1,4,7,10-四硫杂-13-氮杂环十五烷 | 116319-25-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 1,4,7,10-四硫杂-13-氮杂环十五烷
• 英文名称: monoazatetrathia-15-crown-5
• 英文别名: 1,4,7,10-Tetrathia-13-azacyclopentadecane
• CAS: 116319-25-6
• 化学式: C₁₀H₂₁NS₄
• 分子量: 283.547
• InChiKey: SDWWDPMXNIVDMR-UHFFFAOYSA-N

物化性质

• 熔点：
  82℃ (ethanol )
• 沸点：
  458.1±35.0 °C(Predicted)
• 密度：
  1.090±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,4,7,10-四硫杂-13-氮杂环十五烷 在 三乙胺 、 sodium hydroxide 作用下， 以 乙腈 为溶剂， 反应 18.33h， 生成
  参考文献：
  名称：

  Azathia crown ether possessing a dansyl fluorophore moiety functionalized silica nanoparticles as hybrid material for mercury detection in aqueous medium

  摘要：

  A novel fluorescent hybrid material for Hg2+ detection using a derivative of dansyl fluorophore with azathia crown ether moiety grafted on silica nanoparticles (SiNPs) was prepared and characterized. The designed nanosensor exhibited pronounced Hg2+ selective ON-OFF type fluorescence switching upon binding. The presence of other metal ions has no observable effect on the sensitivity and selectivity of the prepared nanosensor toward the Hg2+ anions. The new nanosensor provided highly selective sensing to Hg2+) in EtOH/water solvent mixtures (pH=7) with a detection limit of 10(-7) M. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.04.072
• 作为产物：
  描述：

  tert-butyl 1,4,7,10-tetrathia-13-azacyclopentadecane-13-carboxylate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 1,4,7,10-四硫杂-13-氮杂环十五烷
  参考文献：
  名称：

  N，S，O混合给体冠醚的反应性与计算构象和电子性质之间的相关性

  摘要：

  混合供体冠醚[16] aneS 4 N，[15] aneS 4 N，[15] aneO 4 N，[15] aneO 2 S 2 N和[12] aneS 3的仲氮原子的亲核偶联N形成环氧化物的过程出乎意料。偶联程度似乎与冠醚中硫醚的数量成反比。考虑了两种可能的解释：（i）影响孤对在次氮原子上可及性的空间因素，以及（ii）影响氮亲核性的电子因素。为了区分这些可能性，应用了分子建模。首先，通过在分子力学水平（MM3）上进行构象搜索，生成了适合的混合供体冠醚构象。接下来，对这些构象异构体进行（半经验）PM3几何优化，以获得有关电子特性的信息。分子模型研究的结果表明，空间因素和电子因素都可以同时发挥作用，从而为观察到的现象提供了合理的解释：随着冠醚中硫醚数量的增加，氮孤对的方向变得直接。更靠近大环的内部，从而降低了反应的可及性。除此之外，随着硫醚数量的增加，仲氮的亲核性也大大降低，这可以从HOMO的

  DOI：

  10.1039/b005458p

文献信息

• Synthesis and Metal-Ion Binding Properties of Monoazathiacrown Ethers
  作者：Mutsuo Tanaka、Makoto Nakamura、Tomokazu Ikeda、Kiyomi Ikeda、Hisanori Ando、Yasuhiko Shibutani、Setsuko Yajima、Keiichi Kimura

  DOI：10.1021/jo015709i

  日期：2001.10.1

  procedures for monoazathiacrown ethers were explored, and monoazatrithia-12-crown-4, monoazatetrathia-15-crown-5, and monoazapentathia-18-crown-6 were obtained in moderate yields by the reaction of bis(2-chloroethyl)amine with the appropriate dithiols in the presence of lithium hydroxide in THF. To evaluate metal-ion binding properties of the monoazathiacrown ethers by solvent extraction, lipophilic dodecyl

  探索了单氮杂蒽酮醚的合成方法，并通过双（2-氯乙基）胺与双（2-氯乙基）胺的反应以中等收率获得了单氮杂trithia-12-crown-4，单氮杂异硫磷-15-crown-5和单氮杂戊硫杂-18-18-crown-6。在氢氧化锂存在下，在THF中加入合适的二硫醇。为了评估通过溶剂萃取的单氮杂冠氮醚的金属离子结合性能，将亲脂性十二烷基和十二烷酰基结合到单氮杂冠氮醚上。溶剂萃取实验表明，单氮杂冠冕醚具有Ag（+）和Hg（2+）选择性，并且Ag（+）和Hg（2+）之间的相对选择性取决于它们的氮原子特性和反映各自的硫原子数氮和硫原子对Hg（2+）和Ag（+）的亲和力
• A thioether-rich crown-based highly selective fluorescent sensor for Hg2+ and Ag+ in aqueous solution
  作者：Tao Chen、Weiping Zhu、Yufang Xu、Shenyi Zhang、Xiaojun Zhang、Xuhong Qian

  DOI：10.1039/b908969a

  日期：——

  A new fluorescent sensor 1, based on the naphthalimide chromophore and thioether-rich crown receptor, exhibited dual signaling behaviors for Hg2+ and Ag+ in aqueous solution. Upon addition of Hg2+, the fluorescence intensity enhanced in a linear fashion with a quantum yield increase of about 5-fold. Moreover, with the 1-Hg2+ complex, Ag+ was easily recognized by a marked fluorescence quenching. The

  基于萘二甲酰亚胺生色团和富含硫醚的冠状受体的新型荧光传感器1表现出双重信号传导行为汞2+ 和 银+在水溶液中。在添加汞2+，荧光强度以线性方式增强，量子产率提高约5倍。此外，对于1 -Hg 2+络合物，银+通过明显的荧光猝灭容易识别。活细胞图像实验证明了传感器1在荧光可视化中的价值汞2+ 生物系统中的离子。
• Complexation of metal ions with the novel azathia crown ethers carrying anthracene pendant in acetonitrile–dichloromethane
  作者：Ümmühan Ocak、Miraç Ocak、Aysel Başoğlu、Semanur Parlayan、Dilek Başaran、Hakan Alp、Halit Kantekin

  DOI：10.1016/j.poly.2009.11.010

  日期：2010.2

  A series of crown ethers carrying an anthracene group with nitrogen–sulfur donor atom, which differ in having three, four and five sulfur atoms in the macrocycle was designed and synthesized by the reaction of the corresponding macrocyclic compound and 9-chloromethyl-anthracene. The influence of metal cations such as Al3+, Zn2+, Fe2+, Fe3+, Co2+, Ni2+, Mn2+, Cu2+, Cd2+, Hg2+ and Pb2+ on the spectroscopic

  通过相应的大环化合物与9-氯甲基蒽的反应，设计合成了一系列带有蒽基的氮-硫给体原子的冠醚，它们在大环中具有三个，四个和五个硫原子。Al 3+，Zn 2 +，Fe 2 +，Fe 3+，Co 2 +，Ni 2 +，Mn 2 +，Cu 2 +，Cd 2 +，Hg 2+和Pb 2+等金属阳离子的影响在乙腈-二氯甲烷（1：1）中通过吸收和发射光谱法研究了配体的光谱性质。吸收光谱显示分光光度滴定法中的Al 3+，Zn 2 +，Fe 2 +，Fe 3+，Cu 2 +，Hg 2+和Pb 2+的等吸收点，其结果揭示了该化合物的络合物组成和络合物的稳定常数。具有这些阳离子的新型配体。单氮杂蒽醌冠醚显示出对Al 3+的灵敏度，线性范围和检测极限分别为2.6×10 -6  M–2.6×10 -5  M和8.1×10 -7 M分别。
• Synthesis and Photochromism of Spirobenzopyrans and Spirobenzothiapyran Derivatives Bearing Monoazathiacrown Ethers and Noncyclic Analogues in the Presence of Metal Ions
  作者：Mutsuo Tanaka、Tomokazu Ikeda、Qiang Xu、Hisanori Ando、Yasuhiko Shibutani、Makoto Nakamura、Hidefumi Sakamoto、Setsuko Yajima、Keiichi Kimura

  DOI：10.1021/jo0162843

  日期：2002.4.1

  Spirobenzopyrans bearing monoazathiacrown ethers and noncyclic analogues were synthesized, and their ion-responsive photochromism depending on the dual metal ion interaction with the crown ether and the phenolate anion moieties was examined using alkali and alkaline-earth metal ions, Ag+, Tl+, Pb2+, Hg2+, and Zn2+. The prepared spirobenzopyrans showed a selective binding ability to Mg2+ and Ag+ with negative and positive photochromism, respectively. Among the metal ions, only Ag+ facilitated photoisomerization to the corresponding merocyanine form. Depending on the ring size of the monoazathiacrown ether moieties, soft metal ions such as Hg2+ and Ag+ showed significant shifts in the UV-vis absorption spectra, while hard metal ions such as Mg2+, Zn2+, and Pb2+ did not afford any meaningful shift. This result reflects that the monoazathiacrown ether and phenolate anion moieties prefer soft and hard metal ions, respectively. Therefore, the Mg2+ and Ag+ selectivities are mainly derived from the phenolate anion and monoazathiacrown ether moieties, respectively. On the other hand, a spirobenzothiapyran bearing 3,9-dithia-6-monoazaundecane showed a remarkable selectivity to Ag+.
• Synthesis of 15- and 18-membered polythiamacrocylic ligands
  作者：V. V. Pavlishchuk、P. E. Strizhak

  DOI：10.1007/bf00482505

  日期：1989.5