N,N'-Bis(4-methoxyphenyl)-N,N'-dimethylmethanediamine | 62895-91-4

• 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: N,N'-Bis(4-methoxyphenyl)-N,N'-dimethylmethanediamine
• 英文别名: N,N'-bis(4-methoxyphenyl)-N,N'-dimethylmethanediamine
• CAS: 62895-91-4
• 化学式: C₁₇H₂₂N₂O₂
• 分子量: 286.374
• InChiKey: YVLLJVRSQBQVSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  24.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (4-甲氧基苯基)-二甲胺 在 四丁基醋酸铵 、 tetramethylammonium tetrafluoroborate 作用下， 以 乙腈 为溶剂， 生成 N,N'-Bis(4-methoxyphenyl)-N,N'-dimethylmethanediamine 、 N-甲基-P-氨基苯甲醚
  参考文献：
  名称：

  Facile proton-transfer reactions of N,N-dimethylaniline cation radicals

  摘要：

  Ring-substituted NN-dimethylaniline (DMA) cation radicals undergo rapid proton transfer reactions with acetate ion or pyridine in acetonitrile. The difference in pK(a) of the parent DMA and DMA.+ was estimated to equal 27 using electrode potentials in a thermochemical cycle. Second-order rate constants for the reaction with acetate ion at 298 K ranged from 3.2 X 10(6) for the p-methoxy-substituted cation radical to 3 X 10(9) M-1 s-1 for the corresponding p-nitro derivative. Rate constants for the reactions of the cation radicals with pyridine were observed to be as much as 10(6) lower than with acetate ion. Activation parameters for the two series of reactions differed markedly. Enthalpies of activation (DELTA-H) on the order of 20 kcal/mol and large positive activation entropies (DELTA-S), 35-53 eu, were characteristic of the acetate ion reactions, whiLe for pyridine, DELTA-H ranged from 2 to 13 kcaL/mol and DELTA-S values were large and negative, -15 to -29 eu. Large k(H)/k(D) values for reactions of ArN(CD3)2.+ implicate proton transfer as the rate-determining step in both reaction series. The differences in activation parameters for the two sets of reactions were attributed to differences in the position of the preequilibrium between base and cation radicals. A large equilibrium constant is expected for the reversible ion combination between acetate ion and the cation radicals.

  DOI：

  10.1021/ja00023a026

文献信息

• Bridging Amines with CO₂: Organocatalyzed Reduction of CO₂ to Aminals
  作者：Xavier Frogneux、Enguerrand Blondiaux、Pierre Thuéry、Thibault Cantat

  DOI：10.1021/acscatal.5b00734

  日期：2015.7.2

  The four-electron reduction of CO2 in the presence of secondary aromatic amines is described for the first time to access aminals. Under metal-free hydrosilylation conditions, the four C-O bonds of CO2 are cleaved, and the organocatalysts are able to balance the reactivity of CO2 to promote the selective formation of two C-N and two C-H bonds. The methodology enables the formation of various symmetrical and unsymmetrical aminals.
• Facile proton-transfer reactions of N,N-dimethylaniline cation radicals
  作者：Vernon D. Parker、Mats Tilset

  DOI：10.1021/ja00023a026

  日期：1991.11

  Ring-substituted NN-dimethylaniline (DMA) cation radicals undergo rapid proton transfer reactions with acetate ion or pyridine in acetonitrile. The difference in pK(a) of the parent DMA and DMA.+ was estimated to equal 27 using electrode potentials in a thermochemical cycle. Second-order rate constants for the reaction with acetate ion at 298 K ranged from 3.2 X 10(6) for the p-methoxy-substituted cation radical to 3 X 10(9) M-1 s-1 for the corresponding p-nitro derivative. Rate constants for the reactions of the cation radicals with pyridine were observed to be as much as 10(6) lower than with acetate ion. Activation parameters for the two series of reactions differed markedly. Enthalpies of activation (DELTA-H) on the order of 20 kcal/mol and large positive activation entropies (DELTA-S), 35-53 eu, were characteristic of the acetate ion reactions, whiLe for pyridine, DELTA-H ranged from 2 to 13 kcaL/mol and DELTA-S values were large and negative, -15 to -29 eu. Large k(H)/k(D) values for reactions of ArN(CD3)2.+ implicate proton transfer as the rate-determining step in both reaction series. The differences in activation parameters for the two sets of reactions were attributed to differences in the position of the preequilibrium between base and cation radicals. A large equilibrium constant is expected for the reversible ion combination between acetate ion and the cation radicals.