4-<2-Hydroxy-4-(1,1-dimethylheptyl)-6-methoxyphenyl>-6,6-methylbicyclo<3.3.1>heptan-2-one | 132345-26-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-<2-Hydroxy-4-(1,1-dimethylheptyl)-6-methoxyphenyl>-6,6-methylbicyclo<3.3.1>heptan-2-one
• CAS: 132345-26-7
• 化学式: C₂₅H₃₈O₃
• 分子量: 386.575
• InChiKey: STRWQVFWZDSDEC-CEXWTWQISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.37
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-<2-Hydroxy-4-(1,1-dimethylheptyl)-6-methoxyphenyl>-6,6-methylbicyclo<3.3.1>heptan-2-one 在 四氯化锡 作用下， 以 氯仿 为溶剂， 以80%的产率得到(6aS,10aR)-(-)-1-Methoxy-3-(1,1-dimethylheptyl)-6,6a,7,8,10,10a-hexahydro-6,6-dimethyl-9H-dibenzopyran-9-one
  参考文献：
  名称：

  Synthesis of both enantiomers of nabilone from a common intermediate. Enantiodivergent synthesis of cannabinoids

  摘要：

  Both enantiomers of the synthetic cannabinoid nabilone (4) have been synthesized from a common intermediate, enone 7. Enone 7 was prepared by reaction of [2,6-dimethoxy-4-(1,1-dimethylheptyl)phenyl]lithium with (+)-apoverbenone (2), followed by PDC oxidation. Li/NH3 reduction of 7 gave saturated ketone 9, which, after ether cleavage to 10, afforded (6aS,10aR)-hexahydrodibenzopyran 15 on reaction with SnCl4. Isomerization to 6aR,10aR ketone 16 followed by ether cleavage gave the 6aR,10aR enantiomer of nabilone (4). The 6aS,10aS enantiomer of 4 (24) was prepared from 7 by ether cleavage to 18 and rearrangement to nonracemic tetrahydrodibenzopyran 20 using AlCl3. Dissolving metal reduction of 20 followed by ether cleavage gave the 6aS,10aS enantiomer of nabilone (24). A model sequence employing (2,6-dimethoxyphenyl)lithium at the first step was carried out and the structure of one of the intermediates, ketone 12, was established by X-ray crystallography. A new preparation of apoverbenone (2) has been developed.

  DOI：

  10.1021/jo00006a021
• 作为产物：
  描述：

  (+)-apoverbenone 在 jones' reagent 、 丙烷-1-硫醇 、 氨 、 叔丁基锂 、 lithium 、 sodium hydride 作用下， 反应 21.0h， 生成 4-<2-Hydroxy-4-(1,1-dimethylheptyl)-6-methoxyphenyl>-6,6-methylbicyclo<3.3.1>heptan-2-one
  参考文献：
  名称：

  Synthesis of both enantiomers of nabilone from a common intermediate. Enantiodivergent synthesis of cannabinoids

  摘要：

  Both enantiomers of the synthetic cannabinoid nabilone (4) have been synthesized from a common intermediate, enone 7. Enone 7 was prepared by reaction of [2,6-dimethoxy-4-(1,1-dimethylheptyl)phenyl]lithium with (+)-apoverbenone (2), followed by PDC oxidation. Li/NH3 reduction of 7 gave saturated ketone 9, which, after ether cleavage to 10, afforded (6aS,10aR)-hexahydrodibenzopyran 15 on reaction with SnCl4. Isomerization to 6aR,10aR ketone 16 followed by ether cleavage gave the 6aR,10aR enantiomer of nabilone (4). The 6aS,10aS enantiomer of 4 (24) was prepared from 7 by ether cleavage to 18 and rearrangement to nonracemic tetrahydrodibenzopyran 20 using AlCl3. Dissolving metal reduction of 20 followed by ether cleavage gave the 6aS,10aS enantiomer of nabilone (24). A model sequence employing (2,6-dimethoxyphenyl)lithium at the first step was carried out and the structure of one of the intermediates, ketone 12, was established by X-ray crystallography. A new preparation of apoverbenone (2) has been developed.

  DOI：

  10.1021/jo00006a021

文献信息

• Synthesis of both enantiomers of nabilone from a common intermediate. Enantiodivergent synthesis of cannabinoids
  作者：John W. Huffman、H. Howard Joyner、Melissa D. Lee、Robert D. Jordan、William T. Pennington

  DOI：10.1021/jo00006a021

  日期：1991.3

  Both enantiomers of the synthetic cannabinoid nabilone (4) have been synthesized from a common intermediate, enone 7. Enone 7 was prepared by reaction of [2,6-dimethoxy-4-(1,1-dimethylheptyl)phenyl]lithium with (+)-apoverbenone (2), followed by PDC oxidation. Li/NH3 reduction of 7 gave saturated ketone 9, which, after ether cleavage to 10, afforded (6aS,10aR)-hexahydrodibenzopyran 15 on reaction with SnCl4. Isomerization to 6aR,10aR ketone 16 followed by ether cleavage gave the 6aR,10aR enantiomer of nabilone (4). The 6aS,10aS enantiomer of 4 (24) was prepared from 7 by ether cleavage to 18 and rearrangement to nonracemic tetrahydrodibenzopyran 20 using AlCl3. Dissolving metal reduction of 20 followed by ether cleavage gave the 6aS,10aS enantiomer of nabilone (24). A model sequence employing (2,6-dimethoxyphenyl)lithium at the first step was carried out and the structure of one of the intermediates, ketone 12, was established by X-ray crystallography. A new preparation of apoverbenone (2) has been developed.