420-46-2Relevant articles and documents
Formation of CF3O- in the gas phase
Morris, Robert A.
, p. 8436 - 8442 (1999)
We report experimental studies of the formation of CF3O- by ion-molecule and electron attachment reactions, and theoretical investigations of the structure and energetics of CF3O- and its neutral counterpart CF3O. The anion CF3O- is formed from the rapid attachment of free electrons to its neutral dimer, (CF3O)2. Potential sources of CF3O- through ion-molecule reactions of CF3- and F- were surveyed. CF3O- is formed in the bimolecular ion-molecule reaction of CF3- with SO2 and the third-order association reaction of F- with CF2O. In addition, rate constants for the reactions of CF3- with a variety of neutral compounds were measured. A number of cases were found in which formation of CF3O- was energetically allowed but was not observed. The potential energy surfaces of CF3O and CF3O- have been investigated using a variety of density functional theory (DFT) techniques. The ground-state minimum energy structure of CF3O was found to be a 2A′ Jahn-Teller distorted Cs-symmetry structure, while for the anion the ground state is 1A1 with a C3v-symmetry minimum. A search for other low-energy minima for CF3O- was unsuccessful. The DFT methods support a value for the adiabatic electron affinity of CF3O near 4.1 eV.
Direct Superacid-Promoted Difluoroethylation of Aromatics
Artault, Maxime,Martin-Mingot, Agnès,Thibaudeau, Sébastien,Vitse, Kassandra
supporting information, (2021/12/22)
Under superacid conditions, aromatic amines are directly and regioselectively 1,1-difluoroethylated. Low temperature in situ NMR studies confirmed the presence of benzylic α-fluoronium and α-chloronium ions as key intermediates in the reaction. This method has a wide substrate scope and can be applied to the late-stage functionalization of natural alkaloids and active pharmaceutical ingredients.
Using Chlorotrifluoroethane for Trifluoroethylation of (Hetero)aryl Bromides and Chlorides via Nickel Catalysis
Li, Xuefei,Gao, Xing,He, Chun-Yang,Zhang, Xingang
supporting information, p. 1400 - 1405 (2021/02/20)
A nickel-catalyzed reductive cross-coupling between industrial chemical CF3CH2Cl and (hetero)aryl bromides and chlorides has been reported. The reaction is synthetically simple without the preparation of arylmetals and exhibits high functional group tolerance. The utility of this protocol has been demonstrated by the late-stage modification of pharmaceuticals, providing a facile route for medicinal chemistry.
C(sp3)-CF3Reductive Elimination from a Five-Coordinate Neutral Copper(III) Complex
Liu, Shuanshuan,Liu, Shuanshuan,Liu, He,Liu, Shihan,Lu, Zehai,Lu, Changhui,Leng, Xuebing,Lan, Yu,Shen, Qilong
supporting information, p. 9785 - 9791 (2020/07/10)
The reductive elimination from a high-valent late-transition-metal complex for the formation of a carbon-carbon or carbon-heteroatom bond represents a fundamental product-forming step in a number of catalytic processes. While reductive eliminations from well-defined Pt(IV), Pd(IV), Ni(III)/Ni(IV), and Au(III) complexes have been studied, the analogous reactions from neutral Cu(III) complexes remain largely unexplored. Herein, we report the isolation of a stable, five-coordinate, neutral square pyramidal Cu(III) complex that gives CH3-CF3 in quantitative yield via reductive elimination. Mechanistic studies suggest that the reaction occurs through a synchronous bond-breaking/bond-forming process via a three-membered ring transition state.
Improved Access to Organo-Soluble Di- and Tetrafluoridochlorate(I)/(III) Salts
Kaupp, M.,Müller, R.,Pr?hm, P.,Riedel, S.,Schattenberg, C. J.,Schmid, J. R.,Sonnenberg, K.,Steinhauer, S.,Vo?nacker, P.
supporting information, p. 16002 - 16006 (2020/07/20)
A facile one-pot gram-scale synthesis of tetraalkylammonium tetrafluoridochlorate(III) [cat][ClF4] ([cat]=[NEt3Me]+, [NEt4]+) is described. An acetonitrile solution of the corresponding alkylammonium chloride salt is fluorinated with diluted fluorine at low temperatures. The reaction proceeds via the [ClF2]? anion which is structurally characterized for the first time. The potential application of [ClF4]? salts as fluorinating agents is evaluated by the reaction with diphenyl disulfide, Ph2S2, to pentafluorosulfanyl benzene, PhSF5. The CN moieties in acetonitrile and [B(CN)4]? are transferred in CF3 groups. Exposure of carbon monoxide, CO, leads to the formation of carbonyl fluoride, COF2, and elemental gold is dissolved under the formation of tetrafluoridoaurate [AuF4]?.
Preparation method of 1,1,1-trifluoroethane
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Paragraph 0021-0035, (2019/06/08)
The invention provides a preparation method of 1,1,1-trifluoroethane (HFC-143a). The HFC-143a is prepared through liquid-phase fluoridation reaction under the presence of a composite catalyst by utilizing hydrogen fluoride (HF) and HCFC-142b as raw materials, the reaction temperature is 10-50 DEG C, preferably 10-40 DEG C, the weight ratio of the HF to the HCFC-142b is 1 to (4-5.5), preferably 1 to (4.5-5), the composite catalyst is a mixture of antimony halide and rare earth oxides, and rare earth metal is preferably neodymium or yttrium; the molar ratio of the antimony halide to the rare earth oxides is (20-200) to 1, preferably (20-150) to 1. According to the preparation method, the HFC-143a is prepared through liquid-phase fluoridation of the HF and the HCFC-142b, the conversion rate can reach 99.5% or above, the conversion rate of 98% or above can still be kept after continuous reaction for 1000 h, and the service life of the catalyst is prolonged.
Connecting Organometallic Ni(III) and Ni(IV): Reactions of Carbon-Centered Radicals with High-Valent Organonickel Complexes
Bour, James R.,Ferguson, Devin M.,McClain, Edward J.,Kampf, Jeff W.,Sanford, Melanie S.
supporting information, p. 8914 - 8920 (2019/06/13)
This paper describes the one-electron interconversions of isolable NiIII and NiIV complexes through their reactions with carbon-centered radicals (R?). First, model NiIII complexes are shown to react with alkyl and aryl radicals to afford NiIV products. Preliminary mechanistic studies implicate a pathway involving direct addition of a carbon-centered radical to the NiIII center. This is directly analogous to the known reactivity of NiII complexes with R?, a step that is commonly implicated in catalysis. Second, a NiIV-CH3 complex is shown to react with aryl and alkyl radicals to afford C-C bonds via a proposed SH2-type mechanism. This pathway is leveraged to enable challenging H3C-CF3 bond formation under mild conditions. Overall, these investigations suggest that NiII/III/IV sequences may be viable redox pathways in high-oxidation-state nickel catalysis.
A catalytic fluoride-rebound mechanism for C(sp3)-CF3 bond formation
Levin, Mark D.,Chen, Tiffany Q.,Neubig, Megan E.,Hong, Cynthia M.,Theulier, Cyril A.,Kobylianskii, Ilia J.,Janabi, Mustafa,O'Neil, James P.,Toste, F. Dean
, p. 1272 - 1275 (2017/06/30)
The biological properties of trifluoromethyl compounds have led to their ubiquity in pharmaceuticals, yet their chemical properties have made their preparation a substantial challenge, necessitating innovative chemical solutions. We report the serendipitous discovery of a borane-catalyzed formal C(sp3)-CF3 reductive elimination from Au(III) that accesses these compounds by a distinct mechanism proceeding via fluoride abstraction, migratory insertion, and C-F reductive elimination to achieve a net C-C bond construction. The parent bis(trifluoromethyl)Au(III) complexes tolerate a surprising breadth of synthetic protocols, enabling the synthesis of complex organic derivatives without cleavage of the Au-C bond. This feature, combined with the fluoride-rebound mechanism, was translated into a protocol for the synthesis of 18F-radiolabeled aliphatic CF3-containing compounds, enabling the preparation of potential tracers for use in positron emission tomography.
Silver-Catalyzed Decarboxylative Trifluoromethylation of Aliphatic Carboxylic Acids
Tan, Xinqiang,Liu, Zhonglin,Shen, Haigen,Zhang, Pei,Zhang, Zhenzhen,Li, Chaozhong
, p. 12430 - 12433 (2017/09/25)
The silver-catalyzed decarboxylative trifluoromethylation of aliphatic carboxylic acids is described. With AgNO3 as the catalyst and K2S2O8 as the oxidant, the reactions of aliphatic carboxylic acids with (bpy)C
PROCESS FOR THE CO-PRODUCTION OF OF 2,3,3,3-TETRAFLUOROPROPENE AND 1,3,3,3-TETRAFLUOROPROPENE
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Page/Page column 11, (2017/02/09)
The present invention provides a method of producing 2,3,3,3-tetrafluoropropene (HFO- 1234yf), wherein the method comprises two or more reaction steps, at least one of said reaction steps comprising the production of 1,3,3,3-tetrafluoropropene (HFO-1234ze) and/or one or more HFO-1234ze precursors from one or more HFO-1234yf precursors, wherein at least a portion of the HFO-1234ze is recovered.
