| 51219-93-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• CAS: 51219-93-3
• 化学式: C₂₈H₁₉N₂O
• 分子量: 399.472
• InChiKey: KFWSNOJTJJIERC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  21.7
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  在 lead dioxide 作用下， 生成 2,2'-diphenyl-[3,3']biindolylidene 1-oxide
  参考文献：
  名称：

  Electron-transfer reactions. Oxidation of Grignard reagents in the presence of an aminoxyl as a radical-trapping agent

  摘要：

  The indole bisnitrone 1 (E1/2red = -0.125 V vs NHE in DMF) reacts with a series of Grignard reagents (RMgX) including primary, secondary, and tertiary alkyls and benzyl and phenyl derivatives, which show different E(OX), by single electron transfer to form C-centered radicals corresponding to the Grignard used. The radicals produced in the reaction were trapped by the (arylimino)indolinone nitroxide 5 to form the alkylated hydroxylamines 6. When the reaction is carried out with a ''cyclizing Grignard'' such as 5-hexenylmagnesium bromide, the uncyclized (5-hexen-1-yl) 6g and cyclized (methylcyclopentyl) 6h alkylated hydroxylamines are both isolated. In all cases, the Marcus theory treatment predicts high electron-transfer rate constants.

  DOI：

  10.1021/jo00015a029
• 作为产物：
  描述：

  2,2'-diphenyl-[3,3']biindolylidene 1-oxide 在 苯肼 作用下， 生成
  参考文献：
  名称：

  Electron-transfer reactions. Oxidation of Grignard reagents in the presence of an aminoxyl as a radical-trapping agent

  摘要：

  The indole bisnitrone 1 (E1/2red = -0.125 V vs NHE in DMF) reacts with a series of Grignard reagents (RMgX) including primary, secondary, and tertiary alkyls and benzyl and phenyl derivatives, which show different E(OX), by single electron transfer to form C-centered radicals corresponding to the Grignard used. The radicals produced in the reaction were trapped by the (arylimino)indolinone nitroxide 5 to form the alkylated hydroxylamines 6. When the reaction is carried out with a ''cyclizing Grignard'' such as 5-hexenylmagnesium bromide, the uncyclized (5-hexen-1-yl) 6g and cyclized (methylcyclopentyl) 6h alkylated hydroxylamines are both isolated. In all cases, the Marcus theory treatment predicts high electron-transfer rate constants.

  DOI：

  10.1021/jo00015a029

文献信息

• Hydroxylamines as Oxidation Catalysts:  Thermochemical and Kinetic Studies
  作者：Riccardo Amorati、Marco Lucarini、Veronica Mugnaini、Gian Franco Pedulli、Franceso Minisci、Francesco Recupero、Francesca Fontana、Paola Astolfi、Lucedio Greci

  DOI：10.1021/jo026660z

  日期：2003.3.1

  hydroxylamines containing alkyl, aryl, vinyl, and carbonyl substituents at the nitrogen atom have been determined by using the EPR radical equilibration technique in order to study the effect of the substituents on the O-H bond strength of these compounds. It has been found that substitution of an alkyl group directly bonded to the nitrogen atom with vinyl or aryl groups has a small effect, while substitution

  为了研究取代基对这些化合物的OH键强度的影响，已经通过使用EPR自由基平衡技术确定了在氮原子上包含烷基，芳基，乙烯基和羰基取代基的羟胺的键解离焓（BDE）。已经发现，用乙烯基或芳基取代与氮原子直接键合的烷基的作用很小，而用酰基取代引起的OH BDE值大大增加。因此，二烷基羟胺的OH键强度仅为约1。70 kcal / mol，而酰基羟胺和N-羟基邻苯二甲酰亚胺（NHPI）在氮上含有两个酰基取代基，其BDE值约为。分别为80 kcal / mol和88 kcal / mol。由于最近已提出邻苯二甲酰亚胺N-氧基自由基（PINO）作为烃或其他底物的有效氧化催化剂，因此对于母体羟胺（NHPI）发现的大BDE值证明了这一建议的合理性。为了更好地理解NHPI催化的异丙基苯好氧氧化的机理进行的动力学研究与简单的动力学模型相符，其中速率确定步骤是由枯基过氧自由基从羟胺中提取氢原子。