methyl 7,7-diphenylhept-6-enoate | 87274-21-3

• 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: methyl 7,7-diphenylhept-6-enoate
• CAS: 87274-21-3
• 化学式: C₂₀H₂₂O₂
• 分子量: 294.393
• InChiKey: PGKXEQFONPGCTM-UHFFFAOYSA-N

物化性质

• 沸点：
  428.0±45.0 °C(Predicted)
• 密度：
  1.040±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  二苯基溴甲烷 在 正丁基锂 作用下， 反应 16.0h， 生成 methyl 7,7-diphenylhept-6-enoate
  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

• Alkenylation of unactivated alkyl bromides through visible light photocatalysis
  作者：Quan-Quan Zhou、Simon Josef Siegfried Düsel、Liang-Qiu Lu、Burkhard König、Wen-Jing Xiao

  DOI：10.1039/c8cc08362b

  日期：——

  Two visible-light driven alkenylation reactions of unactivated alkyl bromides, which were enabled by the use of Ir(dF(CF₃)ppy)₂(dtbbpy)PF₆ as the photocatalyst and (TMS)₃SiH as the atom transfer reagent to activate the alkyl bromides, were described for the first time.

  两种未活化的烷基溴化物的可见光驱动烯烃化反应首次利用Ir(dF(CF3)ppy)2(dtbbpy)PF6作为光催化剂和(TMS)3SiH作为原子转移试剂来激活烷基溴化物。
• Photochemistry of α,α-disubstituted bicyclic cyclobutanones - a potential thermal-photochemical metathesis reaction
  作者：Edward Lee-Ruff、Alan C. Hopkinson、Hira Kazarians-Moghaddam

  DOI：10.1016/s0040-4039(00)81845-6

  日期：1983.1

  Under certain conditions the photolysis of α,α-disubstituted cyclobutanones give terminal olefinic esters. A two-stage thermal photochemical metathesis is described.

  在某些条件下，α，α-二取代的环丁酮的光解反应可生成末端烯烃酯。描述了两阶段热光化学复分解。
• Photoinduced Metal‐Free Decarboxylative Transformations: Rapid Access to Amines, Alkyl Halides, and Olefins
  作者：Jia‐jing Luo、Dong Jing、Cong Lu、Ke Zheng

  DOI：10.1002/ejoc.202300167

  日期：——

  variety of alkyl halides, amines, and olefins in the presence of nBu4NI in a single-step. It is a straightforward method which is applied to the functionalization of a series of primary, secondary, and tertiary aliphatic carboxylic acid derivatives and complex natural products. Mechanistically, a charge transfer complex (CTC) was formed through non-covalent interaction between RAE and nBu4NI. Upon photoexcitation

  在此，我们描述了一种多功能的光催化策略，用于在n Bu 4 NI 存在下一步将氧化还原活性酯 (RAE) 脱羧转化为各种卤代烷、胺和烯烃。它是一种直接的方法，适用于一系列伯、仲、叔脂肪族羧酸衍生物和复杂天然产物的功能化。从机制上讲，电荷转移复合物 (CTC) 是通过 RAE 和n Bu 4之间的非共价相互作用形成的你。在光激发后，氨盐充当有效的电子供体和自由基重组的碘源。温和的反应条件使该方法可用于复杂天然产物的修饰和多功能的后续转化。
• LEE-RUFF, E.;HOPKINSON, A. C.;KAZARIANS-MOGHADDAM, H., TETRAHEDRON LETT., 1983, 24, N 20, 2067-2070
  作者：LEE-RUFF, E.、HOPKINSON, A. C.、KAZARIANS-MOGHADDAM, H.

  DOI：——

  日期：——