3-(α,α,α-Trifluoromethyl)nitrobenzene radical anion | 34526-71-1

• 物质功能分类: 有机原料 - 有机氟化合物 - 氟甲苯系列
• 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-(α,α,α-Trifluoromethyl)nitrobenzene radical anion
• 英文别名: m-(trifluoromethyl)nitrobenzene anion
• CAS: 34526-71-1；98-46-4
• 化学式: C₇H₄F₃NO₂
• 分子量: 191.109
• InChiKey: HVWMLEFLPVWXEF-UHFFFAOYSA-N

物化性质

• 熔点：
  -5 °C
• 沸点：
  200-205 °C(lit.)
• 密度：
  1.436 g/mL at 25 °C(lit.)
• 闪点：
  190 °F
• 暴露限值：
  ACGIH: TWA 2.5 mg/m3NIOSH: IDLH 250 mg/m3

计算性质

• 辛醇/水分配系数(LogP)：
  2.36
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  46.2
• 氢给体数：
  0.0
• 氢受体数：
  2.0

安全信息

• TSCA：
  Yes
• 危险等级：
  6.1

制备方法与用途

化学性质 

本品为无色液体，b.p.200～205℃，n²⁰_D 1.4720，相对密度1.436，f.p.87℃，溶于乙醇、乙醚、苯、甲苯等溶剂。

用途 

3-三氟甲基硝基苯是除草剂氟草隆、氟咯草酮和吡氟苯胺的中间体，也是医药氟灭酸丁酯、莫尼氟酯、氟沙伦、莫尼弗乙酯、三氟噻嗪、氟奋乃静、三氟丙嗪等的中间体。

用途 

用于有机合成。在医药上用于合成苄氟噻嗪等。

用途 

用作医药、农药、染料中间体

生产方法 

由三氟甲苯经硝化而得。将浓硫酸加入反应锅内，在搅拌冷却下加入发烟硫酸及浓硝酸，加热至40℃，滴加三氯甲苯，控制温度40-45℃。加毕，在50-55℃反应3h，冷至室温，静置分去下层酸液。上层液放入5倍量冰水中，静置分层，分出的硝基物用2%碳酸钠溶液及水洗涤，即得间硝基三氟甲苯。收率接近93%。

生产方法 

其制备方法是在反应瓶中加入浓硫酸、浓硝酸，开动搅拌，滴加三氟甲苯，控制反应温度在50℃左右，滴加完后再继续搅拌反应2 h，然后静置分层，分出废酸，有机相依次用水、碱和水洗涤至pH=7～8，粗产品中约含间位体91%、邻位体6.8％、对位体2.0％，将粗产物进行分馏得3-三氟甲基硝基苯。

类别

有毒物品

毒性分级

中毒

急性毒性

口服-大鼠 LD50: 610 毫克/公斤; 口服-小鼠 LD50: 520 毫克/公斤

可燃性危险特性

可燃; 受热分解有毒氟化物及氧化氮气体

储运特性

库房通风低温干燥; 与氧化剂, 食品分开储运

灭火剂

雾状水, 泡沫, 二氧化碳

职业标准

STEL 1 毫克/立方米

反应信息

• 作为反应物：
  描述：

  3-(α,α,α-Trifluoromethyl)nitrobenzene radical anion 在 水 、 dioxide titanium 、 异丙醇 作用下， 生成 间硝基三氟甲苯
  参考文献：
  名称：

  Photocatalytic Reduction of Nitroorganics over Illuminated Titanium Dioxide:  Electron Transfer between Excited-State TiO₂ and Nitroaromatics

  摘要：

  The present study investigates the steady-state photocatalytic reduction of methyl viologen and a suite of monosubstituted nitrobenzenes. Reduction was carried out in deoxygenated, illuminated aqueous slurries of titanium dioxide (Degussa P25) in the presence of a sacrificial electron donor, 2-propanol. Langmuir-Hinshelwood plots were obtained for the reduction of each compound and found to be linear, with an average correlation of 0.98 and with a standard deviation on the correlations of 0.02. The concentration independent rates for nitroaromatic reduction obtained from these plots were normalized against the rate of methyl viologen reduction, and the ratio was used to solve for the rate constant of nitroaromatic reduction, assuming a bimolecular model. The assumptions behind this procedure were tested by the use of the Marcus expression. Using the reorganization energy for the reaction as the fitting variable, it was possible to fit the measured rates to the predicted rates with a reorganization energy of 138 kJ/mol.

  DOI：

  10.1021/jp973224l
• 作为产物：
  描述：

  间硝基三氟甲苯 在 e(-) 作用下， 生成 3-(α,α,α-Trifluoromethyl)nitrobenzene radical anion
  参考文献：
  名称：

  气相电子转移平衡引起的熵变和电子亲和力：A- + B = A + B-

  摘要：

  DOI：

  10.1021/j100403a037

文献信息

• Electron affinities from electron-transfer equilibria: A- + B = A + B-
  作者：Eric P. Grimsrud、Gary Caldwell、Swapan Chowdhury、Paul Kebarle

  DOI：10.1021/ja00302a005

  日期：1985.8

  L'etude est faite pour 34 composes, principalement des nitrobenzenes substitues, des quinones substituees et des molecules conjuguees contenant des atomes d'oxygene

  L'练习曲EST faite倾34层构成，principalement DES硝基苯subSTitues，脱醌subSTituees和des分子conjuguees contenant DES atomes D'OXYGENE
• Gas-phase electron-transfer reactions between selected molecular anions and halogenated methanes
  作者：W. B. Knighton、E. P. Grimsrud

  DOI：10.1021/ja00033a006

  日期：1992.3

  The products and rate constants for the thermal gas-phase reactions of eight halogenated methanes (RX), including CCl 4 , CFCl 3 , CF 2 Cl 2 , CHCl 3 , CH 3 I, CCl 3 Br, CF 2 Br 2 , and CH 2 Br 2 , with selected molecular anions (A - ), including azulene(-), nitrobenzene(-), and several substituted nitrobenzenes(-), are reported. The electron affinities of the donor molecules (A) range from 16 kcal

  八种卤代甲烷 (RX) 的热气相反应产物和速率常数，包括 CCl 4 、CFCl 3 、CF 2 Cl 2 、CHCl 3 、CH 3 I、CCl 3 Br、CF 2 Br 2 和 CH 2 Br 2 具有选定的分子阴离子 (A - )，包括薁(-)、硝基苯(-) 和几种取代的硝基苯(-)。供体分子 (A) 的电子亲合力范围从 16 kcal mol -1 的 azulene 到 46 kcal mol -1 的对二硝基苯
• Resonance Electron Capture Rate Constants for Substituted Nitrobenzenes
  作者：W. B. Knighton、R. S. Mock、D. S. McGrew、E. P. Grimsrud

  DOI：10.1021/j100065a036

  日期：1994.4

  We report here a new method for the determination of electron capture (EC) rate constants that utilizes a pulsed electron beam mass spectrometer. The method is first tested by measurements of the known dissociative electron capture rate constants for several halogenated methanes that have been extensively studied by other techniques. The resonance electron capture (REC) rate constants of nitrobenzene (NB) and 23 substituted nitrobenzenes (SNB's) are then determined for the first time at 125 degrees C in 10 Torr of methane buffer gas. The SNB's studied here include several sets of closely related structural isomers whose electron affinities (EA's) have been previously determined. It is shown that the REC rate constants of these compounds bear little systematic relationship with the EA's of these compounds. The REC rate constants of the SNB's are also compared with other previously reported characteristics associated with the negative ionization of these compounds, including their entropies of negative ionization, the lifetimes against autodetachment of their initially formed molecular anions, and the rates of autodetachment from electronically excited states of their molecular anions.
• Electron affinities of di- and tetracyanoethylene and cyanobenzenes based on measurements of gas-phase electron-transfer equilibria
  作者：Swapan. Chowdhury、Paul. Kebarle

  DOI：10.1021/ja00278a014

  日期：1986.9
• Electron affinity of SF₆ and perfluoromethylcyclohexane. The unusual kinetics of electron transfer reactions A⁻+B=A+B⁻, where A=SF₆ or perfluorinated cyclo‐alkanes
  作者：E. P. Grimsrud、S. Chowdhury、P. Kebarle

  DOI：10.1063/1.449468

  日期：1985.8

  Measurements of the equilibria (1): A−+B=A+B− with a pulsed electron high pressure mass spectrometer lead to ΔG01, ΔH01, and ΔS01. Equilibria involving SF6 as A and perfluoromethylcyclohexane C7F14 provide electron affinities E.A.(SF6)=1.05±0.1 eV and E.A.(C7F14)=1.06±0.15 eV. The kinetics of reactions (1) involving the above two compounds were studied. The rate constants kf for SF−6 +B=SF6+B− were found to increase with exothermicity of the reaction. The temperature dependence for kf was determined. B compounds leading to high exothermicities were associated with kf at the collision limit and essentially no temperature dependence. B of progressively lower electron affinity led to kf below the collision limit and negative temperature dependence, while B with the lowest E.A. but still leading to exothermic reaction produced lowest kf with positive temperature dependence. A model is provided explaining the above behavior. The known large change of geometry between SF−6 and SF6 introduces an internal barrier in the reaction coordinate for the reactions (1) involving SF6.