tris(7H-dibenzofluorenylidenemethyl)methane | 15300-69-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: tris(7H-dibenzofluorenylidenemethyl)methane
• 英文别名: 1,1-Bis-(dibenzofluorenyliden-methyl)-2-(dibenzofluoren-9-yl)-ethylen；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-decaenyl)-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)prop-2-enylidene]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: 15300-69-3
• 化学式: C₆₇H₄₀
• 分子量: 845.055
• InChiKey: WFPUACXAVYVXFI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.87
• 重原子数：
  67.0
• 可旋转键数：
  3.0
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.01
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  tris(7H-dibenzofluorenylidenemethyl)methane 生成 Tris(7H-dibenzofluorenylidenemethyl)methide potasium salt
  参考文献：
  名称：

  OKAMOTO, KUNIO;KITAGAWA, TOSHIKAZU;TAKEUCHI, KENICHI;KOMATSU, KOICHI;KINO+, J. ORG. CHEM., 55,(1990) N, C. 996-1002

  摘要：

  DOI：

文献信息

• Steric and solvation effects in the heterolysis of carbon-carbon .sigma. bonds in hydrocarbons giving stable carbocations and carbanions
  作者：Atsushi Miyabo、Toshikazu Kitagawa、Kenichi Takeuchi

  DOI：10.1021/jo00061a015

  日期：1993.4

  Twelve ionically dissociative hydrocarbons (1-2b-m) and a bromo derivative (1-2a) have been synthesized by the carbocation-carbanion combination reaction of tris(7H-dibenzo[cg]fluorenylidenemethyl)methide ion (C67H39-, 1-) and substituted tropylium ions (2a-m+). The reaction of 1,3- and 1,4-disubstituted tropylium ions gave a single product, but monosubstituted tropylium ions gave two positional isomers. The bicyclo[2.2.l]heptenotropylium ion 2i+ gave a single product, whereas the bicyclo[2.2.2]octenotropylium ion 2j+ gave two positional isomers. MMP2 calculations on model compounds suggested that the difference in the behavior between 2i+ and 2j+ may be explained on the basis of the relative steric energies of the covalent products. Spectrophotometric studies for the behavior of 1-2a-j revealed their reversible ionization in DMSO or 5/95 3-methyl-sulfolane/sulfolane into the corresponding ionic species. Conductometric studies have also shown the partial ionization of 1-2c,e,f in DMSO. When the cationic part has a methyl, ethyl, or isopropyl group (1-2k-m), the ionization becomes irreversible owing to the polymerization of the tropylium ions via heptafulvene intermediates. The standard free energies of heterolysis (DELTAG-degrees(het)) for 1-2a-j were lower by approximately 10 kcal/mol than those predicted from pK(R+) and pK(a) values by Arnett's master equations, indicating that steric congestion in the covalent compounds plays an important role in enhancing the cleavage. The entropy term (-TDELTAS(het)) of the heterolysis of 1-2c was found to be approximately +5 kcal/mol, which is interpreted as a result of solvation to the tropylium ion. The significance of the steric factor was similarly demonstrated for the heterolysis which leads to phenylmalononitrile anion and tri-tert-butylcyclopropenylium ion in acetonitrile.