bis(7,7-diphenylhept-6-enoyl)peroxide | 146511-37-7

• 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: bis(7,7-diphenylhept-6-enoyl)peroxide
• 英文别名: 7,7-Diphenylhept-6-enoyl 7,7-diphenylhept-6-eneperoxoate
• CAS: 146511-37-7
• 化学式: C₃₈H₃₈O₄
• 分子量: 558.717
• InChiKey: LSCSHJGVHOCXLF-UHFFFAOYSA-N

物化性质

• 沸点：
  695.2±65.0 °C(Predicted)
• 密度：
  1.108±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  42
• 可旋转键数：
  17
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(7,7-diphenylhept-6-enoyl)peroxide 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 氢氧化钾 、 氯化亚砜 、 sodium peroxide 、 水 、 N,N-二甲基甲酰胺 作用下， 以 乙醚 、 乙醇 、 苯 为溶剂， 反应 8.0h， 生成 bis(7,7-diphenylhept-6-enoyl)peroxide
  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

• 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.