3-(4,4-Dimethyl-pent-2-ynylidene)-cyclobutanone | 189825-00-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(4,4-Dimethyl-pent-2-ynylidene)-cyclobutanone
• 英文别名: 3-(4,4-Dimethylpent-2-yn-1-ylidene)cyclobutan-1-one；3-(4,4-dimethylpent-2-ynylidene)cyclobutan-1-one
• CAS: 189825-00-1
• 化学式: C₁₁H₁₄O
• 分子量: 162.232
• InChiKey: XKBSYDAQEWGHGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  4,4-二甲基-2-戊炔醛 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 3-(4,4-Dimethyl-pent-2-ynylidene)-cyclobutanone
  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.