2,4-dichlorophenyl nitrone | 53548-18-8

• 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: 2,4-dichlorophenyl nitrone
• 英文别名: N-phenyl-C-(2,4-dichlorophenyl)nitrone；2,4-Dichlorbenzyliden-anilin-N-oxyd; Nitron；1-(2,4-dichlorophenyl)-N-phenylmethanimine oxide
• CAS: 53548-18-8
• 化学式: C₁₃H₉Cl₂NO
• 分子量: 266.127
• InChiKey: HUEMILSYRIWOAB-UHFFFAOYSA-N

物化性质

• 熔点：
  92-93 °C
• 沸点：
  408.3±55.0 °C(Predicted)
• 密度：
  1.352±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,4-dichlorophenyl nitrone 、 依达拉奉 在 dodecatungstosilic acid 作用下， 以 乙醇 、 水 为溶剂， 反应 0.33h， 以90%的产率得到4,4′-[(2,4-dichlorophenyl)methylene]-bis(3-methyl-1-phenyl-1H-pyrazol-5-ol)
  参考文献：
  名称：

  An Unexpected Catalytic Synthesis of Novel and Known Bis(Pyrazolyl) Methanes by the use of α-aryl-N-phenyl Nitrones in Aqueous Media

  摘要：

  在一定量的硅钨酸催化下，在 EtOH/H2O 溶液中，芳基 N-苯基硝基腈与 3-甲基-1-苯基-2-吡唑啉-5-酮反应，意外地得到了高产率的双(3-羟基-1-苯基吡唑基)芳基甲烷，而不是两种可能的 1,3-加成产物。这是首次报道通过硝基化合物和吡唑啉-5-酮反应合成双（3-羟基-1-苯基吡唑基）芳基甲烷。文中提出了这一过程的可能机理。

  DOI：

  10.3184/174751914x14114871789226
• 作为产物：
  描述：

  硝基苯 在 氯化铵 、 锌 作用下， 以 乙醇 为溶剂， 生成 2,4-dichlorophenyl nitrone
  参考文献：
  名称：

  An Unexpected Catalytic Synthesis of Novel and Known Bis(Pyrazolyl) Methanes by the use of α-aryl-N-phenyl Nitrones in Aqueous Media

  摘要：

  在一定量的硅钨酸催化下，在 EtOH/H2O 溶液中，芳基 N-苯基硝基腈与 3-甲基-1-苯基-2-吡唑啉-5-酮反应，意外地得到了高产率的双(3-羟基-1-苯基吡唑基)芳基甲烷，而不是两种可能的 1,3-加成产物。这是首次报道通过硝基化合物和吡唑啉-5-酮反应合成双（3-羟基-1-苯基吡唑基）芳基甲烷。文中提出了这一过程的可能机理。

  DOI：

  10.3184/174751914x14114871789226

文献信息

• Trimethylsilyl chloride promoted synthesis of α-branched amines by nucleophilic addition of organozinc halides to nitrones
  作者：Ying Fu、Yanhua Liu、Yaojuan Chen、Helmut M. Hügel、Minzhu Wang、Danfeng Huang、Yulai Hu

  DOI：10.1039/c2ob26202a

  日期：——

  general procedure for the nucleophilic addition of organozinc halides with nitrones in the presence of trimethylsilyl chloride has been developed. Trimethylsilyl chloride was found to be both an indispensable reaction promoter and a ready hydroxylamine protective agent in these reactions. The produced O-(trimethylsilyl)hydroxylamines can be easily reduced into corresponding amines just by a zinc–copper

  在乙腈存在下进行有机卤化物与硝基亲核加成的一般程序。 三甲基氯硅烷 已经被开发出来。 三甲基氯硅烷在这些反应中，发现其既是必不可少的反应促进剂又是现成的羟胺保护剂。只需在饱和的NH 4 Cl水溶液中进行锌铜偶联，即可将生成的O-（三甲基甲硅烷基）羟胺轻松还原为相应的胺。
• Microwave-Assisted Stereoselective 1,3-Dipolar Cycloaddition of C,N-Diarylnitrone (i.e., N-(Arylmethylidene)benzenamine N-Oxide) and Bis(arylmethylidene)acetone (=1,5-Diarylpenta-1,4-dien-3-one): NMR and Crystal Analysis of Diastereoisomeric Bis(isoxazoli
  作者：Nidhin Paul、Selvam Kaladevi、Shanmugam Muthusubramanian

  DOI：10.1002/hlca.201100263

  日期：2012.1

  Microwave‐assisted stereoselective 1,3‐dipolar cycloaddition of C,N‐diarylnitrones (i.e., N‐(arylmethylidene)benzenamine N‐oxides) 2 to substituted bis(arylmethylidene)acetones (=1,5‐diarylpenta‐1,4‐dien‐3‐ones) 1 leading to diastereoisomer pairs of bis‐isoxazolidines 3 and 4 in good to excellent yield is described (Scheme 2 and Table 2). The configuration outcome of the reaction is discussed based on the NMR and

  微波辅助将C，N-二芳基硝酮（即N-（芳基亚甲基）苯甲胺N-氧化物）2立体选择性1,3-偶极环加成（= 1,5-二芳基戊-1,4-丁） ‐3‐ones）1描述了以良好或优异的收率生成双异氰酸酯3和4的非对映异构体对（方案2和表2）。基于产物的NMR和X射线数据讨论了反应的构型结果。
• Esters of Feist's Acid: Some Insights into the Electronic Structure and Reactivity of Methylenecyclopropanes Ring-Substituted with Acceptor Groups
  作者：Vyacheslav V. Diev、Tran Q. Tung、Alexander P. Molchanov

  DOI：10.1002/ejoc.200800975

  日期：2009.2

  π-HOMO energies by substitution with an acceptor group. B3LYP calculations of addends and transition states forthe interaction of methylenecyclopropane with C,N-diphenylnitrone correctly predict regiochemical outcome. However, B3LYP calculations do not account for the observed regiochemical outcome and diminished reactivity in reactions of Feist's esters with C,N-diphenylnitrone.(© Wiley-VCH Verlag GmbH

  C-芳基-N-芳基-或N-甲基硝酮与Feist酸（3-亚甲基环丙烷-反式-1,2-二羧酸）的酯发生1,3-偶极环加成反应，形成相应的螺[环丙烷-1 ,4-异恶唑烷]环加合物作为单一异构体，产率范围为 17-59%。与未取代的亚甲基环丙烷的环加成相比，该反应以相反的区域化学结果进行。与亚甲基环丙烷相比，Feist 酯对与硝酮的环加成反应的活性明显较低，并且反应需要在高温下长时间加热。通过分子光电子能谱和理论计算 (HF/6-31G*, B3LYP/6-31G*) 研究了 Feist 酯的电子结构。两个都，Feist 酯的测量光电子 HeI 光谱和基态计算 (HF/6-31G*) 表明，通过用受体基团取代，亚甲基环丙烷 π-HOMO 能量显着降低。亚甲基环丙烷与 C,N-二苯基硝酮相互作用的加数和过渡态的 B3LYP 计算正确预测区域化学结果。然而，B3LYP 计算没有考虑观察到的区域化学结果和
• Silver-Assisted [3 + 2] Annulation of Nitrones with Isocyanides: Synthesis of 2,3,4-Trisubstituted 1,2,4-Oxadiazolidin-5-ones
  作者：Xuanyu Shen、Andrey Shatskiy、Yan Chen、Markus D. Kärkäs、Xiang-Shan Wang、Jian-Quan Liu

  DOI：10.1021/acs.joc.9b03279

  日期：2020.3.6

  A silver-assisted method for [3 + 2] annulation of nitrones with isocyanides has been developed. The developed protocol allows access to a variety of 2,3,4-trisubstituted 1,2,4-oxadiazolidin-S-one derivatives as single diastereomers in good to excellent yields using silver oxide as the catalyst and molecular oxygen as the terminal oxidant. A plausible mechanism involving a nucleophilic addition/cyclization/protodeargentation/oxidation pathway is proposed on the basis of experimental results.
• Cycloadditions of nitrile oxides and nitrones to 4,4-methylene-1-methylpiperidine: Studies in regio- and stereoselectivity
  作者：L. Fišera、F. Sauter、J. Fröhlich、Y. Feng、P. Ertl、K. Mereiter

  DOI：10.1007/bf00811848

  日期：1994.5

  A series of spiro-substituted isoxazole derivatives were synthesized by 1,3-dipolar cycloadditions of nitrile oxides and nitrones to 4,4-methylene-1-methylpiperidine. Since nmr studies confirmed that only one regioisomer was formed selectively, semi-empirical quantum mechanical methods (AM1) were used to rationalize this regiochemical preference via calculation and inspection of HOMO-LUMO-energy and coefficients. X-ray structure analysis carried out for one of these products showed the occurrence of only one stereoisomer, explicable by comparing AM1-calculated DELTAH(f)-values of all possible cycloadducts.