(Z,Z)-1,3-cyclononadiene | 3726-88-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (Z,Z)-1,3-cyclononadiene
• 英文别名: 1,3-cyclononadiene；cis,cis-cyclonona-1,3-diene；(1Z,3Z)-1,3-Cyclononadiene；cis,cis-1,3-cyclononadiene；cis-cis-1,3-cyclononadiene；cyclononadiene；(1Z,3Z)-cyclonona-1,3-diene
• CAS: 3726-88-3
• 化学式: C₉H₁₄
• 分子量: 122.21
• InChiKey: HVSYSQGJZITGQV-CCAGOZQPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  (Z,Z)-1,3-cyclononadiene 在 palladium on activated charcoal sodium hydroxide 、 水 、 氢气 、 copper(II) sulfate 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 30.75h， 生成 10-acetyl-cis-bicyclo<7.1.0>decane tosylhydrazone
  参考文献：
  名称：

  Thermal valence isomerization of cis-fused bicyclic cyclobutenes. A study of orbital symmetry control

  摘要：

  DOI：

  10.1021/ja00399a025
• 作为产物：
  描述：

  cis,trans-cyclonona-1,3-diene 以 正戊烷 为溶剂， 生成 (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

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
• Thermal [1,5] Hydrogen Sigmatropic Shifts in <i>cis,cis</i>-1,3-Cyclononadienes Probed by Gas-Phase Kinetic Studies and Density Functional Theory Calculations
  作者：John E. Baldwin、Anuradha S. Raghavan、B. Andes Hess,、Lidia Smentek

  DOI：10.1021/ja065656s

  日期：2006.11.1

  transition states for [1,5] hydrogen shifts responsible for isomerizations among the five labeled dienes. A generalized formulation of the Winstein-Holness equation is presented and applied to the complex system, one that involves 11 ground-state conformers, 10 transition states separating them, and five transition states for [1,5] hydrogen shifts. The value for the empirical Ea derived from calculated mole

  在 240 至 287 摄氏度的四个温度下，对五种异构体单氘标记的顺式、顺式-1,3-环壬二烯相互转化的气相热 [1,5] 氢位移动力学进行了跟踪。发现的活化参数为Ea = 37.1 +/- 0.8 kcal/mol，log A = 11.6 +/- 0.3，DeltaH++ = 36.0 +/- 0.8 kcal/mol，DeltaS++ = -9.0 +/- 0.3 eu。基于密度泛函理论的计算为基态环壬二烯构象异构体、连接彼此的过渡态以及负责五种标记二烯之间异构化的 [1,5] 氢位移的过渡态提供了几何形状和能量。提出了 Winstein-Holness 方程的广义公式并将其应用于复杂系统，该系统涉及 11 个基态构象异构体，将它们分开的 10 个过渡态和 [1,5] 氢位移的五个过渡态。从基态构象异构体的计算摩尔分数和特定基态构象异构体和 [1,5] 氢位移跃迁结构的计算能量得出的经验
• Thermal isomerization of cyclic cis, trans, cis-trienes
  作者：William G. Dauben、Drake M. Michno、Eric G. Olsen

  DOI：10.1021/jo00317a008

  日期：1981.2
• The chemistry of humulene. Part V
  作者：R. W. Fawcett、J. O. Harris

  DOI：10.1039/jr9540002673

  日期：——
• Dehmlow, Eckehard V.; Kramer, Roland, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1987, vol. 42, # 4, p. 489 - 494
  作者：Dehmlow, Eckehard V.、Kramer, Roland

  DOI：——

  日期：——