3-deutero-1,2,4-trimethoxybenzene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-deutero-1,2,4-trimethoxybenzene
• 英文别名: 2-Deuterio-1,3,4-trimethoxybenzene
• 化学式: C₉H₁₂O₃
• 分子量: 169.185
• InChiKey: AGIQIOSHSMJYJP-RAMDWTOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1,2,4-三甲氧基苯 在 四氢呋喃 、 sodium diisopropylamide 、 氘代甲醇-d 作用下， 以 正己烷 为溶剂， 生成 3-deutero-1,2,4-trimethoxybenzene
  参考文献：
  名称：

  四氢呋喃中的二异丙基氨基钠：选择性，速率和芳烃金属化的机制。

  摘要：

  描述了在四氢呋喃（THF）/己烷或THF / Me 2 NEt溶液中，二异丙基氨基钠（NaDA）介导的芳烃金属化。对超过40种具有一系列取代基的基于苯并吡啶和吡啶的芳烃的研究表明，其金属化的功效和区域选择性都很高。活化的二取代的芳烃和选定的单取代的芳烃在-78°C时快速金属化。1,3-二甲氧基苯和相关甲氧基化芳烃的速率研究表明，基于单体的原金属具有两个或三个配位的THF配体。苯和具有弱活化基团的单取代芳烃的同位素交换速率研究表明，类似的二溶剂化和三溶剂化的单体基金属化反应。讨论了协同的诱导，消旋，空间和螯合作用。

  DOI：

  10.1021/jacs.7b08734

文献信息

• Enhanced Basicity of the 2-Position of 1,3-Dialkoxybenzenes in S1: Acid Catalyzed Photochemical Proton/Deuteron Exchange
  作者：Renee Mosi、Guangzhong Zhang、Peter Wan

  DOI：10.1021/jo00107a021

  日期：1995.1

  The photochemistry of several 1,3-dialkoxy-substitute d benzenes 1-8 has be en studied in aqueous H2SO4 (D2SO4) solution. In contrast to ground state behavior, all of these compounds (with the exception of 7) are photoprotonated efficiently (via S-1) and almost exclusively at the 2-position (and to a much lesser extent at the 5-position) to give dialkoxy-substituted cyclohexadienyl cation intermediates (2,6-dialkoxybenzenonium ions), resulting in proton/deuteron exchange of the 2-position of the benzene ring for all systems except 4 (and 7). In the ground state, protonation takes place predominantly at the 4-position for 1-4 and at the 6-position for 5 and 6. In the case of 4, photoprotonation at the 2-position is implicated by observation of fluorescence quenching by acid but deuterium exchange at this position is not possible. Photoprotonation (quenching) rate constants (k(H)) were calculated by Stern-Volmer analysis of steady state fluorescence quenching by proton and are in the range 0.9-3 x 10(9) M(-1) s(-1). anduantum yields for deuterium incorporation in 4:1 aqueous D2SO4-CH3CN are reported for several substrates at selected acidities. The sigmoid dependence of plots of fluorescence quenching vs acidity is used to give estimated PKBH* of approximate to 0.1 - 0.5 for these substrates, indicating that they are much more basic in S-1 than in S-0.
• Synthesis of 1,2,4-Trimethoxybenzene and Its Selective Functionalization at C-3 by Directed Metalation
  作者：Ana P. L. Alves、Jose Augusto B. C. Júnior、Glaucia B. A. Slana、Jari N. Cardoso、Qiang Wang、Rosangela S. C. Lopes、Claudio C. Lopes

  DOI：10.1080/00397910902805598

  日期：2009.9.18

  A new and efficient strategy was developed for the preparation of 1,2,4-trimethoxybenzene (3, a powerful attractant of Euglossini bees) and its C-3 derivatives (7a-j), from vanillin (2) in 56% overall yield.
• Sodium Diisopropylamide in Tetrahydrofuran: Selectivities, Rates, and Mechanisms of Arene Metalations
  作者：Russell F. Algera、Yun Ma、David B. Collum

  DOI：10.1021/jacs.7b08734

  日期：2017.10.25

  Sodium diisopropylamide (NaDA)-mediated metalations of arenes in tetrahydrofuran (THF)/hexane or THF/Me2NEt solutions are described. A survey of >40 benzenoid- and pyridine-based arenes with a range of substituents demonstrates the efficacy and regioselectivity of metalation. Metalations of activated disubstituted arenes and selected monosubstituted arenes are rapid at −78 °C. Rate studies of 1,3-dimethoxybenzene

  描述了在四氢呋喃（THF）/己烷或THF / Me 2 NEt溶液中，二异丙基氨基钠（NaDA）介导的芳烃金属化。对超过40种具有一系列取代基的基于苯并吡啶和吡啶的芳烃的研究表明，其金属化的功效和区域选择性都很高。活化的二取代的芳烃和选定的单取代的芳烃在-78°C时快速金属化。1,3-二甲氧基苯和相关甲氧基化芳烃的速率研究表明，基于单体的原金属具有两个或三个配位的THF配体。苯和具有弱活化基团的单取代芳烃的同位素交换速率研究表明，类似的二溶剂化和三溶剂化的单体基金属化反应。讨论了协同的诱导，消旋，空间和螯合作用。