4-phenoxy-N-methyl-N-trideuteriomethylaniline | 1023324-56-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-phenoxy-N-methyl-N-trideuteriomethylaniline
• CAS: 1023324-56-2
• 化学式: C₁₄H₁₅NO
• 分子量: 216.255
• InChiKey: RFMYZHXUKTUIFW-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  12.47
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-phenoxy-N-methyl-N-trideuteriomethylaniline 在 lead(IV) tetraacetate 、 1-羟基苯并三唑 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 生成 、 N-methyl-4-phenoxyaniline
  参考文献：
  名称：

  ň的-Demethylation N，N- -Dimethylanilines由苯并三唑Ñ -1-氧基部首：证据两步电子转移，质子转移机制

  摘要：

  苯并三唑N-氧基自由基（BTNO）与一系列4-X- N，N-二甲基苯胺（X = CN，CF 3，CO 2 CH 2 CH 3，CH 3，OC 6 H 5，OCH 3）已在CH 3 CN中进行了研究。产物分析表明，首先形成了自由基4-XC 6 H 4 N（CH 3）CH 2 •，这可能导致生成N-脱甲基产物或与BTNO偶联的产物。发现反应速率通过增加芳基取代基的供电子能力而显着提高（ρ + = -3.8）。使用给电子性取代基（X = CH 3，OC 6 H 5，OCH 3），未观察到分子间氘动力学同位素效应（DKIE）和基本的分子内DKIE。在具有吸电子取代基（X ＝ CN，CF 3，CO 2 CH 2 CH 3）的情况下，观察到分子间和分子内DKIE的实质值。这些结果可以根据N的电子转移机理来解释，N-二甲基苯胺到BTNO自由基，然后使苯胺自由基阳离子去质子化（ET-PT机理）。通过将Marcus方程应用于X

  DOI：

  10.1021/jo100040y
• 作为产物：
  描述：

  氘代碘甲烷 、 N-methyl-4-phenoxyaniline 在 四丁基碘化铵 、 potassium hydroxide 作用下， 以 水 、 苯 为溶剂， 生成 4-phenoxy-N-methyl-N-trideuteriomethylaniline
  参考文献：
  名称：

  ň的-Demethylation N，N- -Dimethylanilines由苯并三唑Ñ -1-氧基部首：证据两步电子转移，质子转移机制

  摘要：

  苯并三唑N-氧基自由基（BTNO）与一系列4-X- N，N-二甲基苯胺（X = CN，CF 3，CO 2 CH 2 CH 3，CH 3，OC 6 H 5，OCH 3）已在CH 3 CN中进行了研究。产物分析表明，首先形成了自由基4-XC 6 H 4 N（CH 3）CH 2 •，这可能导致生成N-脱甲基产物或与BTNO偶联的产物。发现反应速率通过增加芳基取代基的供电子能力而显着提高（ρ + = -3.8）。使用给电子性取代基（X = CH 3，OC 6 H 5，OCH 3），未观察到分子间氘动力学同位素效应（DKIE）和基本的分子内DKIE。在具有吸电子取代基（X ＝ CN，CF 3，CO 2 CH 2 CH 3）的情况下，观察到分子间和分子内DKIE的实质值。这些结果可以根据N的电子转移机理来解释，N-二甲基苯胺到BTNO自由基，然后使苯胺自由基阳离子去质子化（ET-PT机理）。通过将Marcus方程应用于X

  DOI：

  10.1021/jo100040y

文献信息

• A Kinetic Study of the Reaction of <i>N</i>,<i>N</i>-Dimethylanilines with 2,2-Diphenyl-1-picrylhydrazyl Radical: A Concerted Proton−Electron Transfer?
  作者：Enrico Baciocchi、Alessandra Calcagni、Osvaldo Lanzalunga

  DOI：10.1021/jo8001672

  日期：2008.6.1

  The reactivity of the 2,2-diphenyl-1-picrylhydrazyl radical (dpph(center dot)) toward the N-methyl C-H bond of a number of 4-X-substituted-N,N-dimethylanilines (X = OMe, OPh, CH3, H) has been investigated in MeCN, in the absence and in the presence of Mg(ClO4)(2), by product, and kinetic analysis. The reaction was found to lead to the N-demethylation of the N,N-dimethylaniline with a rate quite sensitive to the electron donating power of the substituent (rho(+) = -2.03). With appropriately deuterated N,N-dimethylanilines, the intermolecular and intramolecular deuterium kinetic isotope effects (DKIEs) were measured with the following results. Intramolecular DKIE [(k(H)/k(D))(intra)] was found to always be similar to intermolecular DKIE [(k(H)/k(D))(inter)]. These results suggest a single-step hydrogen transfer mechanism from the N-C-H bond to dpph(center dot) which might take the form of a concerted proton-electron transfer (CPET). An electron transfer (ET) step from the aniline to dpph(center dot) leading to an anilinium radical cation, followed by a proton transfer step that produces an alpha-amino carbon radical, appears very unlikely. Accordingly, a rate-determining ET step would require no DKIE or at least different inter and intramolecular isotope effects. On the other hand, an equilibrium-control led ET is not compatible with the small slope value (-0.22 kcal(-1) K-1) of the log k(H)/Delta G degrees plot. Furthermore, the reactivity increases by changing the solvent to the less polar toluene whereas the reverse would be expected for an ET mechanism. In the presence of Mg2+, a strong rate acceleration was observed, but the pattern of the results remained substantially unchanged: inter and intramolecular DKIEs were again very similar as well as the substituent effects. This suggests that the same mechanism (CPET) is operating in the presence and in the absence of Mg2+. The significant rate accelerating effect by Mg2+ is likely due to a favorable interaction of the Mg2+ ion with the partial negatively charged alpha-methyl carbon in the polar transition state for the hydrogen transfer process.