trans-1,12-Dimethyl-5,6,6a,7,8,12b-hexahydrobenzophenanthrene-5,8-dione | 172876-77-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: trans-1,12-Dimethyl-5,6,6a,7,8,12b-hexahydrobenzophenanthrene-5,8-dione
• 英文别名: trans-5,6,6a,7,8,12b-hexahydro-1,12-dimethylbenzophenanthrene-5,8-dione
• CAS: 172876-77-6
• 化学式: C₂₀H₁₈O₂
• 分子量: 290.362
• InChiKey: JFSZSPOUMXKZNI-UWELNFAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  22.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  trans-1,12-Dimethyl-5,6,6a,7,8,12b-hexahydrobenzophenanthrene-5,8-dione 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以98%的产率得到(5R,8R)-1,12-Dimethyl-5,6,6a,7,8,12b-hexahydro-benzo[c]phenanthrene-5,8-diol
  参考文献：
  名称：

  Synthesis of a Chiral Helical Molecular Template Based on trans-5,6,6a,7,8,12b-Hexahydro-1,12-dimethylbenzo[c]phenanthrene- 5,8-dione

  摘要：

  Reduction of trans-5,5,6a,7,8,12b-hexahydro-1,12-dimethylbenzo[c]phenanthrene-5,8-dione (1, R(1)=R(4)=H, R(2)=R(3)=CH3) with lithium aluminum hydride yielded stereoselectively (5RS,8RS)-trans-5,6,6a,7,8,12b-hexahydro-1,12-dimethylbenzo[c]phenanthrene 2, X=H. These diols proved to be configurationally stable chiral molecular templates capable of straightforward modification by attachment of molecular elements of different length and kind. The structures of the diacetate 2, X=COCH3, and (5R,8R)-(-)-trans-5,6,6a,7,8,12b-hexahydro-1,12-dimethylbenzo- [c]phenanthrene-5,8-diyl di-p-bromobenzoate (2a, X=p-BrC6H4CO), as well as the absolute configuration of the latter were obtained by X-ray crystallography.

  DOI：

  10.1021/jo961254z
• 作为产物：
  描述：

  diethyl 2-(1,1-bis(2-methylphenyl)methyl) malonate 在 吡啶 、 氢氧化钾 、 lithium aluminium tetrahydride 、 PPA 、 potassium iodide 作用下， 以 乙醚 、 乙醇 、 乙二醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.17h， 生成 trans-1,12-Dimethyl-5,6,6a,7,8,12b-hexahydrobenzophenanthrene-5,8-dione
  参考文献：
  名称：

  Synthesis of Helical Molecules Based on 5,6,6a,7,8,12b-Hexahydrobenzo[c]phenanthrene-5,8-dione

  摘要：

  在纽曼 1-7 合成一些多环芳香烃的基础上，对合成路线进行了修改和发展，从而方便地制备出 11 种正式基于己二酮 (1) 的螺旋分子（方案 1）。与纽曼的工作不同的是，我们确定了 (1a-k) 中 C6a-C12b 的立体化学结构，并在某些情况下能够对其进行控制。我们还研究了在生成六环衍生物（1d, e）的反应中，六元环和七元环的竞争性形成。此外，我们还报告了在合成(1h)的过程中出现的一种不寻常的裂解（方案 2），由此产生了意想不到的副产物 4-甲氧基苯乙酮 (16)。

  DOI：

  10.1071/ch9951707

文献信息

• Synthesis of Symmetrical Polynitrohelicenes and Their Chiral Recognition in the Charge Transfer Complexation
  作者：Hitoshi Okubo、Daisuke Nakano、Shuzo Anzai、Masahiko Yamaguchi

  DOI：10.1021/jo001419a

  日期：2001.1.1

  former compound is converted to a 2,4,9,11-tetranitrohelicene. The tetranitrohelicenes form charge-transfer (CT) complexes with an electron-rich chiral diaminohelicene in solution. The studies on the chiral recognition reveal that the combinations of the same configuration of the helicenes form more stable complexes than that of the enantiomeric helicenes.

  光学活性的1,12-二甲基苯并[c]菲-5,8-二羧酸的衍生物可以被区域选择性地硝化，从而得到对称的多官能团螺旋烯。用发烟硝酸在乙酸的4,9位上将二羧酸或其二甲酯酯化。当反应在发烟硝酸中进行时，得到2,4,9,11-四硝基nitro烯。类似地，根据条件，1,12-二甲基苯并[c]菲-5,8-二腈得到2,11-二硝基或4,9-二硝基nitro烯，前一种化合物被转化为2,4,9,11 -四硝基hel烯。四硝基螺旋酮与溶液中的富电子手性二氨基螺旋烯形成电荷转移（CT）络合物。
• Macrocyclic Amides Consisting of Helical Chiral 1,12-Dimethylbenzo[<i>c</i>]phenanthrene-5,8-dicarboxylate
  作者：Hitoshi Okubo、Masahiko Yamaguchi、Chizuko Kabuto

  DOI：10.1021/jo981720f

  日期：1998.12.1

  Helical chiral 1,12-dimethylbenzo[c]phenanthrene-5,8-dicarboxylic acid was synthesized and resolved in multigram quantities. The absolute configuration was determined by X-ray analysis of the bis(camphorsultamamide) derivative. A series of optically active macrocyclic amides consisting of the chiral unit and a dianiline spacer were synthesized by one-pot procedures, and their structures were compared by spectroscopy and X-ray crystallography. One of the cycloamides exhibited catalytic activity in the asymmetric addition of diethylzinc to aromatic aldehydes. N-Alkylated derivatives were also synthesized, which possessed folded structures distinct from those of the parent cyclic amides.