(difluoromethyl)(phenyl)selane | 101220-61-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (difluoromethyl)(phenyl)selane
• 英文别名: Difluoromethyl phenyl selenide；PhSeCF2H；Difluoromethylselanylbenzene
• CAS: 101220-61-5
• 化学式: C₇H₆F₂Se
• 分子量: 207.081
• InChiKey: ILVPMVFRPCCMCM-UHFFFAOYSA-N

物化性质

• 沸点：
  63-64 °C(Press: 9 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  1.24
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (difluoromethyl)(phenyl)selane 在 双氧水 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 3-propyl acetate
  参考文献：
  名称：

  Reaction of Difluoromethyl Phenyl Selenoxide with Acetic Anhydride. A Route to Difluoro(phenylseleno)methylation of Ethers

  摘要：

  Difluoromethyl phenyl selenoxide (2) has been prepared and allowed to react with acetic anhydride in the presence of cyclic ethers and sulfides. Difluorophenylselenomethylation occurred smoothly on reacting 2 with Ac2O in refluxing dichloromethane to give omega-[difluoro(phenylseleno)methoxy]alkyl acetates 4 in 34-87% yields. A sequential reaction of Pummerer type rearrangement, difluorocarbene formation, electrophilic addition of the carbene to oxygen of ethers leading to oxonium ylide, and trapping with phenylselenenyl acetate is proposed.

  DOI：

  10.1021/jo00107a016
• 作为产物：
  描述：

  二苯基二硒醚 在 sodium tetrahydroborate 、 4 A molecular sieve 、 四丁基氟化铵 、 magnesium 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.83h， 生成 (difluoromethyl)(phenyl)selane
  参考文献：
  名称：

  Synthesis and Transformation of [Difluoro(phenylseleno)methyl]- trimethylsilane

  摘要：

  [GRAPHIC]A novel and efficient strategy was developed to synthesize [difluoro(phenylseleno)methyl]trimethylsilane (PhSeCF2-TMS, 2), which was further utilized as a nucleophilic difluoromethylating reagent to incorporate the difluoro(phenylseleno)methyl (PhSeCF2) group into carbonyl compounds in good yields. The resulting PhSeCF2-containing alcohols 3 could be conveniently converted into corresponding difluoromethyl alcohols 4 by a radical deselenylation.

  DOI：

  10.1021/jo051119z

文献信息

• S-, N-, and Se-Difluoromethylation Using Sodium Chlorodifluoroacetate
  作者：Vaibhav P. Mehta、Michael F. Greaney

  DOI：10.1021/ol402370f

  日期：2013.10.4

  thiols is reported using chlorodifluoroacetate as the difluoromethylating agent. This cheap reagent undergoes smooth decarboxylation at 95 °C to afford difluorocarbene, which can be trapped with a variety of aromatic and heteroaromatic thiols. The reaction is also effective for the difluoromethylation of heterocyclic nitrogen compounds and phenylselenol.

  据报道，使用氯代二氟乙酸酯作为二氟甲基化剂的硫醇二氟甲基化的简单方案。这种廉价的试剂可在95°C的条件下顺利脱羧，得到二氟卡宾，可被多种芳族和杂芳族硫醇捕获。该反应对于杂环氮化合物和苯基硒醇的二氟甲基化也是有效的。
• Difluorophenylselenomethylation of ethers
  作者：Kenji Uneyama、Yukio Tokunaga、Kazuhiro Maeda

  DOI：10.1016/s0040-4039(00)91782-9

  日期：1993.2

  Pummerer reaction of difluoromethyl phenyl selenoxide with acetic anhydride proceeds at refluxing temperature of CH2Cl2, generating difluorophenylselenomethyl carbocation equivalent which can be trapped with cyclic ethers to give ω-(difluorophenylselenomethoxy)alkyl acetates 3.

  二氟甲基苯基亚硒酸酯与乙酸酐的Pummerer反应在CH 2 Cl 2的回流温度下进行，生成了二氟苯基硒代甲基碳阳离子当量，该当量可被环醚捕获，得到ω-（二氟苯基硒代甲氧基）烷基乙酸酯3。
• Difluoro(phenylchalcogen)methylation of aldehydes, ketones, and imines with S-, Se-, and Te-containing reagents PhXCF2H (X=S, Se, Te)
  作者：Mingyou Hu、Fei Wang、Yanchuan Zhao、Zhengbiao He、Wei Zhang、Jinbo Hu

  DOI：10.1016/j.jfluchem.2011.08.007

  日期：2012.3

  prepared, and their relative reactivity towards aldehydes, ketones, and imines was investigated. Compared to the former developed (phenylchalcogen)difluoromethylation reagents, these reagents are relatively easily available and more atom-economical in fluoroalkylation reactions. It was found that the efficient nucleophilic (phenylchalcogen)difluoromethylation of aldehydes, ketones, and imines could be

  制备了一系列含硫，硒和碲的（苯基硫属元素）二氟甲基化试剂PhSCF 2 H（1a），PhSeCF 2 H（1b）和PhTeCF 2 H （1c），它们对醛，酮，对亚胺进行了调查。与以前开发的（苯基硫属元素化物）二氟甲基化试剂相比，这些试剂相对容易获得，并且在氟代烷基化反应中更经济。发现用1a - 1c可以实现醛，酮和亚胺的有效亲核性（苯硫族元素）二氟甲基化。试剂1a和1b与羰基化合物和亚胺的反应活性比1c高，并且PhOCF 2 H（1d）无法进行类似的氟烷基化反应。
• A convenient, transition metal-free synthesis of difluoromethyl selenoethers from organic selenocyanates and TMSCF2H
  作者：Tao Dong、Jing Nie、Cheng-Pan Zhang

  DOI：10.1016/j.tet.2018.08.001

  日期：2018.9

  for the synthesis of aryl or alkyl difluoromethyl selenides (RSeCF2H) from the corresponding selenocyanates (RSeCN) and TMSCF2H/t-BuOK is described. The reaction performed in THF at 0 °C for 24 h or at room temperature for 6 h supplied a series of RSeCF2H in good to high yields. The successful preparation of difluoromethylselenolated sulfadimethoxine derivative and the scaled-up synthesis of 1-ben

  描述了一种由相应的硒氰酸酯（RSeCN）和TMCSF 2 H / t -BuOK合成芳基或烷基二氟甲基硒化物（RSeCF 2 H）的有效且无过渡金属的方法。在THF中于0°C进行24小时或在室温下进行6小时的反应可提供一系列RSeCF 2H以高产到高产。例如，成功制备了二氟甲基硒化的磺基二甲恶英衍生物并按比例放大合成了1-苄基-5-（（二氟甲基）硒基）二氢吲哚，表明该方法具有良好的实用性。该反应的优点包括温和的反应条件，良好的官能团耐受性，多种底物和高效率。该方案提供了许多新颖的二氟甲基硒醚，这些醚将加速此类化合物在生命科学领域的使用。
• Radical Difluoromethylation of Thiols with (Difluoromethyl)triphenylphosphonium Bromide
  作者：Niklas B. Heine、Armido Studer

  DOI：10.1021/acs.orglett.7b02109

  日期：2017.8.4

  A method for facile difluoromethylation of various thiols using (difluoromethyl)triphenylphosphonium bromide under mild reaction conditions is presented. The transformation proceeds in the absence of any transition metal using a bench-stable and readily accessible phosphonium salt. Deuterium labeling experiments and cyclic voltammetry measurements reveal that the difluoromethylation occurs via a S(RN)1-type mechanism. Substrate scope is broad, and various functional groups are tolerated (OH, NH2, amide, ester).