allyl 2,4,6-trichlorophenyl ether | 15890-54-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: allyl 2,4,6-trichlorophenyl ether
• 英文别名: allyl-(2,4,6-trichloro-phenyl)-ether；3-(2.4.6-Trichlor-phenoxy)-propen-(1)；Allyl-(2,4,6-trichlor-phenyl)-aether；2.4.6-Trichlor-1-allyloxy-benzol；1,3,5-Trichloro-2-(prop-2-en-1-yloxy)benzene；1,3,5-trichloro-2-prop-2-enoxybenzene
• CAS: 15890-54-7
• 化学式: C₉H₇Cl₃O
• 分子量: 237.513
• InChiKey: ZQGMMQSTKGOKGH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  allyl 2,4,6-trichlorophenyl ether 在 氯仿 、 溴 作用下， 生成 (2,3-dibromo-propyl)-(2,4,6-trichloro-phenyl)-ether
  参考文献：
  名称：

  一些高度卤化的酚醚作为抑菌化合物。

  摘要：

  DOI：

  10.1021/jo01166a015
• 作为产物：
  描述：

  sodium 2,4,6-trichlorophenolate 在 samarium diiodide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 6.0h， 生成 allyl 2,4,6-trichlorophenyl ether
  参考文献：
  名称：

  Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals

  摘要：

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.

  DOI：

  10.1021/jo00128a013

文献信息

• Lewis acid promoted double bond migration in O-allyl to Z-products by Ru-H complexes
  作者：Haibin Wang、Shaodong Liu、Tingting Sun、Zhanao Lv、Zhen Zhan、Guochuan Yin、Zhuqi Chen

  DOI：10.1016/j.mcat.2019.02.007

  日期：2019.5

  and convenient ruthenium(II) complex for the catalytic isomerization of O-allylethers, leading to thermodynamic-unfavored Z-product under mild conditions. The model substrate of allyl phenyl ether can be simply scaled up to 20 mmol to produce Z-product with TON of 2453 and TOF of 13,430 h−1 at 40–60 °C. The system of Ru(II)/Lewis Acid catalysts was suitable for various substituted O-allylethers and other

  在催化双键迁移反应中，通常以E-构型烯烃为主要产物，因为E-构型在热力学上是有利的。然而，由于结构-活性关系，有时在药物化学中需要Z-构型产物。在本文中，我们证明了一种新的策略，即路易斯酸促进了广泛使用且方便的钌（II）络合物用于O-烯丙基醚的催化异构化，导致在温和条件下产生热力学不利的Z产物。烯丙基苯基醚的模型底物可以简单地按比例放大至20 mmol以生产TON为2453，TOF为13,430 h -1的Z产物在40–60°C下。Ru（II）/路易斯酸催化剂体系适用于各种取代的O-烯丙基醚和其他类型的底物。通过包括动力学研究，配体抑制作用和分子光谱在内的机理研究，通过添加路易斯酸使PPh 3配体解离，以及由嵌合助剂形成五元Ru络合物均被认为是提高反应性和稳定性的必要步骤。通过金属氢化物加成消除机理控制催化双键迁移反应的立体选择性。这一新策略可能为生产用于药物化学的杂环化合物中热力学不利的产品提供新的机会。
• Addition of Nitrile Oxides to Aryl Allyl Ethers
  作者：E. Alksnis、V. Muravenko、V. Dirnens、E. Lukevics

  DOI：10.1023/b:cohc.0000040778.88220.e3

  日期：2004.6
• Reactivity of allyl aryl ethers in diene condensation with hexachlorocyclopentadiene
  作者：B. I. Musaeva、N. N. Novotorzhina、G. A. Gakhramanova、I. P. Ismailov

  DOI：10.1134/s1070363212120122

  日期：2012.12

  The reactivity of allyl aryl ethers in the diene condensation with hexachlorocyclopentadiene was studied. The reactivity of aryl allyl ethers and product yield in this reaction significantly decreases when electron-withdrawing groups are introduced into the benzene ring. The reactivity is also influenced by the temperature, reaction time, and the molar ratio of the diene and dienophile.
• US4168365A
  申请人：——

  公开号：US4168365A

  公开（公告）日：1979-09-18
• SOME HIGHLY HALOGENATED PHENOLIC ETHERS AS FUNGISTATIC COMPOUNDS
  作者：LLOYD C. FELTON、C. BAXTER McLAUGHLIN

  DOI：10.1021/jo01166a015

  日期：1947.3