4,5α-epoxy-3,6-dimethoxy-N-methyl-2'-phenyl-6α,14α-endo-ethenopyrrolo<3,4-i>isomorphinane-1',3'-dione | 26237-85-4

• 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-3,6-dimethoxy-N-methyl-2'-phenyl-6α,14α-endo-ethenopyrrolo<3,4-i>isomorphinane-1',3'-dione
• 英文别名: 4,5α-epoxy-3,6-dimethoxy-17-methyl-1'-phenyl-(7β,8β)-7,8-dihydro-6α,14α-etheno-pyrrolo[3',4':7,8]morphinane-2',5'-dione
• CAS: 26237-85-4
• 化学式: C₂₉H₂₈N₂O₅
• 分子量: 484.552
• InChiKey: HOPYOUDXKXJONB-WIAZSDGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  36.0
• 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：

  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 作用下， 反应 1.5h， 以64.4%的产率得到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 hydrobromide
  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：

  N-苯基马来酰亚胺 、 蒂巴因 以 苯 为溶剂， 生成 4,5α-epoxy-3,6-dimethoxy-N-methyl-2'-phenyl-6α,14α-endo-ethenopyrrolo<3,4-i>isomorphinane-1',3'-dione
  参考文献：
  名称：

  吗啡-蒂巴因类药物的新型镇痛药和分子重排。第十七部分。与蒂巴因-马来酸酐加合物有关的化合物

  摘要：

  制备了蒂巴因-马来酸酐，蒂巴因-马来酸乙酯和蒂巴因-N-苯基-马来酰亚胺加合物的许多衍生物。一些衍生物是有效的吗啡样药物。

  DOI：

  10.1039/j39700000560

文献信息

• Pindur, Ulf; Keilhofer, Diana, Liebigs Annalen der Chemie, 1993, # 9, p. 947 - 954
  作者：Pindur, Ulf、Keilhofer, Diana

  DOI：——

  日期：——
• Synthetic transformations of isoquinoline alkaloids. Synthesis of N′-substituted 1-alkynyl-7α,8α-(2,5-dioxopyrrolidino)-[3,4-h]-6,14-endo-ethenotetrahydrothebaines and their transformations
  作者：V. T. Bauman、E. E. Shults、M. M. Shakirov、G. A. Tolstikov

  DOI：10.1134/s1070428012110103

  日期：2012.11

  The iodination of N'-substituted (2,5-dioxopyrrolidino)[3,4-h]-6,14-endo-ethenotetrahydrothebaines with N-iodosuccinimide in trifluoroacetic acid afforded depending on the excess of the reagent either 1-iodo- or 1,2-diiodoendo-ethenotetrahydrothebaines. The Sonogashira reaction of 1-iodo-6,14-endo-ethenotetrahydrothebaines with trimethylsilylacetylene led to the formation of N'-substituted 1-(trimethylsilylethynyl)-(2,5-dioxopyrrolidino)-[3,4-h]-6,14-endo-ethenotetrahydrothebaines whose desilylation cleanly furnished the corresponding 1-ethynylendo-ethenotetrahydrothebaines. The Mannich reaction of the acetylene derivatives of tetrahydrothebaine with amines and formaldehyde catalyzed by compounds of Cu(I) provided 1-[3-(morpholin-4-yl)propynyl]-, 1-[3-(4-methylpiperazin-1-yl)propynyl]-, and 1-[3-(4-tert-butoxycarbonylpiperazin-1-yl)propynyl]-(2,5-dioxopyrrolidino)[3,4-h]-6,14-endo-ethenotetrahydrothebaines.