4-(2,2,2-trifluoroethoxy)-N,N-dimethylaniline | 1007222-89-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-(2,2,2-trifluoroethoxy)-N,N-dimethylaniline
• 英文别名: N,N-dimethyl-4-(2,2,2-trifluoroethoxy)aniline
• CAS: 1007222-89-0
• 化学式: C₁₀H₁₂F₃NO
• 分子量: 219.207
• InChiKey: UGMKPGWLWNDUOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 4-(dimethylamino)benzenediazonium tetrafluoroborate 反应 4.5h， 以52%的产率得到4-(2,2,2-trifluoroethoxy)-N,N-dimethylaniline
  参考文献：
  名称：

  Using Phenyl Cations as Probes for Establishing Electrophilicity−Nucleophilicity Relations

  摘要：

  N,N-Dimethyl-4-aminophenyl cation is used as an electrophilic probe for determining the relative reactivity of nucleophiles. The singlet state ((3)1) of this cation is completely unselective (reaction rates with benzene, MeCN, and trifluoroethanol within a factor of 5). The corresponding triplet (11) does not react with alcohols and MeCN. The rates of reaction of the latter intermediate with 23.7 pi,sigma and n nucleophiles are measured by competition experiments and found to vary over only 2 orders of magnitude over a range of 22 units of the nucleophilicity parameter N introduced by Mayr. As far as one can judge with the considerable scatter of the data, fitting the data of both amines and pi nucleophiles is possible only by using a modified Mayr's equation: log k = s(E + eN) with e = 0.33. The reduced dependence on N is explained by the fact that in the case of diradicalic triplet (3)1 interaction with the nucleophile involves a half-filled (sigma) orbital, which is empty in singlet (1)1. It is suggested that Mayr's equation can be extended to quite diverse reactions, but a scaling factor of e < I may have to be introduced in some cases, according to the electronic structure of the electrophilic probe used.

  DOI：

  10.1021/jo7019509

文献信息

• Using Phenyl Cations as Probes for Establishing Electrophilicity−Nucleophilicity Relations
  作者：Valentina Dichiarante、Maurizio Fagnoni、Angelo Albini

  DOI：10.1021/jo7019509

  日期：2008.2.1

  N,N-Dimethyl-4-aminophenyl cation is used as an electrophilic probe for determining the relative reactivity of nucleophiles. The singlet state ((3)1) of this cation is completely unselective (reaction rates with benzene, MeCN, and trifluoroethanol within a factor of 5). The corresponding triplet (11) does not react with alcohols and MeCN. The rates of reaction of the latter intermediate with 23.7 pi,sigma and n nucleophiles are measured by competition experiments and found to vary over only 2 orders of magnitude over a range of 22 units of the nucleophilicity parameter N introduced by Mayr. As far as one can judge with the considerable scatter of the data, fitting the data of both amines and pi nucleophiles is possible only by using a modified Mayr's equation: log k = s(E + eN) with e = 0.33. The reduced dependence on N is explained by the fact that in the case of diradicalic triplet (3)1 interaction with the nucleophile involves a half-filled (sigma) orbital, which is empty in singlet (1)1. It is suggested that Mayr's equation can be extended to quite diverse reactions, but a scaling factor of e < I may have to be introduced in some cases, according to the electronic structure of the electrophilic probe used.