3-(dichloromethyl)-3,5,5-trimethylcyclohexene | 123827-01-0

• 分子结构分类: 有机化合物
• 英文名称: 3-(dichloromethyl)-3,5,5-trimethylcyclohexene
• CAS: 123827-01-0
• 化学式: C₁₀H₁₆Cl₂
• 分子量: 207.143
• InChiKey: PXBDHNZKVXZABJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  (1α,2β,6α)-7,7-dichloro-4,4,6-trimethylbicyclo<4.1.0>heptan-2-yl 4-methylbenzenesulfonate 在 六甲基磷酰三胺 、 三乙基硼 、 三苯基氢化锡 、 sodium hydride 作用下， 以 正己烷 为溶剂， 反应 19.83h， 生成 3-(dichloromethyl)-3,5,5-trimethylcyclohexene
  参考文献：
  名称：

  Use of radical ring opening for introduction of alkyl and substituted alkyl groups with stereochemical control: a synthetic application of cyclopropylcarbinyl radicals

  摘要：

  Cyclopropylcarbinols 2a and 2b (see Scheme I), which are accessible by a number of routes, can be converted into the corresponding radicals 3a and 3b, respectively. These radicals undergo peripheral ring-opening of the cyclopropyl substructure to afford substituted cycloalkenes 4a and 4b. The whole sequence represents a general method for attaching alkyl, and substituted alkyl, groups to an existing cyclic structure, and it can often be carried out with predictable stereo- and regiochemical control. Reaction conditions for the ring-opening depend on the substitution pattern of the cyclopropane: where the non-bridgehead carbon of the cyclopropane carries a strongly electron-withdrawing group, the ring-opening can be done at the reflux temperature of benzene. However, in the absence of such electron-withdrawing groups, a low temperature is best used in order to suppress ring expansion. Various methods that accommodate these requirements are available for generating the radicals.

  DOI：

  10.1021/jo00012a009

文献信息

• Synthetic applications of radical ring-opening: use of cyclopropylmethyl radicals
  作者：Derrick L. J. Clive、Sylvain Daigneault

  DOI：10.1039/c39890000332

  日期：——

  Cyclopropanation of cyclic allylic alcohols followed by radical deoxygenation leads, by peripheral ring-opening of the cyclopropylmethyl system, to alkyl-substituted cycloalkenes (Scheme 1); the alkyl group can itself be substituted (during the cyclopropanation stage), synthetic equivalents of allylic alcohols can be used, and the overall process occurs with predictable stereo- and regio-chemistry

  环状烯丙基醇的环丙烷化，然后进行自由基脱氧，通过环丙基甲基系统的周边开环，导致烷基取代的环烯烃（方案1）；烷基本身可以被取代（在环丙烷化阶段），可以使用烯丙基醇的合成等价物，整个过程以可预测的立体化学和区域化学发生。
• CLIVE, DERRICK L. J.;DAIGNEAULT, SYLVAIN, J. CHEM. SOC. CHEM. COMMUN.,(1989) N, C. 332-335
  作者：CLIVE, DERRICK L. J.、DAIGNEAULT, SYLVAIN

  DOI：——

  日期：——
• CLIVE, DERRICK L. J.;DAIGNEAULT, SYLVAIN, J. ORG. CHEM., 56,(1991) N2, C. 3801-3814
  作者：CLIVE, DERRICK L. J.、DAIGNEAULT, SYLVAIN

  DOI：——

  日期：——