4-iodo-1-methyl-3-nitropyrazole | 75092-34-1

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 4-iodo-1-methyl-3-nitropyrazole
• 英文别名: 4-iodo-1-methyl-3-nitro-1H-pyrazole
• CAS: 75092-34-1
• 化学式: C₄H₄IN₃O₂
• mdl: MFCD00465281
• 分子量: 252.999
• InChiKey: JEPMYVGWQWTBSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  63.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-iodo-1-methyl-3-nitropyrazole 在 盐酸 、 tin(ll) chloride 作用下， 以 水 为溶剂， 反应 2.0h， 以51%的产率得到N-甲基-3-氨基吡唑
  参考文献：
  名称：

  Synthesis of vicinal aminoiodo- and (acetylamino)iodo-l-alkylpyrazoles

  摘要：

  3- and 5-(Acetylamino)-4-iodo-1-alkylpyrazoles were obtained by successive acylation and iodination from 3- and 5-amino-1-alkylpyrazoles without isolating intermediate (acetylamino)pyrazoles. 3- and 5-Iodo- and 3,5-diiodo-4-amino-1-methylpyrazoles were synthesized from appropriate iodonitropyrazoles by reduction with SnCl2 in HCl.

  DOI：

  10.1007/bf01431121
• 作为产物：
  描述：

  1-甲基-3-硝基吡唑 在 potassium iodate 、 硫酸 、 potassium iodide 作用下， 以 四氯化碳 、 水 为溶剂， 反应 3.0h， 以58.7%的产率得到4-iodo-1-methyl-3-nitropyrazole
  参考文献：
  名称：

  Efficient iodination of structurally varying pyrazoles in heterophase medium

  摘要：

  通过在异相（H2O/CHCl3 (CCl4)）介质中，使用KI-KIO3体系和H2SO4添加剂对吡唑及其衍生物进行碘化，成功合成了4-碘取代的吡唑。吡唑、3,5-二甲基吡唑、吡唑-3(5)-羧酸、1-甲基吡唑-3-羧酸、1-甲基吡唑-5-羧酸、3-硝基吡唑、1-甲基-3-硝基吡唑、1-甲基吡唑、1-乙基吡唑和1-异丙基吡唑的4-碘取代吡唑的产率在80%至97%之间，而3-硝基吡唑-5-羧酸的产率为32%。

  DOI：

  10.1007/s11172-013-0140-z

文献信息

• Peculiarities of copper(I)- and palladium-catalyzed cross-coupling of terminal alkynes with vicinal amino- and (N-acetylamino)-iodopyrazoles. Synthesis of alkynylaminopyrazoles
  作者：Eugene V. Tretyakov、David W. Knight、Sergei F. Vasilevsky

  DOI：10.1039/a903754c

  日期：——

  A number of vicinal amino- and (N-acetylamino)-alkylpyrazoles have been synthesized by cross-coupling reactions of iodopyrazoles with alk-1-ynes using a combination of Pd(PPh3)2Cl2 and CuI as catalyst in Et3N or with copper acetylides. The latter Stephens–Castro reaction of copper acetylides with these amino- and (N-acetylamino)-iodopyrazoles was established as a common method for the preparation of (N-acetylamino)alkynylpyrazoles. The Pd/Cu-catalyzed cross-coupling of iodopyrazoles (Sonogashira reaction) with alk-1-ynes bearing electron-releasing substituents was unsuitable for the synthesis of alkynylpyrazoles: 3- and 5-iodopyrazoles were unreactive but, in the case of 4-iodo derivatives, reductive deiodination, accompanied by homocoupling of the alk-1-yne component, was the only reaction.

  通过使用Pd(PPh3)2Cl2和CuI作为催化剂在Et3N中，或与铜炔化物的组合，合成了一系列邻位氨基和（N-乙酰氨基）烷基吡唑。这种铜炔化物与这些氨基和（N-乙酰氨基）碘吡唑的斯蒂芬斯-卡斯特罗反应被确立为制备（N-乙酰氨基）炔基吡唑的常用方法。使用Pd/Cu催化的碘吡唑（索诺加希拉反应）与具有电子供给取代基的烷-1-炔的交叉耦合不适合合成炔基吡唑：3-和5-碘吡唑不反应，但在4-碘衍生物的情况下，只有还原去碘反应发生，同时伴随烷-1-炔组分的同偶联反应。
• Functionalized buta-1,3-diynyl- N -methylpyrazoles by sequential “diacetylene zipper” and Sonogashira coupling reactions
  作者：Anastasiya I. Govdi、Alexandra E. Kulyashova、Sergey F. Vasilevsky、Irina A. Balova

  DOI：10.1016/j.tetlet.2017.01.032

  日期：2017.2

  A reaction sequence consisting of the “Diacetylene zipper” of buta-1,3-diynes from internal to terminal isomers, followed by Sonogashira cross-coupling with 3-,4- or 5-iodopyrazoles, was investigated as a new approach to buta-1,3-diynyl-N-methylpyrazoles. Various pyrazoles bearing alkyl and hydroxyalkyl containing buta-1,3-diyne substituents in the 3-,4- or 5-position and functional groups at the neighboring

  研究了由内部异构体到末端异构体的Buta-1,3-diynes的“二乙炔拉链”，然后将Sonogashira与3-，4-或5-碘吡唑交叉偶联的反应顺序，是一种新的Buta- 1,3-二炔基-N-甲基吡唑。得到了各种带有在3-，4-或5-位上含有buta-1，3-diyne取代基和在环的相邻位置上具有官能团的烷基和羟烷基的吡唑。
• Catalytic System for Cross-Coupling of Heteroaryl Iodides with a Nitronyl Nitroxide Gold Derivative at Room Temperature
  作者：Igor Zayakin、Galina Romanenko、Irina Bagryanskaya、Bogdan Ugrak、Matvey Fedin、Evgeny Tretyakov

  DOI：10.3390/molecules28227661

  日期：——

  effective methodology for the cross-coupling of heteroaryl iodides with NN–AuPPh3 at room temperature is reported. The protocol is based on a novel catalytic system consisting of Pd2(dba)3·CHCl3 and the phosphine ligand MeCgPPh having an adamantane-like framework. The present protocol was found to be well compatible with various heteroaryl iodides, thus opening new horizons in directed synthesis of functionalized

  报道了一种在室温下杂芳基碘化物与 NN-AuPPh3 交叉偶联的简单且高效的方法。该方案基于由 Pd2(dba)3·CHCl3 和具有金刚烷样框架的膦配体 MeCgPPh 组成的新型催化系统。发现本方案与各种杂芳基碘化物具有良好的相容性，从而为功能化硝基氮氧化物和高自旋分子的定向合成开辟了新的视野。
• Oxidative iodination of substituted N-methylpyrazoles
  作者：S. F. Vasilevskii、M. S. Shvartsberg

  DOI：10.1007/bf00949685

  日期：1980.5
• Silica–Sulfuric Acid Catalyzed Nitrodeiodination of Iodopyrazoles
  作者：P. Ravi、Girish M. Gore、Arun K. Sikder、Surya P. Tewari

  DOI：10.1080/00397911.2011.584261

  日期：2012.12.1

  We report here the synthesis of nitropyrazoles in good to excellent yields from iodopyrazoles over silica-sulfuric acid catalyst for the first time. The present procedure require less acid, offers a simplified workup procedure, and may be applied for the nitration of a wide variety of iodoazoles in drug and pharmaceutical industries.