1-ethynyl-7α,8α-(N-methyl-2,5-dioxopyrrolidino)[3,4-h]-6,14-endo-etheno-6,7,8,14-tetrahydrothebaine | 1416673-13-6

• 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-ethynyl-7α,8α-(N-methyl-2,5-dioxopyrrolidino)[3,4-h]-6,14-endo-etheno-6,7,8,14-tetrahydrothebaine
• CAS: 1416673-13-6
• 化学式: C₂₆H₂₆N₂O₅
• 分子量: 446.503
• InChiKey: FAGPGPKBTZTSFD-LPUZPFMXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.12
• 重原子数：
  33.0
• 可旋转键数：
  2.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  聚合甲醛 、 1-ethynyl-7α,8α-(N-methyl-2,5-dioxopyrrolidino)[3,4-h]-6,14-endo-etheno-6,7,8,14-tetrahydrothebaine 、 N-Boc-哌嗪 在 copper(l) iodide 作用下， 以 1,4-二氧六环 为溶剂， 反应 12.5h， 以80%的产率得到1-[3-(4-tert-butoxycarbonylpiperazin-1-yl)propynyl]-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：

  1-(2-trimethylsilylethynyl)-7α,8α-(N-methyl-2,5-dioxopyrrolidino)[3,4-h]-6,14-endo-etheno-6,7,8,14-tetrahydrothebaine 在 四丁基氟化铵 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以78%的产率得到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