cas 88-16-4, 2-Chlorobenzotrifluoride | Articles data

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Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
supporting information
p. 15396 - 15405
(2021/10/12)

Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst
Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one—light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
Antonietti, Markus,Guldi, Dirk M.,Markushyna, Yevheniia,Savateev, Aleksandr,Schü?lbauer, Christoph M.,Ullrich, Tobias
supporting information
p. 20543 - 20550
(2021/08/12)

Novel synthesis method of chlorobenzotrifluoride
The invention discloses a novel synthesis method of chlorobenzotrifluoride, wherein o-chlorotoluene is used as a raw material, copper chloride or cuprous chloride is used as a catalyst, and o-chlorobenzotrifluoride is synthesized through two steps of chlorination and fluorination. Compared with the method in the prior art, the method of the invention has the following characteristics that raw materials are subjected to heating dehydration treatment in the dehydration kettle, so that the chlorination side reactions are few, the product purity is high, the graded chlorination device does not need to be additionally arranged, the technological process is simple, and the operation is convenient. According to the chlorination process of the invention, the catalyst is added in batches to increase the efficiency of the catalyst, so that the by-product generated by thechlorination reaction and the emission of waste gas in the production are greatly reduced, and the emission of pollutants in the production process is reduced.
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Paragraph 0015-0023

(2020/01/14)

Au@ZnO Core-Shell: Scalable Photocatalytic Trifluoromethylation Using CF3CO2Na as an Inexpensive Reagent under Visible Light Irradiation
Trifluoromethylation is of significant importance for the synthesis of many small molecules vital for medicinal and agrochemical research. The importance of the CF3 group as well as the related synthetic challenges is so evident that many reagents have been reported for the synthesis of trifluoromethylated compounds, but these typical reagents are expensive and the methods for preparing them are difficult. Here, we report a new scalable and operationally simple trifluoromethylation reaction using sodium trifluoroacetate as a reagent and Au-modified ZnO as a photocatalyst under visible light irradiation. The reaction proceeds via trifluoromethylation of a broad range of aryl halides, arylboronic acids, and arene and heteroarene substrates. Some pharmaceutical and agrochemical compounds have been trifluoromethylated directly to demonstrate the applicability of the method.
Bazyar, Zahra,Hosseini-Sarvari, Mona
supporting information
p. 2345 - 2353
(2019/10/16)

Cathodic C-H Trifluoromethylation of Arenes and Heteroarenes Enabled by an in Situ-Generated Triflyltriethylammonium Complex
While several trifluoromethylation reactions involving the electrochemical generation of CF3 radicals via anodic oxidation have been reported, the alternative cathodic, reductive radical generation has remained elusive. Herein, the first cathodic trifluoromethylation of arenes and heteroarenes is reported. The method is based on the electrochemical reduction of an unstable triflyltriethylammonium complex generated in situ from inexpensive triflyl chloride and triethylamine, which produces CF3 radicals that are trapped by the arenes on the cathode surface.
Cantillo, David,Jud, Wolfgang,Kappe, C. Oliver,Maljuric, Snjezana
supporting information

(2019/10/08)

PROCESS FOR THE PREPARATION OF ORGANIC HALIDES
The present invention provides a halo-de-carboxylation process for the preparation of organic chlorides, organic bromides and mixtures thereof, from their corresponding carboxylic acids, using a chlorinating agent selected from trichloroisocyanuric acid (TCCA), dichloroisocyanuric acid (DCCA), or combination thereof, and a brominating agent.
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Paragraph 00146

(2017/08/01)

Trifluoromethylation of (hetero)aryl iodides and bromides with copper(i) chlorodifluoroacetate complexes
A new copper-mediated trifluoromethylation reaction using copper(i) chlorodifluoroacetate complexes as reagents is reported. The complex [L2Cu][O2CCF2Cl] (L = bpy, dmbpy, phen) reacted with (hetero)aryl iodides and bromides in the presence of CsF in DMF at 75 °C to afford the trifluoromethylarenes in good to excellent yields. High compatibility with various chemical functions or (hetero)cycles was also observed in the reaction. A reaction mechanism involving a difluorocarbene intermediate, along with a subsequent formation of a -CF3 anion was proposed.
Lin, Xiaoxi,Li, Zhengyu,Han, Xiaoyan,Weng, Zhiqiang
p. 75465 - 75469
(2016/08/24)

Copper-catalyzed C-N bond cross-coupling of aryl halides and amines in water in the presence of ligand derived from oxalyl dihydrazide: Scope and limitation
An efficient and convenient method has been developed for the copper-catalyzed C-N bond cross-coupling of aryl bromides with electron-donor substituents and aliphatic amines in water. The new ligand system N-phenyloxalyl bishydrazide/hexane-2,5-dione has been shown to be considerably more efficient in the copper-catalyzed C-N bond cross-coupling reaction as compared to the ligands described in the literature and allowed decreasing of the catalyst amount (up to 2 mol %) to achieve acceptable yields of isolated products (46-84%). Acceptor substituted aryl bromides, aryl bromides with substituents in the ortho-position, and some aryl dichlorides can undergo the C-N cross-coupling under the developed conditions, but their reactivity is lower.
Kurandina,Eliseenkov,Khaibulova,Petrov,Boyarskiy
p. 7931 - 7937
(2015/09/15)

Introducing a new radical trifluoromethylation reagent
Perfluoro-3-ethyl-2,4-dimethyl-3-pentyl radical (PPFR) is a persistent radical stable at room temperature, but easily decomposes at 90 °C to produce a CF3 radical which is able to react with a variety of aromatic compounds to afford the corresponding trifluoromethyl derivatives, usually as mixtures of regioisomers in good to excellent overall yields.
Sato, Azusa,Han, Jianlin,Ono, Taizo,Wzorek, Alicja,Ace?a, José Luis,Soloshonok, Vadim A.
supporting information
p. 5967 - 5970
(2015/03/30)

Trifluoromethylation of arenediazonium salts with fluoroform-derived CuCF3 in aqueous media
A new protocol has been developed for trifluoromethylation of arenediazonium salts with moisture-sensitive CuCF3 (from fluoroform) in aqueous media. The reaction is governed by a radical mechanism, tolerates a broad variety of functional groups, and is applicable to the synthesis of complex, polyfunctionalized molecules. This journal is the Partner Organisations 2014.
Lishchynskyi, Anton,Berthon, Guillaume,Grushin, Vladimir V.
supporting information
p. 10237 - 10240
(2014/08/18)

Palladium-catalyzed trifluoromethylation of aromatic C-H bond directed by an acetamino group
The first palladium-catalyzed ortho-trifluoromethylation of the aromatic C-H bond directed by an acetamino group is reported. This method provides an efficient and green approach to synthesize the highly biological potential key structure of ortho-CF3 acetanilides and anilines.
Zhang, Li-Sheng,Chen, Kang,Chen, Guihua,Li, Bi-Jie,Luo, Shuang,Guo, Qing-Yun,Wei, Jiang-Bo,Shi, Zhang-Jie
p. 10 - 13
(2013/04/10)

FLUOROALKYLATION METHODS AND REAGENTS
A method of forming a fluorinated molecular entity includes reacting in a reaction mixture an aromatic halide, copper, a fluoroalkyl group, and a ligand. The aromatic halide includes an aromatic group and a halogen substituent bonded to the aromatic group. The ligand includes at least one group-V donor selected from phosphorus and an amine. The overall molar ratio of copper to aromatic halide in the reaction mixture is from 0.2 to 3. The method further includes forming a fluoroalkylarene including the aromatic group and the fluoroalkyl group bonded to the aromatic group. A composition, which may be used in the method, consists essentially of copper, the fluoroalkyl group, and the ligand, where the molar ratio of copper to the fluoroalkyl group is approximately 1.
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Page/Page column title page; 6; 28

(2012/03/11)

A ligand-free copper-catalyzed decarboxylative trifluoromethylation of aryliodides with sodium trifluoroacetate using Ag2O as a promoter
A practical and ligand-free Cu-catalyzed decarboxylative trifluoromethylation of aryl iodides with sodium trifluoroacetate using Ag 2O as a promoter was reported. A variety of trifluoromethyl- substituted aromatics are synthesized in moderate to excellent yields and with wide functional-group tolerance under relatively mild reaction conditions. Georg Thieme Verlag Stuttgart · New York.
Li, Yaming,Chen, Tao,Wang, Huifeng,Zhang, Rong,Jin, Kun,Wang, Xiuna,Duan, Chunying
supporting information; experimental part
p. 1713 - 1716
(2011/09/12)

A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides
(Chemical Presented) Well compatible: The trifluoromethylations and perfluoroalkylations of aryl iodides and some aryl bromides with trifluoromethyl and perfluoroalkylcopper(I) phenanthroline complexes occur with broad scope at 25-50 8C (see scheme). The trifluoromethyl complex is prepared from inexpensive reagents and can be used in situ or isolated. The reactions tolerate a range of substituents and also occur with heteroaromatic systems.
Morimoto, Hiroyuki,Tsubogo, Tetsu,Litvinas, Nichole D.,Hartwig, John F.
supporting information; experimental part
p. 3793 - 3798
(2011/05/15)

Selective fluorination of substituted trichloromethyl benzenes by HF in liquid phase: Preparation of fluorinated building blocks
The selective fluorination by successive Cl/F exchanges of α,α,α-trichlorotoluene, substituted or not by a chlorine atom, was studied in the presence of HF as the fluorinating agent. The influence of the presence of a catalyst or a basic solvent (such as dioxane, pyridine, tributylphosphate) in order to control the fluorination was also investigated. In mild conditions (50 °C and after 1 h of reaction), HF in excess was required in order to obtained the trifluoromethylation by Cl/F exchanges. The presence of SbCl5 in small amount activated the Cl/F exchanges and only a stoichiometric amount of HF was required whatever the chlorinated molecules. Selective mono and difluorination could be obtained by using basic solvents.
Piou, Alexandre,Celerier, Stephane,Brunet, Sylvette
experimental part
p. 1241 - 1246
(2011/01/12)

From carboxylic acids to the trifluoromethyl group using BrF3
Organic trifluoromethyl derivatives were made from aromatic and aliphatic carboxylic acids by transforming them first into the corresponding dithioesters followed by reaction with bromine trifluoride under mild conditions (0 °C, 2 min).
Cohen, Or,Mishani, Eyal,Rozen, Shlomo
experimental part
p. 3579 - 3582
(2010/07/04)

A Novel Method for Converting Aromatic Acids into Trifluoromethyl Derivatives using BrF3
Aryltrifluoromethyl derivatives are obtained in good yields from the corresponding aryl carboxylic acids by reacting their dithionic esters with BrF3 under very mild conditions.
Rozen, Shlomo,Mishani, Eyal
p. 2081 - 2082
(2007/10/02)

TRIFLUOROMETHYLATION OF AROMATIC COMPOUNDS WITH BIS(TRIFLUOROACETYL) PEROXIDE
Bis(trifluoroacetyl) peroxide was found to be thermally stable, and trifluoromethylation of aromatic compounds was studied using this peroxide.Trifluoromethylation of electron-rich benzenes, furan, thiophene, or their benzo derivatives proceeded with the peroxide in moderate to high yields.
Sawada, Hideo,Nakayama, Masaharu,Yoshida, Masato,Yoshida, Tatsuro,Kamigata, Nobumasa
p. 423 - 431
(2007/10/02)

TRIFLUORMETHYLIERUNGSREAKTIONEN VON Te(CF3)2 MIT HALOGENBENZOLEN UND METHYLBENZOLEN
Substituent effects on yields and regioselectivity of photochemical and thermal trifluoromethylation reactions of Te(CF3)2 with halogen benzenes and methyl benzenes are investigated under comparable conditions.All reactions lead to trifluoromethylated products.The yields of the thermal are always higher than those of the corresponding photochemical reactions.The reactivity of the halobenzenes increases in the series C6H5-F a sidereaction, but H-substitution is the primary reaction pathway.During the reactions with iodobenzene tellurium containing compounds are also formed.The reactions with methyl benzenes show an increase in reactivity in the series hexamethylbenzene mesitylene toluene p-xylene.In all cases only ring substituted products are detected.Reactions with toluene and p-xylene yield tellurium containing compounds as well as addition products.The 19F-n.m.r spectra of the products are given.
Naumann, Dieter,Kischkewitz, Jurgen
p. 283 - 299
(2007/10/02)

Sodium Perfluoroalkane Carboxylates as Sources of Perfluoroalkyl Groups
Sodium trifluoroacetate, in the presence of copper(I) iodide, is used as a source of trifluoromethyl to replace halogen by trifluoromethyl in benzenoid and heterocyclic aromatic systems, as well as in alkenyl and alkyl halogen compounds.The mechanism of this interesting copper-assisted process has been explored and an intermediate of the form - is proposed.Introduction of higher perfluoroalkyl groups from their respective sodium perfluoroalkane carboxylates has been demonstrated and the machanistic features are compared with those of the trifluoromethylation process.
Carr, Gillian E.,Chambers, Richard D.,Holmes, Thomas F.,Parker, David G.
p. 921 - 926
(2007/10/02)

Preparation of Fluorine-Containing Phenylacetylenes by the Method of Introduction of the Ethynyl Group Using 1,1-Dichloro-2,2-difluroethene
Phenylacetylenes (ArCCH) having fluoro- or trifluoromethyl substituents (o-, m-, p-F; o-, m-, p-CF3; 2,4-, 2,5-, 2,6-, 3,5-(CF3)2) have been prepared from bromobenzenes (ArBr) and benzenes (ArH) using 1,1,-dichloro-2,2-difluoroethene (1) by a two-step route: ArLi or ArMgBr->ArCF=CCl2->ArCCLi.Upon careful treatment at -70 deg C with 1, o-fluorophenyllithium gave o-FC6H4CF=CCl2 in good yield, together with benzyne-derived products, such as o-(o-FC6H4)C6H4CF=CCl2.Lithiation of m-bis(trifluoromethyl)benzene at 0 deg C for 9 h (24 h) followed by treatment with bromine gave 1-bromo-2,4-, 2,6-, and 3,5-bis(trifluoromethyl)benzene in 35 (38), 31 (36), and 8percent (6percent) yield, respectively.
Kodaira, Kazuo,Okuhara, Kunio
p. 1625 - 1632
(2007/10/02)

Pregeneration, Spectroscopic Detection, and Chemical Reactivity of (Trifluoromethyl)copper, an Elusive and Complex Species
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Wiemers, Denise M.,Burton, Donald J.
p. 832 - 834
(2007/10/02)

RELATIONSHIPS AND KINETICS OF THE EXHAUSTIVE CHLORINATION OF m-CHLOROTRIFLUOROMETHYLBENZENE AND TRIFLUOROMETHYLBENZENE
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.
Alikhanov, P. P.,Ushakov, A. A.,Kuznetsova, G. N.,Kalinachenko, V. R.,Motsarev, G. V.
p. 734 - 740
(2007/10/02)

FEATURES OF THE HIGH CHLORINATION OF 4-CHLORO- AND 2,4-DICHLOROTRIFLUOROMETHYLBENZENE
The high electrophilic chlorination of 4-chloro- and 2,4-dichlorotrifluoromethylbenzenes was investigated under the conditions of catalysis by ferric chloride (80 deg C).The chlorination of 4-chlorotrifluoromethylbenzene gives only the 3,4-dichloride, and further substitution leads to a mixture of the 3,4,5-trichloride (72percent), the 2,4,5-trichloride (23percent), the 2,3,4-trichloride (5percent), and then 2,3,4,5-tetrachlorotrifluoromethylbenzene.The chlorination of 2,4-dichlorotrifluoromethylbenzene gives the 2,4,5-trichloride (80percent), the 2,3,4-trichloride (20percent), and the 2,3,4,5-tetrachloride.The reactivities of the compounds are consistent with the principle of additivity in the free energy of activation.
Ushakov, A. A.,Alikhanov, P. P.,Motsarev, G. V.,Kalinachenko, V. R.,Kuznetsova, G. N.,Kolbasov, V. I.
p. 1993 - 1996
(2007/10/02)

FLUOROALKYLATION OF AROMATIC COMPOUNDS
Perfluoroalkylation of benzene, halobenzenes, pyridine, furan and thiophene has been accomplished through thermolysis of perfluoroalkyl iodides (CF3I, n-C10F21I and RfORfI) in the presence of the appropriate aromatic compound.Yields of alkylated products vary depending on temperature, presence of an HI acceptor and reactants ratio.Isomeric mixtures are obtained with halobenzenes, pyridine and thiophene.Furan however yields only the alpha substituted product.
Cowell, Allan B.,Tamborski, Christ
p. 345 - 356
(2007/10/02)