(Z)-O-methyl-p-nitrobenzohydroximoyl chloride | 41071-37-8

• 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: (Z)-O-methyl-p-nitrobenzohydroximoyl chloride
• 英文别名: (Z)-O-methyl-4-nitrobenzohydroximoyl chloride；N-methoxy-4-nitrobenzenecarboximidoyl chloride；(1Z)-N-methoxy-4-nitrobenzenecarboximidoyl chloride
• CAS: 41071-37-8
• 化学式: C₈H₇ClN₂O₃
• 分子量: 214.608
• InChiKey: ZPUNURBDCBQXAC-NTMALXAHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  67.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (Z)-O-methyl-p-nitrobenzohydroximoyl chloride 在 盐酸 、 铁粉 作用下， 以 乙醇 、 水 为溶剂， 反应 3.0h， 以35%的产率得到(Z)-O-methyl-4-aminobenzohydroximoyl chloride
  参考文献：
  名称：

  Synthesis and methemoglobinemia-inducing properties of analogues of para-aminopropiophenone designed as humane rodenticides

  摘要：

  A number of structural analogues of the known toxicant para-aminopropiophenone (PAPP) have been prepared and evaluated for their capacity to induce methemoglobinemia-with a view to their possible application as humane pest control agents. It was found that an optimal lipophilicity for the formation of methemoglobin (metHb) in vitro existed for alkyl analogues of PAPP (aminophenones 1-20; compound 6 metHb% = 74.1 +/- 2). Besides lipophilicity, this structural sub-class suggested there were certain structural requirements for activity, with both branched (10-16) and cyclic (17-20) alkyl analogues exhibiting inferior in vitro metHb induction. Of the four candidates (compounds 4, 6, 13 and 23) evaluated in vivo, 4 exhibited the greatest toxicity. In parallel, aminophenone bioisosteres, including oximes 30-32, sulfoxide 33, sulfone 34 and sulfonamides 35-36, were found to be inferior metHb inducers to lead ketone 4. Closer examination of Hammett substituent constants suggests that a particular combination of the field and resonance parameters may be significant with respect to the redox mechanisms behind PAPPs metHb toxicity. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2013.10.046
• 作为产物：
  描述：

  (E)-4-硝基苯甲醛O-甲基肟 在 N-氯代丁二酰亚胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 以39%的产率得到(Z)-O-methyl-p-nitrobenzohydroximoyl chloride
  参考文献：
  名称：

  Synthesis and methemoglobinemia-inducing properties of analogues of para-aminopropiophenone designed as humane rodenticides

  摘要：

  A number of structural analogues of the known toxicant para-aminopropiophenone (PAPP) have been prepared and evaluated for their capacity to induce methemoglobinemia-with a view to their possible application as humane pest control agents. It was found that an optimal lipophilicity for the formation of methemoglobin (metHb) in vitro existed for alkyl analogues of PAPP (aminophenones 1-20; compound 6 metHb% = 74.1 +/- 2). Besides lipophilicity, this structural sub-class suggested there were certain structural requirements for activity, with both branched (10-16) and cyclic (17-20) alkyl analogues exhibiting inferior in vitro metHb induction. Of the four candidates (compounds 4, 6, 13 and 23) evaluated in vivo, 4 exhibited the greatest toxicity. In parallel, aminophenone bioisosteres, including oximes 30-32, sulfoxide 33, sulfone 34 and sulfonamides 35-36, were found to be inferior metHb inducers to lead ketone 4. Closer examination of Hammett substituent constants suggests that a particular combination of the field and resonance parameters may be significant with respect to the redox mechanisms behind PAPPs metHb toxicity. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2013.10.046

文献信息

• Mechanisms of Acid-Catalyzed <i>Z</i>/<i>E</i> Isomerization of Imines
  作者：James E. Johnson、Nora M. Morales、Andrea M. Gorczyca、Debra D. Dolliver、Michael A. McAllister

  DOI：10.1021/jo010067k

  日期：2001.11.1

  The kinetics and mechanism of acid-catalyzed Z/E isomerization of O-methylbenzohydroximoyl chloride (1Za and 1Ea), methyl O-methylbenzohydroximate (1Zb and 1Eb), ethyl O-methylbenzohydroximate (1Zc and 1Ec and five para and meta substituted derivatives), O-methylcinnamohydroximoyl chloride (2Za and 2Ea), and methyl O-methylcinnamohydroximate (2Zb and 2Zb) have been investigated. The kinetics of Z/E

  酸催化O-甲基苯并氢氧肟基氯（1Za和1Ea），O-甲基苯并氢肟酸甲酯（1Zb和1Eb），O-甲基苯并氢肟酸乙酯（1Zc和1Ec以及五种对位和间位取代的衍生物）的Z / E异构化动力学和机理，研究了O-甲基肉桂氢氧肟基氯（2Za和2Ea）和O-甲基肉桂氢氧肟酸甲酯（2Zb和2Zb）。这些亚胺的Z / E异构化动力学已在冰醋酸（1Ea和1Zc）和含HCl，三氟甲磺酸或四氟硼酸（1Ea，1Zb，2Ea和2Zb）的二恶烷溶液中进行了研究。异构化是通过（a）围绕质子化亚胺的碳-氮双键旋转（亚胺离子旋转）或（b）对质子化亚胺的亲核攻击形成四面体中间体而经历立体突变和亲核体损失（亲核催化）。羟肟基氯1Ea和2Ea仅通过亲核催化机理进行异构化。羟肟酸酯1Zb似乎能够通过任一机理异构化。羟肟酸酯2Zb可以仅通过亚胺离子旋转进行异构化。理论计算支持以下观念：质子化亚胺中的共轭增加会提高亚胺离子旋转的速率。氢
• Mechanism of bimolecular substitution reactions of hydroximoyl halides with amines in actonitrile solution
  作者：James E. Johnson、Susan M. Dutson、Debra D. Dolliver、Susan L. Todd、Martha Hotema

  DOI：10.1002/poc.610080505

  日期：1995.5

  ρ-value (with σ) for the reaction with pyrrolidine is +0·92. The reaction of the p-nitro compound with pyrrolidine gives a significant element effect [k(p-nitrobenzohydroximoyl bromide)/k(p)-nitrobenzohydroximoyl chloride = 10]. A Brϕonsted β-value of 0·38 was estimated from the reactions of morpholine and piperidine with the p-nitrohydroximoyl chloride. The slower reaction of (E)-O-methyl-p-nitrobenzohydroximoyl

  （Z）-O-甲基苯并氢氧氯化物[ArC（Cl）NOCH 3 ]在乙腈溶液中与吗啉，吡咯烷和氮杂环丁烷反应，得到相应的（Z）-氨基肟[ArC（NR 1 R 2）NOCH 3 ]在乙腈中的反应。这些反应的速率是在拟一级条件（过量胺）下测量的。发现反应遵循总体二级动力学（在胺中一级）。与吡咯烷反应的哈米特ρ值（带有σ）为+ 0·92。对硝基化合物与吡咯烷的反应产生了显着的元素效应[ k（p-硝基苯甲氧基肟基溴化物/ k（p）-硝基苯甲氧基肟基氯＝ 10]。从吗啉和哌啶与对-硝基羟肟基氯的反应估计布朗斯通的β值为0·38 。（E）-O-甲基-对硝基苯并氧肟基氯与氮杂环丁烷的较慢反应主要产生（E）-ami胺肟（E：Z≈98：2）此反应也遵循二级动力学。将该研究中的动力学观察结果与在苯溶液中早期工作中获得的相应结果进行比较。建议在乙腈溶液中，反应通过加成消除机理进行，该速率决定氯离子的损失速率（A N
• Mechanism of solvolysis reactions of O-methylbenzohydroximoyl halides. Stereoelectronic control in formation of and nucleophilic addition to nitrilium ions
  作者：James E. Johnson、Sravanthi C. Cornell

  DOI：10.1021/jo01309a015

  日期：1980.10
• Mechanisms of alkoxide substitution reactions at the carbon-nitrogen double bond. Stereoelectronic control during nucleophilic substitution
  作者：James Elver Johnson、Elizabeth Ann Nalley、Charles Weidig、Mohammed Arfan

  DOI：10.1021/jo00331a008

  日期：1981.8
• Mechanism of amine and amide ion substitution reactions at the carbon-nitrogen double bond
  作者：James Elver Johnson、Abdolkarim Ghafouripour、Mohammad Arfan、Susan L. Todd、Deborah A. Sitz

  DOI：10.1021/jo00218a021

  日期：1985.9

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