1-bromo-1-chloro-3-(2,4-dimethyl-3-pentylidene)cyclobutane | 189824-89-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: 1-bromo-1-chloro-3-(2,4-dimethyl-3-pentylidene)cyclobutane
• 英文别名: 1-Bromo-1-chloro-3-(2,4-dimethylpentan-3-ylidene)cyclobutane；1-bromo-1-chloro-3-(2,4-dimethylpentan-3-ylidene)cyclobutane
• CAS: 189824-89-3
• 化学式: C₁₁H₁₈BrCl
• 分子量: 265.621
• InChiKey: TWEABTWBGLGEDB-UHFFFAOYSA-N

物化性质

• 沸点：
  277.0±30.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-bromo-1-chloro-3-(2,4-dimethyl-3-pentylidene)cyclobutane 在 甲基锂 作用下， 以 乙醚 为溶剂， 以64%的产率得到氨基甲硫酸,二甲基-,O,O-(3,3-二甲基1,1-联苯基-2,2-二基)酯
  参考文献：
  名称：

  Synthesis of [1.1.1]Propellanes by Cyclization of 3-Alkylidenecyclobutylidenes

  摘要：

  Starting from tricyclo[3.1.0.0(2,6)]hexane 5 and 1-bromobicyclo[1.1.0 ]butane 6, a series of [1.1.1]propellanes 15 and 21 has been synthesized which carry alkyl, aryl, alkenyl, and alkynyl groups. Propellane formation proceeded via 1-bromo-1-chloro-3-alkylidenecyclobutanes of type 13 and 19, which on treatment with methyllithium gave rise to the generation of carbenes 14 and 20 as short-lived intermediates. For these carbenes, the most efficient path of stabilization is obviously the intramolecular cycloaddition. Ab initio MO calculations at the Becke3LYP/6-31G* and MP2/6-31G* level of theory indicated that 3-alkylidenecyclobutylidenes 4 and 37a-d are not local energy minima but collapse to the corresponding [1.1.1]propellanes. On this basis, propellane formation should follow a carbenoid reaction path.

  DOI：

  10.1002/prac.19973390141
• 作为产物：
  描述：

  2,4-二甲基-3-戊酮 在 N-氯代丁二酰亚胺 、 正丁基锂 、 二甲基硫 、 四甲基乙二胺 、 4-甲基苯磺酰溴 、 叔丁基锂 、 三乙胺 、 lithium chloride 作用下， 以 乙醚 、 二氯甲烷 、 正戊烷 为溶剂， 反应 8.0h， 生成 1-bromo-1-chloro-3-(2,4-dimethyl-3-pentylidene)cyclobutane
  参考文献：
  名称：

  Synthesis of [1.1.1]Propellanes by Cyclization of 3-Alkylidenecyclobutylidenes

  摘要：

  Starting from tricyclo[3.1.0.0(2,6)]hexane 5 and 1-bromobicyclo[1.1.0 ]butane 6, a series of [1.1.1]propellanes 15 and 21 has been synthesized which carry alkyl, aryl, alkenyl, and alkynyl groups. Propellane formation proceeded via 1-bromo-1-chloro-3-alkylidenecyclobutanes of type 13 and 19, which on treatment with methyllithium gave rise to the generation of carbenes 14 and 20 as short-lived intermediates. For these carbenes, the most efficient path of stabilization is obviously the intramolecular cycloaddition. Ab initio MO calculations at the Becke3LYP/6-31G* and MP2/6-31G* level of theory indicated that 3-alkylidenecyclobutylidenes 4 and 37a-d are not local energy minima but collapse to the corresponding [1.1.1]propellanes. On this basis, propellane formation should follow a carbenoid reaction path.

  DOI：

  10.1002/prac.19973390141

文献信息

• Synthesis of [1.1.1]Propellanes by Cyclization of 3-Alkylidenecyclobutylidenes
  作者：Monika Kenndoff、Andrea Singer、Günter Szeimies

  DOI：10.1002/prac.19973390141

  日期：——

  Starting from tricyclo[3.1.0.0(2,6)]hexane 5 and 1-bromobicyclo[1.1.0 ]butane 6, a series of [1.1.1]propellanes 15 and 21 has been synthesized which carry alkyl, aryl, alkenyl, and alkynyl groups. Propellane formation proceeded via 1-bromo-1-chloro-3-alkylidenecyclobutanes of type 13 and 19, which on treatment with methyllithium gave rise to the generation of carbenes 14 and 20 as short-lived intermediates. For these carbenes, the most efficient path of stabilization is obviously the intramolecular cycloaddition. Ab initio MO calculations at the Becke3LYP/6-31G* and MP2/6-31G* level of theory indicated that 3-alkylidenecyclobutylidenes 4 and 37a-d are not local energy minima but collapse to the corresponding [1.1.1]propellanes. On this basis, propellane formation should follow a carbenoid reaction path.