MINA | 75938-09-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: MINA
• CAS: 75938-09-9
• 化学式: C₃H₄NO₂
• 分子量: 86.0703
• InChiKey: OVGLVOLWBBGQHS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.14
• 重原子数：
  6.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.49
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  MINA 、 2,4-二硝基氟苯 以 水 为溶剂， 生成 2-Oxo-propionaldehyde O-(2,4-dinitro-phenyl)-oxime
  参考文献：
  名称：

  SNAr 取代中的 α 效应 - 肟酸亲核试剂与 2,4-二硝基氟苯在水溶液中的反应

  摘要：

  2,4-二硝基氟苯 (DNFB) 被一系列苯氧化物和肟酸盐亲核试剂的 SNAr 取代的二阶速率常数 (k1ArO, k1Ox) 在 25°C 的水溶液中测量，使用两种电位计程序，包括使用氟离子选择性电极 (FISE) 和经典的分光光度法。虽然酚盐离子的速率数据符合线性布朗斯台德图，斜率 (βNu = 0.71) 拟合 SNAr 反应常见的 0.5-0.7 范围，但所研究的各种肟类化合物的速率数据并未定义有意义的线性图。有趣的是，观察到的 k1Ox 变化揭示了 pKa > 7.5-8 的肟化物的反应性有迅速趋于平稳的趋势，这种情况让人想起这些物种在羰基和膦酰基中心的其他亲核反应中遇到的情况。我们目前的发现强化了一种普遍的肟化行为模式的想法，该模式源于在亲核攻击之前对部分去溶剂化的特别强烈的需求，即异步性或 TS 不平衡。观察到的趋平的一个主要结果是，从弱碱性肟酸盐 (k1Ox/k1ArO ≈

  DOI：

  10.1002/1099-0690(200109)2001:17<3279::aid-ejoc3279>3.0.co;2-9
• 作为产物：
  描述：

  亚硝酸甲酯 、 1-methylvinyl oxide ion 以6.3%的产率得到N-oxidomethanimine
  参考文献：
  名称：

  Anion Structure Determination in the Gas Phase:  Chemical Reactivity as a Probe

  摘要：

  In the gas phase, the discrimination between two isomeric anion structures is a challenge that requires different solutions for different applications. The anionic oxy-Cope rearrangement involves the rearrangement of an alkoxide to an isomeric enolate; the mechanistic study of such a process in the gas phase requires a simple and selective probe process. Using a flowing afterglow mass spectrometer, we have examined the utility and limitations of using chemical reactivity to discriminate between alkoxides and enolates in the gas phase. A series of alkoxides and enolates were allowed to react with three chemical probe reagents: methanol-O-d, methyl nitrite, and dimethyl disulfide. Quantitative and qualitative characterization of each probe reagent reveals the especially broad and flexible utility of dimethyl disulfide as a chemical probe. Dimethyl disulfide is a selective reagent with ambident behavior that reacts efficiently with all anions studied and fully capitalizes on the structure/reactivity differences between alkoxides and enolates. Alkoxides behave as classical ''hard bases'' when allowed to react with dimethyl disulfide, effecting elimination across the C-S bond, whereas enolates, ''soft bases'', attack at sulfur. Methyl nitrite is also a selective ambident probe reagent but, due to its particularly slow reaction with enolates, is useful only in conjunction with a more reliable probe such as dimethyl disulfide. Methanol-O-d, for a variety of reasons detailed in the paper, is unsuitable as a chemical probe reagent for the unequivocal discernment between alkoxides and enolates.

  DOI：

  10.1021/jo961463j