八氢-并环戊二烯 | 694-72-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 中文名称: 八氢-并环戊二烯
• 英文名称: bicyclo[3.3.0]octane
• 英文别名: bicyclo<3.3.0>octane；Bicylo<3.3.0>octan；Pentalene, octahydro-；1,2,3,3a,4,5,6,6a-octahydropentalene
• CAS: 694-72-4
• 化学式: C₈H₁₄
• mdl: MFCD00060882
• 分子量: 110.199
• InChiKey: AEBWATHAIVJLTA-UHFFFAOYSA-N

物化性质

• 熔点：
  -30 °C
• 沸点：
  132 °C(Press: 762 Torr)
• 密度：
  0.896±0.06 g/cm3(Predicted)
• 大气OH速率常数：
  1.10e-11 cm3/molecule*sec
• 保留指数：
  859.9;865.2;870;858;863;865;869;874;858;870;870;891

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2912299000

反应信息

• 作为反应物：
  描述：

  八氢-并环戊二烯 在 乙二胺 作用下， 生成 萘
  参考文献：
  名称：

  Synthesis, spectral and structural characterization of Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) complexes with 2-mercapto-5-methyl-1,3,4-thiadiazole: A Zn(II) complex acting as a new sensitive and selective fluorescent probe for the detection of Hg2+ in H2O–MeOH medium

  摘要：

  Five new complexes, [Ni(mthd)(2)(py)(2)] (1), [Cu(en)(2)](mthd)(2) (2), [H(2)en][Hg(mthd)(3)](2)center dot 2H(2)O (3), [Cd(mthd)(2)(o-phen)(2)](2)center dot H2O (4) and [Zn(mthd)(2)(bpy)] (5) (Hmthd = 2-mercapto-5-methyl-1,3,4-thiadiazole), have been synthesized. All the complexes have been fully characterized by various techniques: elemental analyses, IR, electronic and fluorescent spectral data. The ligand is present in the deprotonated thiol form in the complexes [Cu(en)(2)](mthd)(2) (2) and [Cd(mthd)(2)(o-phen)(2)]2 center dot H2O (4). In complex 2, the ligand is ionically bonded, whereas it is covalently bonded through the sulfur in complex 4. In [Ni(mthd)(2)(py)(2)] (1) the ligand is N,S chelating bidentate bonded through the thiol sulfur and the thiadiazole ring nitrogen adjacent to it, forming a four membered chelate ring. The ligand is covalently bonded through the deprotonated thiadiazole ring nitrogen adjacent to the thiol sulfur in [Zn(mthd)(2)(bpy)] (5). The complex anion in [H(2)en][Hg(mthd)(3)](2)center dot 2H(2)O (3) has a triangular planar geometry, with bonding through the deprotonated thiolato sulfur atoms from the three ligands. [Zn(mthd)(2)(bpy)] (5) is highly fluorescent as compared to the other complexes and has been further used as a metal probe for sensing of Hg2+ in H2O-MeOH solution. Complex 5, upon interaction with Hg2+, shows a hypochromic shift in the absorption spectra whereas the emission spectra exhibited 75% quenching fluorescence behavior. The electrochemical studies also suggest the interaction of Hg(II) with the Zn(II) complex, probably via the free thione sulfur. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.07.027
• 作为产物：
  描述：

  环辛烷 在 四氢化物钛 、 Pt/Al₂O₃ 作用下， 反应 8.0h， 生成 八氢-并环戊二烯
  参考文献：
  名称：

  Preparatively useful dehydrogenative method for dodecahedrane synthesis

  摘要：

  DOI：

  10.1021/ja00267a067

文献信息

• High temperature bromination Part XXIII: Bromination of octahydro-1H-indene and octahydro-1H-4,7-methanoindene
  作者：Melek Sermin Ozer、Benan Kilbas、Metin Balci

  DOI：10.3998/ark.5550190.p008.195

  日期：——

  photobromination of octahydro-1H-indene and octahydro-1H-4,7-methanoindene were investigated. Three isomeric tetrabromides (1,3,4,7-tetrabromo-2,3,4,5,6,7-hexahydro-1Hindene) were formed along with a smaller amount of tribromoindane and a pentabromide by thermal bromination of octahydro-1H-indene. The thermodynamically most stable isomers were formed. Morover, thermal and photochemical bromination of octahydro-1H-4

  研究了八氢-1H-茚和八氢-1H-4,7-甲茚的热和光溴化。通过八氢-1H-的热溴化，形成了三种异构四溴化物（1,3,4,7-四溴-2,3,4,5,6,7-六氢-1Hindene）以及少量三溴茚满和五溴化物茚。形成了热力学最稳定的异构体。此外，八氢-1H-4,7-甲茚的热和光化学溴化提供了由五元环的烯丙基溴化产生的区域特异性溴化物。此外，作为中间官能团形成的双键也由于其锥体化而被溴化。讨论了形成产品分布的机制。
• Highly Active Superbulky Alkaline Earth Metal Amide Catalysts for Hydrogenation of Challenging Alkenes and Aromatic Rings
  作者：Johannes Martin、Christian Knüpfer、Jonathan Eyselein、Christian Färber、Samuel Grams、Jens Langer、Katharina Thum、Michael Wiesinger、Sjoerd Harder

  DOI：10.1002/anie.202001160

  日期：2020.6.2

  series of bulky alkaline earth (Ae) metal amide complexes have been prepared: Ae[N(TRIP)2 ]2 (1-Ae) and Ae[N(TRIP)(DIPP)]2 (2-Ae) (Ae=Mg, Ca, Sr, Ba; TRIP=SiiPr3 , DIPP=2,6-diisopropylphenyl). While monomeric 1-Ca was already known, the new complexes have been structurally characterized. Monomers 1-Ae are highly linear while the monomers 2-Ae are slightly bent. The bulkier amide complexes 1-Ae are by far

  制备了两个系列的大体积碱土金属 (Ae) 金属酰胺配合物：Ae[N(TRIP)2 ]2 (1-Ae) 和 Ae[N(TRIP)(DIPP)]2 (2-Ae) (Ae= Mg、Ca、Sr、Ba；TRIP=SiiPr3，DIPP=2,6-二异丙基苯基）。虽然单体 1-Ca 已为人所知，但新复合物的结构已得到表征。单体1-Ae是高度线性的，而单体2-Ae是轻微弯曲的。体积较大的酰胺配合物 1-Ae 是迄今为止烯烃加氢中最活跃的催化剂，其活性从 Mg 增加到 Ba。催化剂 1-Ba 可以还原环己烯或 3-己烯等内烯烃以及 1-Me-环己烯或四苯乙烯等极具挑战性的底物。它还对芳烃氢化还原蒽和萘（即使被烷基取代）以及联苯具有活性。苯可以还原为环己烷，但未达到完全转化。催化氢化的第一步是形成（酰胺）AeH 物质，它可以形成更大的聚集体。增加酰胺配体的体积会降低聚集体尺寸，但尚不清楚真正的催化剂是什么。 DFT
• Catalytic dehydrogenation of cyclooctane with titanium, zirconium and hafnium metallocene complexes
  作者：Sandra Taubmann、Christine E. Denner、Helmut G. Alt

  DOI：10.1016/j.jorganchem.2009.01.048

  日期：2009.6

  structure. Generally, complexes with low steric demands and MAO as cocatalyst gave the highest activities. The comparison of different π-ligands resulted in the following activity order: cyclopentadienyl > indenyl > fluorenyl. The influence of σ-ligands and n-donor ligands gave the following activity order: –Cl > –PMe3 > –CH2Ph > –(CH2)4CH3 > –NPh3. The activities depended on the nature of the cocatalyst

  茂金属配合物与助催化剂（如甲基铝氧烷（MAO））的结合不仅是烯烃聚合的极好催化剂，而且还是在均相（高压釜）和非均相（固定床反应器）反应中活化烷烃的合适催化剂。催化剂的活性取决于温度，助催化剂，添加剂，中心金属和配体结构。通常，低空间需求的配合物和MAO作为助催化剂的活性最高。不同π-配体的比较导致以下活性顺序：环戊二烯基>茚基>芴基。σ-配体和n-给体配体的影响给出以下活性顺序：–Cl> –PMe 3  > –CH 2 Ph> –（CH 2）4 CH 3  > –NPh 3。活性取决于助催化剂的性质并以下列顺序降低：MAOAOAlMe 3  > AlEt 3。铝粉和路易斯碱NPh 3的添加提高了Cp 2 ZrCl 2 / MAO催化剂的活性。Cp 2 ZrCl 2 / MAO / NPh 3催化剂在300°C的16 h内，均相反应具有458次转换的最高活性。Cp 2 ZrCl 2 / MAO
• Catalytic thermal and photo-induced CH and CC activation reactions of alkanes with ansa amido functionalized half-sandwich complexes and methylalumoxane
  作者：H.G. Alt、Christine E. Denner

  DOI：10.1016/j.jorganchem.2009.06.018

  日期：2009.9

  Zr, Hf) for CH and CC activation reactions is completely unknown in the literature. In contrast to the dehydrogenation reactions of cyclooctane and the metallocene complexes of the group 4 metals, where the zirconocene complexes give higher TONs than the titanocene complexes the ansa amido functionalized titanium complexes give more than two times higher TONs than the corresponding Zr or Hf complexes

  在文献中，烷烃的大多数脱氢反应被描述为环辛烷的CH活化反应。已发现CHA活化反应的最佳结果是MAO活化的茂金属络合物与环辛烷在300°C以上的温度下反应。 Ind'Si（Me）2NtBuMCl2（Ind'=单取代的茚基）类型的ansa酰胺基官能化半三明治化合物的应用；CH和CC活化反应的M = Ti，Zr，Hf）在文献中是完全未知的。 与环辛烷和第4组金属的茂金属配合物的脱氢反应相反，其中茂茂锆配合物给出的TONs高于二茂钛配合物，而ansa酰胺基官能化钛配合物给出的TONs则高出相应的Zr或Hf配合物两倍以上。ansa酰胺基官能化的配体会增加Ti络合物的TON，降低Zr络合物的TON。 与茂金属配合物相反，钛的ansa酰胺基官能化的二氯化物配合物也比相应的Zr配合物具有更高的活性。已知有机金属钛，锆和ha（IV）化合物的光解可产生M（III）自由基。与相应的Zr和Hf金属化合物相比，活性Ti金属中心的形成更容易。
• Dehydrogenation of Cycloalkanes by Suspended Platinum Catalysts
  作者：Shunichi Hama、Xiaomei Li、Kiyoshi Yukawa、Yasukazu Saito

  DOI：10.1246/cl.1992.2463

  日期：1992.12

  Heterogenized cluster complex [Pt3(CO)6]52− and reduced platinum metal have catalyzed cyclooctane dehydrogenation at comparable rates, whereas dehydrogeno-aromatization of ethylcyclohexane proceeded predominantly with the latter. Active-site ensembles for the formation of cyclooctene, bicyclooctane and aromatics were discussed on reference to the appropriate stretch of platinum metal atoms.

  杂化簇复合物 [Pt3(CO)6]52- 和还原的铂金属以相当的速率催化环辛烷脱氢，而乙基环己烷的脱氢芳构化主要用后者进行。参考铂金属原子的适当伸展讨论了用于形成环辛烯、双环辛烷和芳烃的活性位点集合。

表征谱图