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。
• Cyclization–endoperoxidation cascade reactions of dienes mediated by a pyrylium photoredox catalyst
  作者：Nathan J Gesmundo、David A Nicewicz

  DOI：10.3762/bjoc.10.128

  日期：——

  Triarylpyrylium salts were employed as single electron photooxidants to catalyze a cyclization–endoperoxidation cascade of dienes. The transformation is presumed to proceed via the intermediacy of diene cation radicals. The nature of the diene component was investigated in this context to determine the structural requirements necessary for successful reactivity. Several unique endoperoxide structures were synthesized in yields up to 79%.

  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%。
• 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
  作者：Masaki Kamata、Jun-ichi Kaneko、Jun-ichi Hagiwara、Ryoichi Akaba

  DOI：10.1016/j.tetlet.2004.08.077

  日期：2004.9

  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.