phenylnitrenium ion | 62-53-3

• 物质功能分类: 有机原料 - 氨基化合物 - 环烷胺、芳香单胺、芳香多胺及其衍生物和盐
• 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: phenylnitrenium ion
• 英文别名: aniline cation
• CAS: 62-53-3
• 化学式: C₆H₇N
• 分子量: 93.1283
• InChiKey: JCBHOUXAWBOKPN-UHFFFAOYSA-N

物化性质

• 熔点：
  -6 °C (lit.)
• 沸点：
  184 °C (lit.)
• 密度：
  1.022 g/mL at 25 °C (lit.)
• 蒸气密度：
  3.22 (185 °C, vs air)
• 闪点：
  76 °C
• 溶解度：
  可溶于水
• 介电常数：
  7.8（0℃）
• 暴露限值：
  TLV-TWA skin 2 ppm (～8 mg/m3) (ACGIH), 5 ppm (～19 mg/m3) (MSHA, OSHA, and NIOSH); IDLH 100 ppm (NIOSH).
• LogP：
  0.900

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  0

安全信息

• 职业暴露限值：
  TWA: None ppm
• TSCA：
  Yes
• 危险等级：
  6.1
• 立即威胁生命和健康浓度：
  100 ppm
• 危险品标志：
  T
• 安全说明：
  S26,S27,S36/37,S36/37/39,S45,S46,S61,S63
• 危险类别码：
  R40,R43,R68,R48/23/24/25,R23/24/25,R50,R41
• WGK Germany：
  2
• 海关编码：
  2921411000
• 危险品运输编号：
  UN 1547 6.1/PG 2
• 危险类别：
  6.1
• RTECS号：
  BW6650000
• 包装等级：
  II
• 危险标志：
  GHS05,GHS06,GHS08,GHS09
• 危险性描述：
  H301 + H311 + H331,H317,H318,H341,H351,H372,H410
• 危险性防范说明：
  P260,P280,P302 + P352 + P312,P304 + P340 + P312,P305 + P351 + P338 + P310

制备方法与用途

这段文本主要介绍了苯胺的生产方法、用途、性质及相关安全信息。

生产方法

• 铁粉还原法：硝基苯用铁粉还原，反应液用石灰中和、洗涤后经蒸馏得成品。
• 加氢还原法：硝基苯在铜催化剂存在下，在沸腾床反应器中进行气相加氢还原，得到粗苯胺。该方法目前是国内外采用的主要生产方法。

用途

1. 作为弱碱使用：

   • 能以氢氧化物的形态沉淀三价和四价元素（如Fe3+、Al3+、Cr3+）的易水解盐类，使与难水解的二价元素（Mn2+）的盐类分离。

2. 显微晶分析：用于检验能生成硫氰酸络合阴离子或其他阴离子（如Cu、Mg、Ni、Co、Zn、Cd、Mo、W、V）的元素。

3. 其他用途：

   • 检验卤素、铬酸盐、钒酸盐、亚硝酸盐和羧酸等。
   • 用作溶剂。
   • 在有机合成及染料制造中应用广泛。

性质

• 毒性分级：高毒
• 急性毒性：
  • 大鼠口服LD50: 250 毫克/ 公斤；
  • 小鼠口服LD50: 464 毫克/ 公斤。
• 刺激数据：
  • 皮肤接触：兔子 20 毫克/ 24小时 中度
  • 眼睛接触：兔子 20 毫克/ 24小时 中度
• 爆炸和燃烧特性：
  • 与空气混合可爆。
  • 与氧化剂反应剧烈。
  • 明火、高温或强氧化剂下易燃，高热分解会产生有毒氮氧化物气体。

安全储存运输

• 库房应通风、低温干燥。
• 需要与其他危险化学品（尤其是氧化剂）分开存放。

灭火方式

• 可使用泡沫灭火器、二氧化碳灭火器或干粉灭火器进行灭火。

反应信息

• 作为反应物：
  描述：

  phenylnitrenium ion 生成 氢氰酸 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  The dissociation dynamics of state selected metastable aniline ions by single and multiphoton ionization

  摘要：

  The lifetimes with respect to dissociation of state selected aniline ions have been investigated by photoion–photoelectron coincidence. Lifetimes between 0.3 and 100 μs have been found when the aniline ion is prepared in energies ranging from 13.6 to 12.6 eV, respectively. These lifetimes are in good agreement with those of a recent study by Proch, Rider, and Zare, who observed metastable aniline ions in a UV multiphoton ionization (MPI) study in which three photons were required to reach the metastable ion energy range. By contrast, our visible MPI study of aniline shows no evidence for long-lived ions. This paradox is resolved by postulating that under the UV MPI conditions, a radiationless transition to the ground electronic state allows the 13 eV ions time to dissociate slowly, while under the much higher photon intensities needed in the visible MPI study, rapid up pumping of the excited ions prevents radiationless transitions. A lower limit for the radiationless transition rate of 2×108 s−1 is derived.

  DOI：

  10.1063/1.443148
• 作为产物：
  描述：

  苯 在 iron imido monocation 作用下， 生成 phenylnitrenium ion
  参考文献：
  名称：

  过渡金属-亚氨基和-氮烯离子络合物的气相化学。氨中氮氢键的氧化加成和 NH 从金属中心转移到烯烃

  摘要：

  本文报道了许多裸过渡金属-氮烯和-亚胺离子配合物MNH/sup +/ 的气相化学。第 3、4 和 5 族原子金属离子在热能下与 NH/sub 3/ 反应，通过脱氢生成 MNH/sup +/。提出了一种反应机制，包括对 NH 键的初始氧化加成，类似于为气态原子金属离子与碳氢化合物的反应提出的机制。Cr/sup +/ 通过缓慢缩合与 NH/sub 3/ 反应形成 CrNH/sub 3//sup +/，所有 6-11 族原子金属离子也是如此。然而，激发态 Cr/sup +/ 通过键插入反应与 NH/sub 3/ 反应形成 CrNH/sub 2//sup +/ 和 CrNH/sup +/。Cr/sup +/ 的一种未知亚稳态电子状态，由铬箔的直接激光解吸产生，反应的效率比动力学激发的 Cr/sup +/ 高得多。FeO/sup +/ 与NH/sub 3/ 反应生成FeNH/sup +/，同时失去H/sub

  DOI：

  10.1021/ja00228a002

文献信息

• Mass-Spectrometric Study on Ion-Molecule Reactions of CF₃⁺with Nitrogen-Containing Benzene Derivatives, Pyridine, Pyrrole, and Acetonitrile at Near-Thermal Energy
  作者：Masaharu Tsuji、Masato Aizawa、Hiroki Ujita、Yukio Nishimura

  DOI：10.1246/bcsj.68.2385

  日期：1995.8

  The gas-phase ion-molecule reactions of CF3+ with nitrogen-containing benzene derivatives (C6H5Y : Y = NH2, NO2, and CN), pyridine, pyrrole, and acetonitrile have been studied at near-thermal energy using an ion-beam apparatus. The major product channels are charge transfer for aniline (71.7 ± 0.5%), O− abstraction for nitrobenzene (91.7 ± 0.5%), electrophilic addition leading to initial adduct ions

  已经使用离子束装置在接近热能下研究了 CF3+ 与含氮苯衍生物（C6H5Y：Y = NH2、NO2 和 CN）、吡啶、吡咯和乙腈的气相离子分子反应。主要的产物通道是苯胺的电荷转移 (71.7 ± 0.5%)、硝基苯的 O− 提取 (91.7 ± 0.5%)、亲电加成导致苯甲腈的初始加成离子 (97.5 ± 0.8%)、乙腈 (100%)、和吡啶 (94.8 ± 0.4%)，以及亲电加成，然后用 HF 消除吡咯 (80.0 ± 1.4%)。基于产物离子分布和反应途径能量的理论计算讨论了反应机理。
• Photoinduced Five‐Component Radical Relay Aminocarbonylation of Alkenes
  作者：Bin Lu、Zhihan Zhang、Min Jiang、Dong Liang、Zi‐Wei He、Feng‐Shuo Bao、Wen‐Jing Xiao、Jia‐Rong Chen

  DOI：10.1002/anie.202309460

  日期：2023.10.9

  Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, and have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double carbonylation reactions has remained a substantial challenge, particularly for the more advanced multicomponent variants, despite their great potential value. Herein, we report a visible‐light‐driven radical relay five‐component radical double aminocarbonylation reaction of unactivated alkenes using CO under metal‐free conditions. This protocol provides direct access to valuable γ‐trifluoromethyl α‐ketoamides with good yields and high chemoselectivity. Crucial was the identification of distinct dual roles of amine coupling partners, sequentially acting as electron donors for the formation of photoactive electron donor‐acceptor (EDA) complexes with radical precursors and then as a CO acceptor via nitrogen radical cations to form carbamoyl radicals. Cross‐coupling of carbamoyl radicals with the acyl radicals that are formed in an alkene‐based relay process affords double aminocarbonylation products.

  摘要 与一氧化碳发生的自由基单羰基化反应是利用现有化学品制备各种羰基化合物的一种直接而稳健的策略，在过去几十年中已得到广泛研究。然而，实现受控自由基双羰基化反应的高选择性催化系统仍然是一个巨大的挑战，特别是对于更先进的多组分变体，尽管它们具有巨大的潜在价值。在此，我们报告了在无金属条件下使用 CO 对未活化烯烃进行可见光驱动的自由基中继五组分自由基双氨羰基化反应。该方法可直接获得有价值的γ-三氟甲基α-酮酰胺，且收率高、化学选择性强。最关键的是确定了胺偶联物的独特双重作用：先作为电子供体与自由基前体形成光活性电子供体-受体（EDA）复合物，然后通过氮自由基阳离子作为 CO 受体形成氨基甲酰基。氨基甲酰基与在烯基中继过程中形成的酰基发生交叉偶联，产生双氨基羰基化产物。
• Benzene as a selective chemical ionization reagent gas
  作者：Charles Allgood、Yi Lin、Yee-Chung Ma、Burnaby Munson

  DOI：10.1002/oms.1210251003

  日期：1990.10

  AbstractDilute mixtures of C6H6 or C6D6 in He provide abundant [C6H6]+· or [C6D6]+· ions and small amounts of [C6H7]+ or [C6D7]+ ions as chemical ionization (CI) reagent ions. The C6H6 or C6D6 CI spectra of alkylbenzenes and alkylanilines contain predominantly M+· ions from reactions of [C6H6]+· or [C6D6]+· and small amounts of MH+ or MD+ ions from reactions of [C6H7]+ or [C6D7]+. Benzene CI spectra of aliphatic amines contain M+·, fragment ions and sample‐size‐dependent MH+ ions from sample ion‐sample molecules reactions. The C6D6 CI spectra of substituted pyridines contain M+· and MD+ ions in different ratios depending on the substituent (which alters the ionization energy of the substituted pyridine), as well as sample‐size‐dependent MH+ ions from sample ion‐sample molecule reactions. Two mechanisms are observed for the formation of MD+ ions: proton transfer from [C6D6]+· or charge transfer from [C6D6]+· to give M+·, followed by deuteron transfer from C6D6 to M+·. The mechanisms of reactions were established by ion cyclotron resonance (ICR) experiments. Proton transfer from [C6H6]+· or [C6D6]+· is rapid only for compounds for which proton transfer is exothermic and charge transfer is endothermic. For compounds for which both charge transfer and proton transfer are exothermic, charge transfer is the almost exclusive reaction.
• Investigating the Mechanisms of Aromatic Amine-Induced Protein Free Radical Formation by Quantitative Structure−Activity Relationships: Implications for Drug-Induced Agranulocytosis
  作者：Arno G. Siraki、JinJie Jiang、Ronald P. Mason

  DOI：10.1021/tx900432d

  日期：2010.5.17

  Aromatic amine drugs have been associated with agranulocytosis (neutrophil depletion) for which the mechanism is unknown. We have previously shown that the metabolism of two aromatic amine drugs by human myeloperoxidase (MPO) results in phenyl radical metabolite formation and also in protein free radical formation on MPO. Because the concentration of drug required to produce a maximum signal for MPO protein free radical (MPO(center dot)) detection was different for each drug, this prompted us to consider that other aromatic amines may also show varying degrees of ability to induce MPO(center dot) formation. Immunoassay experiments using the immuno-spin-trapping technique were performed, which evaluated the potency of different aromatic amines containing the aniline substructure to generate the MPO(center dot). Each reaction contained equal amounts of H(2)O(2), 5,5-dimethyl-1-pyrroline-N-oxide, MPO, and variable concentrations of aniline derivatives. Several physicochemical parameters for aniline derivatives were used to derive quantitative structure-activity relationship equations, which showed that the Hammett constant (sigma) best correlated with the MPO(center dot) formation for all aniline derivatives. More statistically robust equations were derived if the anilines were separated into mono- and disubstituted groups. However, some aniline derivatives did not induce MPO(center dot) formation. Using electron spin resonance spectroscopy, we evaluated the ability of all aniline derivatives tested to produce phenyl radical metabolites, as previously shown by spin trapping for the aromatic amine drugs. Interestingly, we found that only those aniline derivatives that produced a phenyl radical also formed MPO(center dot). We propose that the phenyl radical is the reactive free radical metabolite responsible for generating the MPO(center dot).
• Spin-orbit coupling induced magnetic field effects in electron-transfer reactions with excited triplets: the role of triplet exciplexes and radical pairs in geminate recombination
  作者：Ulrich E. Steiner、Werner Haas

  DOI：10.1021/j100158a003

  日期：1991.3

  The magnetic field dependence of free-radical yield in the electron-transfer quenching of methylene blue triplet by p-iodoaniline has been determined between 0.00 and 3.30 T in methanol/ethylene glycol mixtures of various viscosities by using laser flash spectroscopy and a photostationary flow technique. The observed decrease of the free-radical yield with the magnetic field is interpreted by heavy-atom-induced spin-orbit coupling causing magnetic field sensitivity according to the triplet mechanism (TM) in intermediate triplet exciplexes and to the DELTA-g type radical pair mechanism (RPM) in geminate triplet radical pairs originating from dissociation of the triplet exciplexes. Analytical expressions are provided for a treatment of a combination of both mechanisms including the case of reversible formation of the triplet exciplex from the geminate radical pair. The formalism of Pedersen developed for the high field radical pair mechanism and modified by Vollenweider and Fischer to account for effects of exchange interaction is generalized to include various boundary conditions for the electron spin density matrix suggested in the literature to describe the effects of encounters and chemical reaction. With a physically consistent choice of TM and RPM parameters model calculations provide a very good quantitative fit of the observed magnetic field and viscosity dependence of the yield of free radicals.