1,2-bis(trimethylsilyl)-1,1,2,2-tetrafluoroethane | 186824-44-2

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: 1,2-bis(trimethylsilyl)-1,1,2,2-tetrafluoroethane
• 英文别名: 1,1,2,2-tetrafluoro-1,2-bis(trimethylsilyl)ethane；trimethyl-(1,1,2,2-tetrafluoro-2-trimethylsilylethyl)silane
• CAS: 186824-44-2
• 化学式: C₈H₁₈F₄Si₂
• 分子量: 246.396
• InChiKey: UQEADPSQKLPUDX-UHFFFAOYSA-N

物化性质

• 沸点：
  131.0±40.0 °C(Predicted)
• 密度：
  0.970±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-bis(trimethylsilyl)-1,1,2,2-tetrafluoroethane 在 四丁基氟化铵 作用下， 生成 三甲基(1,2,2-三氟乙烯基)硅烷
  参考文献：
  名称：

  Preparation of and Fluoroalkylation with (Chlorodifluoromethyl)trimethylsilane, Difluorobis(trimethylsilyl)methane, and 1,1,2,2-Tetrafluoro-1,2-bis(trimethylsilyl)ethane

  摘要：

  CF2BrCl reacts with aluminum/N-methylpyrrolidinone in the presence of chlorotrimethylsilane to give Me(3)SiCF(2)Cl in high yield. Similarly, CF2Br2 gives Me(3)SiCF(2)Br with bromotrimethylsilane. Chlorodifluoromethylation of aldehydes using Me(3)SiCF(2)Cl and a catalytic amount of TBAF in polar solvents occurs at room temperature, providing difluoromethylated alcohols in two steps. Electroreduction of Me(3)SiCF(2)Cl in the presence of chlorotrimethylsilane gives Me(3)SiCF(2)SiMe(3) (anion-derived product) and Me(3)SiCF(2)CF(2)SiMe(3) (radical-derived product). Using THF/HMPA strongly favors the former, whereas THF/TDA-1 (tris(3,6-dioxaheptyl)amine) the latter. Me(3)SiCF(2)-SiMe(3) difluoromethylates aldehydes acting as a difluoromethylene dianion (''CF22-'' equivalent), whereas Me(3)SiCF(2)-CF(2)SiMe(3) acts at room temperature as an in situ source for the perfluorovinyl anion (due to beta-elimination of fluorotrimethylsilane). However, at low temperature the elimination pathway is suppressed and tetrafluoroethylene dianion (''-CF2CF2-'' equivalent) behavior is observed, The structure of Me(3)SiCF(2)CF(2)SiMe(3) was analyzed by X-ray diffraction. All of the studied fluoroalkylating reagents are moisture- and air-stable and can be readily obtained from a single convenient precursor (CF2BrCl).

  DOI：

  10.1021/ja962990n
• 作为产物：
  描述：

  二氟溴甲基三甲基硅烷 在 三甲基氯硅烷 、 三(3,6-二氧杂庚基)胺 、 四丁基溴化铵 作用下， 以 四氢呋喃 为溶剂， 生成 1,2-bis(trimethylsilyl)-1,1,2,2-tetrafluoroethane
  参考文献：
  名称：

  Preparation of and Fluoroalkylation with (Chlorodifluoromethyl)trimethylsilane, Difluorobis(trimethylsilyl)methane, and 1,1,2,2-Tetrafluoro-1,2-bis(trimethylsilyl)ethane

  摘要：

  CF2BrCl reacts with aluminum/N-methylpyrrolidinone in the presence of chlorotrimethylsilane to give Me(3)SiCF(2)Cl in high yield. Similarly, CF2Br2 gives Me(3)SiCF(2)Br with bromotrimethylsilane. Chlorodifluoromethylation of aldehydes using Me(3)SiCF(2)Cl and a catalytic amount of TBAF in polar solvents occurs at room temperature, providing difluoromethylated alcohols in two steps. Electroreduction of Me(3)SiCF(2)Cl in the presence of chlorotrimethylsilane gives Me(3)SiCF(2)SiMe(3) (anion-derived product) and Me(3)SiCF(2)CF(2)SiMe(3) (radical-derived product). Using THF/HMPA strongly favors the former, whereas THF/TDA-1 (tris(3,6-dioxaheptyl)amine) the latter. Me(3)SiCF(2)-SiMe(3) difluoromethylates aldehydes acting as a difluoromethylene dianion (''CF22-'' equivalent), whereas Me(3)SiCF(2)-CF(2)SiMe(3) acts at room temperature as an in situ source for the perfluorovinyl anion (due to beta-elimination of fluorotrimethylsilane). However, at low temperature the elimination pathway is suppressed and tetrafluoroethylene dianion (''-CF2CF2-'' equivalent) behavior is observed, The structure of Me(3)SiCF(2)CF(2)SiMe(3) was analyzed by X-ray diffraction. All of the studied fluoroalkylating reagents are moisture- and air-stable and can be readily obtained from a single convenient precursor (CF2BrCl).

  DOI：

  10.1021/ja962990n
• 作为试剂：
  描述：

  、 三甲基氯硅烷 、 溴二氟甲基苯基砜 在 19F 、 溴二氟甲基苯基砜 、 1,2-bis(trimethylsilyl)-1,1,2,2-tetrafluoroethane 、 ice water 、 正戊烷 、 硫酸 、 siloxane 、 silanol 、 碳酸氢钠 、 magnesium sulfate 、 crude product 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以to give 0.40 g crystalline product 20, m.p. 40˜42° C., yield 55%的产率得到1,2-bis(trimethylsilyl)-1,1,2,2-tetrafluoroethane
  参考文献：
  名称：

  Magnesium mediated preparation of fluorinated alkyl silanes

  摘要：

  本发明揭示了一种高效的方法，利用镁金属介导的还原三氟甲基和二氟甲基硅烷化反应，使用三氟甲基和二氟甲基硫化物、亚砜和磺酮来制备三氟甲基和二氟甲基硅烷。该过程的一个副产物是二苯基二硫化物。由于苯基三氟甲基磺酮、亚砜和硫化物可从易得的三氟甲烷和二苯基二硫化物制备而来，因此该方法可被认为是用环保的三氟甲烷制备（三氟甲基）三甲基硅烷的“伪催化”方法。

  公开号：

  US06803477B2

文献信息

• Preparation of Tri- and Difluoromethylsilanes via an Unusual Magnesium Metal-Mediated Reductive Tri- and Difluoromethylation of Chlorosilanes Using Tri- and Difluoromethyl Sulfides, Sulfoxides, and Sulfones
  作者：G. K. Surya Prakash、Jinbo Hu、George A. Olah

  DOI：10.1021/jo030110z

  日期：2003.5.1

  A new and efficient method for the preparation of tri- and difluoromethylsilanes using magnesium metal-mediated reductive tri- and difluoromethylation of chlorosilanes is reported using tri- and difluoromethyl sulfides, sulfoxides, and sulfones. The byproduct of the process is diphenyl disulfide. Since phenyl trifluoromethyl sulfone, sulfoxide, and sulfide are readily prepared from trifluoromethane

  据报道，使用三和二氟甲基硫化物，亚砜和砜，使用镁金属介导的氯硅烷的三和二氟甲基化还原反应来制备三和二氟甲基硅烷的新的有效方法。该方法的副产物是二苯基二硫化物。由于可以很容易地从三氟甲烷（CF（3）H）和二苯基二硫化物制备苯基三氟甲基砜，亚砜和硫化物，因此该方法可以认为是二苯基二硫化物的催化方法，用于制备（三氟甲基）三甲基硅烷（TMS-CF（3 ））来自不消耗臭氧的三氟甲烷。
• Geminal Silicon/Zinc Reagent as an Equivalent of Difluoromethylene Bis-carbanion
  作者：Mikhail D. Kosobokov、Vitalij V. Levin、Artem A. Zemtsov、Marina I. Struchkova、Alexander A. Korlyukov、Dmitry E. Arkhipov、Alexander D. Dilman

  DOI：10.1021/ol5002297

  日期：2014.3.7

  A new difluorinated reagent, [difluoro(trimethylsilyl)methyl]zinc bromide, bearing C-Zn and C-Si bonds is described. The reagent is conveniently prepared by cobalt-catalyzed halogen/zinc exchange. It can be coupled with two different C-electrophiles in a stepwise manner (with allylic halides for C-Zn bond and aldehydes for C-Si bond) affording products containing a difluoromethylene fragment.
• Controllable Fluorocarbon Chain Elongation: TMSCF₂Br-Enabled Trifluorovinylation and Pentafluorocyclopropylation of Aldehydes
  作者：An Liu、Xianghong Zhang、Feng Zhao、Chuanfa Ni、Jinbo Hu

  DOI：10.1021/jacs.3c12919

  日期：2024.1.24
• Preparation of and Fluoroalkylation with (Chlorodifluoromethyl)trimethylsilane, Difluorobis(trimethylsilyl)methane, and 1,1,2,2-Tetrafluoro-1,2-bis(trimethylsilyl)ethane
  作者：Andrei K. Yudin、G. K. Surya Prakash、Denis Deffieux、Michael Bradley、Robert Bau、George A. Olah

  DOI：10.1021/ja962990n

  日期：1997.2.1

  CF2BrCl reacts with aluminum/N-methylpyrrolidinone in the presence of chlorotrimethylsilane to give Me(3)SiCF(2)Cl in high yield. Similarly, CF2Br2 gives Me(3)SiCF(2)Br with bromotrimethylsilane. Chlorodifluoromethylation of aldehydes using Me(3)SiCF(2)Cl and a catalytic amount of TBAF in polar solvents occurs at room temperature, providing difluoromethylated alcohols in two steps. Electroreduction of Me(3)SiCF(2)Cl in the presence of chlorotrimethylsilane gives Me(3)SiCF(2)SiMe(3) (anion-derived product) and Me(3)SiCF(2)CF(2)SiMe(3) (radical-derived product). Using THF/HMPA strongly favors the former, whereas THF/TDA-1 (tris(3,6-dioxaheptyl)amine) the latter. Me(3)SiCF(2)-SiMe(3) difluoromethylates aldehydes acting as a difluoromethylene dianion (''CF22-'' equivalent), whereas Me(3)SiCF(2)-CF(2)SiMe(3) acts at room temperature as an in situ source for the perfluorovinyl anion (due to beta-elimination of fluorotrimethylsilane). However, at low temperature the elimination pathway is suppressed and tetrafluoroethylene dianion (''-CF2CF2-'' equivalent) behavior is observed, The structure of Me(3)SiCF(2)CF(2)SiMe(3) was analyzed by X-ray diffraction. All of the studied fluoroalkylating reagents are moisture- and air-stable and can be readily obtained from a single convenient precursor (CF2BrCl).
• Magnesium mediated preparation of fluorinated alkyl silanes
  申请人：——

  公开号：US20030153778A1

  公开（公告）日：2003-08-14

  An efficient method is disclosed for the preparation of trifluoromethyl- and difluoromethylsilanes using magnesium metal mediated reductive tri- and difluoromethylation of chlorosilanes with tri- and difluoromethyl sulfides, sulfoxides, and sulfones. One byproduct of the process is diphenyl disulfide. Since phenyl trifluoromethyl sulfone, sulfoxide and sulfide are readily prepared from readily available trifluoromethane and diphenyl disulfide, the method can be considered “pseudo-catalytic” for the preparation of (trifluoromethyl)trimethylsilane from environmentally benign trifluoromethane.

  揭示了一种高效的方法，用于利用镁金属介导氯硅烷与三氟甲基硫化物、亚氧化物和砜发生还原三氟甲基和二氟甲基基团的反应制备三氟甲基和二氟甲基硅烷。该过程的副产物之一是二苯基二硫化物。由于苯基三氟甲基砜、亚氧化物和硫化物可以从易得的三氟甲烷和二苯基二硫化物制备而来，因此该方法可以被认为是用于从环境友好的三氟甲烷制备（三氟甲基）三甲基硅烷的“伪催化”方法。