2,2-Bis(ethoxycarbonyl)-3,4-diphenyl-1,2-dihydronaphthalene | 141344-96-9

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: 2,2-Bis(ethoxycarbonyl)-3,4-diphenyl-1,2-dihydronaphthalene
• 英文别名: diethyl 3,4-diphenyl-1H-naphthalene-2,2-dicarboxylate
• CAS: 141344-96-9
• 化学式: C₂₈H₂₆O₄
• 分子量: 426.512
• InChiKey: UOBPJMRRLFSXFV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 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)-3,4-diphenyl-1,2-dihydronaphthalene 在 air 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 ethyl 3,4-diphenyl-2-naphthoate
  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：

  二苯基乙炔 、 苄基丙二酸二乙酯 在 manganese triacetate 作用下， 以 溶剂黄146 为溶剂， 反应 24.0h， 以13%的产率得到2,2,3,3-tetrakis(ethoxycarbonyl)-1,4-diphenylbutane
  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