2,4,6-tri(tert-butyl)-6-((1,3,5-tri(tert-butyl)-4-oxocyclohexa-2,5-dien-1-yl)peroxy)cyclohexa-2,4-dienone | 56501-19-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2,4,6-tri(tert-butyl)-6-((1,3,5-tri(tert-butyl)-4-oxocyclohexa-2,5-dien-1-yl)peroxy)cyclohexa-2,4-dienone
• 英文别名: 2,4,6-Tritert-butyl-6-(1,3,5-tritert-butyl-4-oxocyclohexa-2,5-dien-1-yl)peroxycyclohexa-2,4-dien-1-one
• CAS: 56501-19-0
• 化学式: C₃₆H₅₈O₄
• 分子量: 554.854
• InChiKey: GJOUIVZJJFJWGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.9
• 重原子数：
  40
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,4,6-tri(tert-butyl)-6-((1,3,5-tri(tert-butyl)-4-oxocyclohexa-2,5-dien-1-yl)peroxy)cyclohexa-2,4-dienone 在 三氟乙酸 、 silver(l) oxide 作用下， 生成 2,6-二叔丁基苯醌 、 3,5-二叔丁基邻苯醌
  参考文献：
  名称：

  Reaction of 2,4,6-tri-tert-butylphenoxyl with oxygen in the presence of metal compounds

  摘要：

  DOI：

  10.1007/bf00953251
• 作为产物：
  描述：

  2,4,6-三叔丁基苯酚 在 氧气 、 [Fe(N,N′-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane)(O₂CPh)(OH)](PF₆) 作用下， 以 乙腈 为溶剂， 生成 2,4,6-tri(tert-butyl)-6-((1,3,5-tri(tert-butyl)-4-oxocyclohexa-2,5-dien-1-yl)peroxy)cyclohexa-2,4-dienone 、 2,4,6,2',4',6'-hexa-tert-butyl-4,4'-peroxy-bis-cyclohexa-2,5-dienone
  参考文献：
  名称：

  将铁合成类似物复合物的结构与功能模型特性相结合，用于兔脂氧合酶的活性位点

  摘要：

  描述了模拟兔脂氧合酶中活性铁位点的结构和功能特性的铁复合物。单核拟八面体顺式的配体球-(carboxylato)(hydroxo)iron(III) 复合物由四氮杂大环配体完成，再现了酶中活性位点的第一个配位壳。此外，还提出了两种相应的铁 (II) 配合物，它们在水分子的配位上有所不同。在它们的结构和电子特性中，（羟基）铁（III）和（水）铁（II）复合物都很好地反映了在多不饱和脂肪酸过氧化的酶促机制中发现的仅有的两种基本状态。此外，铁络合物与合适底物的 O-H 和 C-H 键发生夺氢反应，铁络合物配位水配体的键解离自由能为 72.4 kcal·mol – 1. 反应性的理论研究支持协调的质子耦合电子转移机制，与酶机制中的初始步骤非常相似。(羟基)铁(III)配合物发生夺取氢原子反应的倾向是其在2,4,6-三(叔丁基)苯酚有氧过氧化反应中的催化作用及其作为自由基引发剂的基础在二氢蒽与氧气的反应中。

  DOI：

  10.1021/jacs.1c04422

文献信息

• Electron Transfer between Protonated and Unprotonated Phenoxyl Radicals¹
  作者：Kanji Omura

  DOI：10.1021/jo701948a

  日期：2008.2.1

  [GRAPHICS]The reaction of phenoxyl radicals with acids is investigated. 2,4,6-Tri-tert-butylphenoxyl radical (13), a persistent radical, deteriorates in MeOH/PhH in the presence of an acid yielding 4-methoxycyclohexa-2,5-dienone 18a and the parent phenol (14). The reaction is facilitated by a strong acid. Treatment of 2,6-di-tert-butyl-4-methylphenoxyl radical (2), a short-lived radical, generated by dissociation of its dimer, with an acid in MeOH provides 4-methoxycyclohexa-2,5-dienone 4 and the products from disproportionation of 2 including the parent phenol (3). A strong acid in a high concentration favors the formation of 4 while the yield of 3 is always kept high. Oxidation of the parent phenol (33) with PbO2 to generate transient 2,6-di-tert-butylphenoxyl radical (35) in AcOH/H2O containing an added acid provides eventually p-benzoquinone 39 and 4,4'-diphenoquinone 42, the product from dimerization of 35. A strong acid in a high concentration favors the formation of 39. These results suggest that a phenoxyl radical is protonated by an acid and electron transfer takes place from another phenoxyl radical to the protonated phenoxyl radical, thus generating the phenoxyl cation, which can add an oxygen nucleophile, and the phenol (eq 5). The electron transfer is a fast reaction.
• Oxidation of phenols with iodine in alkaline methanol
  作者：Kanji Omura

  DOI：10.1021/jo00191a002

  日期：1984.8
• Mechanism of the Gibbs Reaction. 3. Indophenol Formation via Radical Electrophilic Aromatic Substitution (SREAr) on Phenols
  作者：Istvan Pallagi、Andras Toro、Odon Farkas

  DOI：10.1021/jo00101a013

  日期：1994.11

  Different products are formed, depending on the para substituent (R) when 2,6-dichlorobenzoquinone N-chloroimine (1b) reacts with the anion of the 4-substituted phenol (2). If the group R can leave as a cation (i.e., R is an electrofugal leaving group) such as H, CH(2)NMe(2), CH2OH, etc., then the reaction yields indophenol (3), the normal Gibbs product. If the group R cannot leave as a cation such as CH3, the final product of the reaction will be type 10, 1,1-disubstituted 2,5-cyclohexadienone. If the group R is OH or NH2, then the reaction gives the corresponding benzoquinone 4 or benzoquinone imine 1 and 2,6-dichlorobenzoquinone imine (1d). In all these cases the reaction proceeds at a 1:1 stoichiometry. If, however, the group R can leave as an anion (i.e., R is nucleofugal leaving group) such as halogen, alkoxy, or OCH(2)Ph, then the reaction proceeds at a 1:2 stoichiometry. In this case the reaction of a second mole of phenolate with type 26 intermediate yields the indophenol product 3 and the oxidized product of the phenol. If the two ortho positions of the phenolate are substituted then the oxidized product of the phenol will be the corresponding benzoquinone. The mechanism of the reaction has been studied by kinetic and nonkinetic (NMR) methods. It has been concluded that the first step of the mechanism is a single electron transfer (SET) from the phenolate to the benzoquinone N-chloroimine 1b which is the rate-determining process in most of the cases. In some of the nucleofugal cases the final oxidation, involving the second mole of phenolate, is the rate-determining step. For the radical reaction three different alternatives are suggested: a combination of radicals in a solvent cage (direct reaction) and two different chain reactions (chain A and chain B). Quantum chemical calculations revealed that the direct reaction and the chain A mechanisms were energetically more favored than chain B. The reaction shows an extremely large para selectivity although the substitution does follow a radical mechanism.
• Synthesis and reactions of quinolide peroxides under acid-catalysis conditions
  作者：I. A. Batanov、G. A. Nikiforov、V. V. Ershov

  DOI：10.1007/bf00948250

  日期：1982.2