2,3-Bis-tert-butylperoxy-propionitrile | 169778-69-2

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: 2,3-Bis-tert-butylperoxy-propionitrile
• 英文别名: Propanenitrile, 2,3-bis[(1,1-dimethylethyl)dioxy]-；2,3-bis(tert-butylperoxy)propanenitrile
• CAS: 169778-69-2
• 化学式: C₁₁H₂₁NO₄
• 分子量: 231.292
• InChiKey: CJDDIHOJOZIKLN-UHFFFAOYSA-N

物化性质

• 沸点：
  263.9±35.0 °C(Predicted)
• 密度：
  1.008±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  60.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  二-叔-丁基过氧草酸酯 、 丙烯腈 在 六六六 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 2,3-Bis-tert-butylperoxy-propionitrile
  参考文献：
  名称：

  Ingold−Fischer “Persistent Radical Effect”, Solvent Effect, and Metal Salt Oxidation of Carbon-Centered Radicals in the Synthesis of Mixed Peroxides from tert-Butyl Hydroperoxide

  摘要：

  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.

  DOI：

  10.1021/jo9700944

文献信息

• Hydroperoxides as pseudohalides: oxidation, oxidative alkylation, acylation and arylation of acrylonitrile
  作者：Silvia Araneo、Francesca Fontana、Francesco Minisci、Francesco Recupero、Anna Serri

  DOI：10.1039/c39950001399

  日期：——

  New general syntheses, based on free-radical oxidative alkylation, acylation and arylation of acrylonitrile, in the presence of ButO2H, are reported; the concept of the peroxy group as a pseudohalide is suggested to explain these new reactions.

  报告了基于丙烯腈在 ButO2H 存在下的自由基氧化烷基化、酰基化和芳基化的新的通用合成方法；提出了过氧基团作为假卤化物的概念来解释这些新反应。
• 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.