ethyl 3-oxo-3-phenyl-2-(9H-xanthen-9-yl)propanoate | 141247-91-8

• 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: ethyl 3-oxo-3-phenyl-2-(9H-xanthen-9-yl)propanoate
• CAS: 141247-91-8
• 化学式: C₂₄H₂₀O₄
• 分子量: 372.42
• InChiKey: UPYPFVFZNOLIJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 3-oxo-3-phenyl-2-(9H-xanthen-9-yl)propanoate 在 sodium hydroxide 作用下， 反应 5.0h， 生成 1-phenyl-2-(9H-xanthen-9-yl)ethanone
  参考文献：
  名称：

  Photogeneration of the Xanthyl Cation: .beta.-Cleavage from Excited State Ketones

  摘要：

  Irradiation of 9-xanthylacetone or 9-xanthylacetophenone in dilute acidic aqueous solution results in facile formation of the xanthyl cation. This cation photogeneration is not subject to acid catalysis over the acid range of 5-30% H2SO4. In contrast, the thermal reaction requires considerably stronger acidic media, and its rate shows a strong dependence on acid concentration. Laser flash photolysis studies demonstrate that the excited-state mechanism proceeds through an initial homolytic carbon-carbon beta-bond cleavage to generate the xanthyl radical. The xanthyl cation is produced from the xanthyl radical in a subsequent step, with oxygen acting as the oxidizing agent. The intermediacy of the xanthyl radical in the mechanism is also supported by the isolation of the radical coupling product bixanthyl from preparative irradiations. Triplet sensitization and quenching experiments demonstrate that the reaction proceeds through an excited triplet state of the ketone substrates.

  DOI：

  10.1021/jo00105a017
• 作为产物：
  描述：

  氧杂蒽 、 苯甲酰乙酸乙酯 在 甲烷磺酸 、 氧气 作用下， 40.0 ℃ 、100.0 kPa 条件下， 反应 96.0h， 以80%的产率得到ethyl 3-oxo-3-phenyl-2-(9H-xanthen-9-yl)propanoate
  参考文献：
  名称：

  由碳氢键形成自氧化碳-碳键

  摘要：

  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”。

  DOI：

  10.1002/anie.201000711

文献信息

• Electrochemical dehydrogenative cross-coupling of xanthenes with ketones
  作者：Yong-Zheng Yang、Yan-Chen Wu、Ren-Jie Song、Jin-Heng Li

  DOI：10.1039/d0cc02580a

  日期：——

  functionalized 9-alkyl-9H-xanthenes was developed. This method enables the formation of a new C(sp3)–C(sp3) bond through release of H2 as the major byproduct at room temperature, and features mild conditions, high atom economy, excellent functional-group tolerance, scalability and facile applications in pharmaceutical chemistry.

  开发了一种新的无氧黄酮和酮的无外部氧化剂的电化学脱氢交联反应，用于制备功能化的9-烷基-9 H-黄嘌呤。该方法能够通过在室温下释放H 2作为主要副产物而形成新的C（sp 3）–C（sp 3）键，并且具有温和的条件，高原子经济性，出色的官能团耐受性，可扩展性和在药物化学中的简便应用。
• Semiconductor Quantum Dots Act as Photocatalysts for Carbon–Carbon Bond Formation: Selective Functionalization of Xanthene’s 9H Position
  作者：Jiteshkumar P. Deore、Mrinmoy De

  DOI：10.1021/acs.joc.3c01801

  日期：2023.12.1

  The potential of CdSe, CdS, MoS2, and WS2 QDs as semiconductor photocatalysts for selective functionalization of the xanthene 9H position through carbon–carbon bond formation has been investigated. Our study reveals valuable insights into the energy-transfer and electron-transfer pathways involved in these reactions, as well as the radical polar crossover (RPC) and triplet-to-triplet energy transfer

  研究了CdSe、CdS、MoS 2和 WS 2 QD 作为半导体光催化剂通过碳-碳键形成选择性功能化呫吨 9H 位的潜力。我们的研究揭示了这些反应中涉及的能量转移和电子转移途径以及自由基极性交叉（RPC）和三重态到三重态能量转移（TTEnT）过程的宝贵见解。值得注意的是，这种方法提供了一系列有趣的特征，包括可见光介导的过程、廉价的催化系统、温和的反应条件、广泛的底物范围、非功能化的起始材料以及适合克级合成。这项研究对新兴的量子点催化反应领域做出了重大贡献，为未来的探索铺平了道路。
• 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.
• Fosse; Robyn, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1906, vol. 143, p. 240,241
  作者：Fosse、Robyn

  DOI：——

  日期：——
• Photoredox C( <i>sp</i> ³ )−C( <i>sp</i> ³ ) Cross‐Dehydrogenative Coupling of Xanthene with β‐keto Moiety using MoS ₂ Quantum Dot (QD) Catalyst.
  作者：Jiteshkumar P. Deore、Mrinmoy De

  DOI：10.1002/adsc.202200231

  日期：2022.9.6

  AbstractVisible light‐mediated Cross‐Dehydrogenative Coupling of Xanthene with β‐keto moieties has been developed using MoS2 Quantum Dot (QD) as a photoredox catalyst. Interesting features of this strategy includes circumventing the requisite of pre‐functionalized starting material, broad substrate scope, mild reaction condition, water as a solvent system, and recyclability of catalyst up to six cycles without loss of yield and selectivity. We have also enlightened the Kinetic Solvent Isotope Effect (KSIE) by scrutinizing the aspect of triplet‐to‐triplet photo energy transfer. The reductive quenching mechanism of QD photocatalyst has been endorsed by cyclic voltametric study.magnified image