2,2-Bis(ethoxycarbonyl)-4-phenyl-1,2-dihydronaphthalene | 141344-93-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2,2-Bis(ethoxycarbonyl)-4-phenyl-1,2-dihydronaphthalene
• 英文别名: diethyl 4-phenyl-1H-naphthalene-2,2-dicarboxylate
• CAS: 141344-93-6
• 化学式: C₂₂H₂₂O₄
• 分子量: 350.414
• InChiKey: IDUZSMBOGGQKNG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  2,2-Bis(ethoxycarbonyl)-4-phenyl-1,2-dihydronaphthalene 在 air 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 4-Phenyl-naphthalene-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  Reactivity of malonyl radicals. Synthesis of substituted dihydronaphthalenes by manganese(III) oxidation of diethyl .alpha.-benzylmalonate in the presence of alkynes

  摘要：

  Oxidation of diethyl alpha-benzylmalonate (1) by Mn(III) acetate in acetic acid at 70-degrees-C in the presence of alkynes 2a-j leads to dihydronaphthalene derivatives 3a-j in moderate to good yields. A homolytic mechanism, involving oxidation of 1 to the corresponding malonyl radical, its addition to a triple bond, and intramolecular homolytic aromatic substitution of the vinyl radical adducts, is suggested. Propargylic hydrogen abstraction and dimerization at the malonic position for less reactive alkynes are the main side reactions observed. Relative and absolute rates of addition of alpha-benzylmalonyl radicals to representative alkynes and alkenes, deduced from competitive experiments, indicate a lower reactivity toward alkynes than toward the corresponding substituted alkenes. Both SOMO-LUMO and SOMO-HOMO interactions in the transition state lower the activation energy of these homolytic additions with alkenes, but only the SOMO-HOMO interaction dominates with the examined alkynes. 2-Naphthoic acid derivatives can be efficiently obtained by oxidative decarboxylation of 3 with NaI and air.

  DOI：

  10.1021/jo00041a034
• 作为产物：
  描述：

  diethyl 2-benzyl-2-bromomalonate 、 苯乙炔 在 fac-tris(2-phenylpyridinato-N,C2')iridium(III) 、 水 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以85%的产率得到2,2-Bis(ethoxycarbonyl)-4-phenyl-1,2-dihydronaphthalene
  参考文献：
  名称：

  可见光驱动脱芳香化反应对螺[4.5] deca-1,6,9-trien-8-ones的形成。

  摘要：

  已经开发了在温和条件下导致螺[4,5]癸烷形成的可见光驱动的2-苄基-2-溴丙二酸酯和炔烃之间的区域选择性脱芳香环化反应。在存在H 2 O的情况下，各种2-苄基-2-溴丙二酸酯可通过炔烃平稳地经历5-exo-dig自由基脱芳香环化反应，以分步经济的方式以中等至良好的产率提供相应的螺[4,5]癸烷在无氧化剂的条件下。

  DOI：

  10.1021/acs.orglett.9b04283

文献信息

• 1,5 vs. 1,6 Intramolecular homolytic aromatic substitution by vinyl radicals
  作者：Attilio Citterio、Roberto Sebastiano、Antonietta Maronati、Roberto Santi、Fabrizio Bergamini

  DOI：10.1039/c39940001517

  日期：——

  Manganese(III) acetate oxidation of substituted diethyl benzylmalonates in the presence of alkynes affords tetrahydronaphthalene derivatives 3, 6, 7 and spiro[4,5]decatriene derivatives 4 or 5, through competitive 1,5 and 1,6 intramolecular aromatic substitution by vinyl radicals.

  乙酸锰（III）在炔烃存在下氧化取代的苄基丙二酸二乙酯，通过乙烯基自由基竞争性的 1,5 和 1,6 分子内芳香取代作用，产生四氢萘衍生物 3、6、7 和螺[4,5]癸三烯衍生物 4 或 5。
• Bergamini, Fabrizio; Gatti, Norberto; Santi, Roberto, Journal of Chemical Research, Miniprint, 1993, # 9, p. 2455 - 2466
  作者：Bergamini, Fabrizio、Gatti, Norberto、Santi, Roberto、Citterio, Attilio、Nicolini, Marco、Sebastiano, Roberto

  DOI：——

  日期：——
• Reactivity of malonyl radicals. Synthesis of substituted dihydronaphthalenes by manganese(III) oxidation of diethyl .alpha.-benzylmalonate in the presence of alkynes
  作者：Roberto Santi、Fabrizio Bergamini、Attilio Citterio、Roberto Sebastiano、Marco Nicolini

  DOI：10.1021/jo00041a034

  日期：1992.7

  Oxidation of diethyl alpha-benzylmalonate (1) by Mn(III) acetate in acetic acid at 70-degrees-C in the presence of alkynes 2a-j leads to dihydronaphthalene derivatives 3a-j in moderate to good yields. A homolytic mechanism, involving oxidation of 1 to the corresponding malonyl radical, its addition to a triple bond, and intramolecular homolytic aromatic substitution of the vinyl radical adducts, is suggested. Propargylic hydrogen abstraction and dimerization at the malonic position for less reactive alkynes are the main side reactions observed. Relative and absolute rates of addition of alpha-benzylmalonyl radicals to representative alkynes and alkenes, deduced from competitive experiments, indicate a lower reactivity toward alkynes than toward the corresponding substituted alkenes. Both SOMO-LUMO and SOMO-HOMO interactions in the transition state lower the activation energy of these homolytic additions with alkenes, but only the SOMO-HOMO interaction dominates with the examined alkynes. 2-Naphthoic acid derivatives can be efficiently obtained by oxidative decarboxylation of 3 with NaI and air.
• Visible-Light-Driven Dearomatization Reaction toward the Formation of Spiro[4.5]deca-1,6,9-trien-8-ones
  作者：Wuheng Dong、Yao Yuan、Xiaomin Xie、Zhaoguo Zhang

  DOI：10.1021/acs.orglett.9b04283

  日期：2020.1.17

  cyclization between 2-benzyl-2-bromomalonate and alkynes under mild conditions leading to the formation of spiro[4,5]decanes has been developed. In the presence of H2O, a variety of 2-benzyl-2-bromomalonates smoothly undergo 5-exo-dig radical dearomative cyclization with alkynes to afford the corresponding spiro[4,5]decanes in moderate to good yield in a step-economical manner under oxidant-free conditions.

  已经开发了在温和条件下导致螺[4,5]癸烷形成的可见光驱动的2-苄基-2-溴丙二酸酯和炔烃之间的区域选择性脱芳香环化反应。在存在H 2 O的情况下，各种2-苄基-2-溴丙二酸酯可通过炔烃平稳地经历5-exo-dig自由基脱芳香环化反应，以分步经济的方式以中等至良好的产率提供相应的螺[4,5]癸烷在无氧化剂的条件下。