1,2,3,4,4a,10-hexahydroanthracene | 5915-93-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 1,2,3,4,4a,10-hexahydroanthracene
• 英文别名: Hexahydroanthracene
• CAS: 5915-93-5
• 化学式: C₁₄H₁₆
• 分子量: 184.281
• InChiKey: ARPANWHHRGVXBN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-(bromomethyl)-2-vinylbenzene 在 titanium(III) chloride 、 水 、 臭氧 、 三苯基膦 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 38.67h， 生成 1,2,3,4,4a,10-hexahydroanthracene
  参考文献：
  名称：

  New low-valent titanium reagents for dicarbonyl coupling and their use in a general method of annulation

  摘要：

  New low-valent titanium reagents have been prepared by reducing TiCl3 (1 mol) with C8K (2 mol) or by reducing TiCl4 (1 mol) with Na-naphthalene (2.75 mol). Ketones carrying a chain that incorporates a suitably placed oxo function (aldehyde or ketone) undergo intramolecular dicarbonyl coupling to produce a bicyclic compound when treated with an excess (16-17 mol of titanium halide per mol of dicarbonyl compound) of one of these reagents. The procedure works well even for highly oxygenated substrates and constitutes a general method of annulation. Other reducing agents besides C8K or Na-naphthalene are suitable, and a brief examination of Na(Hg) and Na-K alloy was made. The C8K/TiCl3 system was also used to convert a cis-1,2-diol into the corresponding olefin.

  DOI：

  10.1021/jo00022a042

文献信息

• Catalytic 1,2-dihydronaphthalene and <i>E</i>-aryl-diene synthesis <i>via</i> Co^III–Carbene radical and <i>o</i>-quinodimethane intermediates
  作者：Colet te Grotenhuis、Braja G. Das、Petrus F. Kuijpers、Wouter Hageman、Mees Trouwborst、Bas de Bruin

  DOI：10.1039/c7sc03909c

  日期：——

  yields for substrates with an R2 = COOEt substituent at the vinylic position (~70-90% ). Changing the R2 moiety from an ester to other substituents has a surprisingly large influence on the (isolated) yields. This behaviour is unexpected for a radical rebound ring-closure mechanism, and points to a mechanism proceeding via ortho-quinodimethane (o-QDM) intermediates. Furthermore, substrates with an alkyl

  提出了通过邻苯乙烯基 N-甲苯磺酰腙（( E )-2-(丙-1-烯-1-基)苯-N-甲苯磺酰腙）的金属自由基活化催化合成取代的1,2-二氢萘，钴(III)-卡宾自由基中间体的固有反应性。该方法已成功应用于芳香环上具有各种 R1 取代基的各种底物，对于乙烯基位置上具有 R 2 = COOEt 取代基的底物（约 70-90 %）。将R 2部分从酯变为其他取代基对（分离的）产率具有令人惊讶的巨大影响。这种行为对于自由基回弹闭环机制来说是出乎意料的，并且表明是通过邻醌二甲烷（o -QDM）中间体进行的机制。此外，在烯丙位上具有烷基取代基的底物以优异的产率反应形成E-芳基二烯，而不是预期的1,2-二氢萘。这一结果与支持 DFT 计算的结果相结合，强烈表明在所有情况下都会从金属中心释放反应性 o-QDM 中间体，这些中间体要么经历 6π 环化步骤形成 1,2-二氢萘，要么经过[1,7]-氢化物移位产生E-芳基二烯。使用
• Regiochemistry in Aryl Radical Cyclization onto Methylenecycloalkanes
  作者：Hiroyuki Ishibashi、Tetsuya Kobayashi、Sayaka Nakashima、Osamu Tamura

  DOI：10.1021/jo001086h

  日期：2000.12.1

  Bu(3)SnH-mediated aryl radical cyclization onto methylenecycloalkanes having a phenylthio, an ester, or a nitrile group at the terminus of the alkenic bond provides exclusively exo cyclization products. The results are in sharp contrast to those reported for nonsubstituted methylenecycloalkanes, which give exclusively endo cyclization products. Formation of endo cyclization products has been suggested

  Bu（3）SnH介导的芳基自由基环化成在烯键末端具有苯硫基，酯或腈基的亚甲基环烷烃，仅提供外环化产物。结果与未取代的亚甲基环烷烃报告的结果形成鲜明对比，后者仅产生内环化产物。内环化产物的形成已被认为是芳基连续5-外向环化和新叶重排的结果。选择性外芳基自由基环化提供了一种合成含苄基季碳原子的稠合芳族化合物的新方法。
• 76. Hydroanthracenes and hydrophenanthrenes. Part II
  作者：J. W. Cook、N. A. McGinnis、Stotherd Mitchell

  DOI：10.1039/jr9440000286

  日期：——
• New low-valent titanium reagents for dicarbonyl coupling and their use in a general method of annulation
  作者：Derrick L. J. Clive、Chengzhi Zhang、K. S. Keshava Murthy、William D. Hayward、Sylvain Daigneault

  DOI：10.1021/jo00022a042

  日期：1991.10

  New low-valent titanium reagents have been prepared by reducing TiCl3 (1 mol) with C8K (2 mol) or by reducing TiCl4 (1 mol) with Na-naphthalene (2.75 mol). Ketones carrying a chain that incorporates a suitably placed oxo function (aldehyde or ketone) undergo intramolecular dicarbonyl coupling to produce a bicyclic compound when treated with an excess (16-17 mol of titanium halide per mol of dicarbonyl compound) of one of these reagents. The procedure works well even for highly oxygenated substrates and constitutes a general method of annulation. Other reducing agents besides C8K or Na-naphthalene are suitable, and a brief examination of Na(Hg) and Na-K alloy was made. The C8K/TiCl3 system was also used to convert a cis-1,2-diol into the corresponding olefin.