1-phenyl-1-tertbutylperoxy-2-tert-butyloxy ether

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-phenyl-1-tertbutylperoxy-2-tert-butyloxy ether
• 英文别名: [1-Tert-butylperoxy-2-[(2-methylpropan-2-yl)oxy]ethyl]benzene
• 化学式: C₁₆H₂₆O₃
• 分子量: 266.381
• InChiKey: MSFAIKAZHOTUSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  苯乙烯 、 叔丁基过氧化氢 在 溶剂黄146 、 ferric nitrate 作用下， 以 吡啶 为溶剂， 反应 18.0h， 以16.1%的产率得到1-phenyl-1-tertbutylperoxy-2-tert-butyloxy ether
  参考文献：
  名称：

  Gif-Barton氧化作用下烷基苯，共轭烯烃和烷烃的混合过氧化物的新合成；自由基机制

  摘要：

  混合过氧化物的合成是在烷基芳烃，富电子共轭烯烃（苯乙烯，α-甲基苯乙烯）或环己烷和丙烯腈的Gif氧化作用下进行的；化学和动力学证据支持自由基氧化还原链机理。

  DOI：

  10.1039/c39940001823

文献信息

• Kharasch and Metalloporphyrin Catalysis in the Functionalization of Alkanes, Alkenes, and Alkylbenzenes by t-BuOOH. Free Radical Mechanisms, Solvent Effect, and Relationship with the Gif Reaction
  作者：F. Minisci、F. Fontana、S. Araneo、F. Recupero、S. Banfi、S. Quici

  DOI：10.1021/ja00106a026

  日期：1995.1

  New results for the oxidation of alkanes, alkenes, and alkylbenzenes by t-BuOOH according to the Kharasch reaction and Mn(III)- and Fe(III)-porphyrin catalysis are reported. Chemical and kinetic evidence show the role of t-BuO(.) and t-BuOO(.) radicals in these oxidations and the strict relationship with the Gif reaction, for which recently a free-radical mechanism has been emphasized in contrast with the Barton interpretation. A key step appears to be the hydrogen abstraction from t-BuOOH by t-BuO(.), very fast in nonbasic solvents, but inhibited by solvents which form hydrogen bonds with t-BuOOH. As a consequence, the generally accepted Kochi mechanism of the Kharasch reaction must be modified, and the similar mechanistic features of the three types of catalysis (Kharasch, metalloporphyrins, and Gif) are discussed.
• Ingold−Fischer “Persistent Radical Effect”, Solvent Effect, and Metal Salt Oxidation of Carbon-Centered Radicals in the Synthesis of Mixed Peroxides from <i>tert</i>-Butyl Hydroperoxide
  作者：Anna Bravo、Hans-René Bjørsvik、Francesca Fontana、Lucia Liguori、Francesco Minisci

  DOI：10.1021/jo9700944

  日期：1997.6.13

  Mixed peroxides are formed from tert-butyl hydroperoxide (TBH), tert-butyl peroxalate (TBP), and a variety of substrates (p-cresol, cyclohexene, styrene, alpha-methylstyrene, acrylonitrile, 2-methylcyclohexanone). Also, the oxidation of THF in the presence of acrylonitrile under the same conditions gives the mixed peroxide, generated by addition of the tetrahydrofuranyl radical to the double bond and the cross-coupling of the radical adduct with the tert-butylperoxyl radical. Similarly, benzoyl peroxide, TBH, and acrylonitrile give the mixed peroxide by oxidative arylation of the double bond. Paradoxically, TBH acts as effective inhibitor of the polymerization of vinyl monomers (acrylonitrile, styrene). An overall kinetic evaluation suggests that the conditions for the Ingold-Fischer ''persistent radical effect'', characterized by the simultaneous formation of a persistent and a transient radical, are fulfilled in all cases. The reactions are strongly affected by solvents, which form hydrogen bonds with TBH. Catalytic amounts of Cu(II) and Fe(III) salts influence the selectivity; the possibility that the mixed peroxides can also be generated by metal salt oxidation of carbon-centered radicals is discussed.
• New Pathway for Heterogenization of Molecular Catalysts by Non-covalent Interactions with Carbon Nanoreactors
  作者：Maria A. Lebedeva、Thomas W. Chamberlain、Martin Schröder、Andrei N. Khlobystov

  DOI：10.1021/cm502986d

  日期：2014.11.25

  A novel approach to heterogenization of catalytic molecules is demonstrated using the nanoscale graphitic step edges inside hollow graphitized carbon nanofibers (GNFs). The presence of the fullerene C-60 moiety within a fullerenesalen Cu-II complex is essential for anchoring the catalyst within the GNF nanoreactor as demonstrated by comparison to the analogous catalyst complex without the fullerene group. The presence of the catalyst at the step edges of the GNFs is confirmed by high-resolution transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX) with ultraviolet/visible (UV/vis) spectroscopy, demonstrating only negligible (ca. 3%) desorption of the fullerenesalen CuII complex from the GNFs into solution under typical reaction conditions. The catalyst immobilized in GNFs shows good catalytic activity and selectivity toward styrene epoxidation, comparable to the analogous catalyst in solution. Moreover, the fullerenesalen Cu-II complex in GNFs demonstrates excellent stability and recyclability because it can be readily separated from the reaction mixture and employed in multiple reaction cycles with minimal loss of activity, which is highly advantageous compared to catalysts not stabilized by the graphitic step edges that desorb rapidly from GNFs.
• New syntheses of mixed peroxides under Gif–Barton oxidation of alkylbenzenes, conjugated alkenes and alkanes; a free-radical mechanism
  作者：Francesco Minisci、Francesca Fontana、Silvia Araneo、Francesco Recupero

  DOI：10.1039/c39940001823

  日期：——

  peroxides are performed under Gif oxidation of alkylaromatics, electron-rich conjugated alkenes (styrene, α-methylstyrene) or cyclohexane and acrylonitrile; chemical and kinetic evidence support a free-radical redox chain mechanism.

  混合过氧化物的合成是在烷基芳烃，富电子共轭烯烃（苯乙烯，α-甲基苯乙烯）或环己烷和丙烯腈的Gif氧化作用下进行的；化学和动力学证据支持自由基氧化还原链机理。