(+/-)-11-oxo-Δ⁹-tetrahydrocannabinol tert-butyldimethylsilyl ether | 136954-91-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (+/-)-11-oxo-Δ⁹-tetrahydrocannabinol tert-butyldimethylsilyl ether
• 英文别名: (+/-)-11-oxo-Δ⁹-tetrahydrocannabiol tert-butyldimethylsilyl ether；(6aR,10aR)-1-{[tert-Butyl(dimethyl)silyl]oxy}-6,6-dimethyl-3-pentyl-6a,7,8,10a-tetrahydro-6H-dibenzo[b,d]pyran-9-carbaldehyde；(6aR,10aR)-1-[tert-butyl(dimethyl)silyl]oxy-6,6-dimethyl-3-pentyl-6a,7,8,10a-tetrahydrobenzo[c]chromene-9-carbaldehyde
• CAS: 136954-91-1；138285-36-6
• 化学式: C₂₇H₄₂O₃Si
• 分子量: 442.714
• InChiKey: HBVXWYAVRSNQOZ-FGZHOGPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.59
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (+/-)-11-oxo-Δ⁹-tetrahydrocannabinol tert-butyldimethylsilyl ether 在 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 反应 3.75h， 生成 (-)-11-n-9-羧基-δ9-THC
  参考文献：
  名称：

  Studies on the Synthesis of (-)-11-Nor-9-carboxy-Δ⁹-Tetrahydrocannabinol (THC) and Related Compounds: An Improved Oxidative Procedure

  摘要：

  本文介绍了一种简便的方法，即在大量过量的 2-甲基-2-丁烯存在下，用亚氯酸钠将δ9-四氢大麻酚醛 4 及其叔丁基二甲基硅烷衍生物方便地氧化成相应的酸，而不会发生δ9-双键的异构化。 在四氢呋喃中用四丁基氟化铵对 O 保护基进行脱保护处理，得到酸 2，总收率≥80%。对其他氧化剂和保护基团的研究表明，这是制备 9-羧基-δ9-四氢大麻酚的首选方法。

  DOI：

  10.1055/s-1991-26590
• 作为产物：
  描述：

  (+/-)-4-(1-hydroxy-1-methylethyl)cyclohex-2-enone 在 咪唑 、 正丁基锂 、 potassium carbonate 、 对甲苯磺酸 、 碘甲烷 作用下， 以 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 23.25h， 生成 (+/-)-11-oxo-Δ⁹-tetrahydrocannabinol tert-butyldimethylsilyl ether
  参考文献：
  名称：

  Synthesis of racemic and optically active .DELTA.9-tetrahydrocannabinol (THC) metabolites

  摘要：

  The preparation of racemic and optically active DELTA-9-THC metabolites is described from synthon 13. Racemic synthon 13 is prepared in four steps (46%) from Danishefsky's diene. Optically active synthon 13 is prepared from perillaldehyde via the enone 22 in six steps (23% yield). Alternatively, nopinone can be converted to 13 in three steps (50% yield) via a cyclobutane ring cleavage. The acid-catalyzed condensation of 13 with olivetol (6a) and subsequent conversion to 11-hydroxy and 9-carboxyl DELTA-9-THC metabolites 2a and 4a is described, as well as the preparation of 1',1'-dimethylheptyl THC analogues 2b, 3b, and 4b from 5-(1',1'-dimethylheptyl)resorcinol (6c).

  DOI：

  10.1021/jo00024a031

文献信息

• Studies on the Synthesis of (-)-11-Nor-9-carboxy-Δ⁹-Tetrahydrocannabinol (THC) and Related Compounds: An Improved Oxidative Procedure
  作者：Craig Siegel、Patrick M. Gordon、Raj K. Razdan

  DOI：10.1055/s-1991-26590

  日期：——

  A facile procedure is described whereby Δ9-THC aldehydes 4, as their tert-butyldimethylsilyl derivatives, are conveniently oxidized to the corresponding acids with sodium chlorite in the presence of a large excess of 2-methyl-2-butene without isomerization of the Δ9-double bond. Deprotection of the O-protecting group with tetrabutylammonium fluoride in tetrahydrofuran gave the acids 2 in an overall yield of ≥ 80%. A study of other oxidizing agents and protecting groups demonstrated that this is the procedure of choice for the preparation of 9-carboxy-Δ9-tetrahydrocannabinols.

  本文介绍了一种简便的方法，即在大量过量的 2-甲基-2-丁烯存在下，用亚氯酸钠将δ9-四氢大麻酚醛 4 及其叔丁基二甲基硅烷衍生物方便地氧化成相应的酸，而不会发生δ9-双键的异构化。 在四氢呋喃中用四丁基氟化铵对 O 保护基进行脱保护处理，得到酸 2，总收率≥80%。对其他氧化剂和保护基团的研究表明，这是制备 9-羧基-δ9-四氢大麻酚的首选方法。
• Synthesis of racemic and optically active .DELTA.9-tetrahydrocannabinol (THC) metabolites
  作者：Craig Siegel、Patrick M. Gordon、David B. Uliss、G. Richard Handrick、Haldean C. Dalzell、Raj. K. Razdan

  DOI：10.1021/jo00024a031

  日期：1991.11

  The preparation of racemic and optically active DELTA-9-THC metabolites is described from synthon 13. Racemic synthon 13 is prepared in four steps (46%) from Danishefsky's diene. Optically active synthon 13 is prepared from perillaldehyde via the enone 22 in six steps (23% yield). Alternatively, nopinone can be converted to 13 in three steps (50% yield) via a cyclobutane ring cleavage. The acid-catalyzed condensation of 13 with olivetol (6a) and subsequent conversion to 11-hydroxy and 9-carboxyl DELTA-9-THC metabolites 2a and 4a is described, as well as the preparation of 1',1'-dimethylheptyl THC analogues 2b, 3b, and 4b from 5-(1',1'-dimethylheptyl)resorcinol (6c).
• Syntheses of Cannabinoid Metabolites: Ajulemic Acid and HU-210
  作者：Wenbin Shao、Pingyong Liao、Xiaoyan Zhang、Binbin Fan、Ruijia Chen、Xilong Chen、Xuejun Zhao、Wenbin Liu

  DOI：10.3390/molecules29020526

  日期：——

  Cannabinoid metabolites have been reported to be more potent than their parent compounds. Among them, ajulemic acid (AJA) is a side-chain analog of Δ9-THC-11-oic acid, which would be a good template structure for the discovery of more potent analogues. Herein, we optimized the key allylic oxidation step to introduce the C-11 hydroxy group with a high yield. A series of compounds was prepared with this

  据报道，大麻素代谢物比其母体化合物更有效。其中，ajulemic acid （AJA） 是 Δ9-THC-11-oic acid 的侧链类似物，这将是发现更有效类似物的良好模板结构。在此，我们优化了关键的烯丙基氧化步骤，以高产率引入 C-11 羟基。在此条件下制备了一系列化合物，包括 胡-210、11-nor-Δ8-四氢大麻酚 （THC）-羧酸和 Δ9-THC-羧酸。