dimethyl 2-<(phenylthio)methyl>pyrimidine-4,5-dicarboxylate | 143034-56-4

• 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: dimethyl 2-<(phenylthio)methyl>pyrimidine-4,5-dicarboxylate
• 英文别名: dimethyl 2-(phenylsulfanylmethyl)pyrimidine-4,5-dicarboxylate
• CAS: 143034-56-4
• 化学式: C₁₅H₁₄N₂O₄S
• 分子量: 318.353
• InChiKey: IAYANJYDFDCPEA-UHFFFAOYSA-N

物化性质

• 沸点：
  418.8±35.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.34
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  78.38
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  dimethyl 2-<(phenylthio)methyl>pyrimidine-4,5-dicarboxylate 在 镍 、 sodium hydride 作用下， 以 甲醇 为溶剂， 反应 4.67h， 生成 dimethyl 2-n-butylpyrimidine-4,5-dicarboxylate
  参考文献：
  名称：

  1,3-Diaza-1,3-butadienes. Synthesis and Conversion into Pyrimidines by [4π + 2π] Cycloaddition with Electron Deficient Acetylenes. Synthetic Utility of 2-(Trichloromethyl)pyrimidines¹

  摘要：

  Methods have been devised to generate 1H-1,3-diaza-1,3-butadienes bearing a leaving group at position-4 in latent, masked, and unprotected forms. A hallmark of these azadienes is that they undergo thermal [4 pi + 2 pi] cycloaddition reactions with electron deficient acetylenes to give adducts which are aromatized to pyrimidine derivatives under the reaction conditions. Thus, 1-(methoxycarbonyl)-3-acylamidines 17 on beating in solution are converted in situ into the 1,3-diaza-1,3-dienes 18 and/or 19 which react with dimethyl acetylenedicarboxylate (DMAD) to produce the pyrimidines 20. The 1-Boc-1,3-diaza-1,3-dienes 24 are masked forms of the LH-dienes inasmuch as they react with DMAD under relatively mild conditions to give the dihydropyrimidine adducts 25, which are easily detectable by H-1 NMR spectroscopy, and which aromatize to pyrimidines 26 at higher temperatures. The 4-methylthio compounds 31 and 33, and the 2-(trichloromethyl) compounds 37, are isolable, relatively stable, 1H-1,3-diaza-1,3-butadienes, These easily prepared compounds react with electron deficient acetylenes under mild conditions to provide the pyrimidines 20, 34, and 38, respectively, in fair to excellent yields. The 2-(trichloromethyl)pyrimidines 38 are very useful precursors of a wide variety of other 2-substituted pyrimidines 46-52.

  DOI：

  10.1021/jo952106w
• 作为产物：
  描述：

  dimethyl 2-pyrimidine-4,5-dicarboxylate 在 sodium thiophenolate 、 苯硫酚 作用下， 以 四氢呋喃 为溶剂， 生成 dimethyl 2-<(phenylthio)methyl>pyrimidine-4,5-dicarboxylate
  参考文献：
  名称：

  1,3-Diaza-1,3-butadienes. Synthesis and Conversion into Pyrimidines by [4π + 2π] Cycloaddition with Electron Deficient Acetylenes. Synthetic Utility of 2-(Trichloromethyl)pyrimidines¹

  摘要：

  Methods have been devised to generate 1H-1,3-diaza-1,3-butadienes bearing a leaving group at position-4 in latent, masked, and unprotected forms. A hallmark of these azadienes is that they undergo thermal [4 pi + 2 pi] cycloaddition reactions with electron deficient acetylenes to give adducts which are aromatized to pyrimidine derivatives under the reaction conditions. Thus, 1-(methoxycarbonyl)-3-acylamidines 17 on beating in solution are converted in situ into the 1,3-diaza-1,3-dienes 18 and/or 19 which react with dimethyl acetylenedicarboxylate (DMAD) to produce the pyrimidines 20. The 1-Boc-1,3-diaza-1,3-dienes 24 are masked forms of the LH-dienes inasmuch as they react with DMAD under relatively mild conditions to give the dihydropyrimidine adducts 25, which are easily detectable by H-1 NMR spectroscopy, and which aromatize to pyrimidines 26 at higher temperatures. The 4-methylthio compounds 31 and 33, and the 2-(trichloromethyl) compounds 37, are isolable, relatively stable, 1H-1,3-diaza-1,3-butadienes, These easily prepared compounds react with electron deficient acetylenes under mild conditions to provide the pyrimidines 20, 34, and 38, respectively, in fair to excellent yields. The 2-(trichloromethyl)pyrimidines 38 are very useful precursors of a wide variety of other 2-substituted pyrimidines 46-52.

  DOI：

  10.1021/jo952106w

文献信息

• Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles
  作者：Guillermo Caballero-García、Moisés Romero-Ortega、Joaquín Barroso-Flores

  DOI：10.1039/c6cp04321f

  日期：——

  promote the electrophilic behavior of chlorine atoms in a trichloromethyl group when bound to an electron-withdrawing moiety. A halogen bond-type non-covalent interaction between a chlorine atom and a negatively charged sulfur atom takes place, causing the abstraction of such a chlorine atom while leaving a carbanion, subsequently driving the chemical reduction of the trichloromethyl group to a sulfide

  当与吸电子部分结合时，显示出σ-孔可促进三氯甲基中氯原子的亲电行为。氯原子与带负电荷的硫原子之间发生卤素键型非共价相互作用，导致此类氯原子的提取，同时留下了碳负离子，随后逐步将三氯甲基化学还原为硫化物过程。通过1追踪三氯甲基嘧啶1与硫酚盐和硫酚的模型反应生成苯硫醚4的机理。H-NMR并使用DFT跃迁态计算进行了研究，并充分讨论了该转变的能量分布。为了评估σ孔的存在并通过最大表面静电势对其进行量化，对一系列三氯甲基化合物进行了MP2静电势的计算。这样的计算表明，氯原子作为亲核攻击的亲电离去基团，为三氯甲基的合成化学开辟了新的可能性。
• Synthesis of pyrimidines from 2-trichloromethyl-4-dimethylamino-1,3-diaza-1,3-butadienes and electron deficient acetylenes
  作者：Angel Guzmán、Moisés Romero、Francisco X. Talamás、Joseph M. Muchowski

  DOI：10.1016/s0040-4039(00)92660-1

  日期：1992.6

  2-Trichloromethyl-4-dimethylamino-1,3-diaza-1,3-butadienes(3), prepared from trichloroacetamidine(1) and amide acetals 2, readily react with electron deficient acetylenes 4 to give 2-trichloromethylpyrimidines 5.