1,2,5-trithiacycloheptane | 6576-93-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 有机二硫化物
• 英文名称: 1,2,5-trithiacycloheptane
• 英文别名: 1,2,5-trithiepane；[1,2,5]trithiepane；[1,2,5]Trithiepan；1,2,5-Trithiepan
• CAS: 6576-93-8
• 化学式: C₄H₈S₃
• 分子量: 152.306
• InChiKey: JOAOASQIWYLMQC-UHFFFAOYSA-N

物化性质

• 沸点：
  118-120 °C(Press: 10 Torr)
• 密度：
  1.241±0.06 g/cm3(Predicted)
• 保留指数：
  1375

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  7
• 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：
  75.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,2,5-trithiacycloheptane 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 反应 2.0h， 以50%的产率得到1,2,5-trithiepane 5-S-oxide
  参考文献：
  名称：

  1,2,5-Trithiepin:  A 10π-Electron Heteroaromatic System

  摘要：

  The unsubstituted 1,2,5-trithiepin (1) has been synthesized from the known 1,2,5-trithiepane (6) through two consecutive Pummerer rearrangements. Proton and carbon NMR spectra were completely analyzed, assigned, and correlated. The protons in 1 are shifted downfield by Delta delta = 0.57 ppm for H-3/H-7 (delta = 6.57 ppm) and by 1.10 ppm far H-4/H-6 (delta = 7.24 ppm) relative to the 6,7-dihydro-1,2,5-trithiepin (7), These downfield shifts are comparable to thiophene, thus characterizing 1,2,5-trithiepin (1) as the first multisulfur 10 pi-aromatic diatropic molecule incorporating a disulfide linkage. 6,7-Dihydro-1,2,5-trithiepin (7) is a dynamic system. Variable-temperature H-1-NMR measurements of 7 yielded an estimated free energy of activation at the coalescence temperature (227 K) of Delta G(double dagger) = 9.83 kcal/mol.

  DOI：

  10.1021/jo9519625
• 作为产物：
  描述：

  1-氯-2-(2-氯乙基二硫基)乙烷 在 sodium sulfide 、 乙醇 作用下， 生成 1,2,5-trithiacycloheptane
  参考文献：
  名称：

  Fromm; Joerg, Chemische Berichte, 1925, vol. 58, p. 306

  摘要：

  DOI：

文献信息

• Structure-reactivity relations for thiol-disulfide interchange
  作者：Janette Houk、George M. Whitesides

  DOI：10.1021/ja00256a040

  日期：1987.10

  di- and trithiols and the disulfides derived from either 2-mercaptoethanol or dithiothreitol. Reactions were conducted in methanol-d,/aqueous buffer (pH 7) or methanold, at 25 "C, using NMR spectroscopy to follow the reactions. These data were used to rank the dithiols in terms of reduction potential and to infer the structure of the disulfides formed from them on oxidation. There is a general correlation

  平衡常数由 36 个二硫醇和三硫醇与衍生自 2-巯基乙醇或二硫苏糖醇的二硫化物之间的硫醇-二硫化物交换确定。反应在甲醇-d/水性缓冲液 (pH 7) 或甲醇中进行，在 25°C 下，使用 NMR 光谱跟踪反应。这些数据用于根据还原电位对二硫醇进行排序并推断其结构氧化时由它们形成的二硫化物。二硫醇的还原能力与氧化时形成的含二硫化物环的大小之间存在普遍的相关性：形成六元环的二硫醇还原性最强（K = 103-105 M 相对于氧化的 2-巯基乙醇）；五元和七元环的还原性降低约 1 个数量级。类似于 1 的化合物，2-乙二硫醇在相对稀释的溶液 (- 1 mM) 中形成环状双（二硫化物）二聚体，但在较高浓度下聚合。其他类别的二硫醇在氧化时形成聚合物。
• Nevalainen, Vesa; Pohjala, Esko, Journal of Chemical Research, Miniprint, 1988, # 6, p. 1401 - 1421
  作者：Nevalainen, Vesa、Pohjala, Esko

  DOI：——

  日期：——
• Reactions of 1,2,4‐Trithiolane, 1,2,5‐Trithiepane, 1,2,5‐Trithiocane and 1,2,6‐Trithionane with Nonacarbonyldiiron: Structural Determination and Electrochemical Investigation
  作者：Jochen Windhager、Manfred Rudolph、Silvio Bräutigam、Helmar Görls、Wolfgang Weigand

  DOI：10.1002/ejic.200700049

  日期：2007.6

  AbstractThe reactions of 1,2,4‐trithiolane (1), 1,2,5‐trithiepane (6), 1,2,5‐trithiocane (12) and 1,2,6‐trithionane (10) with nonacarbonyldiiron (2) have been investigated. A novel diiron model complex, which can serve as a model complex of the active site of [Fe‐only]‐hydrogenase, was formed from the reaction with 1. In contrast, the reaction of 6 with 2 afforded the trinuclear iron cluster 7. Interestingly, the diiron compound 11 was obtained with 1,2,6‐trithionane (10), which can be attributed to the more flexible dithiolato ligand 10. Furthermore, the reaction with 1,2,5‐trithiocane (12) yielded the trinuclear cluster 13. X‐ray structure analyses were performed on compounds 3, 7, 10, 11 and 13. The reactions of the reduced iron species 3 with pivalic acid (HP) were studied electrochemically. The most significant features of the experimental cyclic voltammograms (CVs) could be reproduced by digital simulation on the basis of a reaction scheme that includes both the coordination of HP as well as the catalytic generation of hydrogen. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Synthesis of Medium Ring Disulfides by Titrimetry; An Improvement on High Dilution Techniques
  作者：Marvin H. Goodrow、W. Kenneth Musker

  DOI：10.1055/s-1981-29481

  日期：——
• Ray, Journal of the Chemical Society, 1924, vol. 125, p. 1142
  作者：Ray

  DOI：——

  日期：——

表征谱图