1-p-nitrophenyl-3-trifluoromethyl-5-phenylpyrazole | 303130-62-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-p-nitrophenyl-3-trifluoromethyl-5-phenylpyrazole
• 英文别名: 1-(p-nitrophenyl)-5-phenyl-3-trifluoromethylpyrazole；5-(4-nitrophenyl)-1-phenyl-3-trifluoromethylpyrazole；1-(4-nitrophenyl)-5-phenyl-3-(trifluoromethyl)pyrazole
• CAS: 303130-62-3
• 化学式: C₁₆H₁₀F₃N₃O₂
• 分子量: 333.27
• InChiKey: MRNJPCJLQVXYCJ-UHFFFAOYSA-N

物化性质

• 熔点：
  87 °C
• 沸点：
  456.3±45.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  63.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  丙烯酸丁酯 、 1-p-nitrophenyl-3-trifluoromethyl-5-phenylpyrazole 在 palladium diacetate 、 silver carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以78%的产率得到(E)-butyl 3-(1-(4-nitrophenyl)-5-phenyl-3-(trifluoromethyl)-1H-pyrazol-4-yl)acrylate
  参考文献：
  名称：

  A new and direct route to 3-fluoromethyl substituted pyrazol-4-acrylates via Pd-catalyzed C–H activation

  摘要：

  Direct C4-H activation of 3-fluoromethyl pyrazoles followed by an oxidative coupling with acrylates, which is perhaps the most direct method for the synthesis of 3-fluoromethyl substituted pyrazol-4-aciylates of biological interest, remains challenging. Here, the first example of the straightforward olefination via Pd-catalyzed C4-H activation of both C3-CF3 and C3-CF2H substituted pyrazoles is reported. The reaction of various C3-CF3 substituted pyrazoles with acrylates proceeds smoothly in the presence of Pd(OAc)(2) and Ag2CO3, whereas olefination of C3-CF2H substituted pyrazoles requires the addition of benzoquinone. A further computational study reveals that reactivity of the pyrazolyl substrates employed are strongly impacted by the substituents of different nature on their C1 or C5 position, which is in good agreement with the experimental data. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.06.058
• 作为产物：
  描述：

  苯甲酰三氟丙酮 、 4-硝基苯肼 在 sodium acetate 作用下， 以 乙醇 为溶剂， 反应 4.25h， 以62%的产率得到1-p-nitrophenyl-3-trifluoromethyl-5-phenylpyrazole
  参考文献：
  名称：

  肼与β-二羰基化合物之间的反应：机制建议

  摘要：

  芳基或杂芳基肼与氟化 β-二酮 (CF3COCH2COR) 之间的反应生成各种 3-、5- 和 3,5-三氟甲基吡唑和 5-三氟甲基-5-羟基-Δ2-吡唑...

  DOI：

  10.1139/v00-104

文献信息

• Synthesis of 1,3,5-Trisubstituted [4-<i>tert</i>-Butyl 2-(5,5-difluoro-2,2-dimethyl-6-vinyl-1,3-dioxan-4-yl)acetate]pyrazoles via a Pd-Catalyzed CH Activation
  作者：Xiaoguang Wang、Xiang Fang、Xueyan Yang、Meng Ni、Fanhong Wu

  DOI：10.1002/cjoc.201201100

  日期：2012.12

  The gem‐difluoromethylenated acetonide 2 was efficiently synthesized as new precursor of HMG‐CoA reductase inhibitor. Straightforward olefination via Pd‐catalyzed C4‐H activation of 1,3,5‐trisubstituted pyrazoles 1 was proceeded smoothly in the presence of Pd(OAc)2 and AgCO3. This protocol has merits in terms of the improved atomic economy and prevention from the generation of by‐products.

  所述宝石-difluoromethylenated丙酮化合物2作为HMG-CoA还原酶抑制剂的新的前体有效地合成。在Pd（OAc）2和AgCO 3的存在下，通过Pd催化的1,3,5-三取代的吡唑1的C 4 -H活化的直链烯烃化反应顺利进行。该协议在改善原子经济和防止副产物生成方面具有优势。
• The reaction of aryl and heteroarylhydrazines with aryl-trifluoromethyl β-diketones
  作者：Shiv P. Singh、Vinod Kumar、Ranjana Aggarwal、Jose Elguero

  DOI：10.1002/jhet.5570430428

  日期：2006.7

  We report the results obtained when five aromatic or heteroaromatic hydrazines react with six β-diketones bearing trifluoromethyl and aryl substituents. Forty-two compounds have been isolated corresponding to two isomeric trifluoromethyl pyrazoles and the intermediate 5-CF3, 5-OH pyrazolines. The results have provided useful information for establishing the mechanism of the synthesis of pyrazoles.

  我们报告了当五个芳香族或杂芳香族肼与六个带有三氟甲基和芳基取代基的β-二酮反应时获得的结果。四十二个化合物已被分离出对应于两个同分异构的三氟甲基吡唑和中间体5-CF 3，5-OH吡唑啉。该结果为建立吡唑的合成机理提供了有用的信息。
• The reaction between hydrazines and β-dicarbonyl compounds: proposal for a mechanism
  作者：Shiv P Singh、Dalip Kumar、Hitesh Batra、Rajesh Naithani、Isabel Rozas、José Elguero

  DOI：10.1139/v00-104

  日期：2000.8.1

  The reaction between aryl or heteroarylhydrazines with fluorinated β-diketones (CF3COCH2COR) yields a variety of 3-, 5-, and 3,5-trifluoromethylpyrazoles and 5-trifluoromethyl-5-hydroxy-Δ2-pyrazoli...

  芳基或杂芳基肼与氟化 β-二酮 (CF3COCH2COR) 之间的反应生成各种 3-、5- 和 3,5-三氟甲基吡唑和 5-三氟甲基-5-羟基-Δ2-吡唑...
• Pyrazole formation: Examination of kinetics, substituent effects, and mechanistic pathways
  作者：Joseph C. Sloop、Brent Lechner、Gary Washington、Carl L. Bumgardner、W. David Loehle、William Creasy

  DOI：10.1002/kin.20316

  日期：2008.7

  Reaction kinetics for the condensation of 1,3-diketones 1a–o with selected arylhydrazines (aryl = Ph, 4-NO2Ph, 4-CH3OPh, and 2,4-diNO2Ph) was studied using 19F NMR spectroscopy. Product regioselectivity is modulated by reactant ratios, substituents, and acidity. Reaction rates were found to be influenced by substituents on the diketones and on phenylhydrazines as well as by acidity of the reaction

  使用 19F NMR 光谱研究了 1,3-二酮 1a-o 与选定的芳基肼（芳基 = Ph、4-NO2Ph、4-CH3OPh 和 2,4-diNO2Ph）缩合的反应动力学。产物的区域选择性受反应物比例、取代基和酸度的调节。发现反应速率受二酮和苯肼上的取代基以及反应介质酸度的影响，速率变化高达 1000 倍。确定了这些环化的 Hammett ρ 值。发现该反应在二酮和芳基肼中都是一级反应。吡唑形成的速率决定步骤随着 pH 值的变化而变化。提出了支持这些发现的机制细节和反应途径。© 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 370–383, 2008
• Inhibitors against the activation of ap-1 and nfat
  申请人：Muto Susumu

  公开号：US20060100257A1

  公开（公告）日：2006-05-11

  A medicament inhibiting the activation of AP-1 which comprises as an active ingredient a substance selected from the group consisting of a compound represented by the following general formula (I) and a pharmacologically acceptable salt thereof, and a hydrate thereof and a solvate thereof: wherein X represents a connecting group whose number of atoms in the main chain is 2 to 5 (said connecting group may be substituted), A represents hydrogen atom or acetyl group, E represents an aryl group which may be substituted or a hetero aryl group which may be substituted, ring Z represents an arene which may have one or more substituents in addition to the group represented by formula —O-A wherein A has the same meaning as that defined above and the group represented by formula —X-E wherein each of X and E has the same meaning as that defined above, or a heteroarene which may have one or more substituents in addition to the group represented by formula —O-A wherein A has the same meaning as that defined above and the group represented by formula —X-E wherein each of X and E has the same meaning as that defined above.

  一种药物，抑制AP-1的激活，其活性成分为以下通式（I）所表示的化合物或其药学上可接受的盐、水合物或溶剂化物中所选的一种，其中X代表连接基，其主链中的原子数为2至5（该连接基可以被取代），A代表氢原子或乙酰基，E代表芳基或取代的杂芳基，环Z代表芳烃，除了由式—O-A所表示的基团外，可能还有一个或多个取代基，其中A具有上述定义的相同含义，由式—X-E所表示的基团中，X和E的每一个具有上述定义的相同含义，或者是一个杂芳烃，可能还有一个或多个取代基，其中A具有上述定义的相同含义，由式—X-E所表示的基团中，X和E的每一个具有上述定义的相同含义。