2,4,6-trinitro(α,αα-D3)toluene | 52886-05-2

• 英文名称: 2,4,6-trinitro(α,αα-D3)toluene
• 英文别名: 2,4,6-trinitrotoluene-α,α,α-d3；2,4,6-trinitrotoluene-α-d₃；2,4,6-Trinitrotoluene-d₃；2,4,6-trinitrotoluene-α-d3；1,3,5-trinitro-2-trideuteriomethyl-benzene；2,4,6-Trinitrotoluol-α,α,α-d3；1,3,5-Trinitro-2-(trideuteriomethyl)benzene
• CAS: 52886-05-2
• 化学式: C₇H₅N₃O₆
• 分子量: 230.109
• InChiKey: SPSSULHKWOKEEL-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,4,6-trinitro(α,αα-D3)toluene 在 sodium hypochlorite 、 氘氧化钠 作用下， 以 氘代甲醇 、 重水 为溶剂， 反应 0.17h， 以74%的产率得到2,4,6-trinitro(α,α-D2)benzyl chloride
  参考文献：
  名称：

  Dagley, Ian J., Australian Journal of Chemistry, 1988, vol. 41, # 6, p. 855 - 861

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4-二硝基甲苯 在 氘代丙酮 、 氘代甲醇-d 、 硫酸 、 重水 、 硝酸 、 三乙胺 作用下， 反应 3.5h， 生成 2,4,6-trinitro(α,αα-D3)toluene
  参考文献：
  名称：

  同位素标记的2,4,6-三硝基甲苯的合成及高分辨率质谱分析

  摘要：

  DOI：

  10.1021/je00035a030

文献信息

• Kinetic study of proton/deuteron transfer reactions of 2,4,6-trinitrotoluene and its derivatives with tertiary amines
  作者：Yoshimi Sueishi、Takanori Fujimoto、Tohru Yoshida、Takeharu Kurita、Shunzo Yamamoto、Norio Nishimura

  DOI：10.1002/poc.610080602

  日期：1995.6

  parameteres were calculated semi-empirically on the basis of Bell's theory. The observed rate constants at low temperatures agreed well with the predicted values. In the present systems, some side and consecutive reactions involving the formation of 2,2′,4,4′6,6′-hexanitrostilbene took place, and in some cases interrupted the rate measurements in the proton/deuteron transfer steps.

  2,4,6-三硝基甲苯（TNT），2,2'4,4'6,6'-六硝基联苄（HNBB）和2,4,6-三硝基苄基氯（TNB）的质子/氘代转移反应速率分光光度法跟踪叔胺。根据同位素，溶剂和空间效应解释了在各种条件下获得的速率常数。TNT和TNB在低温下的Arrhenius曲线向上弯曲，清楚地表明了隧道效应。隧道参数是根据Bell理论半经验地计算的。在低温下观察到的速率常数与预测值非常吻合。在本系统中，发生了涉及形成2,2'，4,4'6,6'-六硝基二苯乙烯的副反应和连续反应，并且在某些情况下中断了质子/氘核转移步骤中的速率测量。
• Solvent, pressure, and deuterium isotope effects on proton tunnelling. The reaction between 2,4,6-trinitrotoluene and 1,8-diazabicyclo[5.4.0]undec-7-ene in aprotic solvents
  作者：Naoki Sugimoto、Muneo Sasaki、Jiro Osugi

  DOI：10.1039/p29840000655

  日期：——

  Proton tunnelling has been examined for the reaction between 2,4,6-trinitrotoluene and 1,8-diazabicyclo-[5.4.0]undec-7-ene in several aprotic solvents (acetonitrile, benzonitrile, 1,2-dichloroethane, and dichloromethane) in view of the solvent and pressure effects on the rate ratio kH/kD. The reaction rates have been measured in the range 1–1 000 bar, at 25 °C by a high-pressure stopped-flow method

  质子隧穿已研究了2,4,6-三硝基甲苯和1,8-二氮杂双环-[5.4.0]十一碳-7-烯在几种非质子传递溶剂（乙腈，苄腈，1,2-二氯乙烷和二氯甲烷中）之间的反应）考虑到溶剂和压力对比率k H / k D的影响。通过高压停止流方法在25°C下测得的反应速率在1-1 000 bar范围内。在所有这些溶剂中的反应速率比k H / k D均大于主要动力学同位素效应的半经典极限，并显示出显着的隧穿作用。此外，随着压力从1 bar增加到1000 bar，比率k H /25°C下的k D在乙腈中从19.1降低到16.9，在苄腈中从15.9降低到15.0，在1,2-二氯乙烷中从29.9降低到22.5。然而，在所有这些溶剂中，转移颗粒的有效质量随压力的增加被计算为大致相同。
• Kinetics and tunneling in the proton- and deuteron-transfer reaction between 2,4,6-trinitrotoluene and 1,8-diazabicyclo[5.4.0]undec-7-ene in some aprotic solvents
  作者：Naoki Sugimoto、Muneo Sasaki、Jiro Osugi

  DOI：10.1021/j100214a031

  日期：1982.8
• Pressure effect on tunneling of the proton- and deuteron-transfer reaction of 2,4,6-trinitrotoluene with 1,8-diazabicyclo[5.4.0]undec-7-ene in acetonitrile
  作者：Naoki Sugimoto、Muneo Sasaki、Jiro Osugi

  DOI：10.1021/ja00364a036

  日期：1983.12
• Speciation of the Products of and Establishing the Role of Water in the Reaction of TNT with Hydroxide and Amines: Structure, Kinetics, and Computational Results
  作者：Christopher A. Latendresse、Syrena C. Fernandes、Sangmin You、William B. Euler

  DOI：10.1021/jp408992n

  日期：2013.11.7

  The reaction of trinitrotoluene (TNT) with bases has been investigated by NMR and visible spectroscopy methods. Hydroxide ion was found to react in one of two ways, either by deprotonation of the methyl group or by nucleophilic attack on the aromatic ring to form a sigma adduct. The rate of each mode of reaction depends upon the polarity of the solvent. In tetrahydrofuran (THF), a adduct formation is rapid and the long-term equilibrium product is deprotonation of the methyl group. When the solvent is methanol (MeOH), the two reactions have similar rates and the sigma adduct becomes the majority product. Amines were found to be ineffective in directly deprotonating TNT or in forming sigma adducts. Rather, the amines react with ambient water to generate hydroxide ion, which then reacts with TNT. The solvent choice and water content are crucial to understanding the reactivity of bases with TNT. To assist in the interpretation of the experimental results, computational analysis was performed at the B3LYP/6-311+G**//HF/6-311+G** level to determine the thermodynamics of the reactions of TNT. The SM8 implicit solvation model was applied to converged geometries and suggested a strong solvation effect upon product formation. Thermodynamic analysis suggested a significant preference of alkoxide or hydroxide attack versus amine attack in any modeled dielectric, consistent with the experimental observations.