cas 407-14-7, 1-Bromo-4-(trifluoromethoxy)benzene

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Radical C?H Trifluoromethoxylation of (Hetero)arenes with Bis(trifluoromethyl)peroxide
Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro- and medicinal chemistry. Radical C?H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing .OCF3 radical sources make them unsuitable for the large-scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF3OOCF3) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one-step synthesis of valuable pyridine derivatives, which have been previously prepared via multi-step approaches.
Dix, Stefan,Golz, Paul,Schmid, Jonas R.,Riedel, Sebastian,Hopkinson, Matthew N.
supporting information
p. 11554 - 11558
(2021/07/09)

Photocatalytic trifluoromethoxylation of arenes and heteroarenes in continuous-flow
The first example of photocatalytic trifluoromethoxylation of arenes and heteroarenes under continuous-flow conditions is described. Application of continuous-flow microreactor technology allowed to reduce the residence time up to 16 times in comparison t
Cendón, Borja,Gulías, Moisés,Ho, Michelle,No?l, Timothy,Nyuchev, Alexander V.,Sambiagio, Carlo,Struijs, Job J. C.,Wan, Ting,Wang, Ying
supporting information
p. 1305 - 1312
(2020/07/10)

DIFLUOROMETHOXYLATION AND TRIFLUOROMETHOXYLATION COMPOSITIONS AND METHODS FOR SYNTHESIZING SAME
The present invention provides a compound having the structure (I), a processing of making the compound; and a process of using the compound as a reagent for the difluoromethoxylation and trifluoromethoxylation of arenes or heteroarenes.
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Page/Page column 75; 79; 118-119; 120-121

(2019/09/18)

Silver-Mediated Trifluoromethoxylation of (Hetero)aryldiazonium Tetrafluoroborates
Here we report a silver-mediated trifluoromethoxylation of (hetero)aryldiazonium tetrafluoroborates by converting an aromatic amino group into an OCF3 group. This method, which can be considered to be a trifluoromethoxylation variation of the classic Sandmeyer-type reaction, uses readily available aryl and heteroaromatic amines as starting materials and AgOCF3 as trifluoromethoxylating reagents. The broad substrate scope and simple, mild reaction condition made this transformation a valuable method in constructing aryl-OCF3 bonds.
Yang, Yu-Ming,Yao, Jian-Fei,Yan, Wei,Luo, Zhuangzhu,Tang, Zhen-Yu
supporting information
p. 8003 - 8007
(2019/10/11)

Visible-Light Photoredox-Catalyzed and Copper-Promoted Trifluoromethoxylation of Arenediazonium Tetrafluoroborates
We report the development of photoredox-catalyzed and copper-promoted trifluoromethoxylation of arenediazonium tetrafluoroborates, with trifluoromethyl arylsulfonate (TFMS) as the trifluoromethoxylation reagent. This new method takes advantage of visible-light photoredox catalysis to generate the aryl radical under mild conditions, combined with copper-promoted selective trifluoromethoxylation. The reaction is scalable, tolerates a wide range of functional groups, and proceeds regioselectively under mild reaction conditions. Furthermore, mechanistic studies suggested that a Cs[Cu(OCF3)2] intermediate might be generated during the reaction.
Yang, Shaoqiang,Chen, Miao,Tang, Pingping
supporting information
p. 7840 - 7844
(2019/05/15)

Sequential Xanthalation and O-Trifluoromethylation of Phenols: A Procedure for the Synthesis of Aryl Trifluoromethyl Ethers
Molecules containing trifluoromethoxyaryl groups are of interest in pharmaceutical, agrochemical, and materials science research, due to their unique physical and electronic properties. Many of the known methods to synthesize aryl trifluoromethyl ethers require harsh reagents and highly controlled reaction conditions and rarely occur when heteroaromatic units are present. The two-step O-trifluoromethylation of phenols via aryl xanthates is one such method that suffers from these drawbacks. Herein, we report a method for the synthesis of aryl trifluoromethyl ethers from phenols by the facile conversion of the phenol to the corresponding aryl and heteroaryl xanthates with newly synthesized imidazolium methylthiocarbonothioyl salts and conversion of these xanthates to the trifluoromethyl ethers under mild reaction conditions.
Yoritate, Makoto,Londregan, Allyn T.,Lian, Yajing,Hartwig, John F.
p. 15767 - 15776
(2019/12/04)

Redox-Active Reagents for Photocatalytic Generation of the OCF3 Radical and (Hetero)Aryl C?H Trifluoromethoxylation
The trifluoromethoxy (OCF3) radical is of great importance in organic chemistry. Yet, the catalytic and selective generation of this radical at room temperature and pressure remains a longstanding challenge. Herein, the design and development of a redox-active cationic reagent (1) that enables the formation of the OCF3 radical in a controllable, selective, and catalytic fashion under visible-light photocatalytic conditions is reported. More importantly, the reagent allows catalytic, intermolecular C?H trifluoromethoxylation of a broad array of (hetero)arenes and biorelevant compounds. Experimental and computational studies suggest single electron transfer (SET) from excited photoredox catalysts to 1 resulting in exclusive liberation of the OCF3 radical. Addition of this radical to (hetero)arenes gives trifluoromethoxylated cyclohexadienyl radicals that are oxidized and deprotonated to afford the products of trifluoromethoxylation.
Zheng, Weijia,Lee, Johnny W.,Morales-Rivera, Cristian A.,Liu, Peng,Ngai, Ming-Yu
supporting information
p. 13795 - 13799
(2018/09/27)

Radical Trifluoromethoxylation of Arenes Triggered by a Visible-Light-Mediated N?O Bond Redox Fragmentation
A simple trifluoromethoxylation method enables non-directed functionalization of C?H bonds on a range of substrates, providing access to aryl trifluoromethyl ethers. This light-driven process is distinctly different from conventional procedures and occurs through an OCF3 radical mechanism mediated by a photoredox catalyst, which triggers an N?O bond fragmentation. The pyridinium-based trifluoromethoxylation reagent is bench-stable and provides access to synthetic diversity in lead compounds in an operationally simple manner.
Jelier, Benson J.,Tripet, Pascal F.,Pietrasiak, Ewa,Franzoni, Ivan,Jeschke, Gunnar,Togni, Antonio
supporting information
p. 13784 - 13789
(2018/09/14)

Catalytic C?H Trifluoromethoxylation of Arenes and Heteroarenes
The intermolecular C?H trifluoromethoxylation of arenes remains a long-standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a novel trifluoromethoxylating reagent and redox-active catalysts for the direct (hetero)aryl C?H trifluoromethoxylation. Our approach is operationally simple, proceeds at room temperature, uses easy-to-handle reagents, requires only 0.03 mol % of redox-active catalysts, does not need specialized reaction apparatus, and tolerates a wide variety of functional groups and complex structures such as sugars and natural product derivatives. Importantly, both ground-state and photoexcited redox-active catalysts are effective. Detailed computational and experimental studies suggest a unique reaction pathway where photoexcitation of the trifluoromethoxylating reagent releases the OCF3 radical that is trapped by (hetero)arenes. The resulting cyclohexadienyl radicals are oxidized by redox-active catalysts and deprotonated to form the desired products of trifluoromethoxylation.
Zheng, Weijia,Morales-Rivera, Cristian A.,Lee, Johnny W.,Liu, Peng,Ngai, Ming-Yu
supporting information
p. 9645 - 9649
(2018/03/21)

Fluorodecarboxylation: Synthesis of aryl trifluoromethyl ethers (ArOCF3) and thioethers (ArSCF3)
Fluorodecarboxylation of aryloxydifluoroacetic acid (ArOCF2CO2H) and arylmercaptodifluoroacetic acid (ArSCF2CO2H) towards ArXCF3 (X = O, S) using silver (I) salts in the presence of Selectfluor in a biphasic system with trifluoroacetic acid additive is discussed.
Krishanmoorthy, Sankarganesh,Schnell, Simon D.,Dang, Huong,Fu, Fang,Prakash, G.K. Surya
p. 130 - 135
(2017/09/06)

Xenon Difluoride Mediated Fluorodecarboxylations for the Syntheses of Di- and Trifluoromethoxyarenes
XeF2 is demonstrated to be a more proficient fluorine-transfer reagent than either NFSI or Selectfluor in fluorodecarboxylations of both mono- and difluoroaryloxy acetic acid derivatives. This method efficiently converts a wide range of neutral and electron-poor substrates to afford the desired di- and trifluoromethyl aryl ethers in good to excellent yields. The purifications are facile, and the reaction times are less than 5 min, which makes these fluorodecarboxylations promising for future PET-imaging applications.
Chatalova-Sazepin, Claire,Binayeva, Meruyert,Epifanov, Maxim,Zhang, Wei,Foth, Paul,Amador, Carolyn,Jagdeo, Manu,Boswell, Benjamin R.,Sammis, Glenn M.
p. 4570 - 4573
(2016/09/28)

O-Trifluoromethylation of Phenols: Access to Aryl Trifluoromethyl Ethers by O-Carboxydifluoromethylation and Decarboxylative Fluorination
A new strategy for the synthesis of aryl trifluoromethyl ethers (ArOCF3) by combining O-carboxydifluoromethylation of phenols and subsequent decarboxylative fluorination is reported. This protocol allows easy construction of functionalized trifluoromethoxybenzenes and trifluoromethylthiolated arenes (ArSCF3) in moderate to good yields. Moreover, it utilizes accessible and inexpensive reagents sodium bromodifluoroacetate and SelectFluor II and, thus, is practical for O-trifluoromethylation of phenols. The potential application of this method is demonstrated with the preparation of a plant-growth regulator, Flurprimidol.
Zhou, Min,Ni, Chuanfa,He, Zhengbiao,Hu, Jinbo
supporting information
p. 3754 - 3757
(2016/08/16)

Fluorodecarboxylation for the Synthesis of Trifluoromethyl Aryl Ethers
The synthesis of mono-, di-, and trifluoromethyl aryl ethers by fluorodecarboxylation of the corresponding carboxylic acids is reported. AgF2induces decarboxylation of aryloxydifluoroacetic acids, and AgF, either generated in situ or added separately, serves as a source of fluorine to generate the fluorodecarboxylation products. The addition of 2,6-difluoropyridine increased the reactivity of AgF2, thereby increasing the range of functional groups and electronic properties of the aryl groups that are tolerated. The reaction conditions used for the formation of trifluoromethyl aryl ethers also served to form difluoromethyl and monofluoromethyl aryl ethers.
Zhang, Qing-Wei,Brusoe, Andrew T.,Mascitti, Vincent,Hesp, Kevin D.,Blakemore, David C.,Kohrt, Jeffrey T.,Hartwig, John F.
supporting information
p. 9758 - 9762
(2016/08/10)

Synthesis of trifluoromethyl ethers and difluoro(methylthio)methyl ethers by the reaction of dithiocarbonates with IF5-pyridine-HF
Trifluoromethyl ether and difluoro(methylthio)methyl ether of phenols and aliphatic alcohols were selectively synthesized from the corresponding dithiocarbonates. When IF5-pyridine-HF was used alone in the reaction of the dithiocarbonate, the difluoro(methylthio)methyl ether was selectively formed. On the other hand, by the additional use of Et3N-6HF with IF5-pyridine-HF, trifluoromethyl ether was formed selectively. Various functional groups such as ester, ether, amide, and acetonide could tolerate the reaction conditions, and various functionalized difluoro(methylthio)methyl ethers and trifluoromethyl ethers were synthesized.
Inoue, Toshiya,Fuse, Chiaki,Hara, Shoji
p. 48 - 52
(2015/11/10)

METHOD FOR PRODUCING FLUORINATED ORGANIC COMPOUND AND FLUORINATING REAGENT
Object: An object of the present invention is to provide a method for producing, with a high yield, a fluorinated organic compound, the fluorinated organic compound having not been produced with a sufficient yield by a conventional method for producing a fluorinated organic compound using a fluorinating agent containing IF5-pyridine-HF alone. Another object of the present invention is to provide a fluorinating reagent. Means for achieving the object: A method for producing a fluorinated organic compound comprising step A of fluorinating an organic compound by bringing the organic compound into contact with (1) IF5-pyridine-HF and (2) at least one additive selected from the group consisting of amine hydrogen fluorides, XaF (wherein Xa represents hydrogen, potassium, sodium, or lithium), oxidizers, and reducing agents.
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Paragraph 0132; 0137; 0138

(2015/11/24)

C-ARYL GLUCOSIDE DERIVATIVES, PREPARATION PROCESS AND PHARMACEUTICAL USE THEREOF
C-aryl glucoside derivatives, preparation processes and pharmaceutical uses thereof are disclosed. In particular, C-aryl glucoside derivatives represented by formula (I), with each substituent defined in the application, pharmaceutically acceptable salts or stereoisomers thereof, their preparation methods, and pharmaceutical compositions containing the derivatives as well as their uses as therapeutic agents, particularly as sodium-dependent glucose cotransporter (SGLT)-1 inhibitors, are disclosed.
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Paragraph 0150

(2013/06/04)

Silver-mediated trifluoromethoxylation of aryl stannanes and arylboronic acids
A silver-mediated cross-coupling of trifluoromethoxide with aryl stannanes and arylboronic acids to give aryl trifluoromethyl ethers is reported. This is the first report of a transition-metal-mediated Caryl-OCF3 bond formation.
Huang, Chenghong,Liang, Theresa,Harada, Shinji,Lee, Eunsung,Ritter, Tobias
supporting information; experimental part
p. 13308 - 13310
(2011/10/10)

CF3 oxonium salts, O-(trifluoromethyl)dibenzofuranium salts: In situ synthesis, properties, and application as a real CF3+ species reagent
(Chemical Equation Presented) We report in situ synthesis of the first CF3 oxonium salts, thermally unstable O-(trifluoromethyl)- dibenzofuranium salts, which furthermore have different counteranions (BF 4-, PF6-, SbF6 -, and Sb2F11-) and ring substituents (tert-butyl, F, and OCH3), by photochemical decomposition of the corresponding 2-(trifluoromethoxy)biphenylyl-2′- diazonium salts at -90 to -100°C. The yields markedly increased in the order of BF4- 6- 6- 2F11-. The CF3 oxonium salts were fully assigned by means of 1H and 19F NMR spectroscopy at low temperature. The CF3 salts decomposed to form CF4 and dibenzofurans. The half-life times at -60°C of the 2-tert-butyl salts having different counteranions were 29 min for BF4- salt 2d, 36 min for PF6- salt 2c, 270 min for SbF6- salt 2a, and 415 min for Sb2F11- salt 2b. Those at -60°C of the Sb2F11- salts having different 2-substituents were 13 min for F salt 3b, 63 min for H (unsubstituted) salt 1b, and 415 min for tert-butyl salt 2b. Thus, the stability of the CF3 oxonium salts increased in the order of BF4- 6 - 6- 2F 11- and F 3+ species source to the direct O- and N-trifluoromethylations of alcohols, phenols, amines, anilines, and pyridines under very mild conditions. The thermal decomposition method with a mixture of diazonium salt 17a and aryl- or alkylsulfonic acids, pyridine, or pyridines having an electron-withdrawing group also afforded CF3O or CF 3N products. The trifluoromethylation mechanism is discussed and an SN2 mechanism containing the transient formation of free CF 3+ is proposed. Thus, the present study has demonstrated that the exceedingly reactive CF3+ species can be generated much easier than the CH3+ species, contrary to the common sense that CF3+ is extremely difficult to generate in solution.
Umemoto, Teruo,Adachi, Kenji,Ishihara, Sumi
p. 6905 - 6917
(2008/02/11)

1-ARYL-4-SUBSTITUTED PIPERAZINES DERIVATIVES FOR USE AS CCR1 ANTAGONISTS FOR THE TREATMENT OF INFLAMMATION AND IMMUNE DISORDERS
Compounds are provided that act as potent antagonists of the CCR1 receptor, and which have been further confirmed in animal testing for inflammation, one of the hallmark disease states for CCR1. The compounds are generally aryl piperazine derivatives and are useful in pharmaceutical compositions, methods for the treatment of CCR1-mediated diseases, and as controls in assays for the identification of competitive CCR1 antagonists.
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Page 59

(2008/06/13)

A convenient synthesis of trifluoromethyl ethers by oxidative desulfurization-fluorination of dithiocarbonates
Trifluoromethyl ethers R-OCF3 are easily synthesized from the corresponding dithiocarbonates R-OCS2Me (R = aryl or primary alkyl) by a reagent system consisting of 70% HF/pyridine and an N-halo imide. When the reaction is applied to R-OCS2Me wherein R = secondary alkyl, tertiary alkyl, or benzylic group, fluorination leading to the corresponding alkyl fluorides R-F is achieved, whereas a combination of 50% HF/pyridine and N- bromosuccinimide affords the corresponding trifluoromethyl ethers R-OCF3 (R = secondary).
Kanie, Kiyoshi,Tanaka, Yoichiro,Suzuki, Kazundo,Kuroboshi, Manabu,Hiyama, Tamejiro
p. 471 - 484
(2007/10/03)

Insecticidal ethers
This invention relates to novel fluorinated ethers, useful as insecticides and acaricides, to processes and intermediates for their preparation, to insecticidal and acaricidal compositions thereof and to methods of combating and controlling insect and acarine pests therewith.
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(2008/06/13)

Structure-Activity Studies on Benzhydrol-Containing Nipecotic Acid and Guvacine Derivatives as Potent, Orally-Active Inhibitors of GABA Uptake
The introduction of lipophilic groups onto the ring nitrogen of nipecotic acid and guvacine, two known GABA uptake inhibitors, afforded potent, orally-active anticonvulsant drugs.A series of compounds is reported which explores the structure-activity relationships (SAR) in this series.Among the areas explored: side-chain SAR (aromatic-, heterocyclic-, and tricyclic-containing side chains) and modifications to the tetrahydropyridine ring.The benzhydrol ether-containing side chains afforded the most potent compounds with several exhibiting in vitro IC50 values for GABA uptake of 1 μM (including 5, Table I; 37, 43, Table IV; and 44, Table V).Compound 44 was selected for extensive evaluation and subsequently progressed to Phase 1 clinical trials with severe adverse effects seen after single dose administration to humans.
Pavia, Michael R.,Lobbestael, Sandra J.,Nugiel, David,Mayhugh, Daniel R.,Gregor, Vlad E.,et al.
p. 4238 - 4248
(2007/10/02)

Oxidative desulfurization-fluorination of xanthates. A convenient synthesis of trifluoromethyl ethers and difluoro (methylthio)methyl ethers
Treatment of xanthates R-OC(S)SMe with (HF)9/Py and 1,3-dibromo-5,5-dimethylhydantoin gives trifluoromethyl ethers R-OCF3 through intermediates R-OCF2SMe, which could be isolated upon treatment of xanthates with n-Bu4N+H2F3- and N-bromosuccinimide.
Kuroboshi, Manabu,Suzuki, Kazundo,Hiyama, Tamejiro
p. 4173 - 4176
(2007/10/02)

Process for intermediates for insecticidal compounds
The invention provides novel arylalkene compounds of formula I, a process for their preparation and their use as intermediates for insecticidal compounds, comprising, STR1 wherein W represents 1 to 4 substituents selected from halo, alkyl, alkoxy, haloalkyl, haloalkoxy and alkoxyalkyl, or W represents a bidentate alkylene or alkylenedioxy group linking adjacent carbon atoms, X represents fluoroalkyl, and Y is selected from chlorine, bromine and alkoxy; and a process for preparing said ethers. The compounds of formula I are prepared by reacting a ketone of formula: STR2 with a phosphonium salt of formula Hal - (Q) 3 P + -CH 2 -Y, where Hal - represents a halide ion and Q represents alkyl or aryl.
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(2008/06/13)

Azolyl substituted aralkyl compounds and pesticidal use thereof
Compounds of the formula: STR1 The compounds are useful as pesticides, particularly insecticides.
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(2008/06/13)

[Perfluoroalkyl(alkoxy)phenyl]methyldichlorosilanes and method of preparing same
The invention relates to [perfluoroalkyl(alkoxy)phenyl]methyldichlorosilanes characterized by the general formula STR1 where: RF = OCF3 OC2 F5, OC2 F4 OCF3, C2 F4 OCF3, C3 F7 and also to a method of preparing them. The method according to the invention consists in that fluorobromo[alkyl(alkoxy)]benzenes having the general formula STR2 where: RF = OCF3 OC2 F5, OC2 F4 OCF3, C2 F4 OCF3, C3 F7 are treated with magnesium taken in a 5 - 20 per cent excess with respect to the stoichiometric quantity in a solution of absolute diethyl ether or absolute tetrahydrofurane at a temperature of 8° - 60° C. The resulting fluorine-containing magnesiumbromo[alkyl(alkoxy)]benzenes are treated with three-functional silanes -- methyltrichlorosilane -- taken in a 100 - 500 per cent excess with respect to the stoichiometric quantity, or with methylchlorodiethoxysilane, taken in the stoichiometric quantity or in a 50 per cent excess with respect to the stoichiometric quantity, at a temperature of 18° - 60° C. In the case of methylchlorodiethoxysilane, the resultant product is fluorine-containing [alkyl(alkoxy)phenyl]methyldiethoxysilanes which are treated with acetyl chloride taken in a 25 - 50 per cent excess with respect to the stoichiometric quantity, at a temperature of 40° - 70° C, in the presence of ferric chloride as a catalyst. The proposed [perfluoroalkyl(alkoxy)phenyl]methyldichlorosilanes can be used for preparing organofluosilicon lubricants, greases, sealing counds, rubber mixtures having high resistance to heat, frost, petrol and oils, that can be used in various fields of technology. The described method can be used to obtain the proposed end products in yields as high as 96 per cent of theory.
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(2008/06/13)