2,4,6,8-Tetracarbomethoxytetracyclo<3.3.1.0^2,8.0^4,6>nonane-3,7-dione | 155671-77-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,4,6,8-Tetracarbomethoxytetracyclo<3.3.1.0^2,8.0^4,6>nonane-3,7-dione
• 英文别名: Tetramethyl 3,9-dioxotetracyclo[3.3.1.02,8.04,6]nonane-1,2,4,5-tetracarboxylate
• CAS: 155671-77-5
• 化学式: C₁₇H₁₆O₁₀
• 分子量: 380.308
• InChiKey: NCINHMKYZWFZRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  139
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,4,6,8-Tetracarbomethoxytetracyclo<3.3.1.0^2,8.0^4,6>nonane-3,7-dione 在 三异丁基铝 作用下， 以 甲苯 为溶剂， 以79%的产率得到2,4,6,8-Tetracarbomethoxytetracyclo<3.3.1.0^2,8.0^4,6>nonane-3,7(exo,exo)-diol
  参考文献：
  名称：

  2,4,6,8-Tetracarbomethoxybarbaralane

  摘要：

  2,4,6,8-Tetracarbomethoxybarbaralane has been synthesized in four steps from malondialdehyde and dimethyl 1,3-acetonedicarboxylate. The P2I4-induced Grob fragmentation (Kuhn-Winterstein reaction) of 2,4,6,8-tetracarbomethoxytetracyclo[3.3.1.0(2,8).0(4,6)]nonane-3,7-exo, exo-diol gave in addition to 2,4,6,8-tetracarbomethoxybarbaralane (36%), two side products identified as 2,4,6-tricarbomethoxybarbaralane (3%) and 2,4,6,8-tetracarbomethoxybicyclo[3.3.1]nona-2,6-diene, a dihydrobarbaralane (2%). 2,4,6,8-Tetracarbomethoxybarbaralane was shown to undergo a rapid degenerate Cope rearrangement in solution with an activation energy of Delta G*(158) = 5.95 +/- 0.2 kcal/mol, 1.53 kcal/mol lower than that for barbaralane itself. In the solid state the molecule proved to be static on the basis of its CP-MAS C-13 NMR spectrum. The X-ray structure of 2,4,6,8-tetracarbomethoxybarbaralane shows a cyclopropane bond of 1.61 Angstrom (C-2-C-8) and an open-end distance of = 2.40 Angstrom (C-4-C-6). The equilibrium for the tricarbomethoxybarbaralane was found to been the side of the 2,4,6-isomer, on the basis of its spectral data. The X-ray structure confirmed this for the solid state. These findings are in agreement with theoretical expectations.

  DOI：

  10.1021/jo00089a027
• 作为产物：
  描述：

  4,8-Dibromo-3,7-dihydroxy-bicyclo[3.3.1]nona-2,6-diene-2,4,6,8-tetracarboxylic acid tetramethyl ester 在 sodium carbonate 作用下， 以 氯仿 、 水 为溶剂， 生成 2,4,6,8-Tetracarbomethoxytetracyclo<3.3.1.0^2,8.0^4,6>nonane-3,7-dione
  参考文献：
  名称：

  2,4,6,8-Tetracarbomethoxybarbaralane

  摘要：

  2,4,6,8-Tetracarbomethoxybarbaralane has been synthesized in four steps from malondialdehyde and dimethyl 1,3-acetonedicarboxylate. The P2I4-induced Grob fragmentation (Kuhn-Winterstein reaction) of 2,4,6,8-tetracarbomethoxytetracyclo[3.3.1.0(2,8).0(4,6)]nonane-3,7-exo, exo-diol gave in addition to 2,4,6,8-tetracarbomethoxybarbaralane (36%), two side products identified as 2,4,6-tricarbomethoxybarbaralane (3%) and 2,4,6,8-tetracarbomethoxybicyclo[3.3.1]nona-2,6-diene, a dihydrobarbaralane (2%). 2,4,6,8-Tetracarbomethoxybarbaralane was shown to undergo a rapid degenerate Cope rearrangement in solution with an activation energy of Delta G*(158) = 5.95 +/- 0.2 kcal/mol, 1.53 kcal/mol lower than that for barbaralane itself. In the solid state the molecule proved to be static on the basis of its CP-MAS C-13 NMR spectrum. The X-ray structure of 2,4,6,8-tetracarbomethoxybarbaralane shows a cyclopropane bond of 1.61 Angstrom (C-2-C-8) and an open-end distance of = 2.40 Angstrom (C-4-C-6). The equilibrium for the tricarbomethoxybarbaralane was found to been the side of the 2,4,6-isomer, on the basis of its spectral data. The X-ray structure confirmed this for the solid state. These findings are in agreement with theoretical expectations.

  DOI：

  10.1021/jo00089a027