54773-20-5Relevant articles and documents
Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**
Shreiber, Scott T.,Vicic, David A.
supporting information, p. 18162 - 18167 (2021/07/14)
The acetonitrile-solvated [(MeCN)Ni(C2F5)3]? was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)3]? towards organic electrophiles. Both [(MeCN)Ni(CF3)3]? and [(MeCN)Ni(C2F5)3]? successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)NiII(C2F5)3]? suggests that, upon electro-oxidation to [(MeCN)nNiIII(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)2NiII(C2F5)2]. Catalytic C?H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)3]? or the related [Ni(CF3)4]2?. Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.
Method for preparing fipronil key intermediate
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Paragraph 0011-0016, (2019/03/08)
The invention relates to a method for preparing a fipronil key intermediate. According to the method disclosed by the invention, 1-bromo-3,5-dichlorobenzene serves as an initial raw material. The method comprises the following steps: reacting the raw material and potassium 2,2,2-trifluoroacetate, wherein the product does not need to be treated; and carrying out a nitration reaction, thereby obtaining the fipronil key intermediate 1,3-dichloro-2-nitro-5-(trifluoromethyl) benzene. Compared with the traditional synthetic method, the method is convenient to operate, does not have risk of environmental pollution, and has high yield.
Trifluoromethylation of Arylsilanes with [(phen)CuCF3]
Morstein, Johannes,Hou, Haiyun,Cheng, Chen,Hartwig, John F.
, p. 8054 - 8057 (2016/09/13)
A method for the trifluoromethylation of arylsilanes is reported. The reaction proceeds with [(phen)CuCF3] as the CF3source under mild, oxidative conditions with high functional-group compatibility. This transformation complements prior trifluoromethylation of arenes in several ways. Most important, this method converts arylsilanes formed by the silylation of aryl C?H bonds to trifluoromethylarenes, thereby allowing the conversion of arenes to trifluoromethylarenes. The unique capabilities of the reported method are demonstrated by the conversion of a C?H bond into a C?CF3bond in active pharmaceutical ingredients which do not undergo this overall transformation by alternative functionalization processes, including a combination of borylation and trifluoromethylation.
Rapid and efficient trifluoromethylation of aromatic and heteroaromatic compounds using potassium trifluoroacetate enabled by a flow system
Chen, Mao,Buchwald, Stephen L.
supporting information, p. 11628 - 11631 (2013/11/06)
Going to the source: The trifluoromethylation of aryl/heteroaryl iodides has been demonstrated using a flow system, thus enabling a rapid rate of reaction. A broad spectrum of trifluoromethylated compounds was prepared in good to excellent yields using CF3CO2K as the trifluoromethyl source. The process has the advantage of short reaction times and uses convenient [CF3] sources. Copyright
Copper-mediated trifluoromethylation of arylboronic acids by trifluoromethyl sulfonium salts
Zhang, Cheng-Pan,Cai, Ji,Zhou, Chang-Bing,Wang, Xiao-Ping,Zheng, Xing,Gu, Yu-Cheng,Xiao, Ji-Chang
supporting information; experimental part, p. 9516 - 9518 (2011/10/02)
The ligand-free trifluoromethylation of arylboronic acids with a [Ph 2SCF3]+[OTf]-/Cu(0) system has been carefully investigated. Aryl-, alkenyl- and heteroarylboronic acids with a variety of functional groups were suitable substrates for this reaction. It is suggested that a CuCF3 species is formed under the reaction conditions.
Electrosynthesis of (trifluoromethyl)copper complexes from bromotrifluoromethane: reactivities with various organic halides
Paratian, J. M.,Labbe, E.,Sibille, S.,Perichon, J.
, p. 137 - 144 (2007/10/02)
The synthesis of (trifluoromethyl)copper complexes is achieved easily by electroreduction of bromotrifluoromethane in N,N-dimethylformamide, in the presence of a sacrificial copper anode and various potential ligands.Three (trifluoromethyl)copper species are considered; two copper(II) and one copper(I).The mechanism of formation of the (trifluoromethyl)copper species is discussed and a study of their reactivities towards various organic halides is reported. Keywords: Copper; Trifluoromethyl derivatives; Electroreduction; Mechanism; Bromotrifluoromethane; (Trifluoromethyl)copper complexes
An Efficient Electrochemical Trifluoromethylation of Aromatic Halides with Bromotrifluoromethane and a Sacrificial Copper Anode
Paratian, J. M.,Sibille, S.,Perichon, J.
, p. 53 - 54 (2007/10/02)
The electrochemical cross-coupling of bromotrifluoromethane with aromatic or heteroaromatic iodides and bromides is successfully achieved in a one-compartment electrolysis cell fitted with a sacrificial copper anode.
RELATIONSHIPS AND KINETICS OF THE EXHAUSTIVE CHLORINATION OF m-CHLOROTRIFLUOROMETHYLBENZENE AND TRIFLUOROMETHYLBENZENE
Alikhanov, P. P.,Ushakov, A. A.,Kuznetsova, G. N.,Kalinachenko, V. R.,Motsarev, G. V.
, p. 734 - 740 (2007/10/02)
The exhaustive electrophilic chlorination of m-chlorotrifluoromethylbenzene and trifluoromethylbenzene, catalyzed by ferric chloride , was investigated on the basis of a correlation approach.The relationships governing the regulation of the reactivity of the chlorine derivatives of trifluoromethylbenzene were studied.A quantitative relation was established between the direction of chlorination and the effects of the substituents; the effects of the latter remain unchanged in the polychloro derivatives of trifluoromethylbenzene, while the overall effect is close to additive.The distribution of the isomers was determined for various degrees of substitution of trifluoromethylbenzene: monochloro, 2- , 3- , 4- ; dichloro, 2,5- , 3,4- , 2,3- , 3,5- ; trichloro, 2,3,5- and 2,4,5- , 3,4,5- , 2,3,6- , 2,3,4- ; tetrachloro-, 2,3,5,6- , 2,3,4,5- .The following derivatives are formed during the chlorination of m-chlorotrifluoromethylbenzene: dichloro, 2,5- , 3,4- , 2,3- , 3,5- ; trichloro, 2,3,5- and 2,4,5- , 3,4,5- , 2,3,6- , 2,3,4- ; tetrachloro, 2,3,5,6- , 2,3,4,5- .The distribution of the isomers agrees with the distribution calculated on the basis of the employed parameters and the additivity principle.The compositions of the products with various degrees of chlorination are given satisfactorily by kinetic curves describing a multistage system of consecutive and parallel irreversible first-order reactions.
