4-hydroxy-3-nitrobenzyl-cyclopropane | 663952-53-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 4-hydroxy-3-nitrobenzyl-cyclopropane
• 英文别名: 4-hydroxy-3-nitrobenzylcyclopropane；Phenol, 4-(cyclopropylmethyl)-2-nitro-；4-(cyclopropylmethyl)-2-nitrophenol
• CAS: 663952-53-2
• 化学式: C₁₀H₁₁NO₃
• 分子量: 193.202
• InChiKey: OLCQMNNQXGDFTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1,1-dichloro-2-(2-methoxybenzyl)cyclopropane 在 sodium 、 dinitrogen tetraoxide 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 4-hydroxy-3-nitrobenzyl-cyclopropane
  参考文献：
  名称：

  与四氧化二氮反应的环丙基和烯丙基取代的芳烃。底物氧化电位对反应方向的影响

  摘要：

  A correlation was found between oxidation potentials of acylcyclopropanes in solution (in CH2Cl2 and CH3CN) and their HOMO energies calculated by semiempirical (AM1) and nonempirical (HF/6-31G and HF/6-31G**) methods. The correlation provides a possibility to forecast the reaction direction of the mentioned substrates and N2O4. The correlation possesses a general character. It was established for instance that arylcyclopropanes, cyclopropylmethyl- and allylbenzenes oxidized at more positive potentials than reduction potential of NO+ and having more positive epsilon(HOMO) than -9.0 eV (AM1), -8.4 eV (HF/6-31G), and -8.3 eV (HF/6-31 G**) reacted with N2O4 following the mechanism "electron transfer - radical pair recombination" affording nitroaromatic derivatives retaining the cyclopropane (or allyl) fragments. Substrates of the same type where the electron transfer to NO+ should be endothermic process and whose HOMO values are less than the above critical numbers react with N2O4 by the mechanism of electrophilic cyclopropane ring opening (with aryl and benzylcyclopropanes) or by electrophilic addition across the double C=C bond (with allylbenzenes).

  DOI：

  10.1023/b:rujo.0000045888.43245.d7

文献信息

• ——
  作者：S. S. Mochalov、A. N. Fedotov、A. A. Borisenko、V. V. Tkachev、G. V. Shilov、A. N. Utenyshev、S. M. Aldoshin、N. S. Zefirov

  DOI：10.1023/a:1025384619105

  日期：——
• Cyclopropyl- and Allyl-substituted Arenes in Reaction with Dinitrogen Tetroxide. Effect of Substrate Oxidation Potential on Reaction Direction
  作者：S. S. Mochalov、R. A. Gazzaeva、A. N. Fedotov、E. V. Trofimova、I. V. Trushkov、N.S. Zefirov

  DOI：10.1023/b:rujo.0000045888.43245.d7

  日期：2004.8

  A correlation was found between oxidation potentials of acylcyclopropanes in solution (in CH2Cl2 and CH3CN) and their HOMO energies calculated by semiempirical (AM1) and nonempirical (HF/6-31G and HF/6-31G**) methods. The correlation provides a possibility to forecast the reaction direction of the mentioned substrates and N2O4. The correlation possesses a general character. It was established for instance that arylcyclopropanes, cyclopropylmethyl- and allylbenzenes oxidized at more positive potentials than reduction potential of NO+ and having more positive epsilon(HOMO) than -9.0 eV (AM1), -8.4 eV (HF/6-31G), and -8.3 eV (HF/6-31 G**) reacted with N2O4 following the mechanism "electron transfer - radical pair recombination" affording nitroaromatic derivatives retaining the cyclopropane (or allyl) fragments. Substrates of the same type where the electron transfer to NO+ should be endothermic process and whose HOMO values are less than the above critical numbers react with N2O4 by the mechanism of electrophilic cyclopropane ring opening (with aryl and benzylcyclopropanes) or by electrophilic addition across the double C=C bond (with allylbenzenes).