2,4,6-三硝基二苯基胺 | 2919-12-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2,4,6-三硝基二苯基胺
• 英文名称: trinitro-2,4,6 diphenylamine
• 英文别名: 2,4,6-Trinitro-N-phenylaniline
• CAS: 2919-12-2
• 化学式: C₁₂H₈N₄O₆
• mdl: MFCD00024418
• 分子量: 304.219
• InChiKey: GHWYJRRNNWVCPM-UHFFFAOYSA-N

物化性质

• 沸点：
  445.06°C (rough estimate)
• 密度：
  1.4549 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  150
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,4,6-三硝基二苯基胺 在 铁粉 、 溶剂黄146 作用下， 反应 1.0h， 以71%的产率得到2-amino-4,6-dinitrodiphenylamine
  参考文献：
  名称：

  Flippen-Anderson, Judith L.; Gilardi, Richard D.; Pitt, Adrian M., Australian Journal of Chemistry, 1992, vol. 45, # 3, p. 513 - 524

  摘要：

  DOI：
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 盐酸 作用下， 生成 2,4,6-三硝基二苯基胺
  参考文献：
  名称：

  Dziewonski; Russocki, Bulletin International de l'Academie Polonaise des Sciences et des Lettres, Classe des Sciences Mathematiques et Naturelles, Serie A: Sciences Mathematiques, 1929, p. 506,525

  摘要：

  DOI：

文献信息

• Aromatic nucleophilic substitution reactions of 1-dialkylamino-substituted activated benzenes with various amines in dimethyl sulfoxide
  作者：Shizen Sekiguchi、Hiromi Ishikura、Yukitoshi Hirosawa、Nobuyuki Ono

  DOI：10.1016/s0040-4020(01)87755-3

  日期：1990.1

  In the reactions of 1-d1a1kylamino-2,4,6-trinitro- and 1-dialkylam1no-2, 4-dinitrobenzenes with various amines in dimethyl sulfoxide, 1-dialkylamino group is easily replaced with primary n-alkylamines at room temperature, and in a low yield with pyrrolidine only among secondary amines.

  在二甲基亚砜中1-d1a1kylamino-2,4,6-三硝基和1-dialkam1no-2、4-二硝基苯与各种胺的反应中，1-二烷基氨基很容易在室温下被伯正烷基胺取代，并且仅仲胺中吡咯烷的收率低。
• Steric and electronic effects on the mechanism of nucleophilic substitution (SNAr) reactions of some phenyl 2,4,6-trinitrophenyl ethers with aniline and N-methylaniline in acetonitrile and in dimethyl sulfoxide
  作者：Chukwuemeka Isanbor、Thomas A. Emokpae、Michael R. Crampton

  DOI：10.1039/b207997f

  日期：2002.12.6

  Rate data are reported for the reactions of a series of 3′- and 4′-substituted phenyl 2,4,6-trinitrophenyl ethers, 4, with aniline in acetonitrile, leading to 2,4,6-trinitrodiphenylamine. The main reaction flux occurs through a base catalysed pathway involving formation of a zwitterionic intermediate, equilibrium constant K1, and rate-limiting proton transfer to base, rate constant kAn. The effects of ring substituents on values of rate and equilibrium constants are discussed. In contrast the corresponding reactions in DMSO involve both uncatalysed and base catalysed pathways. Reactions of 4 with N-methylaniline are extremely slow, but values of rate constants for reaction of 4-nitrophenyl 2,4,6-trinitrophenyl ether were measured using 1H NMR spectroscopy. The value of the parameter K1kAn is lowered by a factor of 105 for N-methylaniline relative to aniline in both acetonitrile and in DMSO. This reduction is attributed to increased steric hindrance both in formation of the intermediate and to proton transfer.

  速率数据针对一系列3′-和4′-取代苯基2,4,6-三硝基苯基醚4与苯胺在丙酮腈中的反应进行了报告，该反应生成2,4,6-三硝基二苯胺。主要反应通路经由酸催化途径，涉及形成内盐中间体、平衡常数K1以及限制速率的质子转移至碱基，速率常数kAn。讨论了环取代基对速率和平衡常数值的影响。相比之下，在二甲基亚砜中对应的反应涉及未催化与酸催化两条途径。4与N-甲基苯胺的反应极其缓慢，但使用1H核磁共振光谱测量了4-硝基苯基2,4,6-三硝基苯基醚反应的速率常数值。在丙酮腈和二甲基亚砜中，对于N-甲基苯胺相较于苯胺，参数K1kAn的值降低了10的5次方倍。这种降低归因于在中间体形成与质子转移过程中的空间位阻增加。
• The kinetics of the reaction of phenyl 2,4,6-trinitrophenyl ether with aniline in methanol, acetonitrile, tetrahydrofuran, ethyl acetate, and benzene
  作者：Olayinka Banjoko、Paul Otiono

  DOI：10.1039/p29810000399

  日期：——

  The kinetics of the reaction of phenyl 2,4,6-trinitrophenyl ether with aniline have been investigated as a function of the amine concentration in methanol, acetonitrile, tetrahydrofuran, ethyl acetate, and benzene. Base catalysis was observed in all the solvents. The second-order rate constant kA shows a linear correlation with the aniline concentration except in benzene where the linearity is with

  已经研究了苯基2,4,6-三硝基苯基醚与苯胺的反应动力学与甲醇，乙腈，四氢呋喃，乙酸乙酯和苯中胺浓度的关系。在所有溶剂中均观察到碱催化。除苯的线性与苯胺浓度的平方成线性关系外，二阶速率常数k A与苯胺浓度呈线性关系。所述ķ 3乙/ ķ 2溶剂的比率提供了有关亲核芳族取代中形成的中间体的未催化分解机理的信息。提出了一种介电常数和碱度较低的溶剂中碱催化途径的机理。
• Anilinolysis of Picryl Benzoate Derivatives in Methanol: Reactivity, Regioselectivity, Kinetics, and Mechanism
  作者：Mahmoud F. Ibrahim、Mohamed A. El-Atawy、Samir K. El-Sadany、Ezzat A. Hamed

  DOI：10.1002/kin.20779

  日期：2013.9

  The reaction of picryl benzoate derivatives 1a–g with aniline in methanol proceeds through COO and ArO bond cleavage pathways. Furthermore, the reactivity of these esters toward anilinolysis is correlated to the energy gap between highest occupied molecular orbital aniline and lowest unoccupied molecular orbital of each ester. The regioselectivity of acyloxygen versus aryloxygen cleavage is also

  甲醇中苯甲酸吡啶酯衍生物1a–g与苯胺在甲醇中的反应通过COO和ArO键的裂解途径进行。此外，这些酯对苯胺分解的反应性与每个酯的最高占据分子轨道苯胺和最低未占据分子轨道之间的能隙相关。还讨论了酰基氧对芳基氧裂解的区域选择性。整体速率常数ķ TOT分成ķ CO  Ô（酰基-氧裂解速率常数）和ķ氩 Ò（芳基氧裂解速率常数）。该CO 通过逐步机制O键裂解的进步，其中所述四面体中间体的形成是限速步骤。上述Ar  O键裂解继续通过A S Ñ其中所述离去基团从所述迈森海梅复杂离开其在速率决定步骤形成后迅速发生的Ar机制。
• The Synthesis of Vinylogous Amidine Heterocycles
  作者：Daniel V. LaBarbera、Edward B. Skibo

  DOI：10.1021/jo401927n

  日期：2013.12.6

  We report herein a convenient synthetic methodology for the conversion of meta-dinitro heterocyclic rings to iminoquinones with vinylogous amidine functionality. These structures are found in nature, particularly in marine organisms, and may be important for the pigments and biological activity observed with such marine secondary metabolites. Using benzimidazole and indole ring systems we show the

  我们在这里报告了一种方便的综合方法，用于转换元-二硝基杂环成具有乙烯基am官能团的亚氨基醌。这些结构是在自然界中发现的，尤其是在海洋生物中，对于这些海洋次级代谢产物观察到的色素和生物活性可能很重要。使用苯并咪唑和吲哚环系统，我们展示了这些乙烯基ous的有机合成的通用性，包括以下内容：与几乎任何伯胺的氨基转移反应，对乙烯基am之间取代基的取代进行区域控制以及可控制的水解性能或根据所选环网系统的属性进行优化。在一起

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