bis<2-(2-pyridylmethylamino)ethyl> disulfide | 60337-60-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: bis<2-(2-pyridylmethylamino)ethyl> disulfide
• 英文别名: bis[2-[(2-pyridylmethyl)amino]ethyl] disulphide；di-2-[(2-pyridinylmethyl)amino]ethyl disulfide；bis-2-((2-pyridylmethyl)amino)ethyl disulfide；bis-[2-(pyridin-2-ylmethyl-amino)-ethyl]-disulfane；2--ethyl-disulfid；Bis[2-(2-pyridylmethylamino)ethyl] disulfide；N-(pyridin-2-ylmethyl)-2-[2-(pyridin-2-ylmethylamino)ethyldisulfanyl]ethanamine
• CAS: 60337-60-2
• 化学式: C₁₆H₂₂N₄S₂
• 分子量: 334.509
• InChiKey: GSDHHWWUPMKZPC-UHFFFAOYSA-N

物化性质

• 熔点：
  76-77 °C(Solv: ethanol (64-17-5); water (7732-18-5))
• 沸点：
  490.7±45.0 °C(Predicted)
• 密度：
  1.190±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  22
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  100
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  bis<2-(2-pyridylmethylamino)ethyl> disulfide 在 甲酸 、 magnesium sulfate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 6.0h， 生成 C₃₀H₃₇Cu₂N₆S₂⁽¹⁺⁾*2BF₄^(1-)
  参考文献：
  名称：

  Thermodynamics of the Cu^II μ-Thiolate and Cu^I Disulfide Equilibrium: A Combined Experimental and Theoretical Study

  摘要：

  The redox equilibrium between dinuclear Cu-II mu-thiolate and Cu-I disulfide structures has been analyzed experimentally and via DFT calculations. Two new ligands, (LSSL2)-S-2 and (LSSL4)-S-4, and their Cu-II mu-thiolate and Cu-I disulfide complexes were synthesized. For (LSSL2)-S-2, these two redoxisomeric copper species are shown to be in equilibrium, which depends on both temperature and solvent. For (LSSL4)-S-4 the mu-thiolate species forms as the kinetic product and further evolves into the disulfide complex under thermodynamic control, which creates the unprecedented possibility to both species under the same reaction conditions. The energies of the mu-thiolate and disulfide complexes for two series of related ligands have been calculated with DFT; the results rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in the formation of the Cull thiolate structure.

  DOI：

  10.1021/ic501060w
• 作为产物：
  描述：

  在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 bis<2-(2-pyridylmethylamino)ethyl> disulfide
  参考文献：
  名称：

  含吡啶和咪唑的二硫化物配合物中的铜 (II)-硫相互作用。合成、光谱和溶液平衡

  摘要：

  已经对含吡​​啶环、喹啉环和咪唑环的二硫化物和相关化合物的铜 (II) 配合物进行了合成、光谱和电位研究，重点是铜 (II)-硫相互作用。在铜 (II)、二硫化物配体 (RCH2NHCH2CH2S–)2 存在下，其中 R=4-咪唑基 (IMAD)、2-吡啶基 (PMAD)、6-甲基-2-吡啶基 (MPAD) 和 2-喹啉基(QMAD)，在酸性溶液中比在中性碱性溶液中更稳定。稳定的 1:1 铜 (II) 配合物 Cu(IMAD)(ClO4)2·H2O 以晶体形式从水溶液中分离出来，而双核配合物 Cu2(PMAD)Cl4 在乙醇中以晶体形式获得。Cu(II)-IMAD 系统在 585 nm 处显示一个单 dd 峰，表明存在 CuN4 发色团，但在 300-900 nm 区域没有电荷转移 (CT) 带。其他 Cu(II)-二硫化物系统在 650 和 ≈850 nm 处显示 dd 带。分别在 pH

  DOI：

  10.1246/bcsj.56.3258

文献信息

• Interconversion between Bis(<i>μ</i>-thiolato)dicopper(II) and Disulfide-Bridged Dicopper(I) Complexes Mediated by Chloride Ion
  作者：Yoshiki Ueno、Yoshimitsu Tachi、Shinobu Itoh

  DOI：10.1021/ja027397m

  日期：2002.10.1

  An unprecedented clean interconversion between a novel bis(mu-thiolato)dicopper(II) complex (1) and a disulfide-bridged dicopper(I) complex (3) through a disulfide-bridged (mu-chloro)dicopper(I) complex (2) mediated by chloride ion has been established for the first time, providing a new redox chemistry of the transition metal-sulfur complexes. Crystal structures of 1 and 3 as well as spectroscopic

  新型双（mu-硫醇基）二铜（II）配合物（1）和二硫桥连的二铜（I）配合物（3）通过二硫桥（mu-氯）二铜（I）配合物实现前所未有的清洁互变（ 2) 首次建立了由氯离子介导的过渡金属-硫配合物的氧化还原化学。报告了 1 和 3 的晶体结构以及化合物的光谱特征。
• Disulphide bond cleavage in a pyridine-containing disulphide–copper(<scp>II</scp>) system under aerobic conditions. X-Ray crystal structure analysis of the product, diaquabis{µ-2-[(2-pyridymethyl)-amino]ethylsulphinato-O}dicopper(<scp>II</scp>) dichloride
  作者：Akiro Odani、Taeko Maruyama、Osamu Yamauchi、Takaji Fujiwara、Ken-ichi Tomita

  DOI：10.1039/c39820000646

  日期：——

  The diaulphide bond in a pyridine-containing disulphide was cleavage in the presence of copper(II) and dioxygen to give the copper(II) complex of the corresponding sulphinate, whose X-ray crystal structure analysis has disclosed a dimeric structure with the sulphinate oxygen atom bridging the copper(II) ions in a square-pyramidal environment.

  在铜（II）和双氧的存在下，将含吡啶的二硫键中的二硫键断裂，得到相应亚磺酸盐的铜（II）配合物，其X射线晶体结构分析已揭示了亚硫酸盐氧的二聚结构原子桥接铜（II）离子在四方锥的环境。
• FOYE W. O.; LOWE Y. H.; LANZILLO J. J., J. PHARM. SCI. <JPMS-AE>, 1976 65, NO 8, 1247-1251
  作者：FOYE W. O.、 LOWE Y. H.、 LANZILLO J. J.

  DOI：——

  日期：——
• Copper(II)-Sulfur Interactions in Pyridine- and Imidazole-containing Disulfide Complexes. Syntheses, Spectra, and Solution Equilibria
  作者：Osamu Yamauchi、Hiroko Seki、Toshiya Shoda

  DOI：10.1246/bcsj.56.3258

  日期：1983.11

  neutral–alkaline solution. A stable 1 : 1 copper(II) complex, Cu(IMAD)(ClO4)2·H2O, was isolated as crystals from aqueous solution, whereas a binuclear complex, Cu2(PMAD)Cl4, was obtained as crystals in ethanol. The Cu(II)–IMAD systems exhibit a single d-d peak at 585 nm indicative of a CuN4 chromophore but no charge transfer (CT) band in the region 300–900 nm. The other Cu(II)–disulfide systems exhibit

  已经对含吡​​啶环、喹啉环和咪唑环的二硫化物和相关化合物的铜 (II) 配合物进行了合成、光谱和电位研究，重点是铜 (II)-硫相互作用。在铜 (II)、二硫化物配体 (RCH2NHCH2CH2S–)2 存在下，其中 R=4-咪唑基 (IMAD)、2-吡啶基 (PMAD)、6-甲基-2-吡啶基 (MPAD) 和 2-喹啉基(QMAD)，在酸性溶液中比在中性碱性溶液中更稳定。稳定的 1:1 铜 (II) 配合物 Cu(IMAD)(ClO4)2·H2O 以晶体形式从水溶液中分离出来，而双核配合物 Cu2(PMAD)Cl4 在乙醇中以晶体形式获得。Cu(II)-IMAD 系统在 585 nm 处显示一个单 dd 峰，表明存在 CuN4 发色团，但在 300-900 nm 区域没有电荷转移 (CT) 带。其他 Cu(II)-二硫化物系统在 650 和 ≈850 nm 处显示 dd 带。分别在 pH
• Thermodynamics of the Cu^II μ-Thiolate and Cu^I Disulfide Equilibrium: A Combined Experimental and Theoretical Study
  作者：Erica C.M. Ording-Wenker、Martijn van der Plas、Maxime A. Siegler、Sylvestre Bonnet、F. Matthias Bickelhaupt、Célia Fonseca Guerra、Elisabeth Bouwman

  DOI：10.1021/ic501060w

  日期：2014.8.18

  The redox equilibrium between dinuclear Cu-II mu-thiolate and Cu-I disulfide structures has been analyzed experimentally and via DFT calculations. Two new ligands, (LSSL2)-S-2 and (LSSL4)-S-4, and their Cu-II mu-thiolate and Cu-I disulfide complexes were synthesized. For (LSSL2)-S-2, these two redoxisomeric copper species are shown to be in equilibrium, which depends on both temperature and solvent. For (LSSL4)-S-4 the mu-thiolate species forms as the kinetic product and further evolves into the disulfide complex under thermodynamic control, which creates the unprecedented possibility to both species under the same reaction conditions. The energies of the mu-thiolate and disulfide complexes for two series of related ligands have been calculated with DFT; the results rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in the formation of the Cull thiolate structure.