1-<2-(bicyclo<4.1.0>heptyl)acetoxy>-2(H)-pyridinethione | 220389-32-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1-<2-(bicyclo<4.1.0>heptyl)acetoxy>-2(H)-pyridinethione
• 英文别名: (2-Sulfanylidenepyridin-1-yl) 2-(1-bicyclo[4.1.0]heptanyl)acetate
• CAS: 220389-32-2
• 化学式: C₁₄H₁₇NO₂S
• 分子量: 263.36
• InChiKey: DNINCCDQEBHZKU-UHFFFAOYSA-N

物化性质

• 熔点：
  106.0-107.0 °C
• 沸点：
  368.2±25.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-<2-(bicyclo<4.1.0>heptyl)acetoxy>-2(H)-pyridinethione 在 苯硫酚 作用下， 以 四氢呋喃 为溶剂， 反应 0.02h， 以63.2%的产率得到亚甲基环庚烷
  参考文献：
  名称：

  Six- vs Seven-Membered Ring Formation from the 1-Bicyclo[4.1.0]heptanylmethyl Radical:  Synthetic and ab Initio Studies

  摘要：

  The viability of utilizing 1-bicyclo[4.1.0]heptanylmethyl radical (3) to serve as a progenitor of seven-membered carbocycles was examined. Rate constants for the rearrangement of this radical to 3-methylenecycloheptyl radical (4) and 2-methylenecyclohexyl-1-methyl radical (6) were measured using the competition method of 3 with thiophenol over the temperature range of -75 to 59 degrees C. Arrhenius functions were calculated for the conversions of 3 to 4 and 3 to 6 and found to be log (k/s(-1)) = (12.38 +/- 0.20) - (5.63 +/- 0.23)/theta and log(k/s(-1)) = (11.54 +/- 0.32) - (5.26 +/- 0.37)/theta, respectively. The rate-constants for these conversions at 25 degrees C are 1.86 x 10(8) s(-1) and 5.11 x 10(7) s(-1), respectively. Hence, the seven-membered ring-expanded carbocycle is formed 3.6 times faster at 25 degrees C than the nonexpanded species. This suggests that the 1-bicyclo[4.1.0]heptanylmethyl radical system may be synthetically useful in seven-membered ring-forming methodology. Preliminary theoretical examination of this radical system qualitatively predicted the experimentally determined energies of activation: PMP4/6-31G*//HF/6-31G* Delta E-a (3 --> 6 - 3 --> 4) = 3.0 kcal/mol with zero point-energy correction. The HF/6-31G* optimized reaction coordinate stationary points suggest cyclopropyl substituent eclipsing interactions play an important role in determining the kinetic outcome of these rearrangements.

  DOI：

  10.1021/jo981708n
• 作为产物：
  描述：

  2-(环己烯-1-基)乙酸乙酯 在 4-二甲氨基吡啶 、 氢氧化钾 、 乙醇 、 diethylzinc 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 21.33h， 生成 1-<2-(bicyclo<4.1.0>heptyl)acetoxy>-2(H)-pyridinethione
  参考文献：
  名称：

  Six- vs Seven-Membered Ring Formation from the 1-Bicyclo[4.1.0]heptanylmethyl Radical:  Synthetic and ab Initio Studies

  摘要：

  The viability of utilizing 1-bicyclo[4.1.0]heptanylmethyl radical (3) to serve as a progenitor of seven-membered carbocycles was examined. Rate constants for the rearrangement of this radical to 3-methylenecycloheptyl radical (4) and 2-methylenecyclohexyl-1-methyl radical (6) were measured using the competition method of 3 with thiophenol over the temperature range of -75 to 59 degrees C. Arrhenius functions were calculated for the conversions of 3 to 4 and 3 to 6 and found to be log (k/s(-1)) = (12.38 +/- 0.20) - (5.63 +/- 0.23)/theta and log(k/s(-1)) = (11.54 +/- 0.32) - (5.26 +/- 0.37)/theta, respectively. The rate-constants for these conversions at 25 degrees C are 1.86 x 10(8) s(-1) and 5.11 x 10(7) s(-1), respectively. Hence, the seven-membered ring-expanded carbocycle is formed 3.6 times faster at 25 degrees C than the nonexpanded species. This suggests that the 1-bicyclo[4.1.0]heptanylmethyl radical system may be synthetically useful in seven-membered ring-forming methodology. Preliminary theoretical examination of this radical system qualitatively predicted the experimentally determined energies of activation: PMP4/6-31G*//HF/6-31G* Delta E-a (3 --> 6 - 3 --> 4) = 3.0 kcal/mol with zero point-energy correction. The HF/6-31G* optimized reaction coordinate stationary points suggest cyclopropyl substituent eclipsing interactions play an important role in determining the kinetic outcome of these rearrangements.

  DOI：

  10.1021/jo981708n

文献信息

• Six- vs Seven-Membered Ring Formation from the 1-Bicyclo[4.1.0]heptanylmethyl Radical:  Synthetic and ab Initio Studies
  作者：Eric J. Kantorowski、Shawn W. E. Eisenberg、William H. Fink、Mark J. Kurth

  DOI：10.1021/jo981708n

  日期：1999.1.1

  The viability of utilizing 1-bicyclo[4.1.0]heptanylmethyl radical (3) to serve as a progenitor of seven-membered carbocycles was examined. Rate constants for the rearrangement of this radical to 3-methylenecycloheptyl radical (4) and 2-methylenecyclohexyl-1-methyl radical (6) were measured using the competition method of 3 with thiophenol over the temperature range of -75 to 59 degrees C. Arrhenius functions were calculated for the conversions of 3 to 4 and 3 to 6 and found to be log (k/s(-1)) = (12.38 +/- 0.20) - (5.63 +/- 0.23)/theta and log(k/s(-1)) = (11.54 +/- 0.32) - (5.26 +/- 0.37)/theta, respectively. The rate-constants for these conversions at 25 degrees C are 1.86 x 10(8) s(-1) and 5.11 x 10(7) s(-1), respectively. Hence, the seven-membered ring-expanded carbocycle is formed 3.6 times faster at 25 degrees C than the nonexpanded species. This suggests that the 1-bicyclo[4.1.0]heptanylmethyl radical system may be synthetically useful in seven-membered ring-forming methodology. Preliminary theoretical examination of this radical system qualitatively predicted the experimentally determined energies of activation: PMP4/6-31G*//HF/6-31G* Delta E-a (3 --> 6 - 3 --> 4) = 3.0 kcal/mol with zero point-energy correction. The HF/6-31G* optimized reaction coordinate stationary points suggest cyclopropyl substituent eclipsing interactions play an important role in determining the kinetic outcome of these rearrangements.