(4,5-ethylenedioxy-2-nitrobenzyl)cyclopropane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并二恶烷
• 英文名称: (4,5-ethylenedioxy-2-nitrobenzyl)cyclopropane
• 英文别名: 6-nitro-7-cyclopropylmethyl-1,4-benzodioxane；7-cyclopropylmethyl-6-nitro-1,4-benzodioxane；6-(Cyclopropylmethyl)-7-nitro-2,3-dihydro-1,4-benzodioxine；7-(cyclopropylmethyl)-6-nitro-2,3-dihydro-1,4-benzodioxine
• 化学式: C₁₂H₁₃NO₄
• mdl: MFCD00561861
• 分子量: 235.24
• InChiKey: LMMWLAGBPVCKCX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4,5-ethylenedioxy-2-nitrobenzyl)cyclopropane 在 三氟乙酸 、 sodium nitrite 作用下， 以 氯仿 为溶剂， 以98%的产率得到5-[(7-nitro-2,3-dihydro-1,4-benzodioxan-6-yl)methyl]-4,5-dihydroisoxazole
  参考文献：
  名称：

  Benzyl-4,5-dihydroisoxazoles from benzylcyclo-propanes: regioselective insertion of an n=o fragment into the three-membered carbocycle of benzylcyclopropanes by the action of nitrous acid

  摘要：

  The action of equimolar amounts of nitrous acid formed in situ on benzylcyclopropanes with electron-donor and electron-withdrawing substituents in the aromatic part of the substrate lead, at certain temperatures, exclusively to the insertion of an N=O fragment into the three-membered carbocycle with subsequent formation of a heterocyclic isoxazoline (4,5-dihydroisoxazole) system.

  DOI：

  10.1007/s10593-012-1125-9
• 作为产物：
  描述：

  6-(2,2-dichlorocyclopropylmethyl)-1,4-benzodioxane 在 sodium 、 dinitrogen tetraoxide 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (4,5-ethylenedioxy-2-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

• Synthesis and acid-catalyzed transformations of solvomercuration adducts of 2-nitrobenzylcyclopropane. First stable metalated 1-oxo-3,4-dihydro-1H-2,1-benzoxazinium ions
  作者：A. N. Fedotov、E. V. Trofimova、T. E. Gulov、S. G. Bandaev、S. S. Mochalov、N. S. Zefirov

  DOI：10.1134/s1070428013100217

  日期：2013.10

  Sovomercuration adducts of 2-nitrobenzyl-, 2-nitro-4,5-(ethylenedioxy)benzyl-, and 4,5-dimethoxy-2-nitrobenzylcyclopropanes were synthesized. The adducts reacted with sulfuric, fluorosulfonic, or chlorosulfonic acid to give 3-(2-chloromercurio)ethyl-1-oxo-3,4-dihydro-1H-2,1-benzoxazinium ions whose stability depended on the nature of substituents in the aromatic ring. Unstable metalated 1-oxo-3,4-dihydro-1H-2,1-benzoxazinium ions underwent fast protodemercuration to form metal-free 3-ethyl-1-oxo-3,4-dihydro-1H-2,1-benzoxazinium ions. Stable analogs in the above acids did not change to an appreciable extent over a period of 48-72 h. Hydrolysis of stable metalated 1-oxo-1,3-dihydro-2,1-benzoxazolium ions afforded only 4-chloromercurio-1-(2-nitroaryl)butan-2-ol.
• 4H-3,1-benzoxazines from benzyl cyclopropanes. First example of acid catalyzed rearrangement in ortho-substituted benzylcyclo-propanes
  作者：E. V. Trofimova、B. P. Archegov、A. N. Fedotov、R. A. Gazzaeva、S. S. Mochalov、N. S. Zefirov

  DOI：10.1007/s10593-009-0400-x

  日期：2009.9

  The synthesis of 2-N-acylamino-substituted benzylcyclopropanes has been carried out. It was established that under the action of acids 2-N-acylamino-substituted benzylcyclopropanes are rearranged into the corresponding 4H-3,1-benzoxazines and not into the expected 3,1-benzoxazepines. It was shown that a similar type of rearrangement is also characteristic for 2-N-acylamino-substituted allylbenzenes.
• 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).
• Benzyl-4,5-dihydroisoxazoles from benzylcyclo-propanes: regioselective insertion of an n=o fragment into the three-membered carbocycle of benzylcyclopropanes by the action of nitrous acid
  作者：R. A. Gazzaeva、E. V. Trofimova、A. Z. Kadzhaeva、A. N. Fedotov、S. S. Mochalov

  DOI：10.1007/s10593-012-1125-9

  日期：2012.11

  The action of equimolar amounts of nitrous acid formed in situ on benzylcyclopropanes with electron-donor and electron-withdrawing substituents in the aromatic part of the substrate lead, at certain temperatures, exclusively to the insertion of an N=O fragment into the three-membered carbocycle with subsequent formation of a heterocyclic isoxazoline (4,5-dihydroisoxazole) system.