O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine | 72915-12-9

• 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: O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine
• 英文别名: PFBHA；pentafluorobenzylhydroxylamine；O-[(2,3,4,5,6-pentafluorophenyl)methyl]hydroxylamine
• CAS: 72915-12-9
• 化学式: C₇H₄F₅NO
• 分子量: 213.107
• InChiKey: UOISMTPJFYEVBW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  35.2
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine 在 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.67h， 生成 4-methoxy-1-((perfluorophenyl)methoxy)indolin-2-one
  参考文献：
  名称：

  Metal- and Oxidant-Free Modular Approach To Access N-Alkoxy Oxindoles via Aryne Annulation

  摘要：

  An unprecedented metal- and oxidant-free (intermolecular) approach to access N-alkoxy oxindoles via [3 + 2] cycloadition of in situ generated electrophilic species viz. aryne and (putative) aza-oxyallyl cation is reported. This approach is amenable to both C3-unsubstituted as well as C3-substituted oxindoles. A one-pot manipulation further makes this reaction highly practical. The versatility of this approach was demonstrated through valuable synthetic transformations.

  DOI：

  10.1021/acs.orglett.8b01972
• 作为产物：
  描述：

  α-溴-2,3,4,5,6-五氟甲基苯酸酯 在 一水合肼 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 为溶剂， 反应 4.0h， 生成 O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine
  参考文献：
  名称：

  铑催化重氮酰胺环化合成N-(2,3,4,5,6-五氟苄氧基)-γ-内酰胺

  摘要：

  描述了 N-(2,3,4,5,6-五氟-苄氧基) 重氮酰胺的铑催化环化，产生相应的 γ-内酰胺。环化基于分子内催化插入 C-H 键。获得了 14 种内酰胺，产率高达 91%，ee 高达 88%。加巴喷丁盐酸盐，一种 GABA 类似物，也通过这种方法合成，这表明 2,3,4,5,6-五氟苄氧基的脱保护是可能的。

  DOI：

  10.1002/ejoc.201402571

文献信息

• LC−MS Analysis of Carbonyl Compounds and Their Occurrence in Diesel Emissions
  作者：Chris A. Jakober、M. Judith Charles、Michael J. Kleeman、Peter G. Green

  DOI：10.1021/ac060301c

  日期：2006.7.1

  carbonyls investigated. For all but five of the carbonyls examined, a pseudomolecular (M + H)+ ion is the base peak in the APCI positive ion mass spectra of PFBHA oxime derivatives and is observed in four of the five exceptions. Application of the evaluated analysis methodology to heavy-duty diesel source emissions facilitated the quantification of 10 aliphatic carbonyls (5 C5-C9 ketones, 4 C6 unsaturated

  液相色谱结合大气压化学电离（APCI）离子阱质谱（ITMS）被应用于大气中与气溶胶有关的羰基化合物。给出了以未衍生和O-（2,3,4,5,6-五氟苄基）羟胺（PFBHA）肟形式分析的24种模型化合物的正负离子检测质谱的表征。PFBHA衍生化的加入增强了许多被研究的羰基化合物的检测和灵敏度。对于除五个以外的所有羰基，在PFBHA肟衍生物的APCI正离子质谱图中，假分子（M + H）+离子是基峰，在五个例外中的四个中均观察到。将评估的分析方法应用于重型柴油机排放源，有助于定量10种脂肪族羰基（5个C5-C9酮，4个C6不饱和酮，1个C6二羰基）和14个芳族羰基（1个C9醛，5个C8-C13酮） ，8个C6-C14醌）。测量了气相和颗粒相羰基化合物的柴油卡车发动机排放因子，范围为0.55-540 microg km（-1）。气相色谱排放因子与ITMS气相色谱分析结果吻合良好。
• Identification and Quantification of Aerosol Polar Oxygenated Compounds Bearing Carboxylic or Hydroxyl Groups. 1. Method Development
  作者：M. Jaoui、T. E. Kleindienst、M. Lewandowski、E. O. Edney

  DOI：10.1021/ac049919h

  日期：2004.8.1

  In this study, a new analytical technique was developed for the identification and quantification of multifunctional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) of the multifunctional compound using an alcohol (e.g., methanol, 1-butanol) in the presence of a relatively strong Lewis acid (BF3) as a catalyst. This esterification reaction quickly and quantitatively converts carboxylic acids to their ester forms. The second step is based on silylation of the ester compounds using bis(trimethylsilyl) trifluoroacetamide (BSTFA) as the derivatizing agent. For compounds bearing ketone groups in addition to carboxylic and hydroxyl groups, a third step was used based on PFBHA derivatization of the carbonyls. Different parameters including temperature, reaction time, and effect due to artifacts were optimized. A GC/MS in EI and in methane-CI mode was used for the analysis of these compounds. The new approach was tested on a number of multifunctional compounds. The interpretation of their EI (70 eV) and CI mass spectra shows that critical information is gained leading to unambiguous identification of unknown compounds. For example, when derivatized only with BF3−methanol, their mass spectra comprise primary ions at m/z M•+ + 1, M•+ + 29, and M•+ − 31 for compounds bearing only carboxylic groups and M•+ + 1, M•+ + 29, M•+ − 31, and M+. − 17 for those bearing hydroxyl and carboxylic groups. However, when a second derivatization (BSTFA) was used, compounds bearing hydroxyl and carboxylic groups simultaneously show, in addition to the ions observed before, ions at m/z M•+ + 73, M•+ − 15, M•+ − 59, M•+ − 75, M•+ − 89, and 73. To the best of our knowledge, this technique describes systematically for the first time a method for identifying multifunctional oxygenated compounds containing simultaneously one or more hydroxyl and carboxylic acid groups.

  在本研究中，开发了一种新的分析技术，用于鉴定和定量含有至少一个羟基或一个羧基或两者的多官能团化合物。该技术基于首先使用醇（例如甲醇、1-丁醇）在相对较强的路易斯酸（BF3）催化下对多官能团化合物的羧基进行衍生化。这种酯化反应迅速且定量地将羧酸转化为酯形式。第二步是使用双(三甲基硅基)三氟乙酰胺（BSTFA）作为衍生化剂对酯化合物进行硅烷化。对于除羧基和羟基外还含有酮基的化合物，采用了基于PFBHA对羰基进行衍生化的第三步。优化了包括温度、反应时间和因人工产物引起的影响等多个参数。使用电子轰击源（EI）和甲烷化学电离（CI）模式的气相色谱/质谱法（GC/MS）分析了这些化合物。对多种多官能团化合物测试了新方法。对其EI（70 eV）和CI质谱的解释表明，获得了关键信息，从而能够明确鉴定未知化合物。例如，仅通过 −甲醇衍生化时，它们的质谱包含仅含有羧基的化合物的离子m/z M•+ + 1、M•+ + 29和M•+ − 31，以及同时含有羟基和羧基的化合物的离子m/z M•+ + 1、M•+ + 29、M•+ − 31和M•+ − 17。然而，当使用第二步衍生化（BSTFA）时，同时含有羟基和羧基的化合物除了之前观察到的离子外，还显示出m/z M•+ + 73、M•+ − 15、M•+ − 59、M•+ − 75、M•+ − 89和73的离子。据我们所知，这项技术首次系统地描述了一种鉴定同时含有一个或多个羟基和羧酸基团的多官能团含氧化合物的方法。
• Henry's Law Constants of Carbonyl−Pentafluorobenzyl Hydroxylamine (PFBHA) Derivatives in Aqueous Solution
  作者：Hugo Destaillats、M. Judith Charles

  DOI：10.1021/je025545i

  日期：2002.11.1

  components in urban and rural atmospheres. The design of efficient samplers based on aqueous solutions of the derivatization reagent O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) requires knowledge of how the carbonyl−PFBHA derivatives partition between water and air. We have determined the Henry's law constant at 25 °C for 16 PFBHA derivatives of carbonyls that represent typical analytes present

  空气中羰基化合物的原位衍生化可以提高旨在量化城市和农村大气中这些痕量成分的采样方法的效率。基于衍生试剂O-（2,3,4,5,6-五氟苄基）羟胺（PFBHA）的水溶液的高效采样器的设计需要知道羰基-PFBHA衍生物如何在水和空气之间分配。我们已经确定了代表在环境中存在的典型分析物的16种羰基PFBHA衍生物在25°C下的亨利定律常数。采用惰性气体汽提方法，然后通过GC-离子阱质谱法（GC / ITMS）测量衍生物的水溶液浓度。亨利定律常数的取值范围是（37至268）Pa·m3 ·mol -1。我们评估了几个分子描述符，以研究这些化合物的分配行为的定量结构-性质关系（QSPR）。分子体积，分子表面积和极化率与k H更好地相关，而偶极矩被证明是极不敏感的描述子。评估了K H在（5至25）°C范围内的温度依赖性。这些数据导致的估计Δ ħ ∞和Δ小号∞，其范围为从Δ ħ ∞ =（17至60）千焦·摩尔-1和Δ小号∞
• A Remarkable Oxidative Cascade That Replaces the Riboflavin C8 Methyl with an Amino Group during Roseoflavin Biosynthesis
  作者：Isita Jhulki、Prem K. Chanani、Sameh H. Abdelwahed、Tadhg P. Begley

  DOI：10.1021/jacs.6b02469

  日期：2016.7.13

  Roseoflavin is a naturally occurring riboflavin analogue with antibiotic properties. It is biosynthesized from riboflavin in a reaction involving replacement of the C8 methyl with a dimethylamino group. Herein we report the identification of a flavin-dependent enzyme that converts flavin mononucleotide (FMN) and glutamate to 8-amino-FMN via the intermediacy of 8-formyl-FMN. A mechanistic proposal for

  玫瑰黄素是一种天然存在的核黄素类似物，具有抗生素特性。它是由核黄素在涉及用二甲氨基取代 C8 甲基的反应中生物合成的。在此，我们报告了一种黄素依赖性酶的鉴定，该酶通过 8-甲酰基-FMN 的中介作用将黄素单核苷酸 (FMN) 和谷氨酸转化为 8-氨基-FMN。提出了针对这一显着转变的机械建议。
• Detection limits of electron and electron capture negative ionization-mass spectrometry for aldehydes derivatized with <i>o</i>-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride
  作者：Josef Beránek、Darrin A. Muggli、Alena Kubátová

  DOI：10.1016/j.jasms.2009.12.009

  日期：2010.4.1

  In contrast to common expectations, the differences in limits of detection (LODs) between electron capture negative ionization (ECNI) and electron ionization (EI) mass spectrometry (MS) were found to be insignificant for a wide range of aldehydes derivatized with o-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride. Comparison of the two ionization methods based on LOD confidence intervals revealed that a traditional presentation of the LOD or limit of quantitation (LOQ) as a single value may over/underestimate the significance of obtained results. LODs were between 20 and 150 pg injected for the majority of tested derivatized carbonyls using both ionization methods. ECNI-MS improved LODs by ∼10- to 20-fold only for two derivatized aldehydes, 4-hydroxybenzaldehyde and 5-(hydroxymethyl)furfural. Selectivity of ECNI did not appear to be beneficial when analyzing a wood smoke particulate matter (WS-PM) extract, possibly because the majority of interferences were removed during sample preparation (i.e., liquid-liquid extraction). The impact of four different data acquisition modes of transmission quadrupole (TQ)-MS on LODs and their precisions was also investigated. As expected, LODs in the selected ion monitoring (SIM) were ∼two to four times lower than those obtained using total ion current (TIC) mode. More importantly, TQ-MS in the selected ion-total ion (SITI) mode (i.e., acquiring SIM and TIC data in a single analysis) provided signal-to-noise ratios and precisions, which were comparable to SIM alone.

  与常见预期相反，电子捕获负离子化（ECNI）和电子离子化（EI）质谱（MS）在检测限（LOD）方面的差异，对于一系列与o-(2,3,4,5,6-五氟苯基)-羟胺盐酸盐衍生化的醛类物质，发现并不显著。基于LOD置信区间对这两种离子化方法的比较显示，传统将LOD或定量限（LOQ）呈现为单一值的方法，可能会高估或低估所获得结果的重要性。使用这两种离子化方法测试的大多数衍生化羰基物质的LOD在20到150皮克克之间。ECNI-MS仅对两个衍生化醛类物质，即4-羟基苯甲醛和5-(羟甲基)呋喃醛，将LOD提高了约10到20倍。ECNI的选择性在分析木烟颗粒物（WS-PM）提取物时似乎并不有利，这可能是因为在样品准备过程中（即液-液提取）大多数干扰物质已被去除。还调查了四种不同数据采集模式下的传输四极杆（TQ）-MS对LOD及其精度的影响。正如预期的那样，选择离子监测（SIM）模式下的LOD大约比使用总离子流（TIC）模式获得的值低两到四倍。更重要的是，TQ-MS在选择离子-总离子（SITI）模式下（即在一次分析中同时获得SIM和TIC数据）提供的信噪比和精度与单独的SIM相当。

表征谱图