4-O-tetrahydropyran-2-ylpodophyllotoxin | 62318-97-2

• 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: 4-O-tetrahydropyran-2-ylpodophyllotoxin
• 英文别名: 4-O-tetrahydropyranylpodophyllotoxin；tetrahydropyranyl podophyllotoxin；tetrahydropyranylpodophyllotoxin；Podophyllotoxin-；Podophyllotoxin-(tetrahydropyranyl-(2)-ether)；(5R,5aR,8aR,9R)-5-(oxan-2-yloxy)-9-(3,4,5-trimethoxyphenyl)-5a,6,8a,9-tetrahydro-5H-[2]benzofuro[5,6-f][1,3]benzodioxol-8-one
• CAS: 62318-97-2
• 化学式: C₂₇H₃₀O₉
• 分子量: 498.53
• InChiKey: SWHRJVKQGVUYGL-HZSRLOHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.96
• 重原子数：
  36.0
• 可旋转键数：
  6.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  90.91
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  4-O-tetrahydropyran-2-ylpodophyllotoxin 在 盐酸 、 三氟化硼乙醚 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.42h， 生成 4α-n-butoxy-2β-bromopodophyllotoxin
  参考文献：
  名称：

  立体选择性合成4α-烷氧基-2-α/β-溴代鬼臼毒素作为杀虫剂

  摘要：

  有趣的杀虫剂：由于分子内的空间位阻效应，很容易制备具有良好立体选择性的4α-烷氧基-2α/β-溴鬼臼毒素衍生物（参见方案）。可以通过反应温度很好地控制2α/β-溴-4--4- O-四氢吡喃基鬼臼毒素的两种立体异构体的比例。

  DOI：

  10.1002/chem.201100855
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 鬼臼毒素 在 三氯氧磷 作用下， 反应 3.0h， 以92%的产率得到4-O-tetrahydropyran-2-ylpodophyllotoxin
  参考文献：
  名称：

  立体选择性合成4α-酰氧基-2α/β-溴鬼臼毒素衍生物作为杀虫剂

  摘要：

  为了找到新的基于天然产物的杀虫剂，并大大扩展了我们以前的工作，我们从鬼臼毒素中设计并立体选择性地合成了4α-酰氧基-2α/β-溴鬼臼毒素衍生物。有趣的是，当BF 3 ·Et 2 O存在时，当反应时间延长至4–18 h时，通过分子内Friedel–Crafts烷基化反应，很容易将4α-酰氧基-2α-溴微假鬼臼毒素转化为刚性更高的化合物14。化合物5g，6h，6i和14的杀虫活性比太生丹宁（得自Melia azedarach的商业杀虫剂）显示出更有希望和更明显的杀虫活性。，对付Mythimna separata的三龄前幼虫。

  DOI：

  10.1016/j.tet.2012.10.073

文献信息

• Antitumor Agents LXII: Synthesis and Biological Evaluation of Podophyllotoxin Esters and Related Derivatives
  作者：Ron K. Levy、Iris H. Hall、Kuo-Hsiung Lee

  DOI：10.1002/jps.2600721012

  日期：1983.10

  Synthetic esters of the C-4 hydroxyl group of podophyllotoxin (I) were prepared. In addition, esters were synthesized using the diol system of tetrahydropyranyl podophyllol (XV), produced by reducing the lactone ring of tetrahydropyranyl podophyllotoxin with lithium aluminum hydride. Six compounds, the acrylate (IV), 3,3-dimethyl acrylate (V), phenoxyacetate (IX), and ethyl adipate (XI) of I as well

  制备鬼臼毒素（I）的C-4羟基的合成酯。此外，使用四氢吡喃基鬼臼酚（XV）的二醇体系合成酯，该体系是通过用氢化锂铝还原四氢吡喃基鬼臼毒素的内酯环而制得的。I的六种化合物丙烯酸酯（IV），丙烯酸3,3-二甲基丙烯酸酯（V），苯氧乙酸酯（IX）和己二酸乙酯（XI）以及戊多酚（XIV）和四氢吡喃基戊二酚二甲磺酸酯（XVIII）具有明显的活性使用P-388淋巴细胞白血病筛查以3 mg / kg /天进行测试时。在相同剂量水平下测试时，没有一种酯的活性高于母体分子I的活性。
• 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.
• Laatsch, Hartmut; Ernst, Bernd Peter; Noltemeyer, Mathias, Liebigs Annalen, 1996, # 5, p. 731 - 737
  作者：Laatsch, Hartmut、Ernst, Bernd Peter、Noltemeyer, Mathias

  DOI：——

  日期：——
• Natural products-based insecticidal agents 11. Synthesis and insecticidal activity of novel 4α-arylsulfonyloxybenzyloxy-2β-chloropodophyllotoxin derivatives against Mythimna separata Walker in vivo
  作者：Hui Xu、Jun-Liang Zhang

  DOI：10.1016/j.bmcl.2011.07.075

  日期：2011.9

  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.
• 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.