2,4-dihydroxylamino-6-nitrotoluene | 185376-54-9

• 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: 2,4-dihydroxylamino-6-nitrotoluene
• 英文别名: N-[3-(hydroxyamino)-4-methyl-5-nitrophenyl]hydroxylamine
• CAS: 185376-54-9
• 化学式: C₇H₉N₃O₄
• 分子量: 199.166
• InChiKey: CJOXQEXJXBLWDP-UHFFFAOYSA-N

物化性质

• 沸点：
  365.4±52.0 °C(Predicted)
• 密度：
  1.681±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 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：
  110
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,4-dihydroxylamino-6-nitrotoluene 在 biological components of crude cell extract Clostridium acetobutylicum 、 氢气 作用下， 以 水 为溶剂， 反应 24.0h， 生成 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene
  参考文献：
  名称：

  Bamberger Rearrangement during TNT Metabolism by Clostridium acetobutylicum

  摘要：

  Studies were conducted to isolate and identify polar and oxygen-sensitive intermediates of 2,4,6-trinitrotoluene (TNT) transformation by Clostridium acetobutylicum. Studies conducted in anaerobic cell extracts demonstrated that a polar product formed from the transformation of 2,4-dihydroxylamino-6-nitrotoluene by a mechanism known as the Bamberger rearrangement. The product was stabilized by derivatization with acetic anhydride, and the structure was confirmed by mass spectroscopy, (1)H NMR, and IR spectroscopy techniques. The reaction occurred in the presence of cell extract and H(2) but did not occur in cell extract-free controls. From spectroscopic data, the product of 2,4-dihydroxylamino-6-nitrotoluene rearrangement was identified as either 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) or 2-hydroxylamino-4-amino-5-hydroxyl-6-nitrotoluene (6-amino-4-hydroxylamino-3-methyl-2-nitrophenol). Acid-catalyzed rearrangement of 2,4-dihydroxylamino-6-nitrotoluene resulted in a single product, which after derivatization, was identical to a derivatized product from cell extracts. Acid-catalyzed Bamberger rearrangement occurs with the hydroxyl addition para to the participating hydroxylamine, indicating that the 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) was the product isolated form cell extracts. This product was also confirmed in whole cell systems that had been fed TNT. Following derivatization of the culture broth, a product was isolated that was identical to hose isolated from crude cell extracts and acid catalysis experiments.

  DOI：

  10.1021/es970612s
• 作为产物：
  描述：

  2-羟基氨基-4,6-二硝基甲苯 、 4-羟基氨基-2,6-二硝基甲苯 在 Clostridium acetobutylicum 、 氢气 作用下， 以 甲醇 、 水 为溶剂， 反应 24.0h， 以93%的产率得到2,4-dihydroxylamino-6-nitrotoluene
  参考文献：
  名称：

  Bamberger Rearrangement during TNT Metabolism by Clostridium acetobutylicum

  摘要：

  Studies were conducted to isolate and identify polar and oxygen-sensitive intermediates of 2,4,6-trinitrotoluene (TNT) transformation by Clostridium acetobutylicum. Studies conducted in anaerobic cell extracts demonstrated that a polar product formed from the transformation of 2,4-dihydroxylamino-6-nitrotoluene by a mechanism known as the Bamberger rearrangement. The product was stabilized by derivatization with acetic anhydride, and the structure was confirmed by mass spectroscopy, (1)H NMR, and IR spectroscopy techniques. The reaction occurred in the presence of cell extract and H(2) but did not occur in cell extract-free controls. From spectroscopic data, the product of 2,4-dihydroxylamino-6-nitrotoluene rearrangement was identified as either 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) or 2-hydroxylamino-4-amino-5-hydroxyl-6-nitrotoluene (6-amino-4-hydroxylamino-3-methyl-2-nitrophenol). Acid-catalyzed rearrangement of 2,4-dihydroxylamino-6-nitrotoluene resulted in a single product, which after derivatization, was identical to a derivatized product from cell extracts. Acid-catalyzed Bamberger rearrangement occurs with the hydroxyl addition para to the participating hydroxylamine, indicating that the 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) was the product isolated form cell extracts. This product was also confirmed in whole cell systems that had been fed TNT. Following derivatization of the culture broth, a product was isolated that was identical to hose isolated from crude cell extracts and acid catalysis experiments.

  DOI：

  10.1021/es970612s

文献信息

• NITRO-BASED EXPLOSIVE REMEDIATION
  申请人：Craig A. Morrie

  公开号：US20110052537A1

  公开（公告）日：2011-03-03

  Embodiments of techniques for remediating soil contaminated with compounds, particularly nitro-based explosives, are disclosed. Plants capable of taking up the compounds are grown within contaminated soil for a period of time. The plants are exposed to anaerobic microbes in the rumen of a ruminant animal. The ruminal anaerobic microbes degrade the remediable compounds and render them substantially nontoxic to the animal. In some embodiments, the remediable compounds are nitroaromatic compounds, and are degraded by nitroreductases. In other embodiments, microbes are transferred from a consortium enriched in microbes capable of degrading the remediable compounds to a ruminant animal that lacks microbes capable of degrading the remediable compounds. In other embodiments, methods for isolating and identifying ruminal anaerobic microbes capable of degrading remediable compounds are disclosed.

  本发明揭示了一种用于修复含有化合物的土壤，特别是含有硝基炸药的技术实施方案。在受污染的土壤中种植能够吸收这些化合物的植物，一段时间后，将这些植物暴露在反刍动物瘤胃内的厌氧微生物中。瘤胃内的厌氧微生物降解可修复的化合物，并使其在动物体内基本无毒。在某些实施方案中，可修复的化合物是硝基芳香化合物，并通过硝基还原酶降解。在其他实施方案中，从富含能够降解可修复化合物的微生物群落中转移微生物到缺乏能力降解可修复化合物的反刍动物体内。在其他实施方案中，揭示了用于分离和鉴定能够降解可修复化合物的瘤胃内厌氧微生物的方法。
• Probe compound for detecting and isolating enzymes and means and methods using the same
  申请人：Helmholtz-Zentrum für Infektionsforschung GmbH

  公开号：EP2230312A1

  公开（公告）日：2010-09-22

  The present invention relates to a probe compound that can comprise any substrate or metabolite of an enzymatic reaction in addition to an indicator component, such as, for example, a fluorescence dye, or the like. Moreover, the present invention relates to means for detecting enzymes in form of an array, which comprises any number of probe compounds of the invention which each comprise a different metabolite of interconnected metabolites representing the central pathways in all forms of life. Moreover, the present invention relates to a method for detecting enzymes involving the application of cell extracts or the like to the array of the invention which leads to reproducible enzymatic reactions with the substrates. These specific enzymatic reactions trigger the indicator (e.g. a fluorescence signal) and bind the enzymes to the respective cognate substrates. Moreover, the invention relates to means for isolating enzymes in form of nanoparticles coated with the probe compound of the invention. The immobilisation of the cognate substrates or metabolites on the surface of nanoparticles by means of the probe compounds allows capturing and isolating the respective enzyme, e.g. for subsequent sequencing.

  本发明涉及一种探针化合物，它可以包括酶反应的任何底物或代谢物，此外还包括指示成分，例如荧光染料或类似物。此外，本发明还涉及以阵列形式检测酶的方法，该阵列由任意数量的本发明探针化合物组成，每种探针化合物由代表所有生命形式中中心途径的相互关联的代谢物中的不同代谢物组成。此外，本发明还涉及一种检测酶的方法，该方法涉及将细胞提取物或类似物应用于本发明的阵列，从而导致与底物发生可重复的酶反应。这些特定的酶反应会触发指示剂（如荧光信号），并将酶与各自的同源底物结合。此外，本发明还涉及以涂覆有本发明探针化合物的纳米颗粒形式分离酶的方法。通过探针化合物将同源底物或代谢物固定在纳米颗粒表面，可以捕获和分离相应的酶，例如用于后续测序。
• Characterization of Oxidation Products of TNT Metabolism in Aquatic Phytoremediation Systems of <i>Myriophyllum</i> <i>aquaticum</i>
  作者：R. Bhadra、R. J. Spanggord、D. G. Wayment、J. B. Hughes、J. V. Shanks

  DOI：10.1021/es990436i

  日期：1999.10.1

  TNT transformation processes in sediment-free, "natural", aquatic phytoremediation systems of Myriophyllum aquaticum were investigated with specific interest in oxidation products. Extraction procedures combining liquid-liquid extractions and solid-phase extractions were developed for the isolation of the mostly acidic, oxidized TNT metabolites. Six compounds unique from the reduction products of TNT were isolated and characterized by UV-vis, H-1, and C-13 NMR spectroscopy, by mass spectroscopy, and by chemical synthesis where feasible. These compounds include 2-amino-4,6-dinitrobenzoic acid, 2,4-dinitro-6-hydroxy-benzyl alcohol, 2-N-acetoxyamino-4,6-dinitrobenzaldehyde, 2,4-dinitro-6-hydroxytoluene, and two binuclear metabolites unique from the customary azoxytetranitro-toluenes. The monoaryl compounds show clear evidence of oxidative transformations, methyl oxidation and/or aromatic hydroxylation. It is possible that oxidative transformation(s) preceded nitro reduction since studies on exposure of M. aquaticum to either 2-amino-4,6-dinitrotoluene or 4-amino-2,6-dinitrotoluene did not yield any of the oxidation products identified here. The accumulation of oxidation products was significant: 2-amino-4,6-dinitrobenzoic acid, 4.4%; 2,4-dinitro-6-hydroxy-benzyl alcohol, 8.1%; 2-N-acetoxyamino-4,6-dinitrobenzaldehyde, 7.8%; and, 2,4-dinitro-6-hydroxytoluene, 15.6%. The binuclear metabolites accounted for an estimated 5.6%. This study is the first direct evidence for oxidative transformations in aquatic phytoremediation systems.
• Bamberger Rearrangement during TNT Metabolism by <i>Clostridium acetobutylicum</i>
  作者：J. B. Hughes、C. Wang、K. Yesland、A. Richardson、R. Bhadra、G. Bennett、F. Rudolph

  DOI：10.1021/es970612s

  日期：1998.2.1

  Studies were conducted to isolate and identify polar and oxygen-sensitive intermediates of 2,4,6-trinitrotoluene (TNT) transformation by Clostridium acetobutylicum. Studies conducted in anaerobic cell extracts demonstrated that a polar product formed from the transformation of 2,4-dihydroxylamino-6-nitrotoluene by a mechanism known as the Bamberger rearrangement. The product was stabilized by derivatization with acetic anhydride, and the structure was confirmed by mass spectroscopy, (1)H NMR, and IR spectroscopy techniques. The reaction occurred in the presence of cell extract and H(2) but did not occur in cell extract-free controls. From spectroscopic data, the product of 2,4-dihydroxylamino-6-nitrotoluene rearrangement was identified as either 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) or 2-hydroxylamino-4-amino-5-hydroxyl-6-nitrotoluene (6-amino-4-hydroxylamino-3-methyl-2-nitrophenol). Acid-catalyzed rearrangement of 2,4-dihydroxylamino-6-nitrotoluene resulted in a single product, which after derivatization, was identical to a derivatized product from cell extracts. Acid-catalyzed Bamberger rearrangement occurs with the hydroxyl addition para to the participating hydroxylamine, indicating that the 2-amino-4-hydroxylamino-5-hydroxyl-6-nitrotoluene (4-amino-6-hydroxylamino-3-methyl-2-nitrophenol) was the product isolated form cell extracts. This product was also confirmed in whole cell systems that had been fed TNT. Following derivatization of the culture broth, a product was isolated that was identical to hose isolated from crude cell extracts and acid catalysis experiments.