exo-1-bromo-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: exo-1-bromo-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene
• 英文别名: 1-bromo-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene
• 化学式: C₁₅H₁₁Br
• 分子量: 271.156
• InChiKey: BBUVXSJDRFFWFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  exo-1-bromo-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene 在 叔丁基锂 作用下， 以 四氢呋喃 、 氘代苯 、 正戊烷 为溶剂， 反应 26.25h， 生成 1-苯基-1-丙炔
  参考文献：
  名称：

  An Experimental and Computational Investigation of (α-Methylbenzylidene)carbene

  摘要：

  Photolysis of 1-(1-phenylethylidene)-1a,9b-di-hydro-1H-cydopropa[l]phenanthrene, in C6H6 (or C6D6), at ambient temperature, produces (a-methylbenzylidene)carbene which undergoes a facile Fritsch-Buttenberg-Wiechell (FBW)-type rearrangement to 1-phenylpropyne. The alkyne results exclusively from a 1,2-phenyl shift as evident from the use of a C-13-labeled precursor. This experimental result is consistent with CCSD(T)/cc-pVTZ//B3LYP/6-31+G* calculations which reveal that a 1,2-phenyl shift in the singlet carbene needs to overcome a barrier of only 3.8 kcal/mol whereas the 1,2-methyl shift has to surmount a much larger barrier of 11.9 kcal/mol. The alkyne remains the predominant product when the photolysis is carried out in cyclohexene but the carbene-alkene cycloadduct could be detected, albeit in low yield, in the photolysate.

  DOI：

  10.1021/acs.joc.6b01143
• 作为产物：
  描述：

  1,1-dibromobicyclo<4.1.0>heptane 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 exo-1-bromo-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene
  参考文献：
  名称：

  1-（丙烷-2-亚烷基）-1a，9b-二氢-1 H-环丙烷[ l ]菲的光化学

  摘要：

  碳氢化合物1-（丙烷-2-亚烷基）-1a，9b-二氢-1 H-环丙烷[ l ]菲在环境温度下（〜315-400 nm）光解时提供二甲基亚乙烯基，卡宾可能被碳环己烯。某些前体还通过推定的1，5-σ移位和随后的电环开环重新排列为非光不稳定异构体。

  DOI：

  10.1016/j.tetlet.2015.10.064

文献信息

• Photochemistry of 1-(propan-2-ylidene)-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene
  作者：Tarini S. Hardikar、MacKenzie A. Warren、Dasan M. Thamattoor

  DOI：10.1016/j.tetlet.2015.10.064

  日期：2015.12

  enanthrene, affords dimethylvinylidene upon photolysis (∼315–400 nm) at ambient temperature, and the carbene may be trapped by cyclohexene. Some of the precursor also rearranged to a non-photolabile isomer via a putative 1,5-sigmatropic shift followed by an electrocyclic ring opening.

  碳氢化合物1-（丙烷-2-亚烷基）-1a，9b-二氢-1 H-环丙烷[ l ]菲在环境温度下（〜315-400 nm）光解时提供二甲基亚乙烯基，卡宾可能被碳环己烯。某些前体还通过推定的1，5-σ移位和随后的电环开环重新排列为非光不稳定异构体。
• An Experimental and Computational Investigation of (α-Methylbenzylidene)carbene
  作者：Xi Yang、Keith Languet、Dasan M. Thamattoor

  DOI：10.1021/acs.joc.6b01143

  日期：2016.9.16

  Photolysis of 1-(1-phenylethylidene)-1a,9b-di-hydro-1H-cydopropa[l]phenanthrene, in C6H6 (or C6D6), at ambient temperature, produces (a-methylbenzylidene)carbene which undergoes a facile Fritsch-Buttenberg-Wiechell (FBW)-type rearrangement to 1-phenylpropyne. The alkyne results exclusively from a 1,2-phenyl shift as evident from the use of a C-13-labeled precursor. This experimental result is consistent with CCSD(T)/cc-pVTZ//B3LYP/6-31+G* calculations which reveal that a 1,2-phenyl shift in the singlet carbene needs to overcome a barrier of only 3.8 kcal/mol whereas the 1,2-methyl shift has to surmount a much larger barrier of 11.9 kcal/mol. The alkyne remains the predominant product when the photolysis is carried out in cyclohexene but the carbene-alkene cycloadduct could be detected, albeit in low yield, in the photolysate.