3-(difluoromethyl)-5-(trifluoromethyl)-1H-pyrazole | 1015780-64-9

• 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-(difluoromethyl)-5-(trifluoromethyl)-1H-pyrazole
• 英文别名: 3-(Difluoromethyl)-5-(trifluoromethyl)-1H-pyrazole；5-(difluoromethyl)-3-(trifluoromethyl)-1H-pyrazole
• CAS: 1015780-64-9
• 化学式: C₅H₃F₅N₂
• 分子量: 186.084
• InChiKey: JNZMCMSGSKHZQW-UHFFFAOYSA-N

物化性质

• 沸点：
  186.2±35.0 °C(Predicted)
• 密度：
  1.519±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  28.7
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  N-tert-butyl-3-difluoromethyl-5-trifluoromethyl-4-pyrazolecarboxylic acid ethyl ester 在 copper(I) oxide 、 1,10-菲罗啉 、 水 、 苯甲醚 、 三氟乙酸 、 sodium hydroxide 作用下， 以 N-甲基吡咯烷酮 、 喹啉 、 乙醇 、 水 为溶剂， 反应 33.0h， 生成 3-(difluoromethyl)-5-(trifluoromethyl)-1H-pyrazole
  参考文献：
  名称：

  A New Synthesis and Process Development of Bis(fluoroalkyl)pyrazoles As Novel Agrophores

  摘要：

  The synthesis of 3,5-bis(fluoroalkyl)-pyrazoles as novel agrophores is described. Commercially available fluoroacetoacetates are treated with BF3-activated TFEDMA affording in a straightforward one-pot sequence pyrazole carboxylates in good yields and with excellent regioselectivity. The carboxylate intermediates have been converted into the corresponding pyrazolic acids and submitted to decarboxylation, affording valuable building blocks for the design of novel bioactive ingredients. The found process is suitable for scale up and preparation of compounds in kilogram quantity.

  DOI：

  10.1021/op500102h

文献信息

• A Major Advance in the Synthesis of Fluoroalkyl Pyrazoles: Tuneable Regioselectivity and Broad Substitution Patterns
  作者：Etienne Schmitt、Armen Panossian、Jean-Pierre Vors、Christian Funke、Norbert Lui、Sergiy Pazenok、Frédéric R. Leroux

  DOI：10.1002/chem.201601621

  日期：2016.8.1

  A novel approach towards highly functionalized fluoroalkyl pyrazoles was developed by using fluoroalkyl amino reagents in combination with a variety of fluorinated ketimines. Tuneable introduction of fluoroalkyl groups in the 3‐ and 5‐positions was possible by using vinamidinium intermediates or the corresponding enamino ketones after hydrolysis. These high‐value building blocks can give rise to a

  通过结合使用氟代烷基氨基试剂和各种氟化酮亚胺，开发了一种高度官能化的氟代烷基吡唑的新方法。在水解后使用乙烯基ami中间体或相应的烯胺酮，可以在3位和5位上引入氟烷基基团。这些高价值的组成部分可以为生物活性筛选和在各种生命科学领域中发现新的杂环生物活性成分提供大量类似物。
• [EN] PROCESS FOR PREPARING 3,5-BIS(HALOALKYL)PYRAZOLE DERIVATIVES FROM α,α-DIHALOAMINES AND KETIMINES<br/>[FR] PROCÉDÉ DE PRÉPARATION DE DÉRIVÉS DE 3,5-BIS(HALOALKYL)PYRAZOLE À PARTIR D'Α,Α-DIHALOAMINES ET DE CÉTIMINES
  申请人：BAYER CROPSCIENCE AG

  公开号：WO2015144578A1

  公开（公告）日：2015-10-01

  Process for preparine3,5-bis(haloalkyl)pyrazolederivatives from a,a-dihaloamines and ketimines The present invention relates to a novel process for preparing 3,5-bis(haloalkyl)pyrazole derivatives from a,a-dihaloamines and ketimines. Intermedaites used in the process are also claimed.

  从α,α-二卤胺和酮亚胺制备3,5-双(卤代烷基)吡唑衍生物的过程。本发明涉及一种从α,α-二卤胺和酮亚胺制备3,5-双(卤代烷基)吡唑衍生物的新方法。该过程中使用的中间体也被要求。
• [EN] PROCESS FOR PREPARING 3,5-BIS(FLUOROALKYL)PYRAZOLE DERIVATIVES FROM α,α-DIHALOAMINES<br/>[FR] PROCÉDÉ DE PRÉPARATION DE DÉRIVÉS DE 3,5-BIS(FLUOROALKYL)PYRAZOLE À PARTIR DE &Agr;,&Agr;-DIHALOAMINES
  申请人：BAYER CROPSCIENCE AG

  公开号：WO2014187773A1

  公开（公告）日：2014-11-27

  The present invention relates to a novel process for preparing 3,5-bis(fluoroalkyl)pyrazole derivatives from α,α-dihaloamines.

  本发明涉及一种从α，α-二卤胺制备3,5-双(氟烷基)吡唑衍生物的新工艺。
• A General Approach towards NH-Pyr­azoles That Bear Diverse Fluoroalkyl Groups by Means of Fluorinated Iminium Salts
  作者：Etienne Schmitt、Grégory Landelle、Jean-Pierre Vors、Norbert Lui、Sergiy Pazenok、Frédéric R. Leroux

  DOI：10.1002/ejoc.201500920

  日期：2015.9

  A new and general approach to important fluoroalkyl-substituted pyrazoles has been developed. The approach is based on the use of fluoroalkyl amino reagents and their Lewis acid activation to form a fluoroalkyl iminium salt that acts as a formal “fluoroacyl transfer reagent”. Their interaction with readily available fluoroalkyl azines followed by spontaneous cyclization of the formed intermediates

  已开发出一种新的通用方法来处理重要的氟代烷基取代的吡唑。该方法基于使用氟烷基氨基试剂及其路易斯酸活化形成氟烷基亚胺盐，作为正式的“氟酰基转移试剂”。它们与容易获得的氟烷基吖嗪相互作用，然后在酸性条件下形成的中间体自发环化，导致形成 3,5-二取代的吡唑。该反应用途广泛，收率高，可以快速获得带有两个氟烷基官能团（相同或不同）的吡唑。否则这些化合物很难制备。该反应具有可扩展性，适合工业化生产。
• [EN] PROCEDURE FOR THE DECARBOXYLATION OF 3,5-BIS(HALOALKYL)-PYRAZOLE-4-CARBOXYLIC ACID DERIVATIVES<br/>[FR] PROCÉDURE DE DÉCARBOXYLATION DE DÉRIVÉS D'ACIDE 3,5-BIS(HALOALKYL)-PYRAZOLE-4-CARBOXYLIQUE
  申请人：BAYER CROPSCIENCE AG

  公开号：WO2014033164A1

  公开（公告）日：2014-03-06

  A new process for the preparation of 3,5-bis(haloalkyl)-pyrazole derivatives of the general formula (I), is described, resulting from the reaction of 3,5-bis(haloalkyl)-pyrazole-4-carboxylic acid derivatives of the general formula (IIa) with a copper compound and a base at elevated temperature wherein R1 is selected from H, C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl or C7-19-alkylaryl, CH2CN, CH2CX3, CH2COOH, CH2COO(C1-12)-alkyl, and X is independently of each other F, Cl, Br, I; R2 and R3 are selected independently of each other from C1-C6-haloalkyl.

  介绍了一种新的制备通式为（I）的3,5-双（卤代烷基）-吡唑衍生物的方法，其结果是将通式为（IIa）的3,5-双（卤代烷基）-吡唑-4-羧酸衍生物与铜化合物和碱在高温下反应，其中R1从H，C1-12-烷基，C3-8-环烷基，C6-18-芳基，C7-19-芳基烷基或C7-19-烷基芳基，CH2CN，CH2CX3，CH2COOH，CH2COO（C1-12）-烷基中选择，而X独立地为F、Cl、Br、I；R2和R3独立地从C1-C6卤代烷基中选择。