1,3-dimethyl-6-(4-methylphenyl)uracil | 105202-39-9

• 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: 1,3-dimethyl-6-(4-methylphenyl)uracil
• 英文别名: 1,3-dimethyl-6-(p-tolyl)uracil；1,3-dimethyl-6-p-tolylpyrimidine-2,4(1H,3H)dione；1,3-Dimethyl-6-(4-methylphenyl)pyrimidine-2,4-dione
• CAS: 105202-39-9
• 化学式: C₁₃H₁₄N₂O₂
• 分子量: 230.266
• InChiKey: PIYZNWKFDDYHDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,3-二甲基脲嘧啶 在 叔丁基过氧化氢 、 copper(l) iodide 、 caesium carbonate 、 三(五氟苯基)膦 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 1,3-dimethyl-6-(4-methylphenyl)uracil
  参考文献：
  名称：

  C-H Trifluoromethylations of 1,3-Dimethyluracil and Reactivity of the Products in C-H Arylations

  摘要：

  Diverse electrophilic, nucleophilic and radical C-H trifluoromethylations of 1,3-dimethyluracil were systematically studied in order to prepare either 5- or 6-(trifluoromethyl)uracil derivatives. Electrophilic reagents led only to dimeric bis-uracil products, whereas the radical trifluoromethylation by CF3SO2Na in presence of t-BuOOH gave 1,3-dimethyl-5-(trifluoromethyl)uracil (2) in good yield. The 6-(trifluoromethyl)uracil derivative 3 was only prepared in low yield and in a mixture with 2 by Ir-catalyzed borylation followed by treatment with the Togni's reagent. Attempted Pd-catalyzed C-H arylations of 2 in the presence of Cs2CO3 gave mixtures of de-trifluoromethylated products, whereas the reaction with 4-iodotoluene in the presence of CsF gave the desired 6-aryl-5-trifluoromethyluracil derivative 8 in moderate yield and the reaction was not general for other aryl halides.

  DOI：

  10.3987/com-14-12958

文献信息

• Pd(II)-catalyzed regioselective direct arylation of uracil via oxidative Heck reaction using arylboronic acids
  作者：Biplab Mondal、Somjit Hazra、B. Roy

  DOI：10.1016/j.tetlet.2013.12.092

  日期：2014.1

  A palladium catalyzed regioselective synthesis of 6-aryl uracils via oxidative Heck reaction (C–H bond functionalization) of uracils and arylboronic acids is reported. The method is simple, atom-economical, and high yielding.

  据报道，钯通过尿嘧啶和芳基硼酸的氧化Heck反应（CH键功能化）催化6-芳基尿嘧啶的区域选择性合成。该方法简单，原子经济且产率高。
• Palladium-catalyzed direct 5-arylation of 1,3-dimethyluracil with aryl bromides: an electrophilic metalation–deprotonation with electrophilic arylpalladium intermediate
  作者：Ko Hoon Kim、Hyun Seung Lee、Jae Nyoung Kim

  DOI：10.1016/j.tetlet.2011.09.066

  日期：2011.11

  An efficient method of palladium-catalyzed direct 5-arylation of 1,3-dimethyluracil was developed with a various range of aryl bromides including electron-deficient aryl bromides. 5-Aryluracil derivatives were obtained in moderate to good yields regioselectively most likely via an electrophilic metalation–deprotonation process.

  开发了一种有效的钯催化的1,3-二甲基尿嘧啶的直接5-芳基化反应，该方法使用了各种范围的芳基溴化物，包括缺电子的芳基溴化物。5-芳基尿嘧啶衍生物是通过亲电金属化-去质子化过程以区域选择性高至中等收率获得的。
• Switching the Regioselectivity of Direct C-H Arylation of 1,3-Dimethyluracil
  作者：Miroslava Čerňová、Radek Pohl、Michal Hocek

  DOI：10.1002/ejoc.200900586

  日期：2009.8

  An interesting dichotomy in the regioselectivity and mechanism of direct C–H arylation of 1,3-dimethyluracil was observed. Its Pd-catalyzed reactions with diverse aryl halides in the absence of CuI lead preferentially to 5-aryluracils, while reactions in the presence of CuI give 6-aryl derivatives as the major products. Cu-mediated reactions (in the absence of a Pd catalyst) proceed with lower efficiency

  观察到 1,3-二甲基尿嘧啶直接 C-H 芳基化的区域选择性和机制的有趣二分法。在不存在 CuI 的情况下，它与多种芳基卤化物的 Pd 催化反应优先导致 5-芳基尿嘧啶，而在 CuI 存在下的反应得到 6-芳基衍生物作为主要产物。Cu 介导的反应（在没有 Pd 催化剂的情况下）以较低的效率进行，但只产生 6-芳基尿嘧啶衍生物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Regioselective Direct C–H Arylations of Protected Uracils. Synthesis of 5- and 6-Aryluracil Bases
  作者：Miroslava Čerňová、Igor Čerňa、Radek Pohl、Michal Hocek

  DOI：10.1021/jo2006494

  日期：2011.7.1

  A new regioselective synthesis of 5- and 6-aryluracil bases based on direct C–H arylations of diverse 1,3-protected uracils has been developed. Benzyl-protected uracils were selected as the most practical in terms of stability during the arylation and facile cleavage of the benzyl groups. Pd-catalyzed C–H arylations in the absence of CuI gave preferentially 5-aryl-, whereas the reactions in the presence

  基于多种1,3保护的尿嘧啶的直接C–H芳基化反应，已开发了一种5和6芳基尿嘧啶碱基的区域选择性合成新方法。就苄基的芳基化和容易裂解过程中的稳定性而言，选择苄基保护的尿嘧啶是最实用的。在没有CuI的情况下，Pd催化的CH芳基化反应优先生成5-芳基-，而在存在CuI的情况下，反应则生成6-芳基-1,3-二苄基尿嘧啶。通过在Pd / C上转移氢解或通过用BBr 3处理而进行的最终脱保护，以良好的收率得到了所需的游离芳基化的尿嘧啶碱。
• Photolysis of 5-bromo-1,3-dimethyluracil in substituted benzenes.
  作者：KOH-ICHI SEKI、KOHKI MATSUDA、YUKO BANDO、KAZUE OHKURA

  DOI：10.1248/cpb.36.4737

  日期：——

  Photolysis of5-bromo-1, 3-dimethyluracil (5-BDMU) in substituted benzenes afforded the corresponding 5-aryl derivatives together with the unexpected 6-isomers as an isomeric mixture. The 6-isomers were found to be derived from the protonated 5-BDMU, presumably via the interaction between LUMO5-BDMU (in the excited triplet state) and LUMOaryl (in the ground state).

  光解取代苯中的 5-溴-1, 3-二甲基尿嘧啶（5-BDMU）可得到相应的 5-芳基衍生物以及意想不到的 6-异构体异构体混合物。研究发现，6-异构体来自质子化的 5-BDMU，可能是通过 LUMO5-BDMU（激发三重态）和 LUMOaryl（基态）之间的相互作用产生的。