Formation of perfluorinated polyphenylenes by multiple pentafluorophenylation using C6F5Si(CH3)3

Nishida, Masakazu; Hayakawa, Yoshio; Ono, Taizo

doi:10.1016/j.jfluchem.2010.09.001

Cited by 9 publications

(15 citation statements)

References 20 publications

(33 reference statements)

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“…This exclusive formation of the linear log‐like‐shaped perfluoro(phenylene) congeners contrasts with the star‐like shapes derived from the successive pentafluorophenylation of cyano‐ or nitro‐substituted perfluorobenzenes . Whereas the electron‐withdrawing cyano or nitro substituent on perfluorobenzenes promotes the successive pentafluorophenylation in three directions starting from the othro and para positions, the bulky electron‐withdrawing T‐2 moiety promotes successive pentafluorophenylation only in one direction starting from the para position, thus, leading to notably different morphologies such as log and star shapes.…”

Section: Resultsmentioning

confidence: 53%

“…Multiple pentafluorophenylation occurred not only on the heterocyclic ring of the oxazine ring, but also in the para position of the introduced C 6 F 5 substituent(s) leading to the compounds with one to three nonafluorobiphenyl (C 12 F 9 ) substituents. Moreover, the multiple pentafluorophenylation by C 6 F 5 Si(CH 3 ) 3 also occurred at both ortho and para positions of perfluoroarenes substituted by electron‐withdrawing groups to provide perfluorinated p ‐phenylene and m ‐phenylene compounds …”

Section: Introductionmentioning

confidence: 99%

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Reactions of Highly Branched Perfluoroolefins with (Pentafluorophenyl)trimethylsilane: Characterization of the Unique Structural Properties of Perfluorinated Super‐Congested Systems

et al. 2016

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Hexafluoropropene trimers were reactedw ith C 6 F 5 Si(CH 3 ) 3 to provide not only pentafluorophenyl but also perfluorophenylene derivatives [F(C 6 F 4 ) n C 9 F 17 ; n = 2-9] by successive pentafluorophenylation of perfluoroaryl rings. Their structures,i ncludingr otational isomers, were determined by MS, 19 Fa nd 13 C-{ 19 F} NMR spectroscopy,a nd/orXray crystallography,a nd were furtherc onfirmed by B3LYP-GIAO calculation of NMR shieldings.F ormation of ap air of gear-meshedr otamers with clockwise and counterclockwise conformations was identified by NMR measurements for the structures having geminal (CF 3 ) 2 CF groups at the C=Cb ond. That the predominantly formed counterclockwise rotamer was gradually converted to the clockwise rotamer over 50 days at room temperature throughasynchronized movement of gears was also confirmed by NMR measurements. A comparison between the X-ray structure and B3LYP calculations showed some structurald ifferences that arise from the crystal packing.

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Section: Resultsmentioning

confidence: 53%

Section: Introductionmentioning

confidence: 99%

Reactions of Highly Branched Perfluoroolefins with (Pentafluorophenyl)trimethylsilane: Characterization of the Unique Structural Properties of Perfluorinated Super‐Congested Systems

et al. 2016

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“…In cases of perfluorinated aromatic compounds containing electron-withdrawing substituents, this multiple pentafluorophenylation occurred at both the para - and ortho -positions of the electron-withdrawing substituents, resulting in not only para -phenylenes but also m -phenylenes. 14…”

Section: Introductionmentioning

confidence: 99%

Reactions of Bifunctional Perfluoroarylsilanes with Activated C–F Bonds in Perfluorinated Arenes

Nishida

Fukaya

et al. 2019

ACS Omega

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Reactions of bifunctional perfluoroarylsilanes, p- and m-C6F4(SiMe3)2 as well as o-BrC6F4SiMe3, with substituted perfluoroarenes having electron-withdrawing groups were investigated using NMR and density functional theory calculation techniques. The C–F bond in perfluoroarenes was activated by the para-position of an electron-withdrawing group, such as CF3, C6F5, CN, and NO2. The reaction of C6F4(SiMe3)2 mainly occurred at the para-position of the perfluoroarenes and also occurred at the ortho-position of C6F5CN and C6F5NO2. Two equivalent reactions of perfluoroarenes with bifunctional p- and m-C6F4(SiMe3)2 provided disubstituted perfluoroarenes, along with a small amount of protonated monosubstituted perfluoroarenes. The reaction of o-BrC6F4SiMe3 with the CF3- and CN-substituted pentafluorobenzenes provided unexpected coupling products between C–Br and C–F bonds, in addition to the coupling products between C–SiMe3 and C–F bonds.

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“…In 2010, Nishida reported that a catalytic amount of KHF 2 triggered successive multiple pentafluorophenylation of perfluoroarenes using C 6 F 5 Si(CH 3 ) 3 as the nucleophilic reagent and DMF as solvent (Scheme 10). [20] For this reaction, the substituents on the polyfluoroarenes and the loading of C 6 F 5 Si(CH 3 ) 3 determined the selectivity of the products. The synthesized perfluorinated polyphenylene compounds found wide application in organic electronics.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

“…Because a strong interaction exists between Si and F, in some organosilicon‐mediated transformations, the fluorine anions are usually employed as the initiator or promoter. In 2010, Nishida reported that a catalytic amount of KHF 2 triggered successive multiple pentafluorophenylation of perfluoroarenes using C 6 F 5 Si(CH 3 ) 3 as the nucleophilic reagent and DMF as solvent (Scheme ) . For this reaction, the substituents on the polyfluoroarenes and the loading of C 6 F 5 Si(CH 3 ) 3 determined the selectivity of the products.…”

Section: Recent Achievements In the Transition‐metal‐free Snar Of Polmentioning

confidence: 99%

Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

Liu

Zhang

2016

The Chemical Record

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The creation of new bonds via C-F bond cleavage of polyfluoroarenes has proven to be an important and powerful tool in synthetic chemistry. Using such a strategy, a myriad of valuable partially fluoroaromatic molecules and building blocks can be obtained. The transition-metal-free nucleophilic aromatic substitution (SN Ar) strategy has aroused the continuing interest of researchers due to its simple, mild, economical, and environmentally benign characteristics, which have been successfully applied to C-F bond functionalizations. In this account, we present a summary of the recent investigations of polyfluoroarenes involving SN Ar reactions and discuss some of our recent endeavors in the construction of partially fluoroaromatic molecules. Through this strategy, many new bonds including C-C, C-N, C-O, C-S, and C-H bonds can be created. Additionally, brief discussions on the transformation mechanisms are also provided. Finally, we discuss the existing limitations of the SN Ar reactions of polyfluoroarenes as well as our perspective on the future development of this chemistry.

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Formation of perfluorinated polyphenylenes by multiple pentafluorophenylation using C6F5Si(CH3)3

Cited by 9 publications

References 20 publications

Reactions of Highly Branched Perfluoroolefins with (Pentafluorophenyl)trimethylsilane: Characterization of the Unique Structural Properties of Perfluorinated Super‐Congested Systems

Reactions of Highly Branched Perfluoroolefins with (Pentafluorophenyl)trimethylsilane: Characterization of the Unique Structural Properties of Perfluorinated Super‐Congested Systems

Reactions of Bifunctional Perfluoroarylsilanes with Activated C–F Bonds in Perfluorinated Arenes

Facile Access to Fluoroaromatic Molecules by Transition-Metal-Free C-F Bond Cleavage of Polyfluoroarenes: An Efficient, Green, and Sustainable Protocol

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