2-chloropodophyllotoxin

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 木脂素内酯
• 英文名称: 2-chloropodophyllotoxin
• 英文别名: 2β-chloropodophyllotoxin；2beta-Chloropodophyllotoxin；(5R,5aS,8aR,9R)-5a-chloro-9-hydroxy-5-(3,4,5-trimethoxyphenyl)-5,8,8a,9-tetrahydro-[2]benzofuro[5,6-f][1,3]benzodioxol-6-one
• 化学式: C₂₂H₂₁ClO₈
• 分子量: 448.857
• InChiKey: URVVYTDBJQTEII-JQJYPRBLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  环戊醇 、 2-chloropodophyllotoxin 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以50%的产率得到(5R,5aS,8aR,9R)-5a-chloro-9-(cyclopentyloxy)-5-(3,4,5-trimethoxyphenyl)-5,8,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6(5aH)-one
  参考文献：
  名称：

  Natural products-based insecticidal agents 7. Semisynthesis and insecticidal activity of novel 4α-alkyloxy-2-chloropodophyllotoxin derivatives against Mythimna separata Walker in vivo

  摘要：

  In continuation of our program aimed at the discovery and development of natural products-based insecticidal agents, 16 novel 4 alpha-alkyloxy-2-chloropodophyllotoxin derivatives were semisynthesized from podophyllotoxin, and preliminarily evaluated for their insecticidal activity against the pre-third-instar larvae of Mythimna separata Walker in vivo. Among all the tested derivatives, especially compounds 4b, 4e, 4g, and 4p exhibited more promising and pronounced insecticidal activity than toosendanin, a commercial insecticide derived from Melia azedarach. Generally, it was obviously demonstrated that the length of straight-chain or branched-chain alkyloxy, and heteroatom-containing cycloalkyloxy at the C-4 position of 2-chloropodophyllotoxin were very important for the insecticidal activity. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2010.07.050
• 作为产物：
  描述：

  鬼臼毒素 在 盐酸 、 lithium diisopropyl amide 、 三氯氧磷 作用下， 以 四氢呋喃 为溶剂， 反应 11.25h， 生成 2-chloropodophyllotoxin
  参考文献：
  名称：

  Natural products-based insecticidal agents 11. Synthesis and insecticidal activity of novel 4α-arylsulfonyloxybenzyloxy-2β-chloropodophyllotoxin derivatives against Mythimna separata Walker in vivo

  摘要：

  In continuation of our program aimed at the discovery and development of natural products-based insecticidal agents, 14 novel 4 alpha-arylsulfonyloxybenzyloxy-2 beta-chloropodophyllotoxin derivatives were stereoselectively semisynthesized from podophyllotoxin, and preliminarily evaluated for their insecticidal activity against the pre-third-instar larvae of Mythimna separata Walker in vivo. Especially compounds 9c' and 9g' exhibited the most promising and pronounced insecticidal activity than toosendanin, a commercial insecticide derived from Melia azedarach at 1 mg/mL. Generally, it was preliminarily demonstrated that arylsulfonyloxy groups at the C-2 position of benzyloxy moiety and the length of the side chain on the benzenesulfonyloxy group of 4 alpha-arylsulfonyloxybenzyloxy-2 beta-chloropodophyllotoxins might be important for the insecticidal activity. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2011.07.075

文献信息

• Unexpectedly convenient and stereoselective synthesis of 4α-acyloxy-2-chloropodophyllotoxins in the presence of BF 3 ·Et 2 O
  作者：Hui Xu、Xiao Xiao、Xue-Fei Zhao、Yong Guo、Xiao-Jun Yao

  DOI：10.1016/j.bmcl.2011.05.004

  日期：2011.7

  configuration was mainly stereocontrolled by the configuration of C-2 chlorine atom, were unexpectedly prepared by the reaction of 2-chloropodophyllotoxin with carboxylic acids in the presence of BF3·Et2O. Compared with ordinary esterifications of carboxylic acids mediated by the condensation agent, for example, N,N’-diisopropylcarbodiimide (DIC), the present method made the procedure for the preparation

  意外地通过2-氯鬼臼毒素与羧酸的反应制备了二十一种4α-酰氧基-2-氯鬼臼毒素衍生物（5a – u），其C-4空间构型主要受C-2氯原子的构型控制。 BF 3 ·Et 2 O的存在。与缩合剂介导的普通羧酸酯化反应（例如N，N'-二异丙基碳二亚胺（DIC））相比，本方法制备了4α-酰氧基- 2-氯鬼臼毒素更方便，实用且容易。同时，化合物5a – u的杀虫活性在体内对浓度为1 mg / mL的Mythimna separata Walker的三龄前幼虫进行了初步评估。
• Natural products-based insecticidal agents 6. Design, semisynthesis, and insecticidal activity of novel monomethyl phthalate derivatives of podophyllotoxin against Mythimna separata Walker in vivo
  作者：Hui Xu、Xiao-Qiang He

  DOI：10.1016/j.bmcl.2010.06.032

  日期：2010.8

  To discover the more potent analogs, 12 novel monomethyl phthalate derivatives of podophyllotoxin were synthesized and preliminarily tested against the pre-third-instar larvae of Mythimna separata Walker in vivo at the concentration of 1 mg/mL. Compounds 8e-i showed the higher insecticidal activity than podophyllotoxin. Especially 8g exhibited the most potent insecticidal activity compared with toosendanin, a commercially available insecticide derived from Melia azedarach. The structure-activity relationships demonstrated that trans-lactone, 4 beta-substitution, 2 beta-chlorine substitution, and 4'-methoxy group were the important structural properties of podophyllotoxins for good insecticidal activity. (C) 2010 Elsevier Ltd. All rights reserved.
• Natural products-based insecticidal agents 4. Semisynthesis and insecticidal activity of novel esters of 2-chloropodophyllotoxin against Mythimna separata Walker in vivo
  作者：Hui Xu、Xiao Xiao

  DOI：10.1016/j.bmcl.2009.07.116

  日期：2009.9

  By using podophyllotoxin as a lead compound, eight novel esters of 2-chloropodophyllotoxin were designed, semisynthesized, and preliminarily evaluated for their insecticidal activity against the pre-third-instar larvae of Mythimna separata Walker in vivo for the first time. Among all the tested compounds, especially three esters of 2-chloropodophyllotoxin 8a, 8c, and 8g, and one intermediate 6 showed more promising and pronounced insecticidal activity than toosendanin, a commercial insecticide derived from Melia azedarach. (C) 2009 Elsevier Ltd. All rights reserved.
• Preparation of 2-substituted podophyllotoxin derivatives
  作者：Margaret B. Glinski、James C. Freed、Tony Durst

  DOI：10.1021/jo00389a020

  日期：1987.6
• Natural products-based insecticidal agents 7. Semisynthesis and insecticidal activity of novel 4α-alkyloxy-2-chloropodophyllotoxin derivatives against Mythimna separata Walker in vivo
  作者：Hui Xu、Xiao Xiao、Qing-tian Wang

  DOI：10.1016/j.bmcl.2010.07.050

  日期：2010.9

  In continuation of our program aimed at the discovery and development of natural products-based insecticidal agents, 16 novel 4 alpha-alkyloxy-2-chloropodophyllotoxin derivatives were semisynthesized from podophyllotoxin, and preliminarily evaluated for their insecticidal activity against the pre-third-instar larvae of Mythimna separata Walker in vivo. Among all the tested derivatives, especially compounds 4b, 4e, 4g, and 4p exhibited more promising and pronounced insecticidal activity than toosendanin, a commercial insecticide derived from Melia azedarach. Generally, it was obviously demonstrated that the length of straight-chain or branched-chain alkyloxy, and heteroatom-containing cycloalkyloxy at the C-4 position of 2-chloropodophyllotoxin were very important for the insecticidal activity. (C) 2010 Elsevier Ltd. All rights reserved.