2-amino-1-benzylpyrrole-3,4-dicarbonitrile

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2-amino-1-benzylpyrrole-3,4-dicarbonitrile
• 化学式: C₁₃H₁₀N₄
• 分子量: 222.249
• InChiKey: AROOOZGGMAVJHK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  78.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  7-benzyl-4-(1,2,4-triazol-1-yl)pyrrolo[2,3-d][1,2,3]triazine-5-carbonitrile 在 氨 作用下， 反应 2.01h， 生成 2-amino-1-benzylpyrrole-3,4-dicarbonitrile
  参考文献：
  名称：

  Synthesis and Unusual Chemical Reactivity of Certain Novel 4,5-Disubstituted 7-Benzylpyrrolo[2,3-d][1,2,3]triazines

  摘要：

  The fact that only two pyrrolo[2,3-d] [1,2,3]triazines heterocycles had been reported in the literature prompted us to initiate studies designed to provide additional members of this ring system. Initial attempts to prepare additional derivatives of the 7-unsubstituted pyrrolo[2,3-d] [1,2,3]triazin-4-ones were limited by their low chemical reactivity. Subsequently, 7-benzyl-5-carboxamidopyrrololo-,3-d] [1,2,3]triazin-4-one (16) was prepared from diethyl 2-nitropyrrole-3,4,-dicarboxylate via an alkylation, ammonolysis, reduction and intramolecular diazocoupling sequence. Conversion of 16 into 7-benzyl-4-( 1,2,4-triazol-1-yl)pyrrolo [2,3-d] [1,2,3]triazine-5-carbonitrile (17) was accomplished, and nucleophilic displacements of the 4-triazol-1- yl group were studied. Treatment of 17 with NH3/CH3CN gave a mixture of 4-amino-7-benzylpyrrolo [2,3-d] [1,2,3] triazine-5-carbonitrile (19) and 2-amino-1-benzylpyrrole-3,4-dicarbonitrile (21), A mechanism to account for the formation of this mixture is described along with studies on the effect that ammonia concentration and a TFA catalyst have on the product ratio. Compound 19 was converted into the 5-carboxamide and 5-thioamide derivatives of 19.

  DOI：

  10.1021/jo001499i

文献信息

• An Unprecedented Nitrogen Elimination Reaction:  Mechanistic Studies Using ¹⁵N-Labeled 4-Amino-7-benzylpyrrolo[2,3-<i>d</i>][1,2,3]triazine-5-carbonitrile
  作者：Michael T. Migawa、Leroy B. Townsend

  DOI：10.1021/ol990006x

  日期：1999.8.1

  [formula: see text] In the course of our work on novel pyrrolo[2,3-d][1,2,3]triazines we have discovered that 1 undergoes an elimination of nitrogen at 250 degrees C to give 2. We have conducted 15N labeling studies that establish that the loss of N-2 and N-3 from 1 had occurred rather than N-1 and N-2, presumably via a retro Diels-Alder reaction of the imino tautomer 7. This study provides an alternative

  [公式：参见文本]在我们研究新型吡咯并[2,3-d] [1,2,3]三嗪的过程中，我们发现1在250℃时会消除氮，从而得到2。进行了15N标记研究，确定发生了1的N-2和N-3的损失，而不是N-1和N-2的损失，大概是通过亚氨基互变异构体7的Diels-Alder逆反应。常见的机理涉及通过短暂形成重氮化合物而损失N-1和N-2，重氮化合物是由4-氨基或4-氧取代的1,2,3-三嗪与碳环或杂环稠合生成的。
• Synthesis and Unusual Chemical Reactivity of Certain Novel 4,5-Disubstituted 7-Benzylpyrrolo[2,3-<i>d</i>][1,2,3]triazines
  作者：Michael T. Migawa、Leroy B. Townsend

  DOI：10.1021/jo001499i

  日期：2001.7.1

  The fact that only two pyrrolo[2,3-d] [1,2,3]triazines heterocycles had been reported in the literature prompted us to initiate studies designed to provide additional members of this ring system. Initial attempts to prepare additional derivatives of the 7-unsubstituted pyrrolo[2,3-d] [1,2,3]triazin-4-ones were limited by their low chemical reactivity. Subsequently, 7-benzyl-5-carboxamidopyrrololo-,3-d] [1,2,3]triazin-4-one (16) was prepared from diethyl 2-nitropyrrole-3,4,-dicarboxylate via an alkylation, ammonolysis, reduction and intramolecular diazocoupling sequence. Conversion of 16 into 7-benzyl-4-( 1,2,4-triazol-1-yl)pyrrolo [2,3-d] [1,2,3]triazine-5-carbonitrile (17) was accomplished, and nucleophilic displacements of the 4-triazol-1- yl group were studied. Treatment of 17 with NH3/CH3CN gave a mixture of 4-amino-7-benzylpyrrolo [2,3-d] [1,2,3] triazine-5-carbonitrile (19) and 2-amino-1-benzylpyrrole-3,4-dicarbonitrile (21), A mechanism to account for the formation of this mixture is described along with studies on the effect that ammonia concentration and a TFA catalyst have on the product ratio. Compound 19 was converted into the 5-carboxamide and 5-thioamide derivatives of 19.