4,5α-Epoxy-7β,8β-epoxy-3-methoxy-17-methyl-morphinan-6α-ol (Codeine-7,8-oxide) | 72785-20-7

• 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: 4,5α-Epoxy-7β,8β-epoxy-3-methoxy-17-methyl-morphinan-6α-ol (Codeine-7,8-oxide)
• 英文别名: 4,5α:7β,8β-diepoxy-3-methoxy-17-methylmorphinan-6α-ol；codeine-7,8-oxide；4,5α;7β,8β-diepoxy-3-methoxy-17-methyl-morphinan-6α-ol；Codein-7,8-oxid；codeine 7β,8β-oxide；(1S,5R,13R,14R,15S,17R,18R)-10-methoxy-4-methyl-12,16-dioxa-4-azahexacyclo[9.7.1.01,13.05,18.07,19.015,17]nonadeca-7(19),8,10-trien-14-ol
• CAS: 72785-20-7
• 化学式: C₁₈H₂₁NO₄
• 分子量: 315.369
• InChiKey: YKKBRPZURSPTDO-QAGMXBRFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  54.5
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  可待因酮 在 sodium hydroxide 、 sodium tetrahydroborate 、 双氧水 作用下， 以 甲醇 、 乙醇 为溶剂， 生成 4,5α-Epoxy-7β,8β-epoxy-3-methoxy-17-methyl-morphinan-6α-ol (Codeine-7,8-oxide)
  参考文献：
  名称：

  Stereospecific synthesis of codeine 7,8-oxide and codeinone 7,8-oxide.

  摘要：

  Condeinone (1) 被过氧化氢氧化为可待因酮 7，8-氧化物 (2)。硼氢化钠将 2 立体还原，得到了可待因 7，8-氧化物（3）。3 的构型通过 X 射线分析得到了证实。

  DOI：

  10.1248/cpb.27.2257

文献信息

• Analgesic narcotic antagonists. 6. 7.beta.,8.beta.-Methano- and 7.beta.,8.beta.-epoxydihydrocodeinone
  作者：Michael P. Kotick

  DOI：10.1021/jm00138a016

  日期：1981.6

  Reaction of codeinone (2) with CH2N2 in the presence of Pd(OAc)2 yielded mixtures of starting material and (2) and 7 beta, 8 beta-methanodihydrocodeinone (3). Initial resolution of this mixture was achieved via carbonyl reduction followed by chromatography to give pure 7 beta, 8 beta-methanodihydrocodeine (4), which was oxidized to 3. Reaction of the mixture containing 2 and 3 with mercaptoethanol and NaOH [2 leads to 8 beta-[(hydroxyethyl)thio]dihydrocodeinone (5)] allowed selective crystallization of 3. The beta configuration of the cyclopropane ring in 3 was established by cleavage with aqueous HCl to give the 8 beta-(chloromethyl) compound 6, followed by carbonyl reduction and dehalogenation to 8 beta-methyldihydrocodeine (8). Reaction of the N-(cycloalkylmethyl) derivatives (13 and 18) of 2 with CH2N2/Pd(OA)2 gave potential mixed agonist-antagonists and 14 and 19, which were purified by reduction-oxidation (14) or mercaptoethanol-base treatment (19). Compound 2, on oxidation with alkaline peroxide, gave the previously reported 7 beta, 8 beta-epoxydihydrocodeinone (22) as the hemimethanol ketal (21). Compound 3 was about ninefold more potent an agonist than dihydrocodeine, and the N-(cyclopropylmethyl)-7 beta, 8 beta-methano compound 19 had moderately potent mixed agonist-narcotic antagonist properties.
• Stereospecific synthesis of codeine 7,8-oxide and codeinone 7,8-oxide.
  作者：KIYOKO UBA、NAOKI MIYATA、KEIZO WATANABE、MASAAKI HIROBE

  DOI：10.1248/cpb.27.2257

  日期：——

  Condeinone (1) was oxidized to codeinone 7, 8-oxide (2) by hydrogen peroxide. Stereospecific reduction of 2 by sodium borohydride afforded codeine 7, 8-oxide (3). The configuration of 3 was confirmed by X-ray analysis.

  Condeinone (1) 被过氧化氢氧化为可待因酮 7，8-氧化物 (2)。硼氢化钠将 2 立体还原，得到了可待因 7，8-氧化物（3）。3 的构型通过 X 射线分析得到了证实。