1-(7H-dibenzofluoren-7-yl)-2,2-bis(7H-dibenzofluorenylidenemethyl)ethene | 15341-20-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-(7H-dibenzofluoren-7-yl)-2,2-bis(7H-dibenzofluorenylidenemethyl)ethene
• 英文别名: tris(7H-dibenzofluorenylidenemethyl)methane；Tris-(7H-dibenzofluorenylidenmethyl)-methan；12-[3-(12-pentacyclo[11.8.0.02,11.03,8.016,21]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaenylidene)-2-(12-pentacyclo[11.8.0.02,11.03,8.016,21]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaenylidenemethyl)propylidene]pentacyclo[11.8.0.02,11.03,8.016,21]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaene
• CAS: 15341-20-5
• 化学式: C₆₇H₄₀
• 分子量: 845.055
• InChiKey: PDGIKXBJHYHBJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.6
• 重原子数：
  67
• 可旋转键数：
  3
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.01
• 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：

  1-(7H-dibenzofluoren-7-yl)-2,2-bis(7H-dibenzofluorenylidenemethyl)ethene 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 tris(7H-dibenzofluorenylidenemethyl)methyl anion
  参考文献：
  名称：

  Precise control of the formation of a covalent and an ionic bond in carbocation-carbanion combination reactions

  摘要：

  The electronic effect on the selectivity of covalent or ionic bond formation was examined for the reaction of Kuhn's anion 1- (C67H39-; tris(7H-dibenzo[c,g]fluorenylidenemethyl)methide ion) and 1-aryl-2,3-dicyclopropylcyclopropenylium ions. The carbocation stability was progressively changed by varying the substituent on the phenyl ring, while the steric effect was kept essentially unchanged. The cations having the p-chlorophenyl (2a+), phenyl (2b+), m-methylphenyl (2c+), or m,m'-dimethylphenyl (2d+) group gave a covalent product, whereas a carbocation-carbanion salt was obtained from the cations having the p-methylphenyl (2e+) or p-methoxyphenyl (2f+) group. The reduction potentials E(red) of the cations, as determined by cyclic voltammetry, showed that the formation of the covalent or ionic product is switched by a small difference in stability (less-than-or-equal-to 0.4 kcal/mol) between 2d+ and 2e+. In chloroform, the salts 1-2e+ and 1-2f+ were transformed into covalent forms 1-2e and 1-2f, which can exist only in solution. When 1-(2a-d) and 1-2e,f+ were dissolved in DMSO, equilibrium between a covalent compound and ions was established. A plot of the free energy of heterolysis DELTAG(het)-degrees for 1-(2a-f) against the E(red) of the corresponding cations 2a-f+ showed that DELTAG(het)-degrees decreases as the cation is more stabilized. The heterolysis in DMSO was shown to be enhanced by ca. 13 kcal/mol both by the steric congestion in the covalent molecules and the stabilization of the cyclopropenylium ions by solvation.

  DOI：

  10.1021/jo00073a047
• 作为产物：
  描述：

  1,1-bis(7H-dibenzofluorenylidenemethyl)-2-(dimethylamino)ethene 、 lithium dibenzofluorenide 以 四氢呋喃 为溶剂， 反应 1.0h， 以53%的产率得到1-(7H-dibenzofluoren-7-yl)-2,2-bis(7H-dibenzofluorenylidenemethyl)ethene
  参考文献：
  名称：

  Isolation and properties of hydrocarbon salts

  摘要：

  DOI：

  10.1021/jo00290a034

文献信息

• Formation, properties, and reactions of the 1,2:3,4:5,6-tris(bicyclo[2.2.2]octeno)tropylium ion
  作者：Koichi Komatsu、Hidekazu Akamatsu、Shuji Aonuma、Yasuhisa Jinbu、Naoko Maekawa、Ken'ichi Takeuchi

  DOI：10.1016/s0040-4020(01)96150-2

  日期：1991.8

  The titled cation 4 has been synthesized and its properties and chemical reactivities investigated in detail. The cation 4 was shown to be formed in high yields not only by hydride abstraction from but also by the action of halogenoacetic acids upon the cycloheptatriene derivative 6. Based on the results of UV-Vis and NMR spectroscopies together with iodometric analysis, this reaction was shown to

  已经合成了标题为阳离子4的阳离子，并对其性质和化学反应性进行了详细研究。阳离子4不仅通过从中提取氢化物，而且通过卤代乙酸对环庚三烯衍生物6的作用，均以高收率形成。根据UV-Vis和NMR光谱分析的结果以及碘量分析，该反应显示为通过6的质子化，然后用分子氧脱氢进行。还显示阳离子4是由相当弱的布朗斯台德酸（例如H 3 PO 4，H 2 CO 3，H 3）作用形成的。在7-甲氧基环庚三烯10上的BO 3，C 6 H 5 OH和CH 3 NO 2。这些事实与4的极高的热力学稳定性一致，如pK R +值13.0（50％CH 3 CN水溶液，25°C）所示。阳离子4不显示任何反应性朝着与pK值亲核一个共轭酸比10.3较小除了用CN缓慢反应的情况下的-（PK一（新加坡国立大学医院）9.21）。也4不与碳负离子反应ř -用的pK一个（RH）低于8.3，如三（7H-二苯并[c，G] fluorenylide
• Small Difference in Cation Stability in Controlling the Formation of Hydrocarbon Salt or Covalent Hydrocarbon
  作者：Atsushi Miyabo、Ken’ichi Takeuchi、Koichi Komatsu、Toshikazu Kitagawa

  DOI：10.1246/cl.1992.683

  日期：1992.4

  cations, 3-(p-methylphenyl)- and 3-phenyl-1,2-dicyclopropylcyclopropenylium ions with highly stable Kuhn’s anion (C67H39−) gives a hydrocarbon salt and a covalent hydrocarbon, respectively, suggesting that a slight difference in cation stability differentiates the formation of either product.

  空间上可比的阳离子 3-(p-甲基苯基)- 和 3-苯基-1,2-二环丙基环丙烯离子与高度稳定的库恩阴离子 (C67H39-) 的反应分别产生烃盐和共价烃，表明轻微的阳离子稳定性的差异区分了两种产物的形成。
• A hydrocarbon cation-anion system in which ionic, radical, and covalent species coexist in equilibria
  作者：Koichi Komatsu、Shuji Aonuma、Kenichi Takeuchi、Kunio Okamoto

  DOI：10.1021/jo00270a006

  日期：1989.4