3,4-benzo-2-sulfoxy-bicyclo<3.1.0>hex-3-ene | 148323-41-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫铬烷
• 英文名称: 3,4-benzo-2-sulfoxy-bicyclo<3.1.0>hex-3-ene
• 英文别名: 1a,6b-dihydro-1H-cyclopropa[b][1]benzothiole 2,2-dioxide
• CAS: 148323-41-5
• 化学式: C₉H₈O₂S
• 分子量: 180.227
• InChiKey: UMKVTEZGCDAVLG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,4-benzo-2-sulfoxy-bicyclo<3.1.0>hex-3-ene 在 lithium aluminium tetrahydride 作用下， 以 乙醚 、 苯 为溶剂， 反应 1.0h， 以89%的产率得到3,4-benzo-2-thia-bicyclo<3.1.0>hex-3-ene
  参考文献：
  名称：

  The effect of the benzene ring on 1,5-electrocyclizations: Synthesis and thermolysis of optically active benzohomofuran, benzohomothiophene, N-carbmethoxyhomoindole, benzohomophosphole and homoindene.

  摘要：

  Carbonyl ylide-like intermediates are involved in the 1,5-electrocyclization of the benzo-heterocycles 3a-d mentioned in the title. The activation barriers analyzed by the time- and temperature-dependence of the racemisation of the optically active derivatives turned out to be higher by DELTADELTAG(not-equal) = 13 +/- 2 kcal/mol than those determined for the parent systems 1a-d whereas for the corresponding carbocycles 3d and 1d the difference is only DELTADELTAG(not-equal) almost-equal-to 4 kcal/mol as expected from the difference between the bond dissociation energies of toluene and propene (DELTABDE = 3.2 kcal/mol). This result can be considered as an evidence for the electrocyclic character of the ring-opening in the heterocycles 1a-d and 3a-d. The difference between the Gibbs activation enthalpies found for the ring-opening of homofuran 1a and homothiophene 1b (DELTADELTAG(not-equal) = 8.7 kcal/mol) can be attributed to the heteroatom effect on the ground state.

  DOI：

  10.1016/s0957-4166(00)86091-7
• 作为产物：
  描述：

  苯并噻吩砜 以 乙醚 、 甲苯 为溶剂， 反应 75.0h， 生成 3,4-benzo-2-sulfoxy-bicyclo<3.1.0>hex-3-ene
  参考文献：
  名称：

  The effect of the benzene ring on 1,5-electrocyclizations: Synthesis and thermolysis of optically active benzohomofuran, benzohomothiophene, N-carbmethoxyhomoindole, benzohomophosphole and homoindene.

  摘要：

  Carbonyl ylide-like intermediates are involved in the 1,5-electrocyclization of the benzo-heterocycles 3a-d mentioned in the title. The activation barriers analyzed by the time- and temperature-dependence of the racemisation of the optically active derivatives turned out to be higher by DELTADELTAG(not-equal) = 13 +/- 2 kcal/mol than those determined for the parent systems 1a-d whereas for the corresponding carbocycles 3d and 1d the difference is only DELTADELTAG(not-equal) almost-equal-to 4 kcal/mol as expected from the difference between the bond dissociation energies of toluene and propene (DELTABDE = 3.2 kcal/mol). This result can be considered as an evidence for the electrocyclic character of the ring-opening in the heterocycles 1a-d and 3a-d. The difference between the Gibbs activation enthalpies found for the ring-opening of homofuran 1a and homothiophene 1b (DELTADELTAG(not-equal) = 8.7 kcal/mol) can be attributed to the heteroatom effect on the ground state.

  DOI：

  10.1016/s0957-4166(00)86091-7

文献信息

• The effect of the benzene ring on 1,5-electrocyclizations: Synthesis and thermolysis of optically active benzohomofuran, benzohomothiophene, N-carbmethoxyhomoindole, benzohomophosphole and homoindene.
  作者：Frank-Gerrit Klärner、Annette E. Kleine、Dirk Oebels、Friedrich Scheidt

  DOI：10.1016/s0957-4166(00)86091-7

  日期：1993.3

  Carbonyl ylide-like intermediates are involved in the 1,5-electrocyclization of the benzo-heterocycles 3a-d mentioned in the title. The activation barriers analyzed by the time- and temperature-dependence of the racemisation of the optically active derivatives turned out to be higher by DELTADELTAG(not-equal) = 13 +/- 2 kcal/mol than those determined for the parent systems 1a-d whereas for the corresponding carbocycles 3d and 1d the difference is only DELTADELTAG(not-equal) almost-equal-to 4 kcal/mol as expected from the difference between the bond dissociation energies of toluene and propene (DELTABDE = 3.2 kcal/mol). This result can be considered as an evidence for the electrocyclic character of the ring-opening in the heterocycles 1a-d and 3a-d. The difference between the Gibbs activation enthalpies found for the ring-opening of homofuran 1a and homothiophene 1b (DELTADELTAG(not-equal) = 8.7 kcal/mol) can be attributed to the heteroatom effect on the ground state.