1,2-Difluor-1,1-diphenyl-propan | 309-45-5

• 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: 1,2-Difluor-1,1-diphenyl-propan
• 英文别名: (1,2-Difluoro-1-phenyl-propyl)-benzene；(1,2-difluoro-1-phenylpropyl)benzene
• CAS: 309-45-5
• 化学式: C₁₅H₁₄F₂
• 分子量: 232.273
• InChiKey: CBXREZUDHSGYCE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 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-甲基-2,2-二苯基乙烯 在 pyridine hydrofluoride 、 Selectfluor 、 triethylamine tris(hydrogen fluoride) 作用下， 以 氯仿 为溶剂， 以95 %的产率得到1,2-Difluor-1,1-diphenyl-propan
  参考文献：
  名称：

  通过 I(I)/I(III) 催化的环丙烯活化：原理证明和在直接四氟化中的应用

  摘要：

  公开了通过 I(I)/I(III) 催化歧管对环丙烯活化的初步验证，以实现 3,3-二芳基环丙烯的直接四氟化。这种转变是通过原位生成 ArI(III)F 2来实现的，其中廉价的碘苯、胺·HF 络合物和 Selectfluor® 分别用作催化剂、氟化物源和氧化剂。利用这种方法，可以在一次操作中生成四个 C(sp 3 )-F 键（高达 44%）。Hammett 的一项研究表明，该反应相对于p-芳基的取代基。通过反应解构过程，提出了涉及两个离散催化过程的机制。虽然第一个循环导致 3,3-二芳基环丙烯的开环氟化，但第二个循环通过氟化/铪离子重排进行以释放四氟化二芳基乙烷。该研究将高价碘催化添加到促进环丙烯活化的策略中。

  DOI：

  10.1016/j.tet.2022.132925

文献信息

• Fluorination with caesium fluoroxysulphate. Room temperuture flourination of phenyl substituted olefins
  作者：Stojan Stavber、Marko Zupan

  DOI：10.1016/s0040-4020(01)88055-8

  日期：1986.1

  Room-temperature fluorination of 1,1-diphenylethene with caesium fluoroxysulphate in methylene chloride resulted in an addition elimination process, thus yielding 1, 1-diphenyl-2-fluoroethene, while in the presence of nucleophile containing species, i.e., hydrogen fluoride, methanol, or acetic acid, either vicinal difluorides, methoxy fluorides or acetoxy fluorides were formed. Reaction with norbornene

  在二氯甲烷中用氟代硫酸铯在室温下氟化1,1-二苯基乙烯导致加成消除过程，从而生成1,1-二苯基-2-氟乙烯，同时存在含有亲核试剂的物质，即氟化氢，甲醇或乙酸，形成邻位二氟化物，甲氧基氟化物或乙酰氧基氟化物。在没有亲核试剂的情况下与降冰片烯反应仅产生7-氟降三环烷和7-syn-氟降冰片-2-烯，而与2-苯基丙-1-烯的类似反应得到3-氟和3,3-二氟-2-苯基丙酯-1-烯。在各种亲核试剂供体（例如氟化氢，甲醇或氢）的存在下，用氟代硫酸铯转化1,1-二苯基丙-1-烯，1,1-二苯基-2-氟乙烯和1,1-二苯基-2-溴乙烯。醋酸，
• Fluorination with XeF2. Part 40. The Important Role of .pi.-Bond Disruption in Fluorine Addition to Phenyl-Substituted Alkenes
  作者：Stojan Stavber、Tjasa Sotler、Marko Zupan、Arkadij Popovic

  DOI：10.1021/jo00099a015

  日期：1994.10

  Ionization potentials (IP) for 11 mono- and alpha,alpha-diphenyl-substituted acyclic and cyclic alkenes 1-11 were measured under the same conditions, using a mass spectrometric technique and applying electron impact ionization. The values, ranging from 8.68 eV for styrene (1) to as low as 7.67 eV for 1,2-dihydro-4-phenylnaphthalene (10), were correlated with the logarithms of the relative rates (k(rel), relative to 1,1-diphenylethene) of fluorine addition across the carbon-carbon double bond in HF-catalyzed reaction of the alkenes with XeF2 in CH2Cl2 at room temperature. The linear relationship between log k(rel) and IP with a regression slope of -2.08 and a correlation constant of 0.942, presented for the first time for any fluorination reaction of organic compounds, demonstrates that ct-bond disruption is the rate-determining step in the fluorine addition process for the series of alkenes 1-11. The course of reaction of the series of three 1-phenyl-benzocyclenes (10-12) with XeF2 was investigated. The addition-elimination process, forming 3-phenyl-2-fluoro-1H-indene (15a), was found exclusively in the case of 9-phenyl-1H-indene (12), while the formation of diastereoisomeric pairs of vicinal difluorides (13 and 14), with the trans isomers slightly predominant, was established in the case of 1,2-dihydro-4-phenylnaphthalene (10) and 6,7-dihydro-9-phenyl-5H-benzocycloheptene (11). On heating the vicinal difluorides 13 and 14 HF was released, thus yielding 3-fluoro-4-phenyl-1,2-dihydronaphthalene (15b) and 6,7-dihydro-8-fluoro-9-phenyl-5H-benzocycloheptene (15c), respectively.
• Fluorination with xenon difluoride. Reaction with phenylsubstituted olefins
  作者：Marko Zupan、Alfred Pollak

  DOI：10.1021/jo00887a015

  日期：1976.12
• STAVBER S.; ZUPAN M., TETRAHEDRON, 42,(1986) N 18, 5035-5043
  作者：STAVBER S.、 ZUPAN M.

  DOI：——

  日期：——
• Cyclopropene activation via I(I)/I(III) catalysis: Proof of principle and application in direct tetrafluorination
  作者：Stephanie Meyer、Lea Göbel、Keith Livingstone、Christoph Roblick、Constantin G. Daniliuc、Ryan Gilmour

  DOI：10.1016/j.tet.2022.132925

  日期：2022.11

  activation by an I(I)/I(III) catalysis manifold is disclosed to enable the direct tetrafluorination of 3,3-diarylcyclopropenes. This transformation occurs through the in situ generation of ArI(III)F2, with inexpensive iodobenzene, amine·HF complexes and Selectfluor® serving as catalyst, fluoride source and oxidant, respectively. Leveraging this approach, it has been possible to generate four C(sp3)-F

  公开了通过 I(I)/I(III) 催化歧管对环丙烯活化的初步验证，以实现 3,3-二芳基环丙烯的直接四氟化。这种转变是通过原位生成 ArI(III)F 2来实现的，其中廉价的碘苯、胺·HF 络合物和 Selectfluor® 分别用作催化剂、氟化物源和氧化剂。利用这种方法，可以在一次操作中生成四个 C(sp 3 )-F 键（高达 44%）。Hammett 的一项研究表明，该反应相对于p-芳基的取代基。通过反应解构过程，提出了涉及两个离散催化过程的机制。虽然第一个循环导致 3,3-二芳基环丙烯的开环氟化，但第二个循环通过氟化/铪离子重排进行以释放四氟化二芳基乙烷。该研究将高价碘催化添加到促进环丙烯活化的策略中。