dimethyl 2-(trichloromethyl)pyrimidine-4,5-dicarboxylate | 143034-42-8

• 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-(trichloromethyl)pyrimidine-4,5-dicarboxylate
• CAS: 143034-42-8
• 化学式: C₉H₇Cl₃N₂O₄
• 分子量: 313.525
• InChiKey: HQWFULQSEPVSBU-UHFFFAOYSA-N

物化性质

• 沸点：
  309.2±42.0 °C(Predicted)
• 密度：
  1.544±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  78.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(trichloromethyl)pyrimidine-4,5-dicarboxylate 在 镍 、 sodium hydride 作用下， 以 甲醇 为溶剂， 反应 1.5h， 生成 dimethyl 2-methylpyrimidine-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：

  2-trichloromethyl-4-dimethylamino-1,3-diaza-1,3-butadiene 、 丁炔二酸二甲酯 以 甲苯 为溶剂， 反应 0.25h， 以98%的产率得到dimethyl 2-(trichloromethyl)pyrimidine-4,5-dicarboxylate
  参考文献：
  名称：

  Synthesis of pyrimidines from 2-trichloromethyl-4-dimethylamino-1,3-diaza-1,3-butadienes and electron deficient acetylenes

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(00)92660-1

文献信息

• Chemoselective Reduction of Trichloromethyl Compounds to <i>gem</i>-Dichloromethyl Groups Following Appel’s Reaction Protocol
  作者：Moises A. Romero-Reyes、Ivann Zaragoza-Galicia、Horacio F. Olivo、Moises Romero-Ortega

  DOI：10.1021/acs.joc.6b02044

  日期：2016.10.7

  trichloroacetyl compounds following the modification of Appel’s reaction protocol, using triphenylphosphine and methanol, afforded the corresponding dichloroacetyl compounds, with the exception of trichloroacetylmorpholine, in yields of 80–98% under very mild experimental conditions. Likewise, when trichloromethyl heterocyclic compounds contain another reactive functional group, the reaction is highly chemoselective

  修改Appel的反应方案（使用三苯基膦和甲醇）后，简单而轻松地还原三氯乙酰基化合物即可得到相应的二氯乙酰基化合物（三氯乙酰基吗啉除外），在非常温和的实验条件下收率可达80-98％。同样，当三氯甲基杂环化合物包含另一个反应性官能团时，该反应是高度化学选择性的，得到二氯甲基衍生物。
• Facile Synthesis of Thiolacetates from Trichloromethyl Compounds
  作者：Moisés Romero-Ortega、Horacio Reyes、Adrián Covarruvias-Zuñiga、Raymundo Cruz、José Gustavo Avila-Zarraga

  DOI：10.1055/s-2003-42463

  日期：——

  A new method for the conversion of trichloromethyl compounds into the corresponding thiolacetates by treatment with sodium thiolacetate in the presence of thiolacetic acid is described. This transformation proceeds at room temperature in high yield when a strong electron-withdrawing substituent is attached to the trichloromethyl group.

  描述了一种在硫代乙酸存在下用硫代乙酸钠处理将三氯甲基化合物转化为相应硫代乙酸盐的新方法。当强吸电子取代基连接到三氯甲基时，这种转变在室温下以高产率进行。
• 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。
• A new synthesis of 2-substituted-1,3-dithianes from trichloromethyl compounds
  作者：Nancy González Rivera、David Corona Becerril、Carlos Guadarrama-Pérez、Adrian Covarrubias-Zuñiga、José Gustavo Avila-Zárraga、Moisés Romero-Ortega

  DOI：10.1016/j.tetlet.2006.12.066

  日期：2007.2

  Trichloromethyl compounds are efficiently converted into 1,3-dithianes upon reaction with a disodium 1,3-propanedithiolate-1,3-propanedithiol mixture in DMF solution at 0 degrees C. This synthesis is limited to those substrates where the substituent attached to the trichloromethyl group is an electron-withdrawing group. (c) 2006 Elsevier Ltd. All rights reserved.