1-bromo-4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione | 1008355-59-6

• 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: 1-bromo-4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione
• CAS: 1008355-59-6
• 化学式: C₂₉H₂₇BrN₂O₅
• 分子量: 563.448
• InChiKey: NMYDORORDFGJHY-WIAZSDGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  37.0
• 可旋转键数：
  3.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  68.31
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1-bromo-4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione 、 丙烯酸乙酯 在 palladium diacetate 、 三乙胺 、 三(邻甲基苯基)磷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以19%的产率得到ethyl (E)-3-(4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-2',5'-dioxo-1'-phenyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-1-yl)prop-2-enoate
  参考文献：
  名称：

  Synthetic transformations of isoquinoline alkaloids. Synthesis of 1-halo derivatives of endo-ethenotetrahydrothebaine and their behavior in the heck reaction

  摘要：

  Bromination of endo-ethenotetrahydrothebaine derivatives having a pyrrolidine ring fused at the C-7-C-8 stop bond, namely 1'-substituted 4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morphinan-2',5'-diones, 1'-aryl-4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morphinans, and 4,5 alpha-epoxy-6 alpha,14-etheno-2'+/--hydroxy-3,6- dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morpphinan-5'-one, with molecular bromine in formic acid smoothly afforded the corresponding 1-bromo derivatives. Iodination of 4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]-4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]-morphinan-2',5'-dione with iodine(I) chloride gave 4,5 alpha-epoxy-6 alpha,14-etheno-1-iodo-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morphinan-2',5'-dione. The resulting 1-halo derivatives were brought into the Heck reaction with acrylic acid esters to obtain 1-[(E)-2-(alkoxycarbonyl)ethenyl]-substituted compounds. Demethylation of the 6-methoxy group in 1-bromo-endo-ethenotetrahydrothebaines was accomplished using boron(III) bromide in chloroform.

  DOI：

  10.1134/s1070428007040070
• 作为产物：
  描述：

  4,5α-epoxy-3,6-dimethoxy-N-methyl-2'-phenyl-6α,14α-endo-ethenopyrrolo<3,4-i>isomorphinane-1',3'-dione 在 甲酸 、 溴 、 sodium carbonate 作用下， 反应 1.5h， 生成 1-bromo-4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione
  参考文献：
  名称：

  Synthetic transformations of isoquinoline alkaloids. Synthesis of 1-halo derivatives of endo-ethenotetrahydrothebaine and their behavior in the heck reaction

  摘要：

  Bromination of endo-ethenotetrahydrothebaine derivatives having a pyrrolidine ring fused at the C-7-C-8 stop bond, namely 1'-substituted 4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morphinan-2',5'-diones, 1'-aryl-4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morphinans, and 4,5 alpha-epoxy-6 alpha,14-etheno-2'+/--hydroxy-3,6- dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morpphinan-5'-one, with molecular bromine in formic acid smoothly afforded the corresponding 1-bromo derivatives. Iodination of 4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]-4,5 alpha-epoxy-6 alpha,14-etheno-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]-morphinan-2',5'-dione with iodine(I) chloride gave 4,5 alpha-epoxy-6 alpha,14-etheno-1-iodo-3,6-dimethoxy-17-methyl-1'-phenyl-2',5',7 beta,8 beta-tetrahydro-1'H-14 alpha-pyrrolo[3',4':7,8]morphinan-2',5'-dione. The resulting 1-halo derivatives were brought into the Heck reaction with acrylic acid esters to obtain 1-[(E)-2-(alkoxycarbonyl)ethenyl]-substituted compounds. Demethylation of the 6-methoxy group in 1-bromo-endo-ethenotetrahydrothebaines was accomplished using boron(III) bromide in chloroform.

  DOI：

  10.1134/s1070428007040070