Tricyclo[8.6.0.02,9]hexadeca-5,13-diene | 61233-68-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: Tricyclo[8.6.0.02,9]hexadeca-5,13-diene
• CAS: 61233-68-9；61277-43-8；61277-44-9；872357-60-3
• 化学式: C₁₆H₂₄
• 分子量: 216.367
• InChiKey: MOPYLUMINOGAKB-UHFFFAOYSA-N

物化性质

• 沸点：
  309.3±42.0 °C(Predicted)
• 密度：
  0.930±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  1,5-cis,cis-cyclooctadiene 在 bis(1,5-cyclooctadiene)nickel (0) 、 三氟化硼乙醚 作用下， 以85.7%的产率得到1,2,3,3a,4,6alpha-六氢并环戊二烯
  参考文献：
  名称：

  Cycloisomerization and [2+2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system

  摘要：

  The catalytic system Ni(COD)(2)/BF3 OEt2 has been studied in conversions of 1,5-cyclooctadiene under argon and ethylene atmosphere. It has been demonstrated that the catalytic system formed under argon exhibits a high effectiveness in cycloisomerization of 1,5-COD surpassing in this characteristic all known nickel complex catalysts (selectivity to bicyclo-[3 3 0]-octene-2 is up to 99 5% at 100% conversion). In the case of ethylene atmosphere the system produces mainly dinners (yield of cyclodimers above 70%) It has been shown that the catalytic system Ni(COD)(2)/BF3 OEt2 has the feature of "a living catalyst" consisting in resuming the initial activity with a new portion of 1,5-COD added when the monomer was fully exhausted The main and side products of the 1,5-COD conversion have been identified with GC-MS and preparative liquid chromatography combined with NMR and IR spectroscopy Based on EPR and IR spectroscopic data a mechanism for the catalytic performance of the Ni(COD)(2)/BF3 OEt2 system in argon or ethylene atmospheres is Suggested. It has been shown that Ni(0) is oxidized by the lewis acid to Ni(I) which is stabilized by substrate molecules in a mononuclear form without involvement of conventional organoelement entities Three sorts of paramagnetic nickel species have been found ionic complexes containing pi-coordinated COD ligands; ionic complexes sigma-bonded to COD: complexes as intimate pairs with BF4- counter tons. A mechanism for the catalytic conversion of 1,5-cyclooctadiene is proposed (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2009.09.017

文献信息

• Cycloisomerization and [2+2]cyclodimerization of 1,5-cyclooctadiene catalyzed with the Ni(COD)2/BF3·OEt2 system
  作者：V.V. Saraev、P.B. Kraikivskii、D.A. Matveev、V.V. Bocharova、S.K. Petrovskii、S.N. Zelinskii、A.I. Vilms、Hans-Friedrich Klein

  DOI：10.1016/j.molcata.2009.09.017

  日期：2010.1.15

  The catalytic system Ni(COD)(2)/BF3 OEt2 has been studied in conversions of 1,5-cyclooctadiene under argon and ethylene atmosphere. It has been demonstrated that the catalytic system formed under argon exhibits a high effectiveness in cycloisomerization of 1,5-COD surpassing in this characteristic all known nickel complex catalysts (selectivity to bicyclo-[3 3 0]-octene-2 is up to 99 5% at 100% conversion). In the case of ethylene atmosphere the system produces mainly dinners (yield of cyclodimers above 70%) It has been shown that the catalytic system Ni(COD)(2)/BF3 OEt2 has the feature of "a living catalyst" consisting in resuming the initial activity with a new portion of 1,5-COD added when the monomer was fully exhausted The main and side products of the 1,5-COD conversion have been identified with GC-MS and preparative liquid chromatography combined with NMR and IR spectroscopy Based on EPR and IR spectroscopic data a mechanism for the catalytic performance of the Ni(COD)(2)/BF3 OEt2 system in argon or ethylene atmospheres is Suggested. It has been shown that Ni(0) is oxidized by the lewis acid to Ni(I) which is stabilized by substrate molecules in a mononuclear form without involvement of conventional organoelement entities Three sorts of paramagnetic nickel species have been found ionic complexes containing pi-coordinated COD ligands; ionic complexes sigma-bonded to COD: complexes as intimate pairs with BF4- counter tons. A mechanism for the catalytic conversion of 1,5-cyclooctadiene is proposed (C) 2009 Elsevier B.V. All rights reserved.