4,8-bis(trimethylsilyl)-1,5-bis(trimethylsilyloxy)naphthalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 4,8-bis(trimethylsilyl)-1,5-bis(trimethylsilyloxy)naphthalene
• 英文别名: Trimethyl-[5-trimethylsilyl-4,8-bis(trimethylsilyloxy)naphthalen-1-yl]silane；trimethyl-[5-trimethylsilyl-4,8-bis(trimethylsilyloxy)naphthalen-1-yl]silane
• 化学式: C₂₂H₄₀O₂Si₄
• 分子量: 448.9
• InChiKey: AIWPYOYHFJQNER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 1,5-二羟基萘 在 正丁基锂 、 四甲基乙二胺 作用下， 生成 4,8-bis(trimethylsilyl)-1,5-bis(trimethylsilyloxy)naphthalene
  参考文献：
  名称：

  Predicting Directed Lithiations by Means of MNDO-Determined Agostic Interaction Parameters and Proximity Features. Peri Lithiation of Polyhydric Phenolic Compounds

  摘要：

  The feasibility of the direct lithiation of monohydric compounds (such asa secondary benzamide, phenol, and thiophenol) and dihydric and trihydric phenols has been theoretically examined by using the semiempirical MNDO method. MNDO-determined agostic interaction parameters and proximity features show an outstanding capacity in qualitatively predicting the closeness of the corresponding transition states. According to these parameters, peri lithiation of mono- or polyhydric phenolic compounds (whenever possible) should be kinetically favored over alternative processes. Even second peri lithiations appear to be achievable objectives on account of these indicators. These prognostications have been borne out by experiment for the first time as dihydric phenols of the naphthalene, anthracene, and phenanthrene series yielded peri-substituted products on treatment with nBuLi in N,N,N',N'-tetramethylethylenediamine (TMEDA) as solvent, followed by quenching with common electrophiles. Double peri functionalized derivatives of several dihydroxynaphthalenes and phenanthrenes were obtained by directed lithiation of the unprotected compounds. These results strongly suggest the key role that agostic interaction plays on directed lithiations and provide indirect evidence for the intermediacy of such precoordinated species in these reactions.

  DOI：

  10.1021/ja00108a029

文献信息

• Predicting Directed Lithiations by Means of MNDO-Determined Agostic Interaction Parameters and Proximity Features. Peri Lithiation of Polyhydric Phenolic Compounds
  作者：Jose M. Saa、Jeronimo Morey、Antonio Frontera、Pere M. Deya

  DOI：10.1021/ja00108a029

  日期：1995.1

  The feasibility of the direct lithiation of monohydric compounds (such asa secondary benzamide, phenol, and thiophenol) and dihydric and trihydric phenols has been theoretically examined by using the semiempirical MNDO method. MNDO-determined agostic interaction parameters and proximity features show an outstanding capacity in qualitatively predicting the closeness of the corresponding transition states. According to these parameters, peri lithiation of mono- or polyhydric phenolic compounds (whenever possible) should be kinetically favored over alternative processes. Even second peri lithiations appear to be achievable objectives on account of these indicators. These prognostications have been borne out by experiment for the first time as dihydric phenols of the naphthalene, anthracene, and phenanthrene series yielded peri-substituted products on treatment with nBuLi in N,N,N',N'-tetramethylethylenediamine (TMEDA) as solvent, followed by quenching with common electrophiles. Double peri functionalized derivatives of several dihydroxynaphthalenes and phenanthrenes were obtained by directed lithiation of the unprotected compounds. These results strongly suggest the key role that agostic interaction plays on directed lithiations and provide indirect evidence for the intermediacy of such precoordinated species in these reactions.