3,4,5-tris(trifluoromethyl)pyrazole | 19968-20-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 3,4,5-tris(trifluoromethyl)pyrazole
• 英文别名: 3,4,5-tris(trifluoromethyl)-1H-pyrazole
• CAS: 19968-20-8
• 化学式: C₆HF₉N₂
• mdl: MFCD22989471
• 分子量: 272.073
• InChiKey: FTPCKDUEVYSIIY-UHFFFAOYSA-N

物化性质

• 沸点：
  163.4±35.0 °C(Predicted)
• 密度：
  1.684±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  28.7
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  copper(I) oxide 、 3,4,5-tris(trifluoromethyl)pyrazole 反应 4.0h， 以90%的产率得到[(3,4,5-tris(trifluoromethyl)pyrazolyl)Cu]₃
  参考文献：
  名称：

  离散铜（I）配合物的重大固态结构重排实现的乙烯吸附热量低

  摘要：

  三核铜（I）吡唑特配合物[铜3 ]重排的双核类似物[铜2 ⋅（C 2 H ^ 4）2 ]当暴露于乙烯气体。值得注意的是，[铜3 ]↔[铜2 ⋅（C 2 H ^ 4）2 ]重排可逆地在固体状态下发生。此外，这种转变模拟了溶液化学。与固态重排有关的键形成和断裂过程导致观察到的吸附热（每Cu–C 2 H 4为−13±1 kJ mol -1相互作用）显着低于其他Cu–C 2 H 4相互作用（≥−24 kJ mol -1）。较低的总吸附热，“阶跃”等温线，高乙烯容量（2.76 mmol g -1；在293 K下为7.6 wt％）和高乙烯/乙烷选择性（在293 K下为136：1）使[ Cu 3 ]成为合理设计低能耗乙烯/乙烷分离材料的有趣基础。

  DOI：

  10.1002/anie.201810460
• 作为产物：
  描述：

  3,5-双(三氟甲基)吡唑 在 盐酸 、 正丁基锂 、 sulfur tetrafluoride 、 氢氟酸 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 14.25h， 生成 3,4,5-tris(trifluoromethyl)pyrazole
  参考文献：
  名称：

  “Reported, but Still Unknown.” A Closer Look into 3,4-Bis- and 3,4,5-Tris(trifluoromethyl)pyrazoles

  摘要：

  Straightforward practical synthetic approaches to 3,4-bis- and 3,4,5-tris(trifluoromethyl)pyrazoles have been developed. The key step of the both syntheses is a transformation of the carboxylic group in a pyrazole core into the trifluoromethyl group by sulfur tetrafluoride. The elaborated synthetic protocols allow gram-scale preparation of the target products. The obtained compounds are comprehensively characterized by means of crystallographic analysis, determination of pK(a) values and fluorescence measurements.

  DOI：

  10.1021/jo202305c

文献信息

• One-Pot Synthesis of CF₃-Substituted Pyrazolines/Pyrazoles from Electron-Deficient Alkenes/Alkynes and CF₃CHN₂Generated in situ: Optimized Synthesis of Tris(trifluoromethyl)pyrazole
  作者：Evgeniy Y. Slobodyanyuk、Olexiy S. Artamonov、Oleg V. Shishkin、Pavel K. Mykhailiuk

  DOI：10.1002/ejoc.201301852

  日期：2014.4

  The [3+2] cycloaddition of CF3CHN2, generated in situ, with electron-deficient alkenes/alkynes affords CF3-substituted pyrazolines/pyrazoles in quantitative yields. The one-pot three-component reaction between CF3CH2NH2·HCl, NaNO2, and the substrate proceeds at room temperature in dichloromethane/water.

  原位生成的 CHN2 与缺电子烯烃/炔烃的 [3+2] 环加成以定量产率提供 CF3 取代的吡唑啉/吡唑。 CH2NH2·HCl、NaNO2和底物之间的一锅三组分反应在室温下在二氯甲烷/水中进行。
• 1,3-Dipolar Cycloadditions of Ethyl 2-Diazo-3,3,3-trifluoropropanoate to Alkynes and [1,5] Sigmatropic Rearrangements of the Resulting 3<i>H</i>-Pyrazoles: Synthesis of Mono-, Bis- and Tris(trifluoromethyl)-Substituted Pyrazoles
  作者：Daniel Gladow、Sebastian Doniz-Kettenmann、Hans-Ulrich Reissig

  DOI：10.1002/hlca.201400032

  日期：2014.6

  3‐dipolar cycloadditions of ethyl 2‐diazo‐3,3,3‐trifluoropropanoate with electron‐rich and electron‐deficient alkynes, as well as the van AlphenHüttel rearrangements of the resulting 3H‐pyrazoles were investigated. These reactions led to a series of CF3‐substituted pyrazoles in good overall yields. Phenyl‐ and diphenylacetylene proved to be unreactive, but, at high temperature, the diazoalkane and phenylacetylene

  乙基2-重氮-3,3,3- trifluoropropanoate的1,3-偶极环加成与富电子和缺电子炔烃，以及在货车尔芬 Hüttel所得3个的重排ħ -pyrazoles进行了调查。这些反应导致了一系列CF 3取代的吡唑，总收率良好。苯基和二苯基乙炔被证明是不活泼的，但是在高温下，重氮烷烃和苯基乙炔提供了环丙烯衍生物。如所期望的，与胺缺乏电子的炔烃相比，向胺中的1,3-偶极环加成发生的速度快得多。除一个例外，所有环加成反应均具有出色的区域选择性。初级3 H的[1,5]σ重排吡唑为产品提供了转移的酰基；未检测到CF 3基团迁移产生的产物。与文献报道一致，这种带有3个带有吸电子取代基的H-吡唑的重排反应更快。
• Deoxofluorination of (Hetero)aromatic Acids
  作者：Serhii Trofymchuk、Maksym Ya. Bugera、Anton A. Klipkov、Bohdan Razhyk、Sergey Semenov、Karen Tarasenko、Viktoriia S. Starova、Olga A. Zaporozhets、Oksana Yu. Tananaiko、Anatoliy N. Alekseenko、Yurii Pustovit、Oleksandr Kiriakov、Igor I. Gerus、Andrei A. Tolmachev、Pavel K. Mykhailiuk

  DOI：10.1021/acs.joc.9b03011

  日期：2020.3.6

  Diverse trifluoromethyl-substituted compounds were synthesized by deoxofluorination of cinnamic and (hetero)aromatic carboxylic acids with sulfur tetrafluoride. The obtained products were used as starting materials in the preparation of novel fluorinated amino acids, anilines, and aliphatic amines - valuable building blocks for medicinal chemistry and agrochemistry.

  通过用四氟化硫对肉桂酸和（杂）芳族羧酸进行脱氧氟化反应，合成了不同的三氟甲基取代的化合物。所得产物用作制备新型氟化氨基酸，苯胺和脂肪胺的原料，这些氟化物是药物化学和农业化学的重要组成部分。
• [EN] SOLID-STATE COPPER(I) SORBENTS FOR OLEFIN SEPARATIONS<br/>[FR] SORBANTS DE CUIVRE (I) À L'ÉTAT SOLIDE POUR SÉPARATIONS D'OLÉFINES
  申请人：UNIV TEXAS

  公开号：WO2020081540A1

  公开（公告）日：2020-04-23

  Disclosed herein is a process for separating a hydrocarbon feed gas mixture comprising constituents including ethylene to produce a separated ethylene product. The disclosed process employs a solid-state ethylene sorbent and temperature and/or pressure swing adsorption and membrane separation and demonstrates a methodology to reduce the net heat of reaction during the adsorption of ethylene onto an adsorbent.

  本文披露了一种用于分离含有乙烯等成分的烃类原料气混合物以生产分离的乙烯产品的过程。本文披露的过程采用固态乙烯吸附剂和温度和/或压力摆动吸附和膜分离，并展示了一种在乙烯吸附剂上吸附乙烯时减少反应净热的方法论。
• Silver(I) and Copper(I) Adducts of a Tris(pyrazolyl)borate Decorated with Nine Trifluoromethyl Groups
  作者：Naleen B. Jayaratna、Igor I. Gerus、Roman V. Mironets、Pavel K. Mykhailiuk、Muhammed Yousufuddin、H. V. Rasika Dias

  DOI：10.1021/ic302715d

  日期：2013.2.18

  Silver and copper ethylene adducts and the silver carbonyl complex of the tris(pyrazolyl)borate [HB(3,4,5-(CF3)(3)Pz)(3)](-) (which is based on one of the most acidic pyrazoles known) have been synthesized. C-13 NMR resonance signals of metal-bound ethylene carbon atoms of [HB(3,4,5-(CF3)(3)Pz)(3)]Ag(C2H4) and [HB(3,4,5-(CF3)(3)Pz)(3)]Cu(C2H4) appear at delta 111.6 and 94.9, respectively. The CO stretching frequency of the silver adduct [HB(3,4,5-(CF3)(3)Pz)(3)]Ag(CO) is significantly higher than that of free CO, but it appears at a region less sensitive to the ligand electronic effects of tris(azolyl)borate silver adducts.