4a,4b-Dimethyl-4a,4b-dihydro-cyclopropa[cd]pentalene-1,2a,2b,4-tetracarboxylic acid tetramethyl ester | 79150-89-3

• 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: 4a,4b-Dimethyl-4a,4b-dihydro-cyclopropa[cd]pentalene-1,2a,2b,4-tetracarboxylic acid tetramethyl ester
• 英文别名: Tetramethyl 1,5-dimethyltricyclo[3.3.0.02,8]octa-3,6-diene-2,4,6,8-tetracarboxylate
• CAS: 79150-89-3
• 化学式: C₁₈H₂₀O₈
• 分子量: 364.352
• InChiKey: ZLWFJGUNAKPCMZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4a,4b-Dimethyl-4a,4b-dihydro-cyclopropa[cd]pentalene-1,2a,2b,4-tetracarboxylic acid tetramethyl ester 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以40%的产率得到2,6-dimethyl-1,3,5,7-cyclooctatetraene-1,3,5,7-tetracarboxylic acid
  参考文献：
  名称：

  摘要：

  2,6-Dimethyl-1,3,5,7-cyclooctatetraene-1,3,5,7-tetracarboxylic acid 3, C14H14O9, was prepared by thermolysis of the corresponding semibullvalene and characterized by spectroscopic and single-crystal X-ray diffraction studies. The monohydrate of 3 crystallizes in the tetrahedral space group P-4n2, a = 11.0924(3) Angstrom, c = 12.6799(5) Angstrom, V = 1560.15(9) Angstrom (3), Z = 4. The cyclooctatetraene ring adopts a tub-shaped conformation with a crystallograpically imposed twofold rotational symmetry, and is composed of localized C=C double bonds in the 1,3,5, and 7 positions with an average interatomic distance of 1.327 (5) Angstrom and C-C single bonds with an average interatomic distance of 1.489(5) Angstrom. The average C=C-C angle in the ring is 122.6(3)degrees. Each symmetry generated eight-membered ring contains four carboxyl groups, two of which are coplanar with the methyl groups across the C=C ring atoms. However, across the C-C bonds the carboxyl groups and the methyl groups show a torsion angle of 64.3(4)degrees. The presence of a water molecule in the crystal lattice generates a three-dimensional network of close hydrogen bondings between water and the carboxyl groups of multiple rings. This creates a network of orthogonal 10-membered rings between the 8-membered rings. Two given cyclooctatetraene rings are intermolecularly hydrogen bonded not only directly through their carboxyl groups but also via a bridging water molecule. This effect is rare in polycarboxylic acids and their monohydrates which bond only with water or among themselves.

  DOI：

  10.1023/a:1011981630202
• 作为产物：
  描述：

  Tetramethyl 3,7-dihydroxy-1,5-dimethyltetracyclo[3.3.0.02,8.04,6]octane-2,4,6,8-tetracarboxylate 在 三乙胺 、 sodium iodide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 1.0h， 生成 4a,4b-Dimethyl-4a,4b-dihydro-cyclopropa[cd]pentalene-1,2a,2b,4-tetracarboxylic acid tetramethyl ester
  参考文献：
  名称：

  Semibullvalenes. 1. Synthesis and crystal structure of 1,5-dimethyl-2,4,6,8-tetrakis(carbomethoxy)tricyclo[3.3.0.02,8]octa-3,6-diene a donor-acceptor-substituted semibullvalene

  摘要：

  DOI：

  10.1021/ja00410a059

文献信息

• Semibullvalenes. 1. Synthesis and crystal structure of 1,5-dimethyl-2,4,6,8-tetrakis(carbomethoxy)tricyclo[3.3.0.02,8]octa-3,6-diene a donor-acceptor-substituted semibullvalene
  作者：L. S. Miller、K. Grohmann、J. J. Dannenberg、L. Todaro

  DOI：10.1021/ja00410a059

  日期：1981.10
• ——
  作者：Ashwani Vij、Jennifer L. Palmer、Kamlesh Chauhan、Richard Vaughan Williams

  DOI：10.1023/a:1011981630202

  日期：——

  2,6-Dimethyl-1,3,5,7-cyclooctatetraene-1,3,5,7-tetracarboxylic acid 3, C14H14O9, was prepared by thermolysis of the corresponding semibullvalene and characterized by spectroscopic and single-crystal X-ray diffraction studies. The monohydrate of 3 crystallizes in the tetrahedral space group P-4n2, a = 11.0924(3) Angstrom, c = 12.6799(5) Angstrom, V = 1560.15(9) Angstrom (3), Z = 4. The cyclooctatetraene ring adopts a tub-shaped conformation with a crystallograpically imposed twofold rotational symmetry, and is composed of localized C=C double bonds in the 1,3,5, and 7 positions with an average interatomic distance of 1.327 (5) Angstrom and C-C single bonds with an average interatomic distance of 1.489(5) Angstrom. The average C=C-C angle in the ring is 122.6(3)degrees. Each symmetry generated eight-membered ring contains four carboxyl groups, two of which are coplanar with the methyl groups across the C=C ring atoms. However, across the C-C bonds the carboxyl groups and the methyl groups show a torsion angle of 64.3(4)degrees. The presence of a water molecule in the crystal lattice generates a three-dimensional network of close hydrogen bondings between water and the carboxyl groups of multiple rings. This creates a network of orthogonal 10-membered rings between the 8-membered rings. Two given cyclooctatetraene rings are intermolecularly hydrogen bonded not only directly through their carboxyl groups but also via a bridging water molecule. This effect is rare in polycarboxylic acids and their monohydrates which bond only with water or among themselves.