dimethyl 1,4,9,14,19-pentaoxo-1,4,6,7,8,9,14,15,16,17-decahydro-7,16-methanodinaphtho<2,3-a:2',3'-f>cyclodecene-7,16-dicarboxylate | 134591-72-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: dimethyl 1,4,9,14,19-pentaoxo-1,4,6,7,8,9,14,15,16,17-decahydro-7,16-methanodinaphtho<2,3-a:2',3'-f>cyclodecene-7,16-dicarboxylate
• 英文别名: Dimethyl 6,9,17,24,27-pentaoxohexacyclo[12.12.1.03,12.05,10.016,25.018,23]heptacosa-3,5(10),7,11,16(25),18,20,22-octaene-1,14-dicarboxylate
• CAS: 134591-72-3
• 化学式: C₃₁H₂₂O₉
• 分子量: 538.51
• InChiKey: KRIYNYXDVJUXEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  40
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  dimethyl 11-oxodinaphtho<2,3-c;2',3'-h>bicyclo<4.4.1>undeca-3,8-diene-1,6-dicarboxylate 在 sodium dichromate 、 硫酸 作用下， 以 氯仿 、 水 为溶剂， 反应 0.5h， 以7%的产率得到dimethyl 5,9,14,18,19-pentaoxo-5,6,7,8,9,14,15,16,17,18-decahydro-7,16-methanodinaphtho<2,3-a:2',3'-f>cyclodecene-7,16-dicarboxylate
  参考文献：
  名称：

  Effect of 1,4-naphthoquinone annelation on the conformational behavnniour of carbonyl- and methano-bridged cyclodecadiene derivatives

  摘要：

  The Na2Cr2O7 oxidation of hexahydro-7,16-methanodinaphtho[2,3-a:2',3'-f] cyclodecene derivative 2, produced two bis-(1,4-naphthoquinone)s, 7 and 9, and monoquinone compound 8. Benzonaphtho derivative 3 gave two 1,4-naphthoquinone derivatives, 10 and 11, on oxidation.Flexible compounds 7-11 showed temperature-dependent H-1 NMR spectra due to equilibria among chair-boat, twin-chair, and boat-chair conformers, which were H-1 NMR spectroscopically characterized. A twin-chair conformer was detected in products 8, 9 and 10, but not in compounds 7 and 11. A broad absorption band due to an intramolecular C-T interaction in the twin-chair conformer was observed at lambda approximately 400 nm in the electronic spectra of the monoquinones, 8 and 10, but not in the bis(quinone) 9. Population of the twin-chair conformer increased with removal of the ester group on the bridgehead position. Reduction of the carbonyl group on the bridge also favoured the twin-chair conformation, indicating a repulsive interaction between the ester and the carbonyl group of the 1,4-naphthoquinone moiety. Upon irradiation with sunlight, compound 7 gave the [2 + 2]-photoadduct 15.

  DOI：

  10.1039/p19910001107

文献信息

• Effect of 1,4-naphthoquinone annelation on the conformational behavnniour of carbonyl- and methano-bridged cyclodecadiene derivatives
  作者：Shuntaro Mataka、Seung Taeg Lee、Yuriko Tamura、Akihiko Tsuge、Masashi Tashiro

  DOI：10.1039/p19910001107

  日期：——

  The Na2Cr2O7 oxidation of hexahydro-7,16-methanodinaphtho[2,3-a:2',3'-f] cyclodecene derivative 2, produced two bis-(1,4-naphthoquinone)s, 7 and 9, and monoquinone compound 8. Benzonaphtho derivative 3 gave two 1,4-naphthoquinone derivatives, 10 and 11, on oxidation.Flexible compounds 7-11 showed temperature-dependent H-1 NMR spectra due to equilibria among chair-boat, twin-chair, and boat-chair conformers, which were H-1 NMR spectroscopically characterized. A twin-chair conformer was detected in products 8, 9 and 10, but not in compounds 7 and 11. A broad absorption band due to an intramolecular C-T interaction in the twin-chair conformer was observed at lambda approximately 400 nm in the electronic spectra of the monoquinones, 8 and 10, but not in the bis(quinone) 9. Population of the twin-chair conformer increased with removal of the ester group on the bridgehead position. Reduction of the carbonyl group on the bridge also favoured the twin-chair conformation, indicating a repulsive interaction between the ester and the carbonyl group of the 1,4-naphthoquinone moiety. Upon irradiation with sunlight, compound 7 gave the [2 + 2]-photoadduct 15.