diethyl 2-(9H-xanthen-9-yl)malonate | 13210-18-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: diethyl 2-(9H-xanthen-9-yl)malonate
• 英文别名: 1,3-diethyl 2-(9H-xanthen-9-yl)propanedioate；Diethylxanthen-9-malonat；9-(1'-ethoxycarbonyl-2'-oxo-3'-oxapent-1'-yl)xanthene；xanthen-9-yl-malonic acid diethyl ester；diethyl 2-(9H-xanthen-9-yl)propanedioate
• CAS: 13210-18-9
• 化学式: C₂₀H₂₀O₅
• 分子量: 340.376
• InChiKey: UXWRWBJGVQJDJO-UHFFFAOYSA-N

物化性质

• 沸点：
  421.9±33.0 °C(Predicted)
• 密度：
  1.206±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 2-(9H-xanthen-9-yl)malonate 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以94%的产率得到2-Xanthen-9-ylidene-malonic acid diethyl ester
  参考文献：
  名称：

  Manganese(III)-mediated carbon-carbon bond formation in the reaction of xanthenes with active methylene compounds

  摘要：

  Oxidation of xanthenes with manganese(III) acetate in the presence of active methylene compounds such as 1,3-dicarbonyl compounds, malononitrile derivatives, acetone, and nitromethane selectively gives 9-substituted xanthene derivatives in good yields. A similar oxidation of thioxanthene also yields 2-(9-thioxanthenyl)-1,3-dicarbonyl compounds in 57-91% yields. The obtained 2-(9-xanthenyl)-1,3-dicarbonyl compounds are readily converted to 2-(9-xanthenylidene)-1,3-dicarbonyl derivatives using manganese(III) complexes or 2,3-dichloro-5, 6-dicyano-1,4-benzoquinone. The mechanisms for the formation of 9-substituted xanthenes are discussed on the basis of the reaction of intermediates, the electron-donating substituent effect on the xanthene ring system, effect of additives, and comparison with a reaction of radical-trapping reagents.

  DOI：

  10.1021/jo00039a010
• 作为产物：
  描述：

  氧杂蒽 、 丙二酸二乙酯 在 三氟甲磺酸 、 氧气 作用下， 以 二氯甲烷 为溶剂， 20.0~25.0 ℃ 、6.0 MPa 条件下， 反应 144.0h， 以39%的产率得到diethyl 2-(9H-xanthen-9-yl)malonate
  参考文献：
  名称：

  氧气分压升高时磺酸催化的自氧化碳-碳偶联反应

  摘要：

  描述了苄基CH键与各种C-亲核试剂的好氧有机催化氧化CC键形成反应。通过在室温下在磺酸催化剂的存在下在升高的氧分压下简单地搅拌底物来进行偶联反应。压力的升高使得广泛范围的亲核底物能够反应，否则在环境压力下显示出较差的反应性。苄Ç 呫吨，acridanes，isochromane及相关杂环的H键可以与亲核试剂包括酮，1,3-二羰基化合物和醛官能化。富电子芳烃可在高温下用作亲核试剂。该反应被认为是通过以下方式进行的苄基CH键的自氧化与氢过氧化物和随后被磺酸催化的亲核取代。

  DOI：

  10.1002/adsc.201100563

文献信息

• Autoxidative Carbon-Carbon Bond Formation from Carbon-Hydrogen Bonds
  作者：Áron Pintér、Abhishek Sud、Devarajulu Sureshkumar、Martin Klussmann

  DOI：10.1002/anie.201000711

  日期：——

  Only oxygen and acid! The oxidative coupling of xanthene and other activated benzylic compounds with carbon nucleophiles such as ketones, can be performed under ambient conditions without solvent by simply using oxygen and catalytic amounts of methanesulfonic acid. The proposed reaction mechanism involves substrate activation by formation of hydroperoxides; the method can therefore be regarded as an

  只有氧气和酸！an吨和其他活化的苄基化合物与碳亲核试剂（如酮）的氧化偶联可在环境条件下，无需溶剂，只需使用氧气和催化量的甲磺酸即可进行。拟议的反应机理涉及通过氢过氧化物的形成来活化底物。因此，该方法可被视为“自氧化偶联反应”。
• Sulfonic Acid-Catalyzed Autoxidative Carbon-Carbon Coupling Reaction under Elevated Partial Pressure of Oxygen
  作者：Áron Pintér、Martin Klussmann

  DOI：10.1002/adsc.201100563

  日期：2012.3

  reactivity at ambient pressure. The benzylic CH bonds of xanthene, acridanes, isochromane and related heterocycles could be functionalized with nucleophiles including ketones, 1,3‐dicarbonyl compounds and aldehydes. Electron‐rich arenes could be utilized as nucleophiles at elevated temperatures. The reactions are believed to proceed via autoxidation of the benzylic CH bonds to the hydroperoxides and subsequent

  描述了苄基CH键与各种C-亲核试剂的好氧有机催化氧化CC键形成反应。通过在室温下在磺酸催化剂的存在下在升高的氧分压下简单地搅拌底物来进行偶联反应。压力的升高使得广泛范围的亲核底物能够反应，否则在环境压力下显示出较差的反应性。苄Ç 呫吨，acridanes，isochromane及相关杂环的H键可以与亲核试剂包括酮，1,3-二羰基化合物和醛官能化。富电子芳烃可在高温下用作亲核试剂。该反应被认为是通过以下方式进行的苄基CH键的自氧化与氢过氧化物和随后被磺酸催化的亲核取代。
• Manganese(III)-mediated carbon-carbon bond formation in the reaction of xanthenes with active methylene compounds
  作者：Hiroshi Nishino、Hironori Kamachi、Harumi Baba、Kazu Kurosawa

  DOI：10.1021/jo00039a010

  日期：1992.6

  Oxidation of xanthenes with manganese(III) acetate in the presence of active methylene compounds such as 1,3-dicarbonyl compounds, malononitrile derivatives, acetone, and nitromethane selectively gives 9-substituted xanthene derivatives in good yields. A similar oxidation of thioxanthene also yields 2-(9-thioxanthenyl)-1,3-dicarbonyl compounds in 57-91% yields. The obtained 2-(9-xanthenyl)-1,3-dicarbonyl compounds are readily converted to 2-(9-xanthenylidene)-1,3-dicarbonyl derivatives using manganese(III) complexes or 2,3-dichloro-5, 6-dicyano-1,4-benzoquinone. The mechanisms for the formation of 9-substituted xanthenes are discussed on the basis of the reaction of intermediates, the electron-donating substituent effect on the xanthene ring system, effect of additives, and comparison with a reaction of radical-trapping reagents.
• Visible-light induced enhancement in the multi-catalytic activity of sulfated carbon dots for aerobic carbon–carbon bond formation
  作者：Daisy Sarma、Biju Majumdar、Tridib K. Sarma

  DOI：10.1039/c9gc02658d

  日期：——

  ketones, arenes and 1,3-dicarbonyl compounds that showed high efficiency and selectivity under visible-light irradiation. The sulphated carbon dots demonstrate dual catalytic properties, wherein they induced the rapid photooxidation of xanthenes in the presence of molecular oxygen to form a hydroperoxy intermediate followed by coupling of nucleophiles catalysed by the acidic surface functional groups.

  碳质材料作为无金属催化剂的发展，在一个系统中集成了不同类型的催化，代表着级联/串联有机合成的重大进步。零维碳点具有可调节的光学特性和易于修饰的表面功能，可作为碳催化剂用于合并一锅中的光氧化和酸催化反应。在这里，我们探索装饰有硫酸氢基团的碳点作为光催化黄嘌呤与酮，芳烃和1,3-二羰基化合物在可见光照射下具有高效率和选择性的脱氢交叉偶联反应。硫酸化碳点具有双重催化性能，其中他们在分子氧的存在下诱导了黄嘌呤的快速光氧化，形成氢过氧中间体，然后偶联了由酸性表面官能团催化的亲核试剂。该方法代表了在较温和的条件下，在较短的反应时间内生成宽范围的底物范围内生成C-C偶联产物的操作简单途径。该催化剂易于分离并且可以在多个循环中以良好的效率重复使用。