4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-1',17-dimethyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione | 34156-04-2

• 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-6α,14-etheno-3,6-dimethoxy-1',17-dimethyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione
• 英文别名: 7α,8α-(N-methyl-2,5-dioxopyrrolidino)-[3,4-h]-6,14-endo-ethenotetrahydrothebaine；4,5α-epoxy-3,6-dimethoxy-17-methyl-6α,14α-etheno-morphinane-7α,8α-dicarboxylic acid methylimide；4,5α-epoxy-3,6-dimethoxy-17,1'-dimethyl-(7βH,8βH)-7,8-dihydro-6α,14α-etheno-pyrrolo[3',4':7,8]morphin-7-ene-2',5'-dione；4,5α-Epoxy-3,6-dimethoxy-17,1'-dimethyl-(7βH,8βH)-7,8-dihydro-6α,14α-aetheno-pyrrolo[3',4':7,8]morphin-7-en-2',5'-dion
• CAS: 34156-04-2
• 化学式: C₂₄H₂₆N₂O₅
• 分子量: 422.481
• InChiKey: LGHVLOZOEFEVRF-YUXWPGKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.14
• 重原子数：
  31.0
• 可旋转键数：
  2.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.58
• 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-6α,14-etheno-3,6-dimethoxy-1',17-dimethyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione 在 aluminum oxide 、 bis-triphenylphosphine-palladium(II) chloride 、 N-碘代丁二酰亚胺 、 copper(l) iodide 、 四丁基氟化铵 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 、 氯仿 、 苯 为溶剂， 反应 2.25h， 生成 1-ethynyl-7α,8α-(N-methyl-2,5-dioxopyrrolidino)[3,4-h]-6,14-endo-etheno-6,7,8,14-tetrahydrothebaine
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1134/s1070428012110103
• 作为产物：
  描述：

  蒂巴因 在 sodium methylate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-1',17-dimethyl-2',5',7β,8β-tetrahydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione
  参考文献：
  名称：

  Thebain?Maleinimid-und Thebain?N-substituierte Maleinimid-Addukte

  摘要：

  DOI：

  10.1007/bf00909927

文献信息

• Synthetic transformations of isoquinoline alkaloids. Synthesis of 1-halo derivatives of endo-ethenotetrahydrothebaine and their behavior in the heck reaction
  作者：V. T. Bauman、E. E. Shul’ts、M. M. Shakirov、G. A. Tolstikov

  DOI：10.1134/s1070428007040070

  日期：2007.4

  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.
• Sandermann; Striesow, Chemische Berichte, 1957, vol. 90, p. 603,698
  作者：Sandermann、Striesow

  DOI：——

  日期：——