1,1-dichloro-2-(2-methoxybenzyl)cyclopropane | 52178-88-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1,1-dichloro-2-(2-methoxybenzyl)cyclopropane
• 英文别名: 2-(4-methoxybenzyl)-1,1-dichlorocyclopropane；p-(2,2-dichlorocyclopropylmethyl)anisole；1-[(2,2-Dichlorocyclopropyl)methyl]-4-methoxybenzene
• CAS: 52178-88-8
• 化学式: C₁₁H₁₂Cl₂O
• 分子量: 231.122
• InChiKey: ZTQCYPYTWDMMHA-UHFFFAOYSA-N

物化性质

• 沸点：
  169-170 °C(Press: 12 Torr)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,1-dichloro-2-(2-methoxybenzyl)cyclopropane 在 sodium 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 3.0h， 以71%的产率得到1-环丙基甲基-4-甲氧基-苯
  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
• 作为产物：
  描述：

  4-烯丙基苯甲醚 、 氯仿 在 sodium hydroxide 、 苄基三乙基氯化铵 作用下， 反应 3.0h， 以66%的产率得到1,1-dichloro-2-(2-methoxybenzyl)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

• Halocyclopropyl substituted phenoxyalkanoic acids
  申请人：Sterling Drug Inc.

  公开号：US03948973A1

  公开（公告）日：1976-04-06

  Halocyclopropyl substituted phenoxyalkanoic acids and esters thereof, having hypocholesteremic activity are prepared via several alternative synthetic approaches, involving as the key reactions interaction of a substituted phenylalkene with a carbene source to introduce the halocyclopropyl moiety, and reaction of a substituted phenol with chloroform and a lower-alkanone in the presence of base, or with a lower-alkyl .alpha.-bromo-alkanoate, to form the phenoxyalkanoic acid moiety.

  含有降胆固醇活性的卤代环丙基取代的苯氧基烷酸及其酯类，可以通过几种替代合成方法制备，其中关键反应包括取代苯基烯烃与卡宾源相互作用以引入卤代环丙基基团，以及在碱存在下，取代酚与氯仿和较低的烷酮，或与较低烷基α-溴代烷酸酯反应，形成苯氧基烷酸基团。
• Synthesis of 1,1-Bis(trimethylstannyl)cyclopropanes by the S_RN1 Mechanism
  作者：Javier F. Guastavino、Roberto A. Rossi

  DOI：10.1021/om801104e

  日期：2009.4.27

  dichlorocarbene to alkenes, with Me3Sn− anions are reported. The process is described in terms of a photoinduced SRN1 substitution. The 1,1-bis(trimethylstannyl)cyclopropanes were obtained in good to excellent isolated yield (71−90%); 7,7-dichloro-2-oxa-bicyclo[4.1.0]heptane gave the 1,1-bis(trimethylstannyl) product in only 40% yield.

  容易获得的1,1- dichlorocyclopropanes的的反应中，通过加入二氯卡宾为烯烃得到的，与我3的Sn -报道阴离子。根据光诱导的S RN 1取代来描述该过程。得到的1,1-双（三甲基锡烷基）环丙烷的分离收率良好至优异（71-90％）；7,7-二氯-2-氧杂双环[4.1.0]庚烷仅以40％的收率得到1,1-双（三甲基锡烷基）产物。
• 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).