4,6-二甲基-2-苯基嘧啶 | 14164-34-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 中文名称: 4,6-二甲基-2-苯基嘧啶
• 英文名称: 4,6-dimethyl-2-phenylpyrimidine
• CAS: 14164-34-2
• 化学式: C₁₂H₁₂N₂
• mdl: MFCD01436254
• 分子量: 184.241
• InChiKey: TVNUWBFICZWTRU-UHFFFAOYSA-N

物化性质

• 熔点：
  83-84 °C
• 沸点：
  163 °C(Press: 17 Torr)
• 密度：
  1.060±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.166
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,6-二甲基-2-苯基嘧啶 以 乙醇 为溶剂， 生成 (Z)-4-(methylamino)-3-penten-2-one
  参考文献：
  名称：

  Schmidt,R.R. et al., Chemische Berichte, 1970, vol. 103, p. 2760 - 2767

  摘要：

  DOI：
• 作为产物：
  描述：

  双(3,5-二甲基吡唑-1-基)(苯基)甲烷 在 calcium bis{bis(trimethylsilyl)amide} 作用下， 以 四氢呋喃 为溶剂， 生成 4,6-二甲基-2-苯基嘧啶
  参考文献：
  名称：

  Metalation of Aryl‐bis(3‐alkyl‐5‐methylpyrazol‐1‐yl)‐ methane (Alkyl=Me, Ad; Aryl=Ph, C ₆ H ₄ ‐2−OH) with NaN(SiMe ₃ ) ₂ , KN(SiMe ₃ ) ₂ , and Ca{N(SiMe ₃ ) ₂ } ₂

  摘要：

  AbstractDeprotonation of phenyl‐bis(3,5‐dimethylpyrazolyl)methane (HC(Ph)(PzMe2)2, 1 a) with [(thf)2Ca{N(SiMe3)2}2] in THF at −40 °C yields heteroleptic [(thf)2Ca{N(SiMe3)2}{C(Ph)(PzMe2)2}] (2 a) and finally homoleptic [(thf)Ca{C(Ph)(PzMe2)2}2] (2 b). However, these complexes degrade at room temperature to calcium bis(pyrazolate) and 2‐phenyl‐4,6‐dimethylpyrimidine (3 a). This degradation is accelerated when bulky phenyl‐bis(3‐adamantyl‐5‐methylpyrazolyl)methane (HC(Ph)(PzAd,Me)2, 1 b) is treated similarly and 2‐phenyl‐4‐adamantyl‐6‐methylpyrimidine (3 b) forms quickly. Sodiation of 1 a and 1 b with NaN(SiMe3)2 yields [{HC(Ph)(PzMe2)2}Na{C(Ph)(PzMe2)2}] (4 a) and [{HC(Ph)(PzAd,Me)2}Na{C(Ph)(PzAd,Me)2}] (4 b). The stronger metalation reagent benzylpotassium is able to quantitatively deprotonate 1 b leading to dinuclear [K{C(Ph)(PzAd,Me)2}]2 (4 c). The metathetical approach and the reaction of 4 c with metal(II) halides of Mg, Ca and Zn again leads to degradation and formation of pyrimidine 3 b. This decomposition of the ligand can be circumvented when the sidearm contains the anionic charge. Thus, 2‐hydroxyphenyl‐bis(3‐adamantyl‐5‐methylpyrazol‐1‐yl)methane (1 c) reacts with [(thf)2Ca{N(SiMe3)2}2] in THF to the homoleptic complex [(thf)4Ca{O−C6H4−CH(PzAd,Me)2}] (2 c). In this complex, THF and pyrazolyl bases compete in the coordination sphere and preparation of a heteroleptic complex fails. To avoid the binding competition between THF and pyrazolyl bases and to stabilize heteroleptic calcium complexes, the reaction has been repeated in toluene yielding [Ca{N(SiMe3)2}{O−C6H4−CH(PzAd,Me)2}]2 (2 d).

  DOI：

  10.1002/ejic.202101051

文献信息

• Iron Catalysis for Modular Pyrimidine Synthesis through β-Ammoniation/Cyclization of Saturated Carbonyl Compounds with Amidines
  作者：Xue-Qiang Chu、Wen-Bin Cao、Xiao-Ping Xu、Shun-Jun Ji

  DOI：10.1021/acs.joc.6b02767

  日期：2017.1.20

  method for the modular synthesis of various pyrimidine derivatives by means of the reactions of ketones, aldehydes, or esters with amidines in the presence of an in situ prepared recyclable iron(II)-complex was developed. This operationally simple reaction proceeded with broad functional group tolerance in a regioselective manner via a remarkable unactivated β-C–H bond functionalization. Control experiments

  开发了一种有效的方法，用于在原位制备的可回收铁（II）络合物存在下，通过酮，醛或酯与am的反应进行模块化合成各种嘧啶衍生物。该操作简单的反应通过显着的未激活的β-C-H键官能化，以区域选择性的方式在宽泛的官能团耐受性下进行。进行了对照实验以加深对机理的了解，并且反应很可能通过设计的TEMPO络合/烯胺添加/瞬时α占据/β-TEMPO消除/环化顺序进行。
• Ligand-Accelerated Iron- and Cobalt-Catalyzed Cross-Coupling Reactions between N-Heteroaryl Halides and Aryl Magnesium Reagents
  作者：Olesya M. Kuzmina、Andreas K. Steib、John T. Markiewicz、Dietmar Flubacher、Paul Knochel

  DOI：10.1002/anie.201210235

  日期：2013.4.26

  Quinoline and isoquinoline dramatically increase the rate and yield of Fe‐ and Co‐catalyzed cross‐coupling reactions. This new catalytic process extends the scope of such cross‐coupling reactions to include complex functional groups and allows heteroaryl–heteroaryl bond formation to occur.

  喹啉和异喹啉显着提高了Fe和Co催化的交叉偶联反应的速率和收率。这种新的催化过程扩展了这种交叉偶联反应的范围，使其包括复杂的官能团，并允许杂芳基-杂芳基键的形成。
• Iron-Catalyzed Cross-Coupling of <i>N</i>-Heterocyclic Chlorides and Bromides with Arylmagnesium Reagents
  作者：Olesya M. Kuzmina、Andreas K. Steib、Dietmar Flubacher、Paul Knochel

  DOI：10.1021/ol302136c

  日期：2012.9.21

  A simple, practical iron salt catalyzed procedure allows fast cross-couplings of N-heterocyclic chlorides and bromides with various electron-rich and -poor arylmagnesium reagents. A solvent mixture of THF and tBuOMe is found to be essential for achieving high yields mainly by avoiding homocoupling side reactions.

  简单，实用的铁盐催化方法可以使N-杂环氯化物和溴化物与各种富电子和贫-芳基镁试剂快速交叉偶联。发现THF和t BuOMe的溶剂混合物对于实现高收率至关重要，主要是通过避免均偶联副反应。
• Novel multi-component syntheses of pyrimidines using β-CD in aqueous medium
  作者：Chowrasia Rakhi、Katla Ramesh、Mariana P. Darbem、Tabata A. Branquinho、Aline Rufino de Oliveira、Padma Sunitha Manjari、Nelson Luís C. Domingues

  DOI：10.1016/j.tetlet.2016.02.106

  日期：2016.4

  Using β-cyclodextrin (β-CD) as a catalyst pyrimidine derivatives were synthesized for the first time in aqueous medium. β-CD is a recyclable, inexpensive, economically viable, non-toxic, and readily available material. Various aldehydes were used with ammonium acetate, and 1,3-diketones to generate a series of pyrimidine derivatives in good to excellent yields.

  以β-环糊精（β-CD）为催化剂，在水介质中首次合成了嘧啶衍生物。β-CD是一种可回收，廉价，经济可行，无毒且易于获得的材料。各种醛与乙酸铵和1,3-二酮一起使用可生成一系列嘧啶衍生物，收率好至极好。
• A novel convenient one step pyrimidine synthesis
  作者：A.L. Weis、V. Rosenbach

  DOI：10.1016/s0040-4039(01)90348-x

  日期：1981.1

  A new method for the preparation of pyrimidines by condensation of β-dicarbonyl compounds, ammonium salts and carbonyl containing substances has been developed.

  开发了一种通过β-二羰基化合物，铵盐和含羰基物质缩合制备嘧啶的新方法。