4-(dimethylamino)-1-(3-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-6-yl)pyridinium trifluoromethanesulfonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 4-(dimethylamino)-1-(3-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-6-yl)pyridinium trifluoromethanesulfonate
• 英文别名: 6-[4-(dimethylamino)pyridin-1-ium-1-yl]-3-methyl-1H-pyrimidine-2,4-dione;trifluoromethanesulfonate
• 化学式: CF₃O₃S*C₁₂H₁₅N₄O₂
• 分子量: 396.347
• InChiKey: ATSRMMYQBLCRNX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.53
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  122
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  6-氯-3-甲基尿嘧啶 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 4-(dimethylamino)-1-(3-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-6-yl)pyridinium trifluoromethanesulfonate
  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.