3-nitrophenyl 2,4,6-trinitrophenyl ether | 10242-29-2

• 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: 3-nitrophenyl 2,4,6-trinitrophenyl ether
• 英文别名: (3-nitro-phenyl)-picryl ether；(3-Nitro-phenyl)-picryl-aether；(3-Nitro-phenyl)-(2.4.6-trinitro-phenyl)-aether；Pikrinsaeure-(3-nitro-phenyl-aether)；2.4.6.3'-Tetranitro-diphenylaether；2,4,6,3'-Tetranitro-diphenylether；1,3,5-Trinitro-2-(3-nitrophenoxy)benzene
• CAS: 10242-29-2
• 化学式: C₁₂H₆N₄O₉
• 分子量: 350.201
• InChiKey: YKLHNGMJSGZRBH-UHFFFAOYSA-N

物化性质

• 熔点：
  174-175 °C
• 沸点：
  444.5±45.0 °C(Predicted)
• 密度：
  1.688±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  25
• 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：
  193
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3-nitrophenyl 2,4,6-trinitrophenyl ether 在 硫酸 、 硝酸 作用下， 生成 3,4-dinitrophenyl 2,4,6-trinitrophenyl ether
  参考文献：
  名称：

  van Duin; van Lennep, Recueil des Travaux Chimiques des Pays-Bas, 1920, vol. 39, p. 170

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4,6-三硝基氯苯 、 间硝基苯酚 以 乙醇 、 水 为溶剂， 生成 3-nitrophenyl 2,4,6-trinitrophenyl ether
  参考文献：
  名称：

  离开基团对乙腈中某些苯基2,4,6-三硝基苯基醚与苯胺的芳香亲核取代（S N Ar）反应机理的影响

  摘要：

  动力学研究报道了在一系列X -苯基-2,4,6-三硝基苯醚[X = H，2-，3-，4-CH的乙腈与苯胺反应3，2,4-，2,6- - （CH 3）2，2-，3-，4-NO 2，2,4-，2,6-（NO 2）2 ]。X = H，2,6-（CH 3）2和2,6-（NO 2）2的X射线晶体结构据报道，并为这些分子的1位周围的空间拥挤提供了证据。然而，动力学数据表明，增加的取代不会在空间上抑制苯胺对亲核分子的攻击，并且可能出现“早期”过渡态。通常，反应是碱催化的。解释为两性离子中间体的限速去质子化。仅对于二硝基衍生物，才观察到涉及分子内质子转移的未催化反应，当X = 2,6-（NO 2）2时，该途径吸收了全部反应通量。版权所有©2003 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/poc.690

文献信息

• 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。
• Base catalysis in nucleophilic aromatic substitution reactions: evidence for cyclic transition state mechanism over the dimer mechanism in a non-polar aprotic solvent
  作者：Olayinka Banjoko、Chike Ezeani

  DOI：10.1039/p29860000531

  日期：——

  The reactions of X-phenyl 2,4,6-trinitrophenyl ethers [X = 2-NO2, 3-NO2, 4-NO2, 2,4-(NO2)2, 3,4-(NO2)2, 2,5-(NO2)2, and 2,6-(NO2)2] with aniline in benzene display three distinct mechanisms even though all except the 2,6-dinitrophenyl ether are base catalysed. The catalysis of the mononitro-substituted ethers involves two aniline molecules and proceeds at a temperature-independent rate in the temperature

  X -苯基-2,4,6-三硝基苯醚[的反应X = 2-NO 2，3-NO 2，4-NO 2，2,4-（NO 2）2，3,4-（NO 2）2，2,5-（NO 2）2，和2,6-（NO 2）2]与苯胺在苯中的反应显示出三种不同的机理，尽管除2,6-二硝基苯基醚以外的所有碱均被催化。一硝基取代醚的催化反应涉及两个苯胺分子，并且在5–35°C的温度范围内以与温度无关的速率进行，而二硝基取代醚的催化仅涉及一个苯胺分子，并且以与温度无关的速率进行在相同温度范围内。根据涉及过渡状态的四元，六元和八元环的循环机制来解释结果。
• The influence of some steric and electron effects on the mechanism of aromatic nucleophilic substitution (SNAr) reactions in nonpolar solvent
  作者：Thomas A. Emokpae、Nkechi V. Atasie

  DOI：10.1002/kin.20109

  日期：2005.12

  reported for the reactions with aniline in benzene of a series of X-phenyl 2,4,6-trinitrophenyl ethers [X = H; 2-, 3-, 4-CH3; 2,4-, or 2,6-(CH3)2] a–f, and the results compared with those of the corresponding nitro derivatives. In the methyl series, kinetic data show that increasing substitution reduces drastically the rates of reactions indicative of the operation of some kind of steric effect. The unfavorable

  动力学研究报道了一系列 X-苯基 2,4,6-三硝基苯基醚 [X = H; 2-、3-、4-CH3；2,4- 或 2,6-( )2] a-f，并将结果与​​相应的硝基衍生物的结果进行比较。在甲基系列中，动力学数据表明，增加取代会大大降低反应速率，这表明某种空间效应的作用。反应中心不利的空间拥挤似乎对确定反应的动力学顺序并不重要。通常，二级速率常数 kA 线性依赖于亲核试剂浓度的平方。在硝基衍生物中观察到的动力学形式的变化可能主要是由于该基团的吸电子效应。然而，对于 2,6-二硝基衍生物，未催化的途径 k2 占据了所有的反应通量。分子间质子从碱基转移到中间体的醚氧的空间位阻足以使碱基催化途径相对于k2途径无关紧要。© 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 744–750, 2005
• Kinetics of the reaction of phenyl picrates with phenoxide ions in water. Concerted or stepwise?
  作者：Michael R. Crampton、Ian A. Robotham

  DOI：10.1002/poc.3172

  日期：2013.12

  A kinetic study is reported of the exchange reactions of substituted phenoxide ions with some ring‐substituted 2,4,6‐trinitrophenyl ethers in water. The βrønsted diagrams formed by plotting log k, where k is the second‐order rate constant for reaction, versus pKa show a distinct change in slope when ΔpKa = 0 (ΔpKa being the difference in pKa values of the leaving group and nucleophile). This is consistent

  动力学研究报道了取代的酚盐离子与一些环取代的2,4,6-三硝基苯基醚在水中的交换反应。通过绘制日志形成的βrønsted图ķ，其中ķ为反应二阶速率常数，相对于p ķ一个示出斜率的显着变化时ΔP ķ一个 = 0（ΔP ķ一个为P中的差ķ一个离去基团和亲核试剂的值）。这与包含离散σ加合物中间体而非协调过程的两步过程一致。根据正向和反向过程的测得的β值，已构建了总体有效电荷图。版权所有©2013 John Wiley＆Sons，Ltd.
• Etching-enhanced Ablation and the Formation of a Microstructure in Silicon by Laser Irradiation in an SF₆ Atmosphere
  作者：S. Jesse、A. J. Pedraza、J. D. Fowlkes、J. D. Budai

  DOI：10.1557/jmr.2002.0148

  日期：2002.5

  Sequential pulsed-laser irradiation of silicon in SF⁶ atmospheres induced the formation of an ensemble of microholes and microcones. Profilometry measurements and direct imaging with an intensifying charge-coupled device camera were used to study the evolution of this microstructure and the laser-generated plume. Both the partial pressure of SF⁶ and the total pressure of an SF⁶-inert gas mixture strongly influenced the maximum height that the microcones attained over the initial surface. The cones first grew continuously with the number of pulses, reached a maximum, and then began to recede as the number of laser pulses increased further. The growth of the cones was closely connected with the evolution of the laser-generated plume.

  在SF6气氛中对硅进行连续脉冲激光辐照，诱导形成了一系列微孔和微锥。轮廓仪测量和电荷耦合器件相机直接成像被用来研究这种微结构的演变和激光产生的羽流。SF6 的分压和 SF6 惰性气体混合物的总压都对微锥在初始表面上达到的最大高度有很大影响。随着脉冲数的增加，微锥开始持续增长，达到最大值，然后随着激光脉冲数的进一步增加开始后退。微锥的增长与激光产生的羽流的演变密切相关。