1,4-Dichloro-7,7-dimethoxynorbornane | 18341-72-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1,4-Dichloro-7,7-dimethoxynorbornane
• 英文别名: 1,4-Dichlor-7,7-dimethoxy-bicyclo<2.2.1>heptan；1,4-Dichloro-7,7-dimethoxybicyclo[2.2.1]heptane
• CAS: 18341-72-5
• 化学式: C₉H₁₄Cl₂O₂
• 分子量: 225.115
• InChiKey: FPGSNQSYIQVOCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-Dichloro-7,7-dimethoxynorbornane 在 乙醇-D1 、 sodium 作用下， 以 乙醚 为溶剂， 以51%的产率得到1,4-Dideuterio-7,7-dimethoxynorbornane
  参考文献：
  名称：

  Effects of Bridgehead Substitution on Structure and Reactivity of the 7-Norbornyl Cation

  摘要：

  A systematic investigation was undertaken of the effect of bridgehead substitution on the solvolytic reactivity of 7-norbornyl triflates in aqueous TFE. Methyl substitution increases the rate 60-fold and the effect of multiple substitution is additive. Chlorine, on the other hand, exhibits a combined inductive and resonance effect and decreases the reactivity 1700 times. The observed normal secondary P-deuterium isotope effect of the 1,4-d(2) derivative can be rationalized by assuming a tilted C-s geometry for the cationic transition structure which is only slightly higher in energy than the nonclassical intermediate cation of C-1 symmetry. Bridgehead methyl-d(3) kinetic isotope effects are similar to those associated with the nonmigrating methyl group in neopentyl ester solvolyses. These results are in agreement with the recently published structure of the 7-norbornyl cation calculated at the highest ab initio level which has confirmed its nonclassical nature as originally proposed by Winstein.

  DOI：

  10.1021/jo00102a033

文献信息

• Effects of Bridgehead Substitution on Structure and Reactivity of the 7-Norbornyl Cation
  作者：D. E. Sunko、H. Vancik、Z. Mihalic、V. J. Shiner、F. P. Wiglis

  DOI：10.1021/jo00102a033

  日期：1994.11

  A systematic investigation was undertaken of the effect of bridgehead substitution on the solvolytic reactivity of 7-norbornyl triflates in aqueous TFE. Methyl substitution increases the rate 60-fold and the effect of multiple substitution is additive. Chlorine, on the other hand, exhibits a combined inductive and resonance effect and decreases the reactivity 1700 times. The observed normal secondary P-deuterium isotope effect of the 1,4-d(2) derivative can be rationalized by assuming a tilted C-s geometry for the cationic transition structure which is only slightly higher in energy than the nonclassical intermediate cation of C-1 symmetry. Bridgehead methyl-d(3) kinetic isotope effects are similar to those associated with the nonmigrating methyl group in neopentyl ester solvolyses. These results are in agreement with the recently published structure of the 7-norbornyl cation calculated at the highest ab initio level which has confirmed its nonclassical nature as originally proposed by Winstein.