trans-bicyclo<5.2.0>non-8-ene | 96308-43-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: trans-bicyclo<5.2.0>non-8-ene
• 英文别名: trans-bicyclo[5.2.0]non-8-ene；(1R,7R)-bicyclo[5.2.0]non-8-ene
• CAS: 96308-43-9
• 化学式: C₉H₁₄
• 分子量: 122.21
• InChiKey: CESHSOZZPPYUNZ-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  trans-bicyclo<5.2.0>non-8-ene 以 正戊烷 为溶剂， 以15%的产率得到(Z,Z)-1,3-cyclononadiene
  参考文献：
  名称：

  Cyclobutene photochemistry. 4. The photochemistry of cis- and trans-bicyclo[5.2.0]non-8-ene

  摘要：

  Direct photolysis of cis- and trans-bicyclo[5.2.0]non-8-ene in hydrocarbon solution with monochromatic far-UV (185-214 nm) light sources affords cis,cis- and cis,trans-1,3-cyclononadiene via formal electrocyclic ring opening, cycloheptene (and acetylene) via formal (sigma-2s + sigma-2s) cycloreversion, and minor amounts of molecular rearrangement products. Product quantum yields have been determined for the 185-nm photolyses. The two isomers lead to similar distributions of the isomeric 1,3-cyclononadienes, with similar quantum yields at 185 nm; the diene mixtures are in both cases weighted in favor of the less thermodynamically stable cis,trans isomer. The product distributions vary only slightly with excitation wavelength over the 185-214-nm range. Quantum yields for direct photoisomerization of cis,cis- and cis,trans-1,3-cyclononadiene have also been determined. Two mechanisms are considered to explain the nonstereospecificity associated with the ring-opening process: a nonconcerted pathway involving initial cyclobutene bond homolysis and subsequent relaxation of common biradical intermediates, and a pericyclic pathway involving adiabatic, disrotatory ring opening to yield dienes in the first excited singlet state. While the results do not allow a definitive distinction between the two mechanisms, the nonconcerted pathway is suggested to be the more reasonable on the basis of the photobehavior of other cyclobutene derivatives that have been studied. The quantum yield of cycloreversion product is ca. 4 times higher from the cis isomer compared to that from the trans isomer, due to the stereochemical requirements of the process.

  DOI：

  10.1021/jo00004a043
• 作为产物：
  描述：

  环辛烯-1-甲醛甲苯磺酰腙 在 sodium methylate 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 9.0h， 生成 trans-bicyclo<5.2.0>non-8-ene
  参考文献：
  名称：

  Cumulene光化学：1,2-环壬二烯的单线态和三线态光重排

  摘要：

  Obtention du bicyclo [6.1.0] nonene-1(9), du tricyclo [4.3.0.0 2,9 ] nonane et du cyclononyne comme produits majoritaires par photolyse directe。获得 par photolyse sensibilisee du tricyclo [4.3.0.0 2,9 ] nonane, du bicyclo [4.3.0] nonene-1(9), du cis-bicyclo [4.3.0] nonene-2 et du bicyclo [4.3.0]壬烯-1(2)。机制

  DOI：

  10.1021/ja00299a037

文献信息

• Cumulene photochemistry: singlet and triplet photorearrangements of 1,2-cyclononadiene
  作者：Thomas J. Stierman、Richard P. Johnson

  DOI：10.1021/ja00299a037

  日期：1985.6

  Obtention du bicyclo [6.1.0] nonene-1(9), du tricyclo [4.3.0.0 2,9 ] nonane et du cyclononyne comme produits majoritaires par photolyse directe. Obtention par photolyse sensibilisee du tricyclo [4.3.0.0 2,9 ] nonane, du bicyclo [4.3.0] nonene-1(9), du cis-bicyclo [4.3.0] nonene-2 et du bicyclo [4.3.0] nonene-1(2). Mecanismes

  Obtention du bicyclo [6.1.0] nonene-1(9), du tricyclo [4.3.0.0 2,9 ] nonane et du cyclononyne comme produits majoritaires par photolyse directe。获得 par photolyse sensibilisee du tricyclo [4.3.0.0 2,9 ] nonane, du bicyclo [4.3.0] nonene-1(9), du cis-bicyclo [4.3.0] nonene-2 et du bicyclo [4.3.0]壬烯-1(2)。机制
• Cyclobutene photochemistry. 4. The photochemistry of cis- and trans-bicyclo[5.2.0]non-8-ene
  作者：William J. Leigh、Kangcheng Zheng、K. Brady Clark

  DOI：10.1021/jo00004a043

  日期：1991.2

  Direct photolysis of cis- and trans-bicyclo[5.2.0]non-8-ene in hydrocarbon solution with monochromatic far-UV (185-214 nm) light sources affords cis,cis- and cis,trans-1,3-cyclononadiene via formal electrocyclic ring opening, cycloheptene (and acetylene) via formal (sigma-2s + sigma-2s) cycloreversion, and minor amounts of molecular rearrangement products. Product quantum yields have been determined for the 185-nm photolyses. The two isomers lead to similar distributions of the isomeric 1,3-cyclononadienes, with similar quantum yields at 185 nm; the diene mixtures are in both cases weighted in favor of the less thermodynamically stable cis,trans isomer. The product distributions vary only slightly with excitation wavelength over the 185-214-nm range. Quantum yields for direct photoisomerization of cis,cis- and cis,trans-1,3-cyclononadiene have also been determined. Two mechanisms are considered to explain the nonstereospecificity associated with the ring-opening process: a nonconcerted pathway involving initial cyclobutene bond homolysis and subsequent relaxation of common biradical intermediates, and a pericyclic pathway involving adiabatic, disrotatory ring opening to yield dienes in the first excited singlet state. While the results do not allow a definitive distinction between the two mechanisms, the nonconcerted pathway is suggested to be the more reasonable on the basis of the photobehavior of other cyclobutene derivatives that have been studied. The quantum yield of cycloreversion product is ca. 4 times higher from the cis isomer compared to that from the trans isomer, due to the stereochemical requirements of the process.