(7α-R)- and (7α-S)-4,5α-epoxy-3-methoxy-α,N-dimethyl-6,14-ethenoisomorphinan-7α-methanol | 105561-92-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 吗啡烷
• 英文名称: (7α-R)- and (7α-S)-4,5α-epoxy-3-methoxy-α,N-dimethyl-6,14-ethenoisomorphinan-7α-methanol
• CAS: 105561-92-0
• 化学式: C₂₂H₂₇NO₃
• 分子量: 353.461
• InChiKey: RZHHTYUMKYUJJC-WOHABHKXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.53
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  41.93
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (7α-R)- and (7α-S)-4,5α-epoxy-3-methoxy-α,N-dimethyl-6,14-ethenoisomorphinan-7α-methanol 在 吡啶 、 sodium azide 作用下， 以 水 为溶剂， 反应 48.0h， 生成 (2'R,6α,7α,14α)-6-demethoxy-2'-methyl-5',6',6,7-tetrahydro-2'H,8H-1',5';6',14-dicyclopyrido<3',4':7,6>thebaine
  参考文献：
  名称：

  Steric factors in the azidolysis–thermolysis of some 5-tosyloxymethylbi-cyclo[2.2.2]oct-2-enes to yield 4-azatetracyclo[4.4.0.0.0]decanes

  摘要：

  Azidolysis of C-19 diastereoisomer tosylesters of morphine derivatives possessing a bridged ring C has been studied and 4-azatetracyclo[4.4.0(2.4).0(3.8)]decanes 6b, 6d and 6f were formed via the substitution and subsequent intramolecular cyclization of the (R)-C-19 tosylesters 4b, 4d and 4f, and primarily the ethylidene derivatives 7a, 7b and 7c were obtained from (S)-C-19 tosylesters 4c, 4e and 4g. According to our experience the course of the reaction depends on the configuration of the C-19 centre of chirality and on the spatial requirement of the substituent on C-6.

  DOI：

  10.1039/p19910001139
• 作为产物：
  描述：

  6-demethoxy-7α-thevinone 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 (7α-R)- and (7α-S)-4,5α-epoxy-3-methoxy-α,N-dimethyl-6,14-ethenoisomorphinan-7α-methanol
  参考文献：
  名称：

  Steric factors in the azidolysis–thermolysis of some 5-tosyloxymethylbi-cyclo[2.2.2]oct-2-enes to yield 4-azatetracyclo[4.4.0.0.0]decanes

  摘要：

  Azidolysis of C-19 diastereoisomer tosylesters of morphine derivatives possessing a bridged ring C has been studied and 4-azatetracyclo[4.4.0(2.4).0(3.8)]decanes 6b, 6d and 6f were formed via the substitution and subsequent intramolecular cyclization of the (R)-C-19 tosylesters 4b, 4d and 4f, and primarily the ethylidene derivatives 7a, 7b and 7c were obtained from (S)-C-19 tosylesters 4c, 4e and 4g. According to our experience the course of the reaction depends on the configuration of the C-19 centre of chirality and on the spatial requirement of the substituent on C-6.

  DOI：

  10.1039/p19910001139

文献信息

• Synthesis of 6, 14-ethenoisomorphinans and 6, 14-ethenomorphinans based on Diels-Alder adducts of 6-demethoxythebaine and 6-demethoxy-β-dihydrothebaine; pharmacology of the isomorphinans (Chemistry of Opium Alkaloids, Part XIX)
  作者：P. R. Crabbendam、T. S. Lie、J. T. M. Linders、L. Maat

  DOI：10.1002/recl.19841031005

  日期：——

  Two different types of Diels-Alder additions to morphinan-6, 8-dienes have been found. 6-Demethoxythebaine (2) yielded ethyl 4, 5α-epoxy-3-methoxy-N-methyl-6, 14-ethenoisomorphinan–7α-carboxylate (3) with ethyl acrylate, in analogy to the reaction with thebaine. The ester 3 was converted into the alcohol 4, of which the 3-methoxy ether was hydrolyzed to yield 5. Similarly, 2 gave the 7α-acetyl-6,

  已经发现了吗啡喃-6、8-二烯的两种不同类型的Diels-Alder添加物。6- Demethoxythebaine（2），得到4-，5α环氧-3-甲氧基ñ -甲基- 6,14-ethenoisomorphinan-7α羧酸酯（3）与丙烯酸乙酯，类似于与蒂巴因反应。酯3被转化为醇4，其中3-甲氧基醚被水解以产生5。类似地，2给出具有甲基乙烯基酮的7α-乙酰基-6，14-亚乙基异吗啡喃7。使用甲基碘化镁将后一化合物转化为4。含溴化丙基镁7提供了四种化合物；两个是新的依托啡啡类似物（8和9），我们能够为其分配绝对构型；另外两个是格利雅减量产品10和11。