1,4-di(p-methoxyphenyl)-2,3-dioxabicyclo[2.2.2]octane | 114396-01-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,4-di(p-methoxyphenyl)-2,3-dioxabicyclo[2.2.2]octane
• 英文别名: 1,4-Bis(4-methoxyphenyl)-2,3-dioxabicyclo[2.2.2]octane；1,4-bis(4-methoxyphenyl)-2,3-dioxabicyclo[2.2.2]octane
• CAS: 114396-01-9
• 化学式: C₂₀H₂₂O₄
• 分子量: 326.392
• InChiKey: HCXCIOGPIUHGLV-UHFFFAOYSA-N

物化性质

• 沸点：
  434.5±45.0 °C(Predicted)
• 密度：
  1.204±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4-di(p-methoxyphenyl)-2,3-dioxabicyclo[2.2.2]octane 在 2,6-二叔丁基吡啶 、 2,4,6-triphenylpyrylium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以55%的产率得到1,4-二(4-甲氧基苯基)-1,4-丁烷二酮
  参考文献：
  名称：

  Triphenylpyrylium salt-sensitized photoreactions of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes through competitive single electron-transfer pathway and proton-catalyzed pathway

  摘要：

  2,4,6-Triphenylpyrylium tetrafluoroborate (TPPBF4)-sensitized photoinduced electron-transfer (PET) reactions of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes 5 (a: Ar-1 = Ar-2 = p-MeOC6H4, b: Ar-1 = Ar-2 = p-MeC6H4, c: Ar-1 = Ar-2 = Ph) underwent novel fragmentation through their radical cations to give 1,4-diarylbutan-1,4-diones 6 accompanied by elimination of ethylene. On the other hand, 4-aryl-cyclohex-3-en-1-ones 7, p-substituted phenols 8, and 4-aryl-4-aryloxycyclohexanones 9 were produced through proton-catalyzed pathways when the PET reactions of 5 were performed in the absence of a certain base such as 2,6-di-tert-butylpyridine (DTBP). Particularly, the formation of 9 is consistent with the novel cationic rearrangement involving nucleophilic O-1,2-aryl shifts and C-1,4-aryl shifts. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.08.077
• 作为产物：
  描述：

  4,4'-(hexa-1,5-diene-2,5-diyl)bis(methoxybenzene) 在 氧气 、 2,4,6-tri-(p-methoxyphenyl) pyrylium tetrafluoroborate 作用下， 以 乙腈 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 生成 1,4-di(p-methoxyphenyl)-2,3-dioxabicyclo[2.2.2]octane
  参考文献：
  名称：

  Cyclization–endoperoxidation cascade reactions of dienes mediated by a pyrylium photoredox catalyst

  摘要：

  三芳基吡啶盐被用作单电子光氧化剂，催化二烯烃的环化-内过氧化级联反应。该转化被认为是通过二烯烃阳离子自由基的中间体进行的。在这一背景下，研究了二烯烃组分的性质，以确定成功反应所需的结构要求。合成了几种独特的内过氧化物结构，收率高达79%。

  DOI：

  10.3762/bjoc.10.128

文献信息

• Fe(II)-mediated fragmentation of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes through competitive single electron transfer pathway and Lewis acid pathway
  作者：Masaki Kamata、Takashi Kudoh、Jun-ichi Kaneko、Hye-Sook Kim、Yusuke Wataya

  DOI：10.1016/s0040-4039(01)02201-8

  日期：2002.1

  1]heptanes 3a–d. On the other hand, 4-aryl-3-cyclohexenones 4c–d and p-substituted phenols 5c–d were obtained in the reactions of 1c–d with FeBr2 in CH2Cl2. A new fragmentation mechanism involving an electrophilic oxyl radical 1,5-substitution and a nucleophilic O-1,2-aryl shift is proposed based on the product analysis. In addition, the in vitro antimalarial activities of 1a–d were tested.

  1,4-二芳基-2,3-二氧杂双环[2.2.2]辛烷的反应1A - d（1A Ar为：p -FC 6 ħ 4，1B：Ar为PH，1C：Ar为p -MeC 6 ħ 4，1D：Ar为p -MeOC 6 ħ 4）与FeBr 2的THF溶液，得到1,4- diarylbutan -1,4-二酮2A - d和1,4-二芳基-7-氧杂双环〔2.2.1〕庚烷3a中- d。另一方面，4-芳基-3-环己烯酮4c – d1c - d与FeBr 2在CH 2 Cl 2中的反应制得了对位酚5c - d和对位酚。在产物分析的基础上，提出了一种新的涉及亲电子羟基1,5-取代和亲核O -1,2-芳基移位的断裂机理。此外，还测试了1a - d的体外抗疟活性。