(E)-2-methyl-4-(o-tolyl)but-3-en-2-ol | 917507-05-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (E)-2-methyl-4-(o-tolyl)but-3-en-2-ol
• 英文别名: (E)-2-methyl-4-(2-methylphenyl)but-3-en-2-ol
• CAS: 917507-05-2
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: GMMXUPKBPGLUFT-CMDGGOBGSA-N

物化性质

• 沸点：
  291.4±9.0 °C(Predicted)
• 密度：
  0.994±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-2-methyl-4-(o-tolyl)but-3-en-2-ol 在 正丁基锂 、 四甲基乙二胺 、 potassium tert-butylate 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.25h， 生成 1-(deuteriomethyl)-2-[(E)-3-methoxy-3-methylbut-1-enyl]benzene
  参考文献：
  名称：

  Highly Activated Vinyl Hydrogen in a Significantly Twisted Styrene

  摘要：

  The novel example of a vinylic hydrogen more reactive than a benzylic hydrogen was found by treatment of a twisted styrene derivative with a strong base followed by D2O quenching. In this paper, the full details of the examples of the highly activated vinyl hydrogens in twisted styrene derivatives are described, with a discussion on the correlation between the reactivity of the vinyl hydrogens and the magnitude of the twist. The highly reactive vinyl hydrogens could be rationalized by considering the novel orbital interaction between the pi* orbital of the benzene ring and the sigma orbital of the vinylic C-H bond in the twisted styrene derivatives.

  DOI：

  10.1021/jo061092z
• 作为产物：
  描述：

  2-甲基-4-o-甲苯基丁-3-炔-2-醇 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 (E)-2-methyl-4-(o-tolyl)but-3-en-2-ol
  参考文献：
  名称：

  Vinyl hydrogen more reactive than benzyl hydrogen toward base in significantly twisted styrenes

  摘要：

  The novel example of vinyl hydrogen more reactive than benzylic hydrogen was found by treatment of a twisted styrene derivative with a strong base followed by D2O quenching. The characteristic nature of the vinyl hydrogen, which is activated by sigma-pi* orbital interaction, was apparently demonstrated. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00308-2

文献信息

• Transition-Metal Catalyzed Stereoselective γ-Arylation and Friedel-Crafts Alkylation: A Concise Synthesis of Indenes
  作者：Karu Ramesh、Gedu Satyanarayana

  DOI：10.1002/ejoc.202000030

  日期：2020.6.16

  A concise synthesis of Mizoroki–Heck products and corresponding indenes starting with simple tert ‐alkenols and aryl halides is presented. Notably, the γ‐arylation was done under [Pd]‐catalysis by using water as the sole green solvent and the synthesis of indenes via acid‐mediated intramolecular Friedel–Crafts cyclization.

  介绍了从简单的叔烯醇和卤代芳基化合物开始的合成简单的Mizoroki-Heck产物和相应的茚满。值得注意的是，γ芳基化反应是在[Pd]催化下，以水为唯一的绿色溶剂，并通过酸介导的分子内Friedel-Crafts环化反应合成茚满。
• Iridium‐Catalyzed 1,3‐Rearrangement of Allylic Alcohols
  作者：Fei Li、Yicong Luo、Xuejie Zhu、Yong Ye、Qianjia Yuan、Wanbin Zhang

  DOI：10.1002/chem.202300027

  日期：——

  An efficient Ir(III) dihydride complex catalyzed 1,3-rearrangement of allylic alcohols was realized, affording the corresponding less easily accessible allylic alcohols regio- and stereoselectively in high yields from readily available starting materials. The reaction pathway involves a π-allyl-Ir(V) intermediate and the dihydride in Ir(III) dihydride complex acts as the hydrogen switch to modulate

  实现了有效的 Ir(III) 二氢化物络合物催化烯丙醇的 1,3-重排，从容易获得的起始材料中以高收率区域选择性和立体选择性地提供相应的不易获得的烯丙醇。反应途径涉及 π-烯丙基-Ir(V) 中间体，Ir(III) 二氢化物络合物中的二氢化物作为氢开关调节铱中心的化合价。
• Copper-Catalyzed Alkenylation of Alcohols with β-Nitrostyrenes via a Radical Addition–Elimination Process
  作者：Yan-qin Yuan、Sheng-rong Guo

  DOI：10.1055/s-0034-1380445

  日期：——

  A new method for the preparation of allylic alcohol derivatives has been developed via a radical mechanism using DTBP as the radical initiator promoted by copper salt. The C(sp(3))-H bond in various alcohols, toluene derivatives, and alkanes were successfully converted into C-C bonds to yield the desired products in moderate to good yields.
• Heck reactions of aryl bromides with alk-1-en-3-ol derivatives catalysed by a tetraphosphine/palladium complex
  作者：Florian Berthiol、Henri Doucet、Maurice Santelli

  DOI：10.1016/j.tetlet.2004.05.117

  日期：2004.7

  cis,cis,cis-1,2,3,4-Tetrikis(diplienylphosphinomethyl)cyclopentane/[PdCl(C3H5)](2) efficiently catalyses the Heck reaction of alk-1-en-3-ol with a variety of aryl bromides. In the presence of hex-1-en-3-ol or oct-1-en-3-ol, the beta-arylated carbonyl compounds were selectively obtained. Linalool and 2-methylbut-3-en-2-ol led to the corresponding 1-arylalk-1-en-3-ol derivatives. Turnover numbers up to 69,000 can be obtained for this reaction. A minor electronic effect of the substituents of the aryl bromide was observed. Similar reaction rates were observed in the presence of activated aryl bromides Such as bromoacetophenone and deactivated aryl bromides such as bromoanisole. (C) 2004 Elsevier Ltd. All rights reserved.
• US5393461A
  申请人：——

  公开号：US5393461A

  公开（公告）日：1995-02-28