1,4-Bis(4-methylphenyl)-3,6-bis(methoxycarbonyl)-1,4-dihydro-1,2,4,5-tetrazine

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,4-Bis(4-methylphenyl)-3,6-bis(methoxycarbonyl)-1,4-dihydro-1,2,4,5-tetrazine
• 英文别名: Dimethyl 1,4-bis(4-methylphenyl)-1,2,4,5-tetrazine-3,6-dicarboxylate
• 化学式: C₂₀H₂₀N₄O₄
• 分子量: 380.403
• InChiKey: NZRNXFPKPKZPSI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  83.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  methyl 2-chloro-2-(4-methylphenyl-hydrazono)acetate 在 四己基氯化铵 sodium hydroxide 作用下， 以 水 为溶剂， 反应 1.5h， 以92%的产率得到1,4-Bis(4-methylphenyl)-3,6-bis(methoxycarbonyl)-1,4-dihydro-1,2,4,5-tetrazine
  参考文献：
  名称：

  Uncommon aqueous media for nitrilimine cycloadditions. I. Synthetic and mechanistic aspects in the formation of 1-aryl-5-substituted-4,5-dihydropyrazoles

  摘要：

  已通过水性介质和表面活性剂存在下，各种取代的亚胺腈2与相应的烯基亲偶极体3的1,3-偶极环加成反应，合成了多个1-芳基-5-取代的4,5-二氢吡唑4。在这些条件下，对于大多数[3+2]环加成反应来说并不常见，环加成物的电子特征对反应结果影响显著。富电子的亚胺腈与贫电子的亲偶极体之间的环加成反应迅速且效率高，而反应物的电子特性反转则导致结果不佳。表面活性剂浓度的变化提供了一些新的机理见解。

  DOI：

  10.1039/b205063c

文献信息

• Oxygenated monoterpenes as dipolarophiles for nitrilimine cycloadditions
  作者：Lara De Benassuti、Luisa Garanti、Giorgio Molteni

  DOI：10.1016/j.tet.2004.03.077

  日期：2004.5

  A variety of naturally-occurring oxygenated monoterpenes, namely (S)-cis-verbenol, (1R)-(-)-myternol, (1S)-(-)-verbenone, (1R)-(-)-myternal, (S)-(-)-perillyl alcohol, and (S)-(-)-perillaldehyde have been submitted to nitrilimine cycloaddition. These processes were fully regio- and stereoselective for four dipolarophiles. In contrast, regioselective but non-stereoselective cycloadditions occurred in the case of two of the monoterpene derivatives. The configurations of the newly-formed stereocentres of the cycloadducts were assigned on the basis of NOE and NOESY experiments. (C) 2004 Elsevier Ltd. All rights reserved.
• Uncommon aqueous media for nitrilimine cycloadditions. I. Synthetic and mechanistic aspects in the formation of 1-aryl-5-substituted-4,5-dihydropyrazoles
  作者：Giorgio Molteni、Alessandro Ponti、Marco Orlandi

  DOI：10.1039/b205063c

  日期：2002.9.23

  A number of 1-aryl-5-substituted-4,5-dihydropyrazoles 4 have been synthesised by 1,3-dipolar cycloaddition of variously substituted nitrilimines 2 onto the appropriate alkenyl dipolarophiles 3 in aqueous media and in the presence of a surfactant. Under these conditions, uncommon for the large majority of [3 + 2] cycloadditions, the electronic features of both the cycloaddends strongly dictate the reaction outcome. Clean and fast cycloadditions were observed between electron-rich nitrilimines and electron-poor dipolarophiles, while the reversal of the electronic features of the reactants gave poor results. Changes in surfactant concentration leads to some novel mechanistic insights.

  已通过水性介质和表面活性剂存在下，各种取代的亚胺腈2与相应的烯基亲偶极体3的1,3-偶极环加成反应，合成了多个1-芳基-5-取代的4,5-二氢吡唑4。在这些条件下，对于大多数[3+2]环加成反应来说并不常见，环加成物的电子特征对反应结果影响显著。富电子的亚胺腈与贫电子的亲偶极体之间的环加成反应迅速且效率高，而反应物的电子特性反转则导致结果不佳。表面活性剂浓度的变化提供了一些新的机理见解。