337-53-1Relevant academic research and scientific papers
Difluromethylphosphonium salt, and preparation method and application thereof
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Paragraph 0220; 0221; 0222; 0223, (2017/08/02)
The invention discloses difluromethylphosphonium salt, and a preparation method and application thereof. A synthetic method of the difluromethylphosphonium salt disclosed by the invention comprises the following steps of in a solvent, carrying out a react
Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me3SiCF2H
Chen, Dingben,Ni, Chuanfa,Zhao, Yanchuan,Cai, Xian,Li, Xinjin,Xiao, Pan,Hu, Jinbo
supporting information, p. 12632 - 12636 (2016/10/31)
A pentacoordinate bis(difluoromethyl)silicate anion, [Me3Si(CF2H)2]?, is observed for the first time by the activation of Me3SiCF2H with a nucleophilic alkali-metal salt and 18-crown-6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me3SiCF2H by using a combination of CsF and 18-crown-6 as the initiation system. Mechanistic investigations demonstrate that [(18-crown-6)Cs]+[Me3Si(CF2H)2]?is a key intermediate in this catalytic reaction.
Rh-Catalyzed arylation of fluorinated ketones with arylboronic acids
Dobson, Luca S.,Pattison, Graham
supporting information, p. 11116 - 11119 (2016/09/19)
The Rh-catalyzed arylation of fluorinated ketones with boronic acids is reported. This efficient process allows access to fluorinated alcohols in high yields under mild conditions. Competition experiments suggest that difluoromethyl ketones are more reactive than trifluoromethyl ketones in this process, despite their decreased electronic activation, an effect we postulate to be steric in origin.
Transformations of organic molecules with F-TEDA-BF4 in ionic liquid media
Pavlinac, Jasminka,Zupan, Marko,Stavber, Stojan
experimental part, p. 2394 - 2409 (2009/12/03)
The transformations of organic molecules with F-TEDA-BF4 (1) were investigated in the hydrophilic ionic liquid (IL) 1-butyl-3-methyl- imidazolium tetrafluoroborate ([bmim][BF4], 2) and the hydrophobic IL 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6], 3). The range of substrates included alkyl substituted phenols 4a-c, 9, 13, 1,1-diphenylethene (15), alkyl aryl ketones 19-22, aldehydes 23-25 and methoxy-substituted benzene derivatives 26-30. The evaluation of the outcome of reactions performed in IL media in comparison to those of the corresponding reactions in conventional organic solvents revealed that the transformations in IL are less efficient and selective. The effect of the presence of a nucleophile (MeOH, H2O, MeCN) on the course of reaction was also studied.
Nucleophilic difluoromethylation and difluoromethylenation of aldehydes and ketones using diethyl difluoromethylphosphonate
Beier, Petr,Alexandrova, Anastasia V.,Zibinsky, Mikhail,Surya Prakash
experimental part, p. 10977 - 10985 (2009/04/11)
New methodology for difluoromethylation and difluoromethylenation of aldehydes and ketones based on nucleophilic fluorination using diethyl difluoromethylphosphonate (1) was developed.
Facile preparation of difluoromethyl- and monofluoromethyl-containing amides via Ritter reaction
Liu, Jun,Ni, Chuanfa,Li, Ya,Zhang, Laijun,Wang, Guanyu,Hu, Jinbo
, p. 6753 - 6756 (2007/10/03)
Both secondary and tertiary difluoromethylated carbinols were found to readily react with acetonitrile under the catalysis of concentrated sulfuric acid to give the corresponding difluoromethylated acetamides in good yields, which is remarkably more effic
Convenient synthesis of difluoromethyl alcohols from both enolizable and non-enolizable carbonyl compounds with difluoromethyl phenyl sulfone
Prakash, G.K.Surya,Hu, Jinbo,Wang, Ying,Olah, George A.
, p. 2218 - 2223 (2007/10/03)
A general and efficient nucleophilic difluoromethylation of carbonyl compounds (both enolizable and non-enolizable aldehydes and ketones) has been achieved by using a nucleophilic (phenylsulfonyl)difluoromethylation-reductive desul fonylation strategy. Di
Selective and effective fluorination of organic compounds in water using selectfluor F-TEDA-BF4
Stavber, Gaj,Zupan, Marko,Jereb, Marjan,Stavber, Stojan
, p. 4973 - 4976 (2007/10/03)
(Chemical Equation Presented) Selective and effective fluorination of various types of organic compounds performed in water as the reaction medium using 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor F-TEDA-BF
Preparation of and fluoroalkylation with (chlorodifluoromethyl)trimethylsilane, difluorobis(trimethylsilyl)methane, and 1,1,2,2-tetrafluoro-1,2-bis(trimethylsilyl)ethane
Yudin, Andrei K.,Prakash, G. K. Surya,Deffieux, Denis,Bradley, Michael,Bau, Robert,Olah, George A.
, p. 1572 - 1581 (2007/10/03)
CF2BrCl reacts with aluminum/N-methylpyrrolidinone in the presence of chlorotrimethylsilane to give Me3SiCF2Cl in high yield. Similarly, CF2Br2 gives Me3SiCF2Br with bromotrimethylsilane. Chlorodifluoromethylation of aldehydes using Me3SiCF2Cl and a catalytic amount of TBAF in polar solvents occurs at room temperature, providing difluoromethylated alcohols in two steps. Electroreduction of Me3SiCF2Cl in the presence of chlorotrimethylsilane gives Me3SiCF2SiMe3 (anion-derived product) and Me3SiCF2CF2SiMe3 (radical-derived product). Using THF/HMPA strongly favors the former, whereas THF/TDA-1 (tris(3,6-dioxaheptyl)amine) the latter. Me3SiCF2SiMe3 difluoromethylates aldehydes acting as a difluoromethylene dianion ('CF22-'/equivalent), whereas Me3SiCF2CF2SiMe3 acts at room temperature as an in situ source for the perfluorovinyl anion (due to β-elimination of fluorotrimethylsilane). However, at low temperature the elimination pathway is suppressed and tetrafluoroethylene dianion ('-CF2CF2-'/equivalent) behavior is observed. The structure of Me3SiCF2CF2SiMe3 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).
N-Fluorobisimides: Reactions with Some Olefins via α-Fluoro Carbocationic Intermediates
DesMarteau, Darryl D.,Xu, Ze-Qi,Witz, Michael
, p. 629 - 635 (2007/10/02)
N-Fluorobisimides are a new class of electrophilic fluorinating agents.Reaction of (CF3SO2)2NF (1) with olefins gave various products, depending on the reaction conditions and the structure of the substrate.In solvents of higher nucleophilicity such as H2O, acetic acid, aqueous HCl, and (HF)nPy, α-fluorohydrins and their acetates, α,β-chlorofluoro- and α,β-difluoroalkanes were obtained.In acetic acid, trans-stilbene and tetraphenylethylene produced the rearranged, nonfluorinated aldehyde and ketone.Evidence is presented for the reactions proceeding via a one-electron transfer mechanism involving α-fluorocarbocationic intermediates.
