5‑ethoxycarbonyl‑4‑(2‑phenylethyl)‑6‑methyl‑3,4‑dihydropyrimidin‑2(1H)‑one | 363138-51-6

• 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: 5‑ethoxycarbonyl‑4‑(2‑phenylethyl)‑6‑methyl‑3,4‑dihydropyrimidin‑2(1H)‑one
• 英文别名: ethyl 6-methyl-2-oxo-4-(2-phenethyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate；ethyl 6-methyl-2-oxo-4-(1-phenylethyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate；6-methyl-2-oxo-4-phenethyl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid ethyl ester；6-Methyl-2-oxo-4-phenaethyl-1,2,3,4-tetrahydro-pyrimidin-5-carbonsaeure-aethylester；Ethyl 6-methyl-2-oxo-4-phenethyl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylate；ethyl 6-methyl-2-oxo-4-(2-phenylethyl)-3,4-dihydro-1H-pyrimidine-5-carboxylate
• CAS: 363138-51-6
• 化学式: C₁₆H₂₀N₂O₃
• 分子量: 288.346
• InChiKey: DXPSNOSWYXEEPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  67.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5‑ethoxycarbonyl‑4‑(2‑phenylethyl)‑6‑methyl‑3,4‑dihydropyrimidin‑2(1H)‑one 在 potassium permanganate 作用下， 以 丙酮 为溶剂， 以63%的产率得到ethyl 1,2-dihydro-6-methyl-2-oxo-4-(2-phenylethyl)pyrimidine-5-carboxylate
  参考文献：
  名称：

  Biginelli 反应产物的氧化：2-未取代的 1,4-二氢嘧啶、嘧啶和 2-羟基嘧啶的合成

  摘要：

  我们设计了一条从 Biginelli 产物二氢嘧啶-2(1H)-硫酮获得 2-未取代嘧啶衍生物的新途径，分两步进行： 在湿氧化铝或过氧化氢存在下使用 oxone 氧化二氢嘧啶-2(1H)-硫酮催化量的硫酸氧钒提供1,4-二氢嘧啶，通过KMnO 4 的处理将其进一步氧化为2-未取代的嘧啶。KMnO 4 氧化二氢嘧啶-2(1H)-酮以优异的产率形成2-羟基嘧啶，而尝试通过KMnO 4 直接脱硫二氢嘧啶-2(1H)-硫酮导致形成2-羟基嘧啶，相同的产物由二氢嘧啶-2(1H)-one氧化得到。

  DOI：

  10.1055/s-0028-1087920
• 作为产物：
  描述：

  ethyl 6-methyl-2-oxo-4-[(E)-2-phenylethenyl]-1,2,3,4-tetrahydropyrimidine-5-carboxylate 在 copper barium chromium oxide catalyst 作用下， 150.0 ℃ 、19.61 MPa 条件下， 生成 5‑ethoxycarbonyl‑4‑(2‑phenylethyl)‑6‑methyl‑3,4‑dihydropyrimidin‑2(1H)‑one
  参考文献：
  名称：

  Hydrogenation of Cyclic Ureides under Elevated Temperatures and Pressures. I.¹ 2-Keto-1,2,3,4-tetrahydropyrimidines

  摘要：

  DOI：

  10.1021/ja01320a058

文献信息

• Oxidation of Biginelli Reaction Products: Synthesis of 2-Unsubstituted 1,4-Dihydropyrimidines, Pyrimidines, and 2-Hydroxypyrimidines
  作者：Hyunik Shin、Sam Kim、Bo Choi、Jae Lee、Ki Lee、Tae Lee、Young Kim

  DOI：10.1055/s-0028-1087920

  日期：2009.3

  from the Biginelli product, dihydropyrimidin-2(1H)-thiones in two steps: Oxidation of dihydropyrimidin-2(1H)-thiones using oxone on wet alumina or hydrogen peroxide in the presence of catalytic amount of vanadyl sulfate provided 1,4-di-hydropyrimidine, which was further oxidized to 2-unsubstituted pyrimidines by the treatment of KMnO 4 . Oxidation of dihydropyrimidin-2(1H)-ones by KMnO 4 formed 2-hydroxypyrimidine

  我们设计了一条从 Biginelli 产物二氢嘧啶-2(1H)-硫酮获得 2-未取代嘧啶衍生物的新途径，分两步进行： 在湿氧化铝或过氧化氢存在下使用 oxone 氧化二氢嘧啶-2(1H)-硫酮催化量的硫酸氧钒提供1,4-二氢嘧啶，通过KMnO 4 的处理将其进一步氧化为2-未取代的嘧啶。KMnO 4 氧化二氢嘧啶-2(1H)-酮以优异的产率形成2-羟基嘧啶，而尝试通过KMnO 4 直接脱硫二氢嘧啶-2(1H)-硫酮导致形成2-羟基嘧啶，相同的产物由二氢嘧啶-2(1H)-one氧化得到。
• Samarium Triflate–Catalyzed Biginelli Condensation: An Improved Method for the Synthesis of 3,4-Dihydropyrimidin-2(<i>1H</i>)-ones
  作者：A. Venkat Narsaiah、A. Ramesh Reddy、J. S. Yadav

  DOI：10.1080/00397911.2010.515355

  日期：2011.9.15

  Abstract A simple and efficient method for multicomponant synthesis of 3,4-dihydropyrimidinones has been reported. All the reactions were carried out using samarium triflate as catalyst (10 mol%) at acetonitrile reflux. This procedure is applicable to a variety of substrates such as aliphatic, aromatic, and heterocyclic aldehydes.

  摘要 报道了一种简单有效的多组分合成 3,4-二氢嘧啶酮的方法。所有反应均使用三氟甲磺酸钐作为催化剂（10 mol%）在乙腈回流下进行。此程序适用于各种底物，如脂肪族、芳香族和杂环醛。
• One-pot Synthesis of Dihydropyrimidinones Using Polyoxometalate Tri-supported Transition Metal Complexes
  作者：Razieh Fazaeli、Hamid Aliyan、Foroogh Mohammadifar、Amir Abbas Zamani、Mohammad Javad Bagi

  DOI：10.5012/jkcs.2011.55.4.666

  日期：2011.8.20

  Vanadium 치환체인 polyoxometalate 1, [Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_42}]\cdot}1.5H_2O$을 가지고 있는 inorganicorganic complex의 촉매 활성도를 Biginelli 반응에 적용하여 연구하였다. Dihydropyrimidinones를 one-pot 합성하는 반응에서, $H_3PMo_12}O_40}$ 촉매 보다[Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_42}]\cdot}1.5H_2O$ 촉매가 더 좋은 결과를 나타내었다. The catalytic activity of an inorganic-organic complex with a vanadium-substituted polyoxometalate 1, formulated as [Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_42}]\cdot}1.5H_2O$ was studied in the Biginelli reactions. The obtained results showed that, in the one-pot synthesis of dihydropyrimidinones, the turnover frequencies (TOF) for the [Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_42}]\cdot}1.5H_2O$ catalyst were higher than the $H_3PMo_12}O_40}$ catalyst.

  我们研究了一种具有钒取代聚金属氧酸盐1的无机有机复合材料的催化活性，化学式为[Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_42}]\cdot}1.5H_2O$，应用于Biginelli反应。在一锅合成二氢嘧啶酮的反应中，[Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_42}]\cdot}1.5H_2O$催化剂的周转频率（TOF）高于$H_3PMo_12}O_40}$催化剂。
• One-Pot synthesis of dihydropyrimidinones by dodecylphosphonic acid as solid Bronsted Acid Catalyst under Solvent-Free Conditions via Biginelli condensation
  作者：S. Ghassamipour、A. R. Sardarian

  DOI：10.1007/bf03245884

  日期：2010.3

  Dodecylphosphonic acid is a solid Bronsted acid that catalyzes efficiently the preparation of dihydropyrimidinones by Biginelli condensation under solvent-free conditions. This protocol offers several advantages including high yields, short reaction times, easy work-up, and use of cheap, relatively moderate acidic and safe catalyst.

  十二烷基膦酸是一种固体布朗斯台德酸，可在无溶剂条件下通过Biginelli缩合有效催化制备二氢嘧啶酮。该方案具有许多优点，包括产率高，反应时间短，易于后处理以及使用廉价，相对中等酸性和安全的催化剂。
• Light-induced Free Radical Oxidation of 2-Oxo-1,2,3,4-tetrahydropyrimidines
  作者：Hamid Reza Memarian、Leila Hejazi、Asadallah Farhadi

  DOI：10.1515/znb-2012-0313

  日期：2012.3.1

  A variety of 4-substituted 5-acetyl- and 5-carboethoxy-2-oxo-1,2,3,4-tetrahydropyrimidines were oxidized under UV irradiation in the presence or absence of benzoyl peroxide. The nature of the substituents on the 4- and 5-positions of the heterocyclic ring affects the rate of photo-oxidation, and irradiation of these compounds in the presence of benzoyl peroxide decreases the time of reaction drastically. Removal of 4-H by a benzoyloxy radical under formation of a trihydropyrimidinoyl radical intermediate occurs in the rate-determining step. The stability of this benzylic and allylic radical intermediate is affected by the nature and the position of the additional substituent on the phenyl group located at C-4.

  一系列4-取代的5-乙酰基和5-羧乙酯基-2-氧代-1,2,3,4-四氢嘧啶在紫外辐射下在有或无苯甲酰过氧化物存在下被氧化。杂环环上4-和5-位置的取代基的性质影响光氧化的速率，这些化合物在有苯甲酰过氧化物存在下的照射显著减少了反应时间。在速率决定步骤中，苯甲酰氧自由基去除4-H形成三氢嘧啶基自由基中间体。这种苄基和烯丙基自由基中间体的稳定性受到苯基团上附加取代基的性质和位置的影响，该苯基团位于C-4。