5,18-dioxo-5,6,7,8,15,16,17,18-octahydro-7,16-methanodinaphtho<2,3-a:2',3'-f>cyclodecene | 134591-80-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5,18-dioxo-5,6,7,8,15,16,17,18-octahydro-7,16-methanodinaphtho<2,3-a:2',3'-f>cyclodecene
• 英文别名: 5,18-Dioxo-5,6,7,8,15,16,17,18-octahydro-7,16-methanodinaphtho(2,3-A:2',3'-F)cyclodecene；hexacyclo[12.12.1.03,12.05,10.016,25.018,23]heptacosa-3(12),5,7,9,16,18,20,22,24-nonaene-4,11-dione
• CAS: 134591-80-3
• 化学式: C₂₇H₂₂O₂
• 分子量: 378.47
• InChiKey: MBRIKPCLDAAVBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  29
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  dinaphtho<2,3-c;2',3'-h>bicyclo<4.4.1>undeca-3,8-dien-11-one 在 lithium aluminium tetrahydride 、 sodium dichromate 、 titanium(III) chloride 、 硫酸 作用下， 以 四氢呋喃 、 氯仿 、 水 为溶剂， 反应 16.0h， 生成 5,18-dioxo-5,6,7,8,15,16,17,18-octahydro-7,16-methanodinaphtho<2,3-a:2',3'-f>cyclodecene
  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.