1,1,4-trimethoxy-4-(3-nitro-1,2,4-triazol-1-yl)cyclohexa-2,5-diene | 516509-75-4

• 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: 1,1,4-trimethoxy-4-(3-nitro-1,2,4-triazol-1-yl)cyclohexa-2,5-diene
• 英文别名: 1,1,4-trimethoxy-4-(3-nitrotriazol-1H-1-yl)cyclohexa-2,5-diene；1,1,4-Trimethoxy-4-(3-nitro-1,2,4-triazol-1-yl)cyclohexane-2,5-diene；3-nitro-1-(1,4,4-trimethoxycyclohexa-2,5-dien-1-yl)-1,2,4-triazole
• CAS: 516509-75-4
• 化学式: C₁₁H₁₄N₄O₅
• 分子量: 282.256
• InChiKey: JUSYJPDFPTVOLC-UHFFFAOYSA-N

物化性质

• 沸点：
  463.2±55.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1,1,4-trimethoxy-4-(3-nitro-1,2,4-triazol-1-yl)cyclohexa-2,5-diene 反应 5.0h， 以100%的产率得到1,4-dimethoxy-2-(3-nitro-1,2,4-triazol-1H-1-yl)benzene
  参考文献：
  名称：

  摘要：

  The reactions of 1,4-dimethoxybenzene with 4-nitropyrazole, 3,4-dinitro-5-methylpyrazole, 1,2,4-triazole, 3-nitro-1,2,4-triazole, and tetrazole were studied during undivided amperostatic electrolysis on a Pt electrode in MeCN, CH2Cl2, and MeOH. The main reaction products were 2-azolyl-1,4-dimethoxybenzenes and (or) 1,4-diazolyl-1,4-dimethoxycyclohexa-2,5-dienes. In all cases except 1,2,4-triazole, N-arylation occurs only in the presence of the Alk(4)N(+) salts of azoles or 2,4,6-trimethylpyridine as a base. The mechanism of the reactions is discussed.

  DOI：

  10.1023/a:1020979426942
• 作为产物：
  描述：

  3,3,6,6-四甲氧基-1,4-环己二烯 、 3-硝基-1,2,4-三氮唑 在 2,4,6-三甲基吡啶 作用下， 反应 5.0h， 以28%的产率得到1,1,4-trimethoxy-4-(3-nitro-1,2,4-triazol-1-yl)cyclohexa-2,5-diene
  参考文献：
  名称：

  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

  摘要：

  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。

  DOI：

  10.1007/s11172-007-0342-3

文献信息

• 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。
• 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。
• ——
  作者：V. A. Chauzov、V. Z. Parchinskii、E. V. Sinel"shchikova、A. V. Burasov、B. I. Ugrak、N. N. Parfenov、V. A. Petrosyan

  DOI：10.1023/a:1020979426942

  日期：——

  The reactions of 1,4-dimethoxybenzene with 4-nitropyrazole, 3,4-dinitro-5-methylpyrazole, 1,2,4-triazole, 3-nitro-1,2,4-triazole, and tetrazole were studied during undivided amperostatic electrolysis on a Pt electrode in MeCN, CH2Cl2, and MeOH. The main reaction products were 2-azolyl-1,4-dimethoxybenzenes and (or) 1,4-diazolyl-1,4-dimethoxycyclohexa-2,5-dienes. In all cases except 1,2,4-triazole, N-arylation occurs only in the presence of the Alk(4)N(+) salts of azoles or 2,4,6-trimethylpyridine as a base. The mechanism of the reactions is discussed.