octanethiyl radical | 142743-96-2

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: octanethiyl radical
• CAS: 142743-96-2
• 化学式: C₈H₁₇S
• 分子量: 145.289
• InChiKey: KBKKKDRGKPEINH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  9.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  二正辛基二硫 、 octanethiyl radical 生成
  参考文献：
  名称：

  动能和AB由含硫自由基INITIO从硫醇氢原子抽象理论研究：基础速率表达式硫中心自由基的反应

  摘要：

  Arrhenius rate expressions were determined for the abstraction of hydrogen atom from thiophenol and hexanethiol by the octanethiyl radical at 25-100-degrees-C in nonane. Octanethiyl radicals were produced by steady-state photolysis of octyl thiobenzoate. Analysis of octyl disulfide and octanethiol provided relative rate expressions for abstraction of hydrogen atom from thiols versus self-termination of the octanethiyl radical. For hexanethiol, log (k(abs)/k(t)1/2) = (2.94 +/- 0.29) - (3.84 +/- 0.41)/theta, and for thiophenol, log (k(abs)/k(t)1/2) = (2.56 +/- 0.19) - (2.88 +/- 0.28)/theta; theta = 2.3RT kcal/mol. Combining these expressions with the Smoluchowski expression for self-termination of octanethiyl in nonane, log (k(t)1/2) = 5.96 - 1.335/theta, which employs experimental diffusion coefficients of octanethiol and a spin selection factor sigma = 1, yields, for thiophenol, log (k(abs)/M-1 s-1) = (8.52 +/- 0.18) - (4.22 +/- 0.27)/theta, and for hexanethiol, log (k(abs)/M-1 s-1) = (8.90 +/- 0.29) - (5.18 +/- 0.41)/theta (errors are 2-sigma). The rate of disappearance of octanethiyl/diphenylketyl radical pairs in SDS micelles, determined by nanosecond optical spectroscopy, was found to be unchanged in a 700-G magnetic field, providing evidence for rapid intersystem crossing of sulfur-centered radical pairs and support for the assignment of sigma = 1 above. Ab initio electronic structure calculations on the reaction HS. + HSH --> HSH + .SH, performed at AH and correlated levels, predict an activation barrier of DELTA-H double dagger = 4.6 kcal/mol, in close agreement with the experimental barrier for the octanethiyl + hexanethiol reaction.

  DOI：

  10.1021/j100196a036
• 作为产物：
  描述：

  生成 二正辛基二硫 、 octanethiyl radical
  参考文献：
  名称：

  动能和AB由含硫自由基INITIO从硫醇氢原子抽象理论研究：基础速率表达式硫中心自由基的反应

  摘要：

  Arrhenius rate expressions were determined for the abstraction of hydrogen atom from thiophenol and hexanethiol by the octanethiyl radical at 25-100-degrees-C in nonane. Octanethiyl radicals were produced by steady-state photolysis of octyl thiobenzoate. Analysis of octyl disulfide and octanethiol provided relative rate expressions for abstraction of hydrogen atom from thiols versus self-termination of the octanethiyl radical. For hexanethiol, log (k(abs)/k(t)1/2) = (2.94 +/- 0.29) - (3.84 +/- 0.41)/theta, and for thiophenol, log (k(abs)/k(t)1/2) = (2.56 +/- 0.19) - (2.88 +/- 0.28)/theta; theta = 2.3RT kcal/mol. Combining these expressions with the Smoluchowski expression for self-termination of octanethiyl in nonane, log (k(t)1/2) = 5.96 - 1.335/theta, which employs experimental diffusion coefficients of octanethiol and a spin selection factor sigma = 1, yields, for thiophenol, log (k(abs)/M-1 s-1) = (8.52 +/- 0.18) - (4.22 +/- 0.27)/theta, and for hexanethiol, log (k(abs)/M-1 s-1) = (8.90 +/- 0.29) - (5.18 +/- 0.41)/theta (errors are 2-sigma). The rate of disappearance of octanethiyl/diphenylketyl radical pairs in SDS micelles, determined by nanosecond optical spectroscopy, was found to be unchanged in a 700-G magnetic field, providing evidence for rapid intersystem crossing of sulfur-centered radical pairs and support for the assignment of sigma = 1 above. Ab initio electronic structure calculations on the reaction HS. + HSH --> HSH + .SH, performed at AH and correlated levels, predict an activation barrier of DELTA-H double dagger = 4.6 kcal/mol, in close agreement with the experimental barrier for the octanethiyl + hexanethiol reaction.

  DOI：

  10.1021/j100196a036

文献信息

• The Kinetics of Thiyl Radical-Induced Reactions of Monounsaturated Fatty Acid Esters
  作者：Chryssostomos Chatgilialoglu、Alessio Altieri、Hanns Fischer

  DOI：10.1021/ja027428d

  日期：2002.10.1

  The time-dependent isomerizations and thiol additions of several Z- and E-monounsaturated fatty acid methyl esters catalyzed by alkanethiyl radicals during gamma-radiolysis of tert-butyl alcohol solutions are analyzed on the basis of the radiation chemical yield of radicals and established rate data. This provides room-temperature rate constants for the reversible thiyl addition. Within experimental

  基于自由基的辐射化学产率和已建立的速率数据，分析了在叔丁醇溶液的 γ-辐射过程中由烷烃基自由基催化的几种 Z-和 E-单不饱和脂肪酸甲酯的时间依赖性异构化和硫醇加成. 这为可逆的噻吩加成提供了室温速率常数。在实验误差范围内，它们不依赖于烷基链中的双键位置。特别值得注意的是硫基自由基从带有第二个β-取代基的烷基中非常快速地β-消除。它得到了通过激进时钟方法获得的额外证据的支持，
• Hydrogen abstraction by biradicals. Reactions with tri-n-butylstannane and octanethiol
  作者：M. V. Encinas、P. J. Wagner、J. C. Scaiano

  DOI：10.1021/ja00524a021

  日期：1980.2

  The biradicals generated in the Norrish type II reaction abstract hydrogen atoms from mercaptans and Bu/sub 3/SnH with rate constants of 9 x 10/sup 6/ and 1.1 x 10/sup 6/ M/sup -1/ s/sup -1/, respectively (for the biradical from ..gamma..-methylvalerophenone). The data from competitive and time-resolved experiments are in excellent agreement. The results suggest that the reactivity of radical sites

  Norrish II 型反应中生成的双自由基从硫醇和 Bu/sub 3/SnH 中提取氢原子，速率常数为 9 x 10/sup 6/ 和 1.1 x 10/sup 6/ M/sup -1/ s/sup - 1/，分别（对于来自 ..gamma..-methylvalerophenone 的双自由基）。来自竞争性和时间分辨实验的数据非常一致。结果表明双自由基中自由基位点的反应性与单自由基中相同位点的反应性相同。