2-hydroxy-2-acenaphthylen-1-one | 138858-19-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-hydroxy-2-acenaphthylen-1-one
• 英文别名: 2-[Ethoxy(trimethylsilyl)methyl]-2-hydroxyacenaphthylen-1-one
• CAS: 138858-19-2；138858-20-5
• 化学式: C₁₈H₂₂O₃Si
• 分子量: 314.456
• InChiKey: DQCIDABCACKYFY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  苊醌 在 乙氧基甲基(三甲基)硅烷 作用下， 以 甲醇 为溶剂， 反应 5.0h， 以44%的产率得到2-Hydroxy-2-(1-hydroxy-2-oxoacenaphthylen-1-yl)acenaphthylen-1-one
  参考文献：
  名称：

  Photoaddition reactions of acenaphthylenedione with .alpha.-silyl n-electron donors via triplet single electron transfer desilylation and triplet hydrogen atom abstraction pathways

  摘要：

  Studies have been conducted to explore single electron transfer (SET) induced photoaddition reactions of acenaphthylenedione (ACND) with the n-electron donors Et2NCH2SiMe3, n-PrSCH2SiMe3, EtOCH2SiMe3, EtCO2CH2N(CH2Ph)CH2SiMe3, and EtCO2CH2N(CH2Ph)CH3. Photoaddition of alpha-silyl amine Et2NCH2SiMe3 to ACND occurs in CH3OH and CH3CN to produce 2-hydroxy-2-[(diethylamino)methyl]acenaphthylen-1-one. In contrast, photoaddition of n-PrSCH2SiMe3 to ACND generates two photoadducts, 2-hydroxy-2-[(n-propylthio)methyl]acenaphthylen-1-one and 2-hydroxy-2-[(n-propylthio)(trimethylsilyl)methyl]acenaphthylen-1-one, along with a ACND photoreduction dimer. Photoaddition of EtOCH2SiMe3 to ACND produces two diastereomers of 2-hydroxy-2-[ethoxy(trimethylsilyl)methyl]acenaphthylen-1-one along with the reduction dimer. The formation of all photoproducts in these photoreactions is quenched by oxygen, indicating that the triplet of ACND is the reactive excited state. Based on a consideration of the oxidation potentials of the alpha-silyl n-electron donors, and the nature of photoproducts, mechanisms for these photoadditions involving triplet SET-desilylation and triplet H atom abstraction pathways are proposed. Photoaddition of EtCO2CH2N(CH2Ph)CH2SiMe3 to ACND provides two major products, 2-hydroxy-2-[[N-benzyl-N-(carbethoxymethyl)amino]methyl]acenaphthylen-1-one and 2-hydroxy-2-[[N-benzyl-N-[(trimethylsilyl)methyl]amino]carbethoxymethyl]acenaphthylen-1-one along with several minor products. The formation of the major products via sequential SET-deprotonation pathways shows that the electron-withdrawing carbethoxy substituent serves to control the regioselectivity for deprotonation of the amine radical cation intermediate. Results obtained from the study of the photoaddition of the non-silicon-containing amino ester, EtCO2CH2N(CH2Ph)CH3, also demonstrate the effect of electron-withdrawing carbethoxy substituent on amine radical cation deprotonation regiochemistry.

  DOI：

  10.1021/jo00031a020

文献信息

• Photoaddition reactions of acenaphthylenedione with .alpha.-silyl n-electron donors via triplet single electron transfer desilylation and triplet hydrogen atom abstraction pathways
  作者：Ung Chan Yoon、Yong Chul Kim、Jeong Ja Choi、Dong Uk Kim、Patrick S. Mariano、In Seop Cho、Yoon Tag Jeon

  DOI：10.1021/jo00031a020

  日期：1992.2

  Studies have been conducted to explore single electron transfer (SET) induced photoaddition reactions of acenaphthylenedione (ACND) with the n-electron donors Et2NCH2SiMe3, n-PrSCH2SiMe3, EtOCH2SiMe3, EtCO2CH2N(CH2Ph)CH2SiMe3, and EtCO2CH2N(CH2Ph)CH3. Photoaddition of alpha-silyl amine Et2NCH2SiMe3 to ACND occurs in CH3OH and CH3CN to produce 2-hydroxy-2-[(diethylamino)methyl]acenaphthylen-1-one. In contrast, photoaddition of n-PrSCH2SiMe3 to ACND generates two photoadducts, 2-hydroxy-2-[(n-propylthio)methyl]acenaphthylen-1-one and 2-hydroxy-2-[(n-propylthio)(trimethylsilyl)methyl]acenaphthylen-1-one, along with a ACND photoreduction dimer. Photoaddition of EtOCH2SiMe3 to ACND produces two diastereomers of 2-hydroxy-2-[ethoxy(trimethylsilyl)methyl]acenaphthylen-1-one along with the reduction dimer. The formation of all photoproducts in these photoreactions is quenched by oxygen, indicating that the triplet of ACND is the reactive excited state. Based on a consideration of the oxidation potentials of the alpha-silyl n-electron donors, and the nature of photoproducts, mechanisms for these photoadditions involving triplet SET-desilylation and triplet H atom abstraction pathways are proposed. Photoaddition of EtCO2CH2N(CH2Ph)CH2SiMe3 to ACND provides two major products, 2-hydroxy-2-[[N-benzyl-N-(carbethoxymethyl)amino]methyl]acenaphthylen-1-one and 2-hydroxy-2-[[N-benzyl-N-[(trimethylsilyl)methyl]amino]carbethoxymethyl]acenaphthylen-1-one along with several minor products. The formation of the major products via sequential SET-deprotonation pathways shows that the electron-withdrawing carbethoxy substituent serves to control the regioselectivity for deprotonation of the amine radical cation intermediate. Results obtained from the study of the photoaddition of the non-silicon-containing amino ester, EtCO2CH2N(CH2Ph)CH3, also demonstrate the effect of electron-withdrawing carbethoxy substituent on amine radical cation deprotonation regiochemistry.