(3,3-difluoroprop-1-ene-1,3-diyl)dibenzene

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (3,3-difluoroprop-1-ene-1,3-diyl)dibenzene
• 英文别名: [(E)-1,1-difluoro-3-phenylprop-2-enyl]benzene
• 化学式: C₁₅H₁₂F₂
• 分子量: 230.257
• InChiKey: GZWSSPDLDAJTLQ-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (1,1-difluoro-3-(phenylsulfonyl)propane-1,3-diyl)dibenzene 在 potassium tert-butylate 作用下， 以 1,4-二氧六环 为溶剂， 以53 %的产率得到(3,3-difluoroprop-1-ene-1,3-diyl)dibenzene
  参考文献：
  名称：

  使用芳烃硫醇盐作为光还原剂和硫源进行光诱导的烯烃芳基二氟甲基磺酰化/硫醚化

  摘要：

  在此，我们报告了一种实用且温和的烯烃、三氟甲基芳烃和芳硫醇之间三组分反应的合成方案。在此反应中，三氟甲基芳烃发生选择性 C-F 活化。系统中的芳烃硫醇盐起着双重作用：电子供体和自由基捕获剂。该过程仅在 2 小时内释放副产物氟阴离子。此外，所得二氟甲基硫醚可以用间氯过苯甲酸（m -CPBA）进一步氧化，获得独特但具有挑战性且几乎前所未有的磺酰基偕二氟甲基产物，其底物超过36种，产率高达95%。我们的协议可以轻松扩大规模以产生 3.4 克产品，这是进一步功能化所需的核心结构。这些转化可应用于后期分子开发，这在生物相关和制药领域可能具有巨大的兴趣和潜力。本质上，进行了实验研究和 DFT 计算，结果表明存在光诱导 EDA（电子供体-受体）复合物的途径，随后是自由基-自由基交叉偶联过程。

  DOI：

  10.1039/d3gc03471b

文献信息

• METHOD FOR PRODUCING FLUORINATED COMPOUND
  申请人：DAIKIN INDUSTRIES, LTD.

  公开号：US20190071376A1

  公开（公告）日：2019-03-07

  This invention solves the problem of providing an efficient, new method for producing a fluoromethylene-containing compound. The problem can be solved by a method for producing a compound represented by formula (1) or a ring-closed or ring-opened derivative of the compound, wherein R 1 represents an organic group, R X represents hydrogen or fluorine, R 2a , R 2b , R 2c , and R 2d are the same or different, and each represents —Y—R 21 or —N(—R 22 ) 2 , or R 2b and R 2c may join together to form a bond, wherein Y represents a bond, oxygen, or sulfur, R 21 represents hydrogen or an organic group, and R 22 , in each occurrence, is the same or different and represents hydrogen or an organic group; the method comprising step A of reacting a compound represented by formula (2), wherein X represents a leaving group, and other symbols are as defined above, with a compound represented by formula (3), wherein the symbols are as defined above, in the presence of a reducing agent under light irradiation.

  这项发明解决了提供一种用于生产含氟甲烯基化合物的高效新方法的问题。该问题可通过一种用于生产由化学式（1）表示的化合物或该化合物的环闭合或环开放衍生物的方法来解决，其中R1代表有机基团，RX代表氢或氟，R2a、R2b、R2c和R2d相同或不同，每个代表—Y—R21或—N(—R22)2，或者R2b和R2c可以结合形成键，其中Y代表键、氧或硫，R21代表氢或有机基团，每次出现的R22相同或不同，代表氢或有机基团；该方法包括以下步骤：A. 在光照射下，在存在还原剂的条件下，使化学式（2）表示的化合物与化学式（3）表示的化合物发生反应。
• One-Electron Reductive Cleavage of the C–Cl Bond of ArCF₂Cl: Convenient Route for the Synthesis of ArCF₂Derivatives
  作者：Masato Yoshida、Ayako Morishima、Daiki Suzuki、Masahiko Iyoda、Kozo Aoki、Shigeru Ikuta

  DOI：10.1246/bcsj.69.2019

  日期：1996.7

  When ArCF2Cl was reacted with PhSeNa in DMF in the presence of light, it was found that a SRN1 type reaction occurred to give ArCF2SePh. As the reaction did not proceed without light, the substitution reaction should be initiated by photo-induced electron transfer from PhSe− to ArCF2Cl. The cleavage of the C–Cl bond of PhCF2Cl by one-electron reduction with samarium(II) iodide to give a PhCF2 radical and chloride ion was also observed. The PhCF2 radical, thus formed, was trapped by styrene and phenylacetylene before it was reduced to PhCF2 anion. UHF/3-21G calculation demonstrated that one-electron reduction in PhCF2Cl led the spontaneous dissociation of the C–Cl bond to the PhCF2 radical and Cl−, but the PhCF3 radical anion existed as a stable form.

  当ArCF2Cl与PhSeNa在DMF中在光存在下反应时，发现发生SRN1型反应，生成ArCF2SePh。由于反应在没有光的情况下无法进行，因此取代反应应通过光诱导电子从 PhSe− 转移到 ArCF2Cl 来引发。还观察到用碘化钐(II)进行单电子还原，PhCF2Cl的C-Cl键断裂，产生PhCF2自由基和氯离子。由此形成的PhCF2自由基在被还原为PhCF2阴离子之前被苯乙烯和苯乙炔捕获。 UHF/3-21G计算表明，PhCF2Cl中的单电子还原导致C-Cl键自发解离为PhCF2自由基和Cl−，但PhCF3自由基阴离子以稳定形式存在。
• Photoredox-Catalyzed Hydrodifluoroalkylation of Alkenes Using Difluorohaloalkyl Compounds and a Hantzsch Ester
  作者：Shuhei Sumino、Misae Uno、Takahide Fukuyama、Ilhyong Ryu、Makoto Matsuura、Akinori Yamamoto、Yosuke Kishikawa

  DOI：10.1021/acs.joc.7b00609

  日期：2017.5.19

  Photoredox-catalyzed hydrodifluoroalkylation of alkenes proceeded smoothly in the presence of a Hantzsch ester as a hydrogen source under visible light irradiation. The reaction was also applicable to the hydrodifluoroalkylation of alkynes, and a continuous photo flow reaction was also successful.
• Yoshida Masato, Suzuki Daiki, Iyoda Masahiko, Chem. Lett, (1994) N 12, S 2357-2360
  作者：Yoshida Masato, Suzuki Daiki, Iyoda Masahiko

  DOI：——

  日期：——