2-乙烯基环丁烷-1-醇 | 104745-50-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-乙烯基环丁烷-1-醇
• 英文名称: 2-vinylcyclobutanol
• 英文别名: 2-Ethenylcyclobutan-1-ol
• CAS: 104745-50-8
• 化学式: C₆H₁₀O
• 分子量: 98.1448
• InChiKey: SCAOLGUYHGBWLM-UHFFFAOYSA-N

物化性质

• 沸点：
  102.1±19.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-乙烯基环丁烷-1-醇 在 potassium hydride 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 3-cyclohexen-1-ol
  参考文献：
  名称：

  Mechanism of the 1,3-Sigmatropic Shift of 2-Vinylcyclobutanol Alkoxides

  摘要：

  The rate of rearrangement of 2-vinylcyclobutanol was studied in dimethyl sulfoxide and tetrahydrofuran solvents. Rearrangement to 3-cyclohexenol in 1% aqueous DMSO is catalyzed by lithium hydroxide. When lithium bromide is added to this medium, the rate is diminished by a factor of 17, due to the effect of added lithium cation on the ion-pairing equilibrium. Disappearance of the potassium salt (E isomer) in THF at -22 degrees C shows first-order behavior over four half-lives, but the first-order rate constant varies inversely with starting alkoxide concentration, suggesting that an ion pair dissociation equilibrium precedes rearrangement. The rearrangement of the potassium salt in 10:1 THF/HMPA is accelerated ii-fold over the rate in pure THF, due to specific solvation of the cation by HMPA. At 2 degrees C in THF the sodium salt of (Z)-2-vinylcyclobutanol epimerizes to the E isomer at a rate 36-fold faster than the E alkoxide rearranges to the product. The potassium (E)-2-(2-propenyl)cyclobutoxide salt rearranges 17 times slower than potassium 2-vinylcyclobutoxide, in agreement with a previous comparison of rates of fragmentations of homoallylic alkoxides. Secondary deuterium kinetic isotope effect (kie) measurements were made by rearranging mixtures of deuterated and nondeuterated potassium vinylcyclobutoxides at 0 degrees C in diethyl ether and analyzing the extent of reaction by GC and the isotopic content of the mixture by proton NMR. The large normal kie (k(H)/k(D2) = 1.34 +/- 0.04) at the terminal vinyl positions and the small normal kie at the carbinol position (k(H)/k(D) = 1.12 +/- 0.06) are explainable if an allyl anion/aldehyde intermediate species is formed. Ab initio calculations suggest that such an intermediate can exist in several possible conformations and should be nearly as stable in the gas phase as the starting vinylcyclobutoxide.

  DOI：

  10.1021/ja00093a009

文献信息

• Mechanism of the 1,3-Sigmatropic Shift of 2-Vinylcyclobutanol Alkoxides
  作者：Nathan J. Harris、Joseph J. Gajewski

  DOI：10.1021/ja00093a009

  日期：1994.7

  The rate of rearrangement of 2-vinylcyclobutanol was studied in dimethyl sulfoxide and tetrahydrofuran solvents. Rearrangement to 3-cyclohexenol in 1% aqueous DMSO is catalyzed by lithium hydroxide. When lithium bromide is added to this medium, the rate is diminished by a factor of 17, due to the effect of added lithium cation on the ion-pairing equilibrium. Disappearance of the potassium salt (E isomer) in THF at -22 degrees C shows first-order behavior over four half-lives, but the first-order rate constant varies inversely with starting alkoxide concentration, suggesting that an ion pair dissociation equilibrium precedes rearrangement. The rearrangement of the potassium salt in 10:1 THF/HMPA is accelerated ii-fold over the rate in pure THF, due to specific solvation of the cation by HMPA. At 2 degrees C in THF the sodium salt of (Z)-2-vinylcyclobutanol epimerizes to the E isomer at a rate 36-fold faster than the E alkoxide rearranges to the product. The potassium (E)-2-(2-propenyl)cyclobutoxide salt rearranges 17 times slower than potassium 2-vinylcyclobutoxide, in agreement with a previous comparison of rates of fragmentations of homoallylic alkoxides. Secondary deuterium kinetic isotope effect (kie) measurements were made by rearranging mixtures of deuterated and nondeuterated potassium vinylcyclobutoxides at 0 degrees C in diethyl ether and analyzing the extent of reaction by GC and the isotopic content of the mixture by proton NMR. The large normal kie (k(H)/k(D2) = 1.34 +/- 0.04) at the terminal vinyl positions and the small normal kie at the carbinol position (k(H)/k(D) = 1.12 +/- 0.06) are explainable if an allyl anion/aldehyde intermediate species is formed. Ab initio calculations suggest that such an intermediate can exist in several possible conformations and should be nearly as stable in the gas phase as the starting vinylcyclobutoxide.