(E)-1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene | 42006-43-9

• 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: (E)-1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene
• 英文别名: 1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene；1-(4-trifluoromethylphenyl)-1-propene；1-[(E)-prop-1-enyl]-4-(trifluoromethyl)benzene
• CAS: 42006-43-9
• 化学式: C₁₀H₉F₃
• 分子量: 186.177
• InChiKey: RKSHYZZUJFUXEY-NSCUHMNNSA-N

物化性质

• 沸点：
  183.9±35.0 °C(Predicted)
• 密度：
  1.135±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene 以 正己烷 为溶剂， 生成 1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene
  参考文献：
  名称：

  Singlet State Cis,Trans Photoisomerization and Intersystem Crossing of 1-Arylpropenes

  摘要：

  The temperature dependence of the singlet state lifetime and photoisomerization and fluorescence quantum yields for trans- and cis-1-phenylpropene have been determined in hexane solution. Calculated barriers for twisting about the double bond on the singlet potential energy surface are 8.8 and 4.6 kcal/mol for the trans and cis isomer, respectively. The barrier for the trans isomer is sufficiently high to prevent isomerization on the singlet state surface at or below room temperature. However, isomerization occurs at low temperatures as a consequence of intersystem crossing to the triplet state, which undergoes barrierless isomerization. The quantum yield for intersystem crossing, as determined by time-resolved photoacoustic calorimetry, is 0.60 +/- 0.03 and the rate constant for intersystem crossing is 4.7 x 10(7) s(-1). While internal conversion is not significant at or below room temperature, thermally activated internal conversion competes with singlet isomerization at high temperatures. The cis isomer undergoes isomerization predominantly via the singlet state at room temperature. Both electron-donating (p-methoxy) and electron-withdrawing (m- and p-cyano, p-carbomethoxy, and p-trifluormethyl) aromatic substituents are found to lower the barrier for singlet state isomerization. Increased solvent polarity (acetonitrile vs hexane) results in variable decreases in the barrier for singlet state isomerization. Photoisomerization of the p-cyano derivative at room temperature occurs predominantly via the triplet state in hexane solution and via the singlet state in acetonitrile solution. The effects of substituents and solvent are better correlated with the magnitude of the S-2-S-1 energy gap than the stability of either zwitterionic or biradical intermediates. Rate constants for intersystem crossing are, in most cases, not highly dependent upon aromatic substitution or solvent polarity.

  DOI：

  10.1021/ja00102a014
• 作为产物：
  描述：

  1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene 在 cobalt(II) chloride 、 2,2'-bis(diphenylphosphino)phenylamine 、 三乙基硼氢化钠 作用下， 以 甲苯 为溶剂， 反应 1.08h， 以99%的产率得到(E)-1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene
  参考文献：
  名称：

  钴催化烯烃的Z到E异构化：（E）-β取代的苯乙烯的一种方法。

  摘要：

  开发了使用酰胺基-二膦配体的高效钴催化的β-取代的苯乙烯的Z到E异构化方法，提供了具有良好功能耐受性和高立体选择性的（E）异构体。使用（Z）-和（E）-烯烃的混合物作为起始原料，该反应可以在催化剂负载为0.1mol％的情况下按比例放大至克级。初步的机理研究表明，在实验和DFT计算的支持下，钴（I）氢化物和苄基钴可能参与了反应。

  DOI：

  10.1021/acs.orglett.0c00072

文献信息

• Nickel-Catalyzed Allylic C(sp²)-H Activation: Stereoselective Allyl Isomerization and Regiospecific Allyl Arylation of Allylarenes
  作者：Qiang Wu、Lanlan Wang、Rizhe Jin、Chuanqing Kang、Zheng Bian、Zhijun Du、Xiaoye Ma、Haiquan Guo、Lianxun Gao

  DOI：10.1002/ejoc.201600955

  日期：2016.11

  allylarenes with excess Grignard reagent. It occurs regiospecifically at the position of C(sp2)–H activation and represents a new method for the synthesis of 1,1-disubstituted olefins. The results of deuterium labeling experiments reveal an alkenyl/alkyl mechanism involving allylic internal C(sp2)–H activation and multiple intermolecular 1,2-, 1,3-, and 2,3-hydride shifts. These methods represent new

  研究了烯丙基与包含镍 (II) 和芳基格氏试剂的催化体系的立体选择性烯丙基异构化和区域特异性烯丙基芳基化反应。这两个反应都是由原位形成的 Ni0 激活烯丙基内部 C(sp2)-H 触发的，Ni0 被插入到烯丙基部分的 2 位的 C-H 键中，没有导向基团。烯丙基芳烃异构化为 1-丙烯基芳烃有利于 E 异构体并进行定量转化。芳基化通过烯丙基芳烃与过量格氏试剂的氧化交叉偶联发生。它区域特异性地发生在 C(sp2)–H 活化的位置，代表了一种合成 1,1-二取代烯烃的新方法。氘标记实验的结果揭示了烯基/烷基机制，涉及烯丙基内部 C(sp2)–H 活化和多个分子间 1,2-、1,3- 和 2,3- 氢化物位移。这些方法代表了烯烃官能化的新方法，机理研究有助于发现和设计烯烃官能化的新策略。
• [EN] BICYCLIC INHIBITORS OF PAD4<br/>[FR] INHIBITEURS BICYCLIQUES DE PAD4
  申请人：PADLOCK THERAPEUTICS INC

  公开号：WO2017100594A1

  公开（公告）日：2017-06-15

  The present invention provides compounds useful as inhibitors of PAD4, compositions thereof, and methods of treating PAD4-related disorders.

  本发明提供了用作PAD4抑制剂的化合物、其组合物以及治疗与PAD4相关疾病的方法。
• Iron Catalyzed Double Bond Isomerization: Evidence for an Fe ^I /Fe ^III Catalytic Cycle
  作者：Callum R. Woof、Derek J. Durand、Natalie Fey、Emma Richards、Ruth L. Webster

  DOI：10.1002/chem.202004980

  日期：2021.4

  Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre‐catalyst activation step that gives access to an η2‐coordinated alkene FeI complex, followed by oxidative addition of the alkene to give an FeIII intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

  据报道，铁催化的烯烃异构化使用铁(II) β-二酮亚胺预催化剂。该反应在催化量的氢化物源（例如频哪醇硼烷（HBpin）或氨硼烷（H 3 N·BH 3））下进行。已研究了与烯丙基芳烃和脂肪族烯烃的反应性。通过多种手段研究了催化机理，包括氘化研究、密度泛函理论（DFT）和电子顺磁共振（EPR）光谱。获得的数据支持预催化剂活化步骤，该步骤提供了 η 2配位烯烃 Fe I络合物，然后通过氧化加成烯烃得到 Fe III中间体，然后进行还原消除以释放异构化产物。
• A Highly Active Cationic Ruthenium Complex for Alkene Isomerisation: A Catalyst for the Synthesis of High Value Molecules
  作者：Simone Manzini、David J. Nelson、Steven P. Nolan

  DOI：10.1002/cctc.201300396

  日期：2013.10

  You′ve been valorized! A novel cationic ruthenium complex is shown to be efficient in the isomerization of important feedstocks derived from essential oils, which can then be functionalized through olefin metathesis.

  你被吓到了！一种新型的阳离子钌络合物在衍生自香精油的重要原料的异构化中显示出很高的效率，然后可以通过烯烃复分解功能对其进行官能化。
• Controllable Isomerization of Alkenes by Dual Visible‐Light‐Cobalt Catalysis
  作者：Qing‐Yuan Meng、Tobias E. Schirmer、Kousuke Katou、Burkhard König

  DOI：10.1002/anie.201900849

  日期：2019.4.16

  We report herein that thermodynamic and kinetic isomerization of alkenes can be accomplished by the combination of visible light with Co catalysis. Utilizing Xantphos as the ligand, the most stable isomers are obtained, while isomerizing terminal alkenes over one position can be selectively controlled by using DPEphos as the ligand. The presence of the donor–acceptor dye 4CzIPN accelerates the reaction

  我们在本文中报道，烯烃的热力学和动力学异构化可以通过将可见光与Co催化相结合来完成。使用黄磷作为配体，可以获得最稳定的异构体，而通过使用DPEphos作为配体可以选择性地控制末端烯烃的异构化。供体-受体染料4CzIPN的存在进一步促进了反应。在没有任何其他配体的情况下，通过使用4CzIPN和Co（acac）2可以有效地实现环外烯烃向相应内环产物的转化。光谱学和光谱电化学研究表明，Co I参与了Co氢化物的生成，而Co氢化物随后会添加到烯烃中以引发异构化反应。