N-phenyl-2,6-dinitro-4-(trifluoromethyl)aniline | 17474-05-4

• 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-phenyl-2,6-dinitro-4-(trifluoromethyl)aniline
• 英文别名: N-(2,6-dinitro-4-trifluoromethylphenyl)aniline；2.6-Dinitro-4-trifluoromethyldiphenylamine；2,6-dinitro-N-phenyl-4-(trifluoromethyl)aniline
• CAS: 17474-05-4
• 化学式: C₁₃H₈F₃N₃O₄
• mdl: MFCD03703655
• 分子量: 327.219
• InChiKey: DUMAFIRAMXVMFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  104
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  4-氯-3,5-二硝基三氟甲苯 、 苯胺 以 甲醇 为溶剂， 以87%的产率得到N-phenyl-2,6-dinitro-4-(trifluoromethyl)aniline
  参考文献：
  名称：

  4-氯-3,5-二硝基三氟化物与苯胺衍生物的反应。替代效应

  摘要：

  N-(2,6-二硝基-4-三氟甲基苯基)苯胺衍生物通过4-氯-3, 5-二硝基三氟化物的苯胺脱氯制备。IR、UV 和 1H NMR 研究表明氨基氢和一个邻硝基之间存在分子内氢键。基于二阶动力学和速率对苯胺环中取代基的性质和位置的依赖性，以及 ρ(-3.14, -3.16, -) 的高负值，提出了加成消除机制。 3.01）。这些值表明过渡态苯胺氮上带正电荷，并且速率受取代基极性效应的影响。β 值（30°C 时为 0.85）表明在过渡态中键形成的程度可观。

  DOI：

  10.3184/030823407x240926

文献信息

• Regioselectivity and stereoelectronic effects in the reactions of the dinitroaniline herbicides trifluralin and benefin with nucleophiles
  作者：Michael T Annandale、Gary W vanLoon、Erwin Buncel

  DOI：10.1139/v98-089

  日期：1998.6.1

  The reactions of two members of the dinitroaniline class of herbicides, N,N-di-n-propyl-2,6-dinitro-4- (trifluoromethyl)aniline (trifluralin; 1) and N-ethyl-N-n-butyl-2,6-dinitro-4-(trifluoromethyl)aniline (benefin; 2), along with their analogue, N-phenyl-2,6-dinitro-4-(trifluoromethyl)aniline (3), with the nucleophiles, OD^- and SO₃^2- , have been investigated using 400 MHz ¹H NMR spectroscopy. The reactions of both 1 and 2 with OD^- result in formation of Meisenheimer anionic σ -complexes according to a K3T1 (kinetic preference for formation of the C-3 adduct with thermodynamic preference for formation of the C-1 adduct) reaction sequence while the reaction of 3 with OD^- and that of 1 with SO₃^2- follow a K3T3 (kinetic and thermodynamic preference for formation of the C-3 adduct) sequence. There was no observation of the C-1 adducts of 1 and 2 with OD^-, but the products of S_NAr displacement at C-1 were observed as the final thermodynamic products. Geometry optimization calculations support our hypothesis of n –> σ * stabilization of the C-1 adduct leading to S_NAr displacement. In the reaction of 3 with OD^-, initial N-deprotonation to form the anion, 3a, is followed by σ -complex formation. The final thermodynamic product observed in this system is 3,5-dinitro-4-(N-phenylamino)benzoic acid formed through hydrolysis of the trifluoromethyl group on the anion, 3a. Aryl H-D exchange has been found for the systems of 1 and 2 with OD^-, but not for the SO₃^2- system and neither for the reaction of 3 with OD^-. Since dimethylpicramide showed significantly slower H-D exchange under identical conditions, it is argued that this discrepancy has as origin the ability of the amino N lone electron pair to interact with the π -system of the ring. With both 1 and 2 the larger size of the amino alkyl chains prevent the amino N lone pair from aligning with the π -system of the ring, thus hindering electron density donation to the electron-deficient ring carbons.Key words: trifluralin, benefin, herbicides, Meisenheimer complexes, stereoelectronic effects.

  二种硝基苯胺类除草剂成员，N,N-二正丙基-2,6-二硝基-4-(三氟甲基)苯胺（三氟乙草灵；1）和N-乙基-N-正丁基-2,6-二硝基-4-(三氟甲基)苯胺（苯胺；2），以及它们的类似物N-苯基-2,6-二硝基-4-(三氟甲基)苯胺（3），与亲核试剂OD-和SO32-的反应已经通过400兆赫1H核磁共振波谱学进行了研究。 1和2与OD-的反应导致Meisenheimer阴离子σ-络合物的形成，根据K3T1（动力学偏好形成具有热力学偏好形成C-1加合物的C-3加合物）反应序列，而3与OD-的反应以及1与SO32-的反应遵循K3T3（动力学和热力学偏好形成C-3加合物）序列。没有观察到1和2与OD-的C-1加合物，但观察到了在C-1处进行SNAr位移的产物作为最终热力学产物。几何优化计算支持我们的假设，即n->σ*稳定化C-1加合物导致SNAr位移。在3与OD-的反应中，初始N去质子化形成负离子3a，然后形成σ-络合物。在该系统中观察到的最终热力学产物是通过3a负离子上三氟甲基团的水解形成的3,5-二硝基-4-(N-苯基氨基)苯甲酸。已发现1和2与OD-体系的芳基H-D交换，但未发现SO32-体系的芳基H-D交换，也未发现3与OD-的反应。由于二甲基苦味胺在相同条件下显示出明显较慢的H-D交换，据认为这种差异的起源是氨基N孤对电子能够与环的π-系统相互作用。对于1和2，氨基烷基链的较大尺寸阻止了氨基N孤对与环的π-系统对齐，从而阻碍了电子密度对电子亏缺的环碳的捐赠。关键词：三氟乙草灵，苯胺，除草剂，Meisenheimer络合物，立体电子效应。
• Reaction of 4-Chloro-3,5-Dinitrobenzotrifluoride with Aniline Derivatives. Substituent Effects
  作者：Hamida O.M. Al-Howsaway、Magda F. Fathalla、Ali A. El-Bardan、Ezzat A. Hamed

  DOI：10.3184/030823407x240926

  日期：2007.9

  hylphenyl)aniline derivatives were prepared by anilino-dechlorination of 4-chloro-3, 5-dinitrobenzotrifluoride. IR, UV and 1H NMR studies suggested an intramolecular hydrogen bond between the amino hydrogen and one o-nitro group. An addition-elimination mechanism was suggested based on the second-order kinetics and the dependence of rates on the nature and the position of the substituent in the aniline

  N-(2,6-二硝基-4-三氟甲基苯基)苯胺衍生物通过4-氯-3, 5-二硝基三氟化物的苯胺脱氯制备。IR、UV 和 1H NMR 研究表明氨基氢和一个邻硝基之间存在分子内氢键。基于二阶动力学和速率对苯胺环中取代基的性质和位置的依赖性，以及 ρ(-3.14, -3.16, -) 的高负值，提出了加成消除机制。 3.01）。这些值表明过渡态苯胺氮上带正电荷，并且速率受取代基极性效应的影响。β 值（30°C 时为 0.85）表明在过渡态中键形成的程度可观。
• Benzimidazole useful in the treatment of central nervous system disorders
  申请人：NEUROSEARCH A/S

  公开号：EP0616807B1

  公开（公告）日：1998-07-08
• Benbow, John W.; Bernberg, Erin L.; Korda, Anna, Antimicrobial Agents and Chemotherapy, 1998, vol. 42, # 2, p. 339 - 343
  作者：Benbow, John W.、Bernberg, Erin L.、Korda, Anna、Mead, Jan R.

  DOI：——

  日期：——
• US4117167A
  申请人：——

  公开号：US4117167A

  公开（公告）日：1978-09-26