diethyl 1-benzyl-2-nitropyrrole-3,4-dicarboxylate | 244028-93-1

• 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: diethyl 1-benzyl-2-nitropyrrole-3,4-dicarboxylate
• CAS: 244028-93-1
• 化学式: C₁₇H₁₈N₂O₆
• 分子量: 346.34
• InChiKey: RNIYXWORVXSSKZ-UHFFFAOYSA-N

物化性质

• 熔点：
  118-119 °C
• 沸点：
  452.5±40.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  103
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl 1-benzyl-2-nitropyrrole-3,4-dicarboxylate 在 盐酸 、 氨 、 铁粉 、 三乙胺 、 sodium nitrite 、 三氯氧磷 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 50.5h， 生成 7-benzyl-4-(1,2,4-triazol-1-yl)pyrrolo[2,3-d][1,2,3]triazine-5-carbonitrile
  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
• 作为产物：
  描述：

  溴甲苯 、 diethyl 2-nitropyrrole-3,4-dicarboxylate 在 氢氧化钾 作用下， 以 二甲基亚砜 为溶剂， 反应 2.5h， 以86%的产率得到diethyl 1-benzyl-2-nitropyrrole-3,4-dicarboxylate
  参考文献：
  名称：

  2-硝基吡咯-3,4-二甲酰胺的高效合成

  摘要：

  摘要 N-1-取代的 2-硝基吡咯-3,4-二甲酰胺 (4-5, 7-9) 的合成是由 2-硝基吡咯-3,4-二甲酸二乙酯 (2) 合成的。2-硝基-吡咯-3,4-二甲酰胺(1)通过2-硝基-1-[2-(2-吡啶基)乙基]吡咯-3,4-二甲酰胺(9)的脱保护制备。化合物9是通过两种不同的方法获得的。

  DOI：

  10.1080/00397919908086015

文献信息

• An Efficient Synthesis of 2-Nitropyrrole-3,4-dicarboxamide
  作者：Michael T. Migawa、Leroy B. Townsend

  DOI：10.1080/00397919908086015

  日期：1999.11

  Abstract The synthesis of N-1-substituted 2-nitropyrrole-3,4-dicarboxamides (4–5, 7–9) was accomplished from diethyl 2-nitropyrrole-3,4-dicarboxylate (2). 2-nitro-pyrrole-3,4-dicarboxamide (1) was prepared by deprotection of 2-nitro-1-[2-(2-pyridyl)ethyl]pyrrole-3,4-dicarboxamide (9). Compound 9 was obtained by two different methods.

  摘要 N-1-取代的 2-硝基吡咯-3,4-二甲酰胺 (4-5, 7-9) 的合成是由 2-硝基吡咯-3,4-二甲酸二乙酯 (2) 合成的。2-硝基-吡咯-3,4-二甲酰胺(1)通过2-硝基-1-[2-(2-吡啶基)乙基]吡咯-3,4-二甲酰胺(9)的脱保护制备。化合物9是通过两种不同的方法获得的。
• 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.