1-<<(6,6-diphenyl-5-hexenyl)carbonyl>oxy>-2(1H)-pyridinethione | 146511-36-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-<<(6,6-diphenyl-5-hexenyl)carbonyl>oxy>-2(1H)-pyridinethione
• 英文别名: (2-Sulfanylidenepyridin-1-yl) 7,7-diphenylhept-6-enoate
• CAS: 146511-36-6
• 化学式: C₂₄H₂₃NO₂S
• 分子量: 389.518
• InChiKey: YDHLJFWOKODDGB-UHFFFAOYSA-N

物化性质

• 沸点：
  549.7±60.0 °C(predicted)
• 密度：
  1.21±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-<<(6,6-diphenyl-5-hexenyl)carbonyl>oxy>-2(1H)-pyridinethione 以 乙腈 为溶剂， 生成 6,6-diphenyl-5-hexenyl radical
  参考文献：
  名称：

  Kinetic studies of the cyclization of the 6,6-diphenyl-5-hexenyl radical. A test of the accuracy of rate constants for reactions of hydrogen transfer agents

  摘要：

  Cyclization of the 6,6-diphenyl-5-hexenyl radical (1) to the diphenylcyclopentylcarbinyl radical (2) was studied by indirect and direct methods. Indirect kinetic studies were accomplished by the PTOC-thiol method using hydrogen atom transfer trapping from thiophenol and from tert-butylthiol as the competing basis reactions over the temperature range of -47 to +44-degrees-C. Tributyltin hydride trapping at 22-degrees-C also was studied. There was excellent agreement in the rate constants for cyclization determined with the various trapping agents showing that the bimolecular rate constants for hydrogen transfer from these agents are equivalently placed on a kinetic scale. The Arrhenius function for cyclization of 1 was log (k(r)/8-1) = 10.40-3.63/2.3RT. In direct studies, radical 1 was produced by photolysis of the PTOC ester and the diacyl peroxide derived from 7,7-diphenyl-6-heptenoic acid. The rate constant for cyclization of 1 at 22-degrees-C was 4.5 X 10(7) s-1. The good agreement between the direct kinetic value and the value of 5.1 X 10(7) s-1 calculated from the above Arrhenius function confirms that the rate constants for hydrogen atom transfer from the trapping agents are accurate. The rate constant for cyclization of 1 at room temperature is about one-half as great as that for ring opening of the cyclopropylcarbinyl radical, and primary alkyl radical 1 should prove useful as a radical clock for timing fast radical reactions.

  DOI：

  10.1021/jo00057a036
• 作为产物：
  描述：

  methyl 7,7-diphenylhept-6-enoate 在 4-二甲氨基吡啶 、 氢氧化钾 、 氯化亚砜 、 N,N-二甲基甲酰胺 作用下， 以 乙醇 、 苯 为溶剂， 反应 8.0h， 生成 1-<<(6,6-diphenyl-5-hexenyl)carbonyl>oxy>-2(1H)-pyridinethione
  参考文献：
  名称：

  Kinetic studies of the cyclization of the 6,6-diphenyl-5-hexenyl radical. A test of the accuracy of rate constants for reactions of hydrogen transfer agents

  摘要：

  Cyclization of the 6,6-diphenyl-5-hexenyl radical (1) to the diphenylcyclopentylcarbinyl radical (2) was studied by indirect and direct methods. Indirect kinetic studies were accomplished by the PTOC-thiol method using hydrogen atom transfer trapping from thiophenol and from tert-butylthiol as the competing basis reactions over the temperature range of -47 to +44-degrees-C. Tributyltin hydride trapping at 22-degrees-C also was studied. There was excellent agreement in the rate constants for cyclization determined with the various trapping agents showing that the bimolecular rate constants for hydrogen transfer from these agents are equivalently placed on a kinetic scale. The Arrhenius function for cyclization of 1 was log (k(r)/8-1) = 10.40-3.63/2.3RT. In direct studies, radical 1 was produced by photolysis of the PTOC ester and the diacyl peroxide derived from 7,7-diphenyl-6-heptenoic acid. The rate constant for cyclization of 1 at 22-degrees-C was 4.5 X 10(7) s-1. The good agreement between the direct kinetic value and the value of 5.1 X 10(7) s-1 calculated from the above Arrhenius function confirms that the rate constants for hydrogen atom transfer from the trapping agents are accurate. The rate constant for cyclization of 1 at room temperature is about one-half as great as that for ring opening of the cyclopropylcarbinyl radical, and primary alkyl radical 1 should prove useful as a radical clock for timing fast radical reactions.

  DOI：

  10.1021/jo00057a036

文献信息

• Hydropersulfides: H-Atom Transfer Agents Par Excellence
  作者：Jean-Philippe R. Chauvin、Markus Griesser、Derek A. Pratt

  DOI：10.1021/jacs.7b02571

  日期：2017.5.10

  biotransmitter hydrogen sulfide (H2S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H2S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting

  氢过硫化物（RSSH）是通过气态生物递质硫化氢（H 2 S）与二硫化物（RSSR）和/或亚磺酸（RSOH）的反应内生形成的。已经研究了RSSH在体内储存H 2 S的能力以及作为抗氧化应激的防御线，从中可以清楚地看出，RSSH对二电子氧化剂的反应性比硫醇更高。在此，我们描述了对RSSH的H原子转移化学的研究结果，并将其与众所周知的硫醇的H原子转移化学进行了对比。事实上，RSSH优异H-原子供体，以烷基（ķ〜5×10 8中号-1小号-1），烷氧基（ķ〜1×10 9中号-1小号-1），过氧化氢（ķ〜2×10 6中号-1小号-1），和含硫（ķ > 1×10 10中号-1小号-1）自由基，对硫醇的抑制作用可低至1个数量级，最高可至4个数量级。RSSH对H原子转移的固有高反应性很大程度上是基于热力学因素。较弱的RSS–H键解离焓（〜70 kcal / mol）和相关的高硫基自由基稳定性使上述反应放热15–34
• Kinetic studies of the cyclization of the 6,6-diphenyl-5-hexenyl radical. A test of the accuracy of rate constants for reactions of hydrogen transfer agents
  作者：Chau Ha、John H. Horner、Martin Newcomb、Thomas R. Varick、Bradley R. Arnold、Janusz Lusztyk

  DOI：10.1021/jo00057a036

  日期：1993.2

  Cyclization of the 6,6-diphenyl-5-hexenyl radical (1) to the diphenylcyclopentylcarbinyl radical (2) was studied by indirect and direct methods. Indirect kinetic studies were accomplished by the PTOC-thiol method using hydrogen atom transfer trapping from thiophenol and from tert-butylthiol as the competing basis reactions over the temperature range of -47 to +44-degrees-C. Tributyltin hydride trapping at 22-degrees-C also was studied. There was excellent agreement in the rate constants for cyclization determined with the various trapping agents showing that the bimolecular rate constants for hydrogen transfer from these agents are equivalently placed on a kinetic scale. The Arrhenius function for cyclization of 1 was log (k(r)/8-1) = 10.40-3.63/2.3RT. In direct studies, radical 1 was produced by photolysis of the PTOC ester and the diacyl peroxide derived from 7,7-diphenyl-6-heptenoic acid. The rate constant for cyclization of 1 at 22-degrees-C was 4.5 X 10(7) s-1. The good agreement between the direct kinetic value and the value of 5.1 X 10(7) s-1 calculated from the above Arrhenius function confirms that the rate constants for hydrogen atom transfer from the trapping agents are accurate. The rate constant for cyclization of 1 at room temperature is about one-half as great as that for ring opening of the cyclopropylcarbinyl radical, and primary alkyl radical 1 should prove useful as a radical clock for timing fast radical reactions.