ethyl 4-(2,4-dioxopentan-3-yl)benzoate | 871130-37-9

• 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: ethyl 4-(2,4-dioxopentan-3-yl)benzoate
• CAS: 871130-37-9
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: MCLUODGFWLLBHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 4-(2,4-dioxopentan-3-yl)benzoate 在 肼 作用下， 以 乙醇 为溶剂， 反应 63.0h， 生成 Cu₃(ethyl-4'-benzoate-3,5-dimethylpyrazolate)₃
  参考文献：
  名称：

  Mechanically Triggered Fluorescence/Phosphorescence Switching in the Excimers of Planar Trinuclear Copper(I) Pyrazolate Complexes

  摘要：

  Luminescence mechanochromism of the well-known Cu(3)Pz(3)-type (Pz = pyrazolate) complexes is reported here, which is unusual for this family. Two types of new Cu(3)Pz(3) complexes, namely Cu-3(EBPz)(3) (1; EBPz = ethyl-4'-benzoate-3,5-dimethylpyrazolate) and Cu-3(MBPz)(3) (polymorphs 2a-c; MBPz = methyl-4'-benzoate-3,5-dimethylpyrazolate), have been synthesized and characterized. Their crystal structures exhibit a similar chairlike dimer stacking supported by short Cu...Cu contacts, which would facilitate the formation of photoinduced excimers. The dual emission from the organic fluorophore and excimeric copper cluster phosphor is found to undergo mechanically induced intensity switching between their high-energy (HE) and low-energy (LE) bands. Specifically, the relative intensities of crystalline samples are HE > LE, while the ground solid samples show LE > HE, resulting in the overall emission color interchanging between bluish violet and red. This switching can be reversed by application of solvent to the ground samples, presumably due to recrystallization, and also by heating. TD-DFT calculations reveal that the emissive singlet ligand localized state (S-1) and triplet cluster centered state (T-8) lie close in energy (separated by a gap of 0.1788 eV), suggesting the feasibility of dual emission and the possibility of reverse intersystem crossing, consistent with the long fluorescent lifetimes (10(2) ns scale) of the HE bands.

  DOI：

  10.1021/ic5016687
• 作为产物：
  描述：

  对碘苯甲酸乙酯 、 乙酰丙酮 在 potassium phosphate 、 copper(l) iodide 作用下， 以 二甲基亚砜 为溶剂， 以44%的产率得到ethyl 4-(2,4-dioxopentan-3-yl)benzoate
  参考文献：
  名称：

  铜催化 C-C 偶联反应中不稳定的 Cu(I) 催化剂/观察者 Cu(II) 物种：Operando IR，原位 XANES/EXAFS 证据和动力学研究

  摘要：

  通过操作红外和原位 X 射线吸收近边结构/扩展 X 射线吸收精细结构研究了对铜催化 CC 偶联反应的见解。发现由 CuI 与 β-二酮亲核试剂反应形成的 Cu(I) 配合物在交叉偶联条件下很容易，通常被认为是活性催化物种。这种不稳定的 Cu(I) 络合物在反应条件下会迅速与旁观者 Cu(II) 和 Cu(0) 物质不成比例，这是一个非循环过程。在这种铜催化的 CC 偶联反应中，β-二酮可能同时作为底物和配体。

  DOI：

  10.1021/ja310111p

文献信息

• Labile Cu(I) Catalyst/Spectator Cu(II) Species in Copper-Catalyzed C–C Coupling Reaction: Operando IR, in Situ XANES/EXAFS Evidence and Kinetic Investigations
  作者：Chuan He、Guanghui Zhang、Jie Ke、Heng Zhang、Jeffrey T. Miller、Arthur J. Kropf、Aiwen Lei

  DOI：10.1021/ja310111p

  日期：2013.1.9

  Insights toward the Cu-catalyzed C-C coupling reaction were investigated through operando IR and in situ X-ray absorption near-edge structure/extended X-ray absorption fine structure. It was found that the Cu(I) complex formed from the reaction of CuI with β-diketone nucleophile was liable under the cross-coupling conditions, which is usually considered as active catalytic species. This labile Cu(I)

  通过操作红外和原位 X 射线吸收近边结构/扩展 X 射线吸收精细结构研究了对铜催化 CC 偶联反应的见解。发现由 CuI 与 β-二酮亲核试剂反应形成的 Cu(I) 配合物在交叉偶联条件下很容易，通常被认为是活性催化物种。这种不稳定的 Cu(I) 络合物在反应条件下会迅速与旁观者 Cu(II) 和 Cu(0) 物质不成比例，这是一个非循环过程。在这种铜催化的 CC 偶联反应中，β-二酮可能同时作为底物和配体。
• An Efficient and Mild CuI/<scp>l</scp>-Proline-Catalyzed Arylation of Acetylacetone or Ethyl Cyanoacetate
  作者：Yongwen Jiang、Nan Wu、Haihong Wu、Mingyuan He

  DOI：10.1055/s-2005-918921

  日期：——

  The coupling reaction of aryl iodides with acetylacetone or ethyl cyanoacetate under catalysis of CuI/l-proline works at ­relatively mild conditions to provide 3-aryl-2, 4-pentanediones and α-aryl cyanoacetates in moderate to good yields.

  在CuI/l-脯氨酸催化下，芳基碘化物与乙酰乙酮或乙基氰乙酸酯的偶联反应在相对温和的条件下进行，能够生成3-芳基-2, 4-戊二酮和α-芳基氰乙酸酯，产率中等至良好。
• Synthesis of sterically encumbered biaryls based on a ‘copper(I)-catalyzed arylation/[3+3] cyclocondensation’ strategy
  作者：Asad Ali、Ihsan Ullah、Muhammad Sher、Alexander Villinger、Peter Langer

  DOI：10.1016/j.tetlet.2008.10.093

  日期：2009.1

  Sterically encumbered biaryls are prepared in two steps by Cul-proline-catalyzed arylation of acetylacetone to give 3-arylpentane-2,4-diones and subsequent formal [3+3] cyclization of the latter with 1,3-bis(trimethylsilyloxy)-1,3-dienes. (C) 2008 Elsevier Ltd. All rights reserved.
• Synthesis of of sterically encumbered biaryls based on a ‘copper(I)-catalyzed arylation/[3+3] cyclocondensation’ strategy
  作者：Ihsan Ullah、Muhammad Sher、Rasheed Ahmad Khera、Asad Ali、Muhammad Nawaz、Mohanad Shkoor、Inam Iqbal、Muhammad Imran、Alexander Villinger、Christine Fischer、Peter Langer

  DOI：10.1016/j.tet.2010.03.054

  日期：2010.5

  Sterically encumbered biaryls are prepared in two steps by combination of the CuI-proline-catalyzed arylation of acetylacetone with formal [3+3] cyclizations of 1,3-bis(trimethylsilyloxy)-1,3-dienes. In addition, the synthesis of 4,6- and 5,6-diarylsalicylates based on [3+3] cyclizations is reported. (C) 2010 Elsevier Ltd. All rights reserved.
• Mechanically Triggered Fluorescence/Phosphorescence Switching in the Excimers of Planar Trinuclear Copper(I) Pyrazolate Complexes
  作者：Qiong Xiao、Ji Zheng、Mian Li、Shun-Ze Zhan、Jun-Hao Wang、Dan Li

  DOI：10.1021/ic5016687

  日期：2014.11.3

  Luminescence mechanochromism of the well-known Cu(3)Pz(3)-type (Pz = pyrazolate) complexes is reported here, which is unusual for this family. Two types of new Cu(3)Pz(3) complexes, namely Cu-3(EBPz)(3) (1; EBPz = ethyl-4'-benzoate-3,5-dimethylpyrazolate) and Cu-3(MBPz)(3) (polymorphs 2a-c; MBPz = methyl-4'-benzoate-3,5-dimethylpyrazolate), have been synthesized and characterized. Their crystal structures exhibit a similar chairlike dimer stacking supported by short Cu...Cu contacts, which would facilitate the formation of photoinduced excimers. The dual emission from the organic fluorophore and excimeric copper cluster phosphor is found to undergo mechanically induced intensity switching between their high-energy (HE) and low-energy (LE) bands. Specifically, the relative intensities of crystalline samples are HE > LE, while the ground solid samples show LE > HE, resulting in the overall emission color interchanging between bluish violet and red. This switching can be reversed by application of solvent to the ground samples, presumably due to recrystallization, and also by heating. TD-DFT calculations reveal that the emissive singlet ligand localized state (S-1) and triplet cluster centered state (T-8) lie close in energy (separated by a gap of 0.1788 eV), suggesting the feasibility of dual emission and the possibility of reverse intersystem crossing, consistent with the long fluorescent lifetimes (10(2) ns scale) of the HE bands.