5-(difluoromethoxy)benzo[d][1,3]dioxole | 1226157-22-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 5-(difluoromethoxy)benzo[d][1,3]dioxole
• 英文别名: 5-(Difluoromethoxy)-1,3-benzodioxole；5-(difluoromethoxy)-1,3-benzodioxole
• CAS: 1226157-22-7
• 化学式: C₈H₆F₂O₃
• mdl: MFCD16302705
• 分子量: 188.131
• InChiKey: DWPAXKFIAJQZTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  芝麻酚 、 三氟甲烷 在 水 、 potassium hydroxide 作用下， 以 1,4-二氧六环 为溶剂， 50.0 ℃ 、101.33 kPa 条件下， 反应 0.5h， 以69%的产率得到5-(difluoromethoxy)benzo[d][1,3]dioxole
  参考文献：
  名称：

  Use of Fluoroform as a Source of Difluorocarbene in the Synthesis of Difluoromethoxy- and Difluorothiomethoxyarenes

  摘要：

  Fluoroform, CHF3, a non-ozone-depleting, nontoxic, and inexpensive gas can be used as a difluorocarbene source in a process for the conversion of phenols and thiophenols to their difluoromethoxy and difluorothiomethoxy derivatives. The reactions are carried out at moderate temperatures and atmospheric pressure, using potassium hydroxide as base in a two-phase (water/dioxane or water/acetonitrile) process to provide moderate to good yields of the respective products.

  DOI：

  10.1021/jo401392f

文献信息

• [EN] SYNTHESIS OF DIFLUOROMETHYL ETHERS AND SULFIDES<br/>[FR] SYNTHÈSE DE DIFLUOROMÉTHYLÉTHERS ET DE DIFLUOROMÉTHYLSULFURES
  申请人：UNIV CALIFORNIA

  公开号：WO2014107380A1

  公开（公告）日：2014-07-10

  The synthesis of difluoromethyl ethers and sulfides with a simple, non-ozone- depleting reagent is described. The difluoromethylation of phenols with this reagent occurs at room temperature within minutes with exceptional functional group tolerance. The mild conditions makes possible tandem processes for the conversion of aryl boronic acids, aryl halides and arenes to difluoromethyl ethers. Mechanistic studies support a reaction pathway involving nucleophilic attack of the phenolate to difluorocarbene.

  描述了使用一种简单、无臭氧破坏剂的方法合成二氟甲基醚和硫醚。使用这种试剂对酚进行二氟甲基化反应在室温下几分钟内就能完成，并且具有异常的官能团容忍性。温和的条件使得可能进行串联过程，将芳基硼酸、芳基卤代烃和芳烃转化为二氟甲基醚。机理研究支持一个涉及酚酚根攻击二氟卡宾的反应途径。
• Decarboxylative Trifluoromethylating Reagent [Cu(O₂ CCF₃ )(phen)] and Difluorocarbene Precursor [Cu(phen)₂ ][O₂ CCF₂ Cl]
  作者：Xiaoxi Lin、Chuanqi Hou、Haohong Li、Zhiqiang Weng

  DOI：10.1002/chem.201504306

  日期：2016.2.5

  exhibited a linear relationship and a reaction parameter (ρ)=+0.56±0.02, which indicated that the trifluoromethylation reaction proceeded via a nucleophilic reactive species. Complex 2 reacts with phenols to produce aryl difluoromethyl ethers in modest‐to‐excellent yields. Mechanistic investigations revealed that the difluoromethylation reaction proceeds by initial copper‐mediated formation of difluorocarbene

  本文介绍了一种新型的经济型脱羧三氟甲基化试剂[Cu（phen）（O 2 CCF 3）]（1 ; phen = 1,10-菲咯啉）和有效的二氟卡宾前体[Cu（phen）2 ] [O 2 CCF 2 Cl ]（2）。用苯酚处理叔丁醇铜，然后加入三氟乙酸或氯二氟乙酸，分别提供了空气稳定的络合物1和2，其特征在于X射线晶体学分析。在铜（I）离子1由二齿配位体啉，单齿三氟乙基，和CH的分子配位扭曲的四面体配位几何形状的3 CN。的分子结构2采用的是由一个的离子形式[铜（phen）的2 ] +阳离子和氯二氟乙一个阴离子。配合物1与各种芳基和杂芳基卤化物反应以高收率形成三氟甲基（杂）芳烃。相应的哈米特图显示出线性关系和反应参数（ρ）＝ + 0.56±0.02，这表明三氟甲基化反应是通过亲核反应性物质进行的。复杂2与酚反应生成芳基二氟甲基醚，产率中等至优异。机理研究表明，二氟甲基化反应是通过最初的铜介导的
• SYNTHESIS OF DIFLUOROMETHYL ETHERS AND SULFIDES
  申请人：THE REGENTS OF THE UNIVERSITY OF CALIFORNIA

  公开号：US20150336866A1

  公开（公告）日：2015-11-26

  The synthesis of difluoromethyl ethers and sulfides with a simple, non-ozone-depleting reagent is described. The difluoromethylation of phenols with this reagent occurs at room temperature within minutes with exceptional functional group tolerance. The mild conditions makes possible tandem processes for the conversion of aryl boronic acids, aryl halides and arenes to difluoromethyl ethers. Mechanistic studies support a reaction pathway involving nucleophilic attack of the phenolate to difluorocarbene.