ethyl 2-(2',2'-dideuteriovinyl)cyclopropanecarboxylate | 99779-45-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 2-(2',2'-dideuteriovinyl)cyclopropanecarboxylate
• CAS: 99779-45-0
• 化学式: C₈H₁₂O₂
• 分子量: 142.166
• InChiKey: RKAUCEKHTPZRLC-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.37
• 重原子数：
  10.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  ethyl 2-(2',2'-dideuteriovinyl)cyclopropanecarboxylate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以52%的产率得到ethyl 2-(2',2'-dideuteriovinyl)cyclopropanemethanol
  参考文献：
  名称：

  Hydrogen-deuterium fractionation factors for hydrogen-sp2 carbon bonds in olefins and allyl radicals

  摘要：

  Thermally induced 3,3-shift of trans- 1,2-divinylcyclopropane, 1, and trans-1,2-bis(2',2'-dideuteriovinyl)cyclopropane, 1-d4, to cycloheptadiene has a kinetic isotope effect of 1.08 +/- 0.02/D when extrapolated to 25-degrees-C. To the extent that the transition state resembles two allyl radicals, the kinetic effect is the fractionation factor for deuterium between sp2 allyl radical carbon and sp2 olefinic carbon. AM1 calculations on allyl radicals reveal a similar fractionation factor. The new value for the FF of allyl radical requires a correction to previously developed linear free energy relationships for kinetic and equilibrium isotope effect in 3,3-shifts and Diels-Alder reactions. The corrections are moderate, altering the previously determined extent of bond breaking and bond making by up to 50% only when there is little bond making, but do not alter the relative extents of bond making and breaking in the large number of compounds examined.

  DOI：

  10.1021/ja00064a017
• 作为产物：
  描述：

  2-甲酰基-1-环丙烷甲酸乙酯 、 methylene-d2-triphenylphosphorane 以 氘代二甲亚砜 为溶剂， 反应 45.0h， 生成 ethyl 2-(2',2'-dideuteriovinyl)cyclopropanecarboxylate
  参考文献：
  名称：

  Hydrogen-deuterium fractionation factors for hydrogen-sp2 carbon bonds in olefins and allyl radicals

  摘要：

  Thermally induced 3,3-shift of trans- 1,2-divinylcyclopropane, 1, and trans-1,2-bis(2',2'-dideuteriovinyl)cyclopropane, 1-d4, to cycloheptadiene has a kinetic isotope effect of 1.08 +/- 0.02/D when extrapolated to 25-degrees-C. To the extent that the transition state resembles two allyl radicals, the kinetic effect is the fractionation factor for deuterium between sp2 allyl radical carbon and sp2 olefinic carbon. AM1 calculations on allyl radicals reveal a similar fractionation factor. The new value for the FF of allyl radical requires a correction to previously developed linear free energy relationships for kinetic and equilibrium isotope effect in 3,3-shifts and Diels-Alder reactions. The corrections are moderate, altering the previously determined extent of bond breaking and bond making by up to 50% only when there is little bond making, but do not alter the relative extents of bond making and breaking in the large number of compounds examined.

  DOI：

  10.1021/ja00064a017

文献信息

• The diazo route to 2-vinylcyclopropylidenes
  作者：Wolfgang Kirmse、Pham van Chiem、Paul-Georg Henning

  DOI：10.1016/s0040-4020(01)96385-9

  日期：1985.1

  opylidenes (95,97) were generated from the corresponding nitrosoureas in methanol at room temperature. The diazo route is initiated by the formation of 2-vinylcyclopropanediazonium ions (e.g.43) which do not undergo 1,3-carbon shifts. No cyclopentenyl products were found in weakly basic methanol where the diazonium ions prevail. Ring opening of the diazonium ions gives pentadienyl cations and products

  在室温下，由相应的亚硝基脲在甲醇中生成2-乙烯基环亚丙基（2），3-甲基-2-乙烯基环亚丙基（79,81）和2-（1-丙烯基）环亚丙基（95,97）。重氮途径通过不经历1，3-碳移位的2-乙烯基环丙烷重氮离子（例如43）的形成而引发。在重氮离子占优势的弱碱性甲醇中未发现环戊烯基产物。重氮离子的开环得到戊二烯基阳离子和由其衍生的产物。通过氘和甲基标记的分布证明了戊二烯基阳离子的离域化。在强碱存在下，1-重氮-2-乙烯基环丙烷（例如48）是由于重氮离子去质子化而产生的。独立产生潜在的产物4-重氮环戊烯（103）排除了48的重排。从103获得了大量的3-甲氧基环戊烯（108），但没有从48获得。由相应的重氮化合物中的氮损失引起的2-乙烯基环丙叉基2,79和95竞争性地经历了丙二烯形成和Skattebøl重排。C-2（81）或C-2'（97）处的顺式甲基可防止Skattebøl重排。环戊烯基3和83屈服4-