-0.09) was determined for N-3(-), 4.79 (+/-0.07) for NCO-, and 2.72 (+/-0.08) for NCS- SO42-, NO3-, HCO3-, CH3COO-, Cl-, Br- and I-, were instead not bound by the system or bound with log K-obs values << 2. The crystal and molecular structure of the complex [Cu-2(3)(N-3)](3+) was also determined, which evidenced the intrinsically increased length of the cage and of its Cu-2(II) complexes, related to the large atomic radius of the S atom of the thiophene spacers, which prevents the binding of monoatomic anions (halides). (C) 2002 Elsevier Science B.V. All rights reserved.