Ethyl 1-phenylcyclopent-2-ene-1-carboxylate | 156006-04-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ethyl 1-phenylcyclopent-2-ene-1-carboxylate
• CAS: 156006-04-1
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: KZIBENKORAFPLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Ethyl 1-phenylcyclopent-2-ene-1-carboxylate 在 4-二甲氨基吡啶 、 氢氧化钾 、 diethylzinc 、 N,N'-二环己基碳二亚胺 作用下， 以 1,4-二氧六环 、 正己烷 、 二氯甲烷 为溶剂， 生成 (2-Sulfanylidenepyridin-1-yl) 2-phenylbicyclo[3.1.0]hexane-2-carboxylate
  参考文献：
  名称：

  Kinetic Analysis of the Rearrangement of a Conformationally Constrained .alpha.-Cyclopropylbenzyl Radical

  摘要：

  Modulation of the cyclopropylmethyl (CPM)/ homoallyl radical equilibrium by phenyl substitution at the radical center is exploited in determining the kinetic versus thermodynamic preference for bond scission in a bicyclic CPM radical. Exocyclic ring opening is determined to be 28.7 times faster than the respective endocyclic process. This method will be of general use for determining the regioselectivity of radical rearrangements.

  DOI：

  10.1021/jo00092a003
• 作为产物：
  描述：

  2-氧代-1-苯基环戊烷-1-羧酸乙酯 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醇 、 甲苯 为溶剂， 生成 Ethyl 1-phenylcyclopent-2-ene-1-carboxylate
  参考文献：
  名称：

  Kinetic Analysis of the Rearrangement of a Conformationally Constrained .alpha.-Cyclopropylbenzyl Radical

  摘要：

  Modulation of the cyclopropylmethyl (CPM)/ homoallyl radical equilibrium by phenyl substitution at the radical center is exploited in determining the kinetic versus thermodynamic preference for bond scission in a bicyclic CPM radical. Exocyclic ring opening is determined to be 28.7 times faster than the respective endocyclic process. This method will be of general use for determining the regioselectivity of radical rearrangements.

  DOI：

  10.1021/jo00092a003

文献信息

• Benzylic Stabilization as a Mechanistic Tool for Studying Radical Rearrangements
  作者：Hariharan Venkatesan、Marc M. Greenberg

  DOI：10.1021/jo00109a043

  日期：1995.2

  The kinetic parameters for the rearrangement of, and the relative energies of radicals involved in the equilibria of, a bicyclic cyclopropylmethyl/homoallyl system were determined. Benzylic stabilization of the cyclopropylmethyl radical facilitates characterization of all four ring opening and closing processes. Kinetically disfavored endocyclic ring opening produces the thermodynamically favored homoallyl radical(10). Cyclohexenyl radical 10 is approximately 1.7 kcal/mol lower in energy than 9. The regioselectivity of ring opening of 8 is independent of any assumptions involving trapping rate constants of radicals. The regioselectivity for ring opening of 8 (k(1)/k(2) = 30.2 at 298 K) is similar to that of bicyclo[3.1.0]hexan-1-yl (1). These experiments suggest that benzylic stabilization does not significantly perturb the position of the transition state for ring opening. Therefore, phenyl substitution of a bicyclic cyclopropylmethyl radical should be a useful tool for analyzing the effects of substituents elsewhere in the system.
• Kinetic Analysis of the Rearrangement of a Conformationally Constrained .alpha.-Cyclopropylbenzyl Radical
  作者：Hariharan Venkatesan、Marc M. Greenberg

  DOI：10.1021/jo00092a003

  日期：1994.7

  Modulation of the cyclopropylmethyl (CPM)/ homoallyl radical equilibrium by phenyl substitution at the radical center is exploited in determining the kinetic versus thermodynamic preference for bond scission in a bicyclic CPM radical. Exocyclic ring opening is determined to be 28.7 times faster than the respective endocyclic process. This method will be of general use for determining the regioselectivity of radical rearrangements.