(6aS,10aR)-(-)-1-Methoxy-3-(1,1-dimethylheptyl)-6,6a,7,8,10,10a-hexahydro-6,6-dimethyl-9H-dibenzopyran-9-one | 132436-85-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: (6aS,10aR)-(-)-1-Methoxy-3-(1,1-dimethylheptyl)-6,6a,7,8,10,10a-hexahydro-6,6-dimethyl-9H-dibenzopyran-9-one
• 英文别名: (6aS,10aR)-1-methoxy-6,6-dimethyl-3-(2-methyloctan-2-yl)-7,8,10,10a-tetrahydro-6aH-benzo[c]chromen-9-one
• CAS: 132436-85-2
• 化学式: C₂₅H₃₈O₃
• 分子量: 386.575
• InChiKey: OSWZVICHJWTZBE-UXHICEINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (6aS,10aR)-(-)-1-Methoxy-3-(1,1-dimethylheptyl)-6,6a,7,8,10,10a-hexahydro-6,6-dimethyl-9H-dibenzopyran-9-one 在 四氯化锡 作用下， 以 氯仿 为溶剂， 以78%的产率得到nabilone methyl ether
  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：

  (-)-4-<2-Hydroxy-4-(1,1-dimethylheptyl)-6-methoxyphenyl>-6,6a-dimethylbicyclo<3.3.1>hept-3-en-2-one 在 三氯化铝 、 jones' reagent 、 氨 、 lithium 作用下， 以 二氯甲烷 为溶剂， 生成 (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

文献信息

• Preparation of 6a, 10a-trans-hexahydrodibenzopyranones
  申请人：ELI LILLY AND COMPANY

  公开号：EP0096480A2

  公开（公告）日：1983-12-21

  Reaction of an 0-methyl or O-ethyl resorcinol with a cyclohexene carbinol derivative in the presence of a catalyst affords a 6a,10a-trans-1-methoxy or 1-ethoxy-6,6-dimethyl-8,6a,7,8.10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one derivative. Optional deesterification of the product affords the corresponding 1-hydroxy compound.

  在催化剂存在下，0-甲基或 O-乙基间苯二酚与环己烯甲醇衍生物反应，生成 6a,10a-反式-1-甲氧基或 1-乙氧基-6,6-二甲基-8,6a,7,8.10,10a-六氢-9H-二苯并[b,d]吡喃-9-酮衍生物。可选择对产物进行脱酯化处理，得到相应的 1-羟基化合物。
• HUFFMAN, JOHN W.;JOYNER, H. HOWARD;LEE, MELISSA D.;JORDAN, ROBERT D.;PENN+, J. ORG. CHEM., 56,(1991) N, C. 2081-2086
  作者：HUFFMAN, JOHN W.、JOYNER, H. HOWARD、LEE, MELISSA D.、JORDAN, ROBERT D.、PENN+

  DOI：——

  日期：——
• US4395560A
  申请人：——

  公开号：US4395560A

  公开（公告）日：1983-07-26
• 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.