1,4-dimethoxy-2-(pyrazol-1-yl)benzene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1,4-dimethoxy-2-(pyrazol-1-yl)benzene
• 英文别名: 1-(2,5-dimethoxyphenyl)pyrazole
• 化学式: C₁₁H₁₂N₂O₂
• 分子量: 204.228
• InChiKey: XEFLGMOGZKUHOI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对苯二甲醚 在 iron(III) chloride 、 N-碘代丁二酰亚胺 、 copper(l) iodide 、 caesium carbonate 、 (1R,2R)-(-)-N,N'-二甲基-1,2-环己二胺 、 1-丁基-3-甲基咪唑二(三氟甲基磺酰)酰亚胺 作用下， 以 水 、 甲苯 为溶剂， 反应 29.0h， 生成 1,4-dimethoxy-2-(pyrazol-1-yl)benzene
  参考文献：
  名称：

  连续铁和铜催化一锅邻氨基芳基碳氢键的正胺化

  摘要：

  使用连续的铁和铜催化作用，已经开发出一种用于将芳烃与非活性N-亲核试剂进行邻位偶联的一锅法。通过三氟化铁（III）催化的碘化作用，然后进行铜（I）催化，配体辅助的偶联反应，再与N杂环，酰胺和磺酰胺基亲核试剂实现对茴香醚，苯胺和苯酚的区域选择性邻位活化。一锅两步法直接合成邻位氨基甲酸酯的合成工具3,4-二氢喹啉-2-酮的后期官能化表明了芳基CH键。这允许制备TRIM24溴结构域抑制剂和一系列新的类似物。

  DOI：

  10.1039/c9ob00712a

文献信息

• Arenium cation as the key intermediate of the electrosynthesis of N-(2,5-dimethoxyphenyl)azoles. A new approach to the synthesis of N-(dimethoxyphenyl)azoles
  作者：V. A. Petrosyan、A. V. Burasov

  DOI：10.1007/s11172-007-0342-3

  日期：2007.11

  Data on the effect of the acid-base properties of the medium on the yield and composition of the products of N-dimethoxyphenylation of azoles (pyrazole, triazole, their substituted derivatives, and tetrazole) upon galvanostatic electrolysis of azole—1,4-dimethoxybenzene mixtures in nucleophilic (MeOH) and neutral (MeCN) media were considered and the trends of this process were discussed. The generation of arenium cations (1,4-dimethoxy-1-azolylbenzenium in MeCN and 1,1,4-trimethoxybenzenium in MeOH) as the key intermediates of electrosynthesis of N-(dimethoxyphenyl)azoles, was proved experimentally. A new approach to the synthesis of N-(dimethoxyphenyl)azoles through electrosynthesis of 1,1,4,4-tetramethoxycyclohexa-2,5-diene by electrooxidation of 1,4-dimethoxybenzene in MeOH as the first step and the reaction of this quinone diketal with azoles as the second step was suggested. The efficiency of this route to N-(dimethoxyphenyl)azoles is comparable with the efficiency of the purely electrochemical one-step process.

  关于电解质介质的酸碱性质对氮二甲氧基苯化吡唑、三唑及其取代衍生物和四唑（统称为氮二甲氧基苯化唑类）在电化学恒流电解法制备产物产率和组成的影响的数据在亲核（甲醇）和中性（乙腈）介质中进行了考虑和讨论，并讨论了其过程趋势。通过实验证实了芳铵阳离子（乙腈中的1,4-二甲氧基-1-唑基苯铵和甲醇中的1,1,4-三甲氧基苯铵）作为氮（二甲氧基苯基）唑类电合成关键中间体的生成。提出了通过电合成1,4-二甲氧基苯在甲醇中的电氧化生成1,1,4,4-四甲氧基环己-2,5-二烯作为第一步，以及该醌二酮与唑类反应作为第二步的氮（二甲氧基苯基）唑类合成新途径。此途径的效率与纯电化学一步法相当。
• The role of acid catalysis in the electrosynthesis of N-(2,5-dimethoxyphenyl)azoles
  作者：V. A. Petrosyan、A. V. Burasov

  DOI：10.1007/s11172-008-0045-4

  日期：2008.2

  The influence of the acid components of the medium on the anodic 2,5-dimethoxy-phenylation of various azoles at the nitrogen atom was studied for constant-current electrolysis of the mixture azole—1,4-dimethoxybenzene in an undivided cell. Elimination of azole functions in the key steps of the process can be catalyzed by such electrophilic species as Brønsted (AcOH) and Lewis acids (ZnCl2) and even the radical cation generated in the anodic oxidation of 1,4-dimethoxybenzene. The data obtained provided evidence for the existence of the arenonium cation as a key reaction intermediate.

  研究了介质中的酸性成分对各种偶氮唑在氮原子上的阳极 2,5-二甲氧基苯基化反应的影响，该反应是在不分流电池中对偶氮唑-1,4-二甲氧基苯混合物进行恒流电解。在这一过程的关键步骤中，亲电物种（如布氏酸（AcOH）和路易斯酸（ZnCl2）），甚至在 1,4 二甲基苯阳极氧化过程中产生的自由基阳离子，都能催化唑功能的消除。所获得的数据为壬阳离子作为关键反应中间体的存在提供了证据。
• Electrochemical N-arylation of azoles in MeOH using undivided electrolysis of their mixtures with 1,4-dimethoxybenzene
  作者：V. A. Petrosyan、A. V. Burasov、T. S. Vakhotina

  DOI：10.1007/s11172-005-0380-7

  日期：2005.5

  The reactions of 1,4-dimethoxybenzene with azoles (pyrazole, triazole, and their derivatives, as well as tetrazole) were studied by undivided amperostatic electrolysis at Pt electrodes in MeOH. The process proceeds via the formation of a 1,1,4-trimethoxyarenonium cation as the key intermediate and affords 1,1,4,4-tetramethoxycyclohexa-2,5-diene, 1,1,4-trimethoxy-4-(azol-1-yl)cyclohexa-2,5-diene, and 1,4-dimethoxy-2-(azol-1-yl)benzene as the main products. Azole and solvent molecules compete as nucleophiles during electrolysis. A fine mechanism of the process was considered.

  在 MeOH 中，通过在铂电极上进行不分裂的安培静态电解，研究了 1,4 二甲基苯与偶氮唑（吡唑、三唑及其衍生物以及四唑）的反应。该过程以 1,1,4- 三甲氧基壬鎓阳离子的形成为关键中间体，主要产物为 1,1,4,4- 四甲氧基环己-2,5-二烯、1,1,4-三甲氧基-4-(偶氮唑-1-基)环己-2,5-二烯和 1,4- 二甲氧基-2-(偶氮唑-1-基)苯。在电解过程中，偶氮唑和溶剂分子作为亲核体进行竞争。研究考虑了这一过程的精细机制。
• ——
  作者：V. A. Chauzov、V. Z. Parchinskii、E. V. Sinel"shchikova、N. N. Parfenov、V. A. Petrosyan

  DOI：10.1023/a:1019661618450

  日期：——

  The reactions of pyrazole, 3,5-dimethylpyrazole, and its 4-nitro derivatives with 1,4-dimethoxybenzene during undivided amperostatic electrolysis in MeCN (CH2Cl2) were studied. The basicity of the medium, which depends on the solvent nature, the nature and concentration of pyrazole and the acid-base properties of additives, and the amount of electricity passed determine the yield and relative content of the target products, viz., 1,4-dimethoxy-2-(pyrazol-1-yl)benzenes (1) and 1,4-dimethoxy-1,4-di(pyrazol-1-yl)cyclohexa-2,5-dienes (2). The process occurs mainly through the interaction of the nonionized solvato complex of pyrazole with the 1,4-dimethoxybenzene radical cation and affords radical intermediates structurally similar to compounds 1 and 2. The key stage of the process determining the 1 : 2 ratio is the rearrangement of the intermediately produced 1,4-dimethoxy-1-(pyrazol-1-yl)arenonium cation to the 1-(pyrazol-1-yl)-2,5-dimethoxyarenonium cation.
• One-pot <i>ortho</i>-amination of aryl C–H bonds using consecutive iron and copper catalysis
  作者：Martyn C. Henry、Rochelle McGrory、Réka J. Faggyas、Mohamed A. B. Mostafa、Andrew Sutherland

  DOI：10.1039/c9ob00712a

  日期：——

  sequential iron and copper catalysis. Regioselective ortho-activation of anisoles, anilines and phenols was achieved through iron(III) triflimide catalysed iodination, followed by a copper(I)-catalysed, ligand-assisted coupling reaction with N-heterocycle, amide and sulfonamide-based nucleophiles. The synthetic utility of this one-pot, two-step method for the direct amination of ortho-aryl C–H bonds was

  使用连续的铁和铜催化作用，已经开发出一种用于将芳烃与非活性N-亲核试剂进行邻位偶联的一锅法。通过三氟化铁（III）催化的碘化作用，然后进行铜（I）催化，配体辅助的偶联反应，再与N杂环，酰胺和磺酰胺基亲核试剂实现对茴香醚，苯胺和苯酚的区域选择性邻位活化。一锅两步法直接合成邻位氨基甲酸酯的合成工具3,4-二氢喹啉-2-酮的后期官能化表明了芳基CH键。这允许制备TRIM24溴结构域抑制剂和一系列新的类似物。