1,2,3,4-tetrahydro-4-(4-methylphenyl)-2-oxo-6-propyl-5-pyrimidinecarboxylic acid ethyl ester | 419552-31-1

• 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: 1,2,3,4-tetrahydro-4-(4-methylphenyl)-2-oxo-6-propyl-5-pyrimidinecarboxylic acid ethyl ester
• 英文别名: 5-ethoxycarbonyl-4-(4-methylphenyl)-6-propyl-3,4-dihydropyrimidin-2(1H)-one；ethyl 4-(4-methylphenyl)-2-oxo-6-propyl-3,4-dihydro-1H-pyrimidine-5-carboxylate
• CAS: 419552-31-1
• 化学式: C₁₇H₂₂N₂O₃
• 分子量: 302.373
• InChiKey: SDBFFACUSLCLKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  67.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对甲基苯甲醛 、 丁酰乙酸乙酯 、 尿素 在 hafnium tetrakis(trifluoromethanesulfonate) 作用下， 以 neat (no solvent) 为溶剂， 以89%的产率得到1,2,3,4-tetrahydro-4-(4-methylphenyl)-2-oxo-6-propyl-5-pyrimidinecarboxylic acid ethyl ester
  参考文献：
  名称：

  由 Hf(OTf)4 催化的取代 3,4-二氢嘧啶-2-(1H)-酮 (DHPM) 的高效合成：金属路易斯酸催化和无溶剂条件下反应途径的机理洞察

  摘要：

  在我们对 IVB 族过渡金属路易斯酸催化活性的研究中，Hf(OTf)4 被确定为“一锅三组分”Biginelli 反应的高效催化剂。更重要的是，发现与基于溶剂的条件相比，无溶剂条件可以显着促进 Hf(OTf)4 催化的 3,4-二氢-嘧啶-2-(1H)-酮的形成。为了提供机理解释，我们以“顺序双分子缩合”和“一锅三组分”方式仔细研究了 Hf(OTf)4 对所有三种潜在反应途径的催化作用。实验结果表明，无溶剂条件和 Hf(OTf)4 催化的协同作用不仅通过增强亚胺路线和激活烯胺路线大大加速了 Biginelli 反应，而且避免了 Knoevenagel 加合物的形成，这可能导致不需要的副产品。此外，乙酰乙酸甲酯在 MeOH-d4 中的 HD 交换反应的 1H-MMR 示踪表明 Hf(IV) 阳离子可能显着加速酮-烯醇互变异构化并激活 β-酮部分，从而有助于整体反应速率。

  DOI：

  10.3390/molecules24020364

文献信息

• Synthesis of Biginelli dihydropyrimidinone derivatives with various substituents on aluminium-planted mesoporous silica catalyst
  作者：Hiroaki Murata、Haruro Ishitani、Masakazu Iwamoto

  DOI：10.1039/b920821f

  日期：——

  Biginelli reactions were well catalyzed on mesoporous silica MCM-41 (M41) whose activity was much greater than that of amorphous silica. Octane was the most suitable among 6 kinds of solvents examined. The addition of metal ions on M41 enhanced the catalytic activity in the order Al > Ti > Fe = In. Al-planted M41s with Si/Al ratios of 45–35 showed the highest catalytic activity and could be used repeatedly though a small loss of the activity was observed. The catalysis could widely be applied to obtain various substituted dihydropyrimidinones (DHPMs) with high yields, some of which were very difficult to prepare until now. In addition, Biginelli reactions were combined with formyl C–H insertion reactions of diazoester on mesoporous silica; that is, a tandem one-pot four-component DHPM synthesis was attempted. Acetaldehyde, ethyl diazoacetate, p-tolualdehyde, and urea could be condensed and the corresponding DHPM derivative was obtained with 50% yield on Al-planted M41.

  介孔二氧化硅 MCM-41 (M41) 能很好地催化 Biginelli 反应，其活性远远高于无定形二氧化硅。在所考察的 6 种溶剂中，辛烷是最合适的溶剂。在 M41 上添加金属离子可提高催化活性，其顺序为 Al > Ti > Fe = In。硅/铝比为 45-35 的铝植入 M41 显示出最高的催化活性，虽然活性略有下降，但仍可重复使用。该催化反应可广泛应用于高产率获得各种取代的二氢嘧啶酮（DHPM），其中一些到目前为止还很难制备。此外，还在介孔二氧化硅上将 Biginelli 反应与重氮酯的甲酰基 C-H 插入反应相结合，即尝试了串联式一锅四组份 DHPM 合成。乙醛、重氮乙酸乙酯、对甲苯酚和尿素可以缩合，并在 Al-planted M41 上得到相应的 DHPM 衍生物，收率为 50%。
• Highly ordered aluminium-planted mesoporous silica as active catalyst for Biginelli reaction and formyl C–H insertion reaction with diazoester
  作者：Hiroaki Murata、Haruro Ishitani、Masakazu Iwamoto

  DOI：10.1039/c0cp00565g

  日期：——

  Al-planted MCM-41s (Al-M41s) with regular mesoporous structure and Si/Al ratio of 23–32 were successfully prepared by the template-ion exchange method in which the template/Si molar ratio and Si/Al ratio were adjusted at 1.44 and 5–15, and showed much higher catalytic activity for the titled reactions than the other types of Al-M41s prepared by post-synthesis or sol–gel methods.

  采用调整模板/Si摩尔比和Si/Al比的模板离子交换法成功制备了具有规则介孔结构、Si/Al比为23×32的植铝MCM-41s（Al-M41s）其催化活性为 1.44 和 5-15，并且与通过后合成或溶胶凝胶方法制备的其他类型的 Al-M41 相比，对标题反应表现出更高的催化活性。
• Highly Efficient Synthesis of Substituted 3,4-Dihydropyrimidin-2-(1H)-ones (DHPMs) Catalyzed by Hf(OTf)4: Mechanistic Insights into Reaction Pathways under Metal Lewis Acid Catalysis and Solvent-Free Conditions
  作者：Rui Kong、Shuai-Bo Han、Jing-Ying Wei、Xiao-Chong Peng、Zhen-Biao Xie、Shan-Shan Gong、Qi Sun

  DOI：10.3390/molecules24020364

  日期：——

  catalytic activity of Group IVB transition metal Lewis acids, Hf(OTf)4 was identified as a highly potent catalyst for ”one-pot, three-component” Biginelli reaction. More importantly, it was found that solvent-free conditions, in contrast to solvent-based conditions, could dramatically promote the Hf(OTf)4-catalyzed formation of 3,4-dihydro-pyrimidin-2-(1H)-ones. To provide a mechanistic explanation, we closely

  在我们对 IVB 族过渡金属路易斯酸催化活性的研究中，Hf(OTf)4 被确定为“一锅三组分”Biginelli 反应的高效催化剂。更重要的是，发现与基于溶剂的条件相比，无溶剂条件可以显着促进 Hf(OTf)4 催化的 3,4-二氢-嘧啶-2-(1H)-酮的形成。为了提供机理解释，我们以“顺序双分子缩合”和“一锅三组分”方式仔细研究了 Hf(OTf)4 对所有三种潜在反应途径的催化作用。实验结果表明，无溶剂条件和 Hf(OTf)4 催化的协同作用不仅通过增强亚胺路线和激活烯胺路线大大加速了 Biginelli 反应，而且避免了 Knoevenagel 加合物的形成，这可能导致不需要的副产品。此外，乙酰乙酸甲酯在 MeOH-d4 中的 HD 交换反应的 1H-MMR 示踪表明 Hf(IV) 阳离子可能显着加速酮-烯醇互变异构化并激活 β-酮部分，从而有助于整体反应速率。