9-piperidinoisocolchicide

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物 - 环庚三烯酮
• 英文名称: 9-piperidinoisocolchicide
• 英文别名: N-[(7S)-1,2,3-trimethoxy-10-oxo-9-piperidin-1-yl-6,7-dihydro-5H-benzo[a]heptalen-7-yl]acetamide
• 化学式: C₂₆H₃₂N₂O₅
• 分子量: 452.55
• InChiKey: CRLKVEITOSFWMY-FQEVSTJZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  33
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  77.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  9-methylthioisocolchicide 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 9-piperidinoisocolchicide
  参考文献：
  名称：

  ipso-vs. tele-Nucleophilic substitution by piperidine on isocolchicides and colchicides bearing an α-leaving group

  摘要：

  Product studies of the reactions of piperidine with colchicides carrying a C-10 nucleofugic group show that only ipso substitution occurs. For isocolchicides carrying an X nucleofugic group at C-9, similar behaviour was observed for X = F, OTs or OMe, while for X = SMe, SOMe or Cl tele substitution (at C-ll) competes with ipso substitution. These results together with the observation that the reaction rates for the two series are similar, may be useful in guiding the refunctionalization of similar compounds.

  DOI：

  10.1039/p19950002657

文献信息

• Simplified, high-yield regioselective synthesis of 10-aminocolchicides and 2-aminotropones
  作者：Marino Cavazza、Francesco Pietra

  DOI：10.1016/0040-4039(95)00499-3

  日期：1995.5

  Treatment of colchiceine with BF3OEt2, followed by evaporation, addition of DMSO and a secondary amine like piperidine, or sterically hindered like 2-methylpiperidine, was found to result in rapid, quantitative replacement of the hydroxyl group at C-10 or C-9 by the amine to give the 10-aminocolchicide/9-aminoisocolchicide or with high regiospecificity for 10-aminocolchicide; the products could be

  发现用BF 3 OEt 2处理秋水仙碱，然后蒸发，添加DMSO和仲胺（如哌啶）或空间受阻胺（如2-甲基哌啶）可快速，定量地取代C-10或C处的羟基通过胺-9，得到10-氨基杀菌剂/ 9-氨基异杀菌剂或对10-氨基杀菌剂具有高区域特异性的化合物；产品可以轻松分离，方法学扩展到托酚酮和/或伯胺。
• Re-functionalisation of α-substituted isocolchicides via nucleophilic tele-substitution
  作者：Marino Cavazza、Francesco Pietra

  DOI：10.1039/c39940000897

  日期：——

  9-Methoxyisocolchicide 1 in excess methanethiolate–methanol, or Me2SO, slowly undergoes ipso-substitution giving 9-methylthioisocolchicide 3, which then suffers tele-substitution giving 11-methylthioisocolchicide 2; this activation by dicoordinated sulfur is used for amino re-functionalisation of the isocolchicide system.

  过量的甲硫醇盐-甲醇（或Me 2 SO）中的9-甲氧基异杀虫剂1缓慢进行ipso取代，得到9-甲硫基异杀草剂3，然后遭受远位取代，得到11-甲硫基异杀草剂2；通过双配位硫的活化被用于异杀菌剂系统的氨基再官能化。