(3aS,4S,5S,6R,7R,7aS)-5,6-epoxy-4,7-methano-perhydro-isobenzofuranone | 145680-95-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (3aS,4S,5S,6R,7R,7aS)-5,6-epoxy-4,7-methano-perhydro-isobenzofuranone
• 英文别名: (3aRS,4RS,5RS,6SR,7SR,7aRS)-5,6-Epoxy-4,7-methano-perhydro-isobenzofuranon；4-Oxa-8.9epoxy-tricyclo-<5.2.1.0.^2.6endo>decan-3-on；rac-(3aS,4S,5S,6R,7R,7aS)-5,6-epoxyhexahydro-4,7-methanoisobenzofuran-1(3H)-one
• CAS: 145680-95-1；113968-93-7；134877-48-8；144607-58-9；144607-61-4；145680-89-3
• 化学式: C₉H₁₀O₃
• 分子量: 166.177
• InChiKey: JPIYJSNCUGXIAV-NTZPWTIWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.19
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  38.83
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (3aS,4S,5S,6R,7R,7aS)-5,6-epoxy-4,7-methano-perhydro-isobenzofuranone 在 硫酸 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以83%的产率得到(1RS,4SR,5SR,6RS,8SR,9RS)-9-Hydroxy-2-oxa-tricyclo-<4.2.10^4,8>-nonan-5-carbonsaeure
  参考文献：
  名称：

  5,6-dihydroxy-4,7-methano-isobenzofuranones 的合成

  摘要：

  与 KMnO4 的非对映选择性反应导致不饱和降冰片烷内酯 1 和 2 生成二羟基内酯 3b 和 4b，以及通过 3-氯过氧苯甲酸氧化生成环氧内酯 3d 和 4d。顺式二醇3b和4b通过乙酰化衍生为3c和4c。在化合物3b-3d和4b-4d中，新手性中心C-5和C-6的相对构型通过1H和13C NMR光谱研究确定。作为环氧内酯 3d 和 4d 的水解产物，代替预期的反式配置的 1,2-二醇，从 3d 开始得到三环羧酸 5，从 4d 通过降冰片基阳离子重排得到 1,3-二醇 6a。

  DOI：

  10.1002/ardp.19923250910
• 作为产物：
  描述：

  环戊二烯 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 87.0h， 生成 (3aS,4S,5S,6R,7R,7aS)-5,6-epoxy-4,7-methano-perhydro-isobenzofuranone
  参考文献：
  名称：

  Synthesis and Insecticidal Activity of Lactones Derived from Furan-2(5H)-one

  摘要：

  Ten 4,7-methanoisobenzofuran-1(3H)-ones were synthesized and their insecticidal activities against the insect pest Diaphania hyalinata were evaluated. The most active substances have been selected from the initial screening to find the dose to kill 50 (LD50) and 90% (LD90) of the melonworm. Time-mortality curves of the three selected formulations at the LD90 concentration have been made against D. hyalinata. From the time-mortality curves we found that the formulation (3aR,4R,5S,6S,7S,7aS)- and (3aS,4S,5R,6R,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aR,4R,5R,6R,7S,7aS)- and (3aS,4S,5S,6S,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 50% of the melonworm after 2 h, presenting the best knockdown effect. Bioassays against Solenopsis saevissima and Tetragonisca angustula were carried out for the lactones selected in the initial screening against D. hyalinata. The formulation (3aS,4R,5S,6S,7S,7aR)- and (3aR,4S,5R,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aS,4R,5R,6R,7S,7aR)- and (3aR,4S,5S,6S,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 31.25 and 68.30% of the pest natural enemy and the pollinator bee, respectively. At the same concentration this formulation killed 90% of D. hyalinata. The selectivity in favor of the non-target organisms has rendered this formulation a position as a promising agrochemical.

  DOI：

  10.5935/0103-5053.20150217

文献信息

• Computation and structural elucidation of compounds formed via epoxide alcoholysis
  作者：Elson S. Alvarenga、Milena G. Teixeira、Dayane T. Lopes、Antonio J. Demuner

  DOI：10.1002/mrc.4818

  日期：2019.4

  resonance (NMR) chemical shifts for these two candidate structures were calculated and compared with the experimental data using mean absolute error (MAE) and DP4 analyses. Therefore, the relative stereochemistry of (rac)-3a was established by the mechanism, MAE, and DP4 approaches. The hydroxyl group was acetylated to surpass the problem of signal overlapping of H5 and H6 in the 1 H NMR. The relative

  异苯并呋喃酮因其广泛的生物活性而闻名，例如杀菌剂，杀虫剂和抗癌剂。通过使环氧化物2与甲醇，乙醇，丙-1-醇，丙-2-醇和丁-1-醇反应进行新的生物活性化合物的搜索。通过计算两个推定结构（rac）-3a和（rac）-3b的过渡态，可以推断出用甲醇进行立体选择和立体选择性环氧化物打开的机理。化合物（rac）-3a是从其过渡态（TS1）的较低能量推断出的动力学产物。计算了这两个候选结构的1 H和13 C核磁共振（NMR）化学位移，并使用平均绝对误差（MAE）和DP4分析与实验数据进行了比较。因此，（rac）-3a的相对立体化学是通过机理，MAE和DP4方法建立的。羟基被乙酰化，以克服1 H NMR中H5和H6信号重叠的问题。通过NMR解释确定的相应酯的相对立体化学与（rac）-3a的结构一致。
• Preparation of enantiomerically pure 5,6-dihydroxy-isobenzofuranones and 5,6-dihydroxy-4,7-methano-isobenzofuranones
  作者：Anna Edelsbacher、Ernst Urban、Waltraud Weidenauer

  DOI：10.1007/bf00812323

  日期：——

  Optically pure available lactones 1 and 5 were diastereoselectively oxidised to cis-diols 2 and 6 by KMnO4 and to epoxides 3 and 7 by 3-chloroperoxybenzoic acid. Epoxide 3 was cleaved to trans-diol 4, whereas hydrolysis of 7 afforded tricyclic carboxylic acid 8. Optically pure dihydroxylactones 2, 4, and 6 are valuable models for structure determination of the antimicrobial garlic component garlicin.