1,4-二苯基-2,3-二氧杂二环[2.2.2]辛烷 | 114396-00-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 中文名称: 1,4-二苯基-2,3-二氧杂二环[2.2.2]辛烷
• 英文名称: 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]octane
• CAS: 114396-00-8
• 化学式: C₁₈H₁₈O₂
• 分子量: 266.34
• InChiKey: BGNVTDDBJXFGJR-UHFFFAOYSA-N

物化性质

• 熔点：
  193-195 °C(Solv: ethyl ether (60-29-7); dichloromethane (75-09-2))
• 沸点：
  367.8±42.0 °C(Predicted)
• 密度：
  1.194±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-二苯基-2,3-二氧杂二环[2.2.2]辛烷 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94%的产率得到1,2-联苯甲酰乙烷
  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：

  2,5-diphenyl-hexa-1,5-diene 在 二氯乙酸 、 氧气 作用下， 以 乙腈 为溶剂， 反应 0.08h， 以4%的产率得到1,4-二苯基-2,3-二氧杂二环[2.2.2]辛烷
  参考文献：
  名称：

  2,5-二芳基-1,5-己二烯的光致电子转移简并Cope重排：阳离子-自由基环化-双自由基裂解机制

  摘要：

  在 9,10-二氰基蒽 (DCA) 敏化的光诱导电子转移 (PET) 条件下，2,5-二芳基-3,3,4,4-四氘代-1,5-己二烯 (d4-1) 发生简并应对重排以在 52:48 中给出 d4-1 及其 1,1,6,6-四氘类似物 d4-1' 的光稳定混合物。该反应涉及1,4-二芳基-2,2,3,3-四氘代环己烷-1,4-二基阳离子自由基（d4-2•+），可被分子氧捕获为1,4-二芳基-2， 3-二氧杂双环[2.2.2]辛烷(3)。相比之下，d4-1 与硝酸铈 (IV) 铵的非光诱导电子转移 (non-PET) 反应类似地形成 d4-2•+，但不会发生简并的 Cope。这种观察到的 PET 和非 PET 之间的显着对比归因于 1,4-二芳基-2,2,3,3-四氘代环己烷-1 的形成，PET 工艺中的 4-二基 (d4-2) 通过从 DCA•- 到 d4-2•+ 的背电子转移。1,4-二苯基-2

  DOI：

  10.1021/ja971910s

文献信息

• A Radical-Anion Chain Mechanism Initiated by Dissociative Electron Transfer to a Bicyclic Endoperoxide: Insight into the Fragmentation Chemistry of Neutral Biradicals and Distonic Radical Anions
  作者：David C. Magri、Mark S. Workentin

  DOI：10.1002/chem.200701740

  日期：2008.2.18

  however, in competition with the second ET from the electrode, the distonic radical anion undergoes a beta-scission fragmentation yielding 1,4-diphenyl-1,4-butanedione radical anion and ethylene in a mechanism involving less than one electron. These observations are rationalized by an unprecedented catalytic radical-anion chain mechanism, the first ever reported for a bicyclic endoperoxide. The product

  通过异质电化学技术研究了在N，N-二甲基甲酰胺中两个二苯基取代的双环内过氧化物的电子转移（ET）还原。该研究除评估先前未知的热化学参数外，还提供了影响OO键还原机理并决定二甲苯基自由基阴离子反应性的结构参数的见解。值得注意的是，标准还原电势和键离解能（BDEs）分别被评估为-0.55 +/- 0.15 V和20 +/- 3 kcal mol（-1），最后一个代表有史以来最低的BDEs。 。内过氧化物通过OO键的协同离解电子转移（DET）还原反应，生成二异氰酸基自由基阴离子中间体。1,4-二苯基-2,3-二氧杂双环的还原[2.2。2] oct-5-ene（1）通过总的双电子机理定量形成1,4-二苯基环己-2-烯-顺-1,4-二醇。相反，ET与1，4-二苯基-2，3-二氧杂双环[2.2.2]辛烷（2）产生1，4-二苯基环己烷-顺式1，4-二醇作为主要产物。但是，与来自电极的第二个ET竞争时，二
• 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。
• UV-laser photochemistry of azoalkanes: surprising effects of phenyl substitution on the lifetimes of 1,3-cyclopentanediyl and 1,4-cyclohexanediyl triplet diradicals
  作者：Waldemar Adam、Sven Grabowski、Herbert Platsch、Klaus Hannemann、Jakob Wirz、R. Marshall Wilson

  DOI：10.1021/ja00184a064

  日期：1989.1
• 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.
• Photoinduced Electron-Transfer Degenerate Cope Rearrangement of 2,5-Diaryl-1,5-hexadienes:  A Cation-Radical Cyclization−Diradical Cleavage Mechanism
  作者：Hiroshi Ikeda、Tomonori Minegishi、Hideyuki Abe、Akinori Konno、Joshua L. Goodman、Tsutomu Miyashi

  DOI：10.1021/ja971910s

  日期：1998.1.1

  Under the 9,10-dicyanoanthracene (DCA)-sensitized photoinduced electron-transfer (PET) conditions, 2,5-diaryl-3,3,4,4-tetradeuterio-1,5-hexadiene (d4-1) undergoes a degenerate Cope rearrangement to give a photostationary mixture of d4-1 and its 1,1,6,6-tetradeuterio analogue d4-1‘ in 52:48. This reaction involves 1,4-diaryl-2,2,3,3-tetradeuteriocyclohexane-1,4-diyl cation radical (d4-2•+), which can

  在 9,10-二氰基蒽 (DCA) 敏化的光诱导电子转移 (PET) 条件下，2,5-二芳基-3,3,4,4-四氘代-1,5-己二烯 (d4-1) 发生简并应对重排以在 52:48 中给出 d4-1 及其 1,1,6,6-四氘类似物 d4-1' 的光稳定混合物。该反应涉及1,4-二芳基-2,2,3,3-四氘代环己烷-1,4-二基阳离子自由基（d4-2•+），可被分子氧捕获为1,4-二芳基-2， 3-二氧杂双环[2.2.2]辛烷(3)。相比之下，d4-1 与硝酸铈 (IV) 铵的非光诱导电子转移 (non-PET) 反应类似地形成 d4-2•+，但不会发生简并的 Cope。这种观察到的 PET 和非 PET 之间的显着对比归因于 1,4-二芳基-2,2,3,3-四氘代环己烷-1 的形成，PET 工艺中的 4-二基 (d4-2) 通过从 DCA•- 到 d4-2•+ 的背电子转移。1,4-二苯基-2