6-(3-methylimidazolio)-3-methyl-2,4(1H,3H)-pyrimidinedionate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 6-(3-methylimidazolio)-3-methyl-2,4(1H,3H)-pyrimidinedionate
• 英文别名: 1-Methyl-4-(3-methylimidazol-3-ium-1-yl)-6-oxopyrimidin-2-olate
• 化学式: C₉H₁₀N₄O₂
• 分子量: 206.204
• InChiKey: BAMGJVKKEYCJCG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  64.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-(3-methylimidazolio)-3-methyl-2,4(1H,3H)-pyrimidinedionate 在 氢碘酸 作用下， 以 水 、 丙酮 为溶剂， 反应 3.0h， 以76%的产率得到3-methyl-1-(3-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-6-yl)imidazolium iodide
  参考文献：
  名称：

  Charged and Betainic Nucleobases. On Syntheses and Properties of First Mesomeric Uracilylbetaines, Uracilates, and Novel Uracilium Salts

  摘要：

  Nucleophilic heteroaromatic substitution of DMAP and 1-methylimidazole on the 6-chlorouracil 1 gave the uracilyl hetarenium salts 2 and 4, respectively. Depending on the nucleophile, the substitution could be catalyzed by interception of the leaving group either with sodium tetraphenylborate or with antimony pentachloride in a non-coordinating solvent. Catalysis with other Lewis acids failed due to the formation of stable coordination compounds 3. Surprisingly, Finkelstein-type reaction conditions provide an efficient approach to the imidazolium iodide 4. Depending on the reaction conditions, treatment of the 6-chlorouracil 5 with DMAP resulted in the formation of the pyridinium uracilate 6, the uracilyl pyridinium chloride 7a, and the novel pyridinium-uracilate 8 which is a cross-conjugated mesomeric betaine (CCMB). Alkylation of the mesomeric betaine 8 with 1,2-dichloroethane/SbCl5 gave the biscation 9. Analogously, 1-methylimidazole or 2,4,6-trimethylpyridine as nucleophiles formed the salts 10a and 12, respectively, and the imidazolium-uracilate 11. This is the first representative of a cross-conjugated heterocyclic mesomeric betaine isoconjugate with odd nonalternant hydrocarbon anions. PM3 calculations were performed on the cation 2 and on the mesomeric betaine 8. Whereas the cation 2 was found to have an essentially perpendicular torsional angle Phi around the CN+ bond linking the uracil and the pyridinium units, the mesomeric betaine 8 adopts a nearly planar conformation, thus allowing stabilizing pi interactions. Accordingly, upon rotation about the CN+ bond, the expected maxima were found at essentially perpendicular conformations. Due to the balance between three effects which act in opposite directions, (i) stabilizing p overlap, (ii) N(8)/2-H attractive interaction, and (iii) steric repulsion between 6-H and 12-H, two additional small minima were surprisingly found at Phi 36.6 degrees and 219.3 degrees. The charge separation in the ground state of the mesomeric betaine 11, and the ground-state ion-pair complexes of the hetarenium iodides 2d, 4, 7c, and 10b were confirmed by the effect of negative solvatochromism.

  DOI：

  10.1021/jo961890x
• 作为产物：
  描述：

  N-甲基咪唑 、 6-氯-3-甲基尿嘧啶 在 四苯硼钠 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以58%的产率得到6-(3-methylimidazolio)-3-methyl-2,4(1H,3H)-pyrimidinedionate
  参考文献：
  名称：

  Charged and Betainic Nucleobases. On Syntheses and Properties of First Mesomeric Uracilylbetaines, Uracilates, and Novel Uracilium Salts

  摘要：

  Nucleophilic heteroaromatic substitution of DMAP and 1-methylimidazole on the 6-chlorouracil 1 gave the uracilyl hetarenium salts 2 and 4, respectively. Depending on the nucleophile, the substitution could be catalyzed by interception of the leaving group either with sodium tetraphenylborate or with antimony pentachloride in a non-coordinating solvent. Catalysis with other Lewis acids failed due to the formation of stable coordination compounds 3. Surprisingly, Finkelstein-type reaction conditions provide an efficient approach to the imidazolium iodide 4. Depending on the reaction conditions, treatment of the 6-chlorouracil 5 with DMAP resulted in the formation of the pyridinium uracilate 6, the uracilyl pyridinium chloride 7a, and the novel pyridinium-uracilate 8 which is a cross-conjugated mesomeric betaine (CCMB). Alkylation of the mesomeric betaine 8 with 1,2-dichloroethane/SbCl5 gave the biscation 9. Analogously, 1-methylimidazole or 2,4,6-trimethylpyridine as nucleophiles formed the salts 10a and 12, respectively, and the imidazolium-uracilate 11. This is the first representative of a cross-conjugated heterocyclic mesomeric betaine isoconjugate with odd nonalternant hydrocarbon anions. PM3 calculations were performed on the cation 2 and on the mesomeric betaine 8. Whereas the cation 2 was found to have an essentially perpendicular torsional angle Phi around the CN+ bond linking the uracil and the pyridinium units, the mesomeric betaine 8 adopts a nearly planar conformation, thus allowing stabilizing pi interactions. Accordingly, upon rotation about the CN+ bond, the expected maxima were found at essentially perpendicular conformations. Due to the balance between three effects which act in opposite directions, (i) stabilizing p overlap, (ii) N(8)/2-H attractive interaction, and (iii) steric repulsion between 6-H and 12-H, two additional small minima were surprisingly found at Phi 36.6 degrees and 219.3 degrees. The charge separation in the ground state of the mesomeric betaine 11, and the ground-state ion-pair complexes of the hetarenium iodides 2d, 4, 7c, and 10b were confirmed by the effect of negative solvatochromism.

  DOI：

  10.1021/jo961890x

文献信息

• Charged and Betainic Nucleobases. On Syntheses and Properties of First Mesomeric Uracilylbetaines, Uracilates, and Novel Uracilium Salts
  作者：Andreas Schmidt、Markus Karl Kindermann

  DOI：10.1021/jo961890x

  日期：1997.6.13

  Nucleophilic heteroaromatic substitution of DMAP and 1-methylimidazole on the 6-chlorouracil 1 gave the uracilyl hetarenium salts 2 and 4, respectively. Depending on the nucleophile, the substitution could be catalyzed by interception of the leaving group either with sodium tetraphenylborate or with antimony pentachloride in a non-coordinating solvent. Catalysis with other Lewis acids failed due to the formation of stable coordination compounds 3. Surprisingly, Finkelstein-type reaction conditions provide an efficient approach to the imidazolium iodide 4. Depending on the reaction conditions, treatment of the 6-chlorouracil 5 with DMAP resulted in the formation of the pyridinium uracilate 6, the uracilyl pyridinium chloride 7a, and the novel pyridinium-uracilate 8 which is a cross-conjugated mesomeric betaine (CCMB). Alkylation of the mesomeric betaine 8 with 1,2-dichloroethane/SbCl5 gave the biscation 9. Analogously, 1-methylimidazole or 2,4,6-trimethylpyridine as nucleophiles formed the salts 10a and 12, respectively, and the imidazolium-uracilate 11. This is the first representative of a cross-conjugated heterocyclic mesomeric betaine isoconjugate with odd nonalternant hydrocarbon anions. PM3 calculations were performed on the cation 2 and on the mesomeric betaine 8. Whereas the cation 2 was found to have an essentially perpendicular torsional angle Phi around the CN+ bond linking the uracil and the pyridinium units, the mesomeric betaine 8 adopts a nearly planar conformation, thus allowing stabilizing pi interactions. Accordingly, upon rotation about the CN+ bond, the expected maxima were found at essentially perpendicular conformations. Due to the balance between three effects which act in opposite directions, (i) stabilizing p overlap, (ii) N(8)/2-H attractive interaction, and (iii) steric repulsion between 6-H and 12-H, two additional small minima were surprisingly found at Phi 36.6 degrees and 219.3 degrees. The charge separation in the ground state of the mesomeric betaine 11, and the ground-state ion-pair complexes of the hetarenium iodides 2d, 4, 7c, and 10b were confirmed by the effect of negative solvatochromism.