Utilizing the regioselectivity of perfluoropyridine towards the preparation of phenyoxyacetylene precursors for partially fluorinated polymers of diverse architecture

Corley, Cynthia A.; Kobra, Khadijatul; Peloquin, Andrew J.; Salmon, Katelynn; Gumireddy, Lionel; Knoerzer, Timm A.; McMillen, Colin D.; Pennington, William T.; Schoffstall, Allen M.; Iacono, Scott T.

doi:10.1016/j.jfluchem.2019.109409

Cited by 23 publications

(30 citation statements)

References 20 publications

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“…Attempts to react monomer 38 with ROH resulted in a mixture of products and was attributed to the reversibility sometimes observed in the SNAr reaction at the 4-postion [ 45 , 68 ]. The reversibility was also seen when attempts to post-functionalize poly38 with the various ROH nucleophiles resulted in densely cross-linked polymer.…”

Section: Perfluoropyridine Used In Polymers and Materialsmentioning

confidence: 99%

Perfluoropyridine: Discovery, Chemistry, and Applications in Polymers and Material Science

et al. 2022

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Perfluoropyridine (PFPy) is an organofluorine compound that has been employed for a variety of applications, from straightforward chemical synthesis to more advanced functions, such as fluorinated networks and polymers. This can be directly attributed to the highly reactive nature of PFPy, especially towards nucleophilic aromatic substitution (SNAr). The aim of this review is to highlight the discovery and synthesis of PFPy, discuss its reactive nature towards SNAr, and to summarize known reports of the utilization and thermal analysis of PFPy containing fluoropolymers and fluorinated network materials.

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Section: Perfluoropyridine Used In Polymers and Materialsmentioning

confidence: 99%

Perfluoropyridine: Discovery, Chemistry, and Applications in Polymers and Material Science

et al. 2022

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“…Due to their highly electron deficient nature, perfluoroaromatics can have significant effects on the electronics of molecular systems [ 60 ]. Perfluoroaromatic moieties have therefore seen use in materials [ 61 ], catalysis [ 62 , 63 ] and organic synthesis [ 64 , 65 ], and have been exploited in peptide [ 66 , 67 ] and peptoid chemistry [ 68 ]. Access to highly fluorinated amino acids is therefore an area of much research, with several reports detailing the synthesis of aromatic perfluorinated amino acids.…”

Section: Complex Fluorine-containing Aromatic Amino Acidsmentioning

confidence: 99%

Synthesis of complex unnatural fluorine-containing amino acids

Brittain

Lloyd

Cobb

2020

Journal of Fluorine Chemistry

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“…Perfluoroaromatics are a privileged scaffold in organofluorine chemistry, often used in the production of various drugs, agrochemicals, and high-performance fluoropolymers [1][2][3]. Fluoropolymers, particularly those with fluoroaromatics in their architectures, are widely known for their desirable properties such as chemical resistance, thermal stability, and solution and melt processability [3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

“…In the pursuit of other potential fluorinated scaffolds with unique chemical properties, diazaperfluoro-heteroaromatics such as perfluoropyrazine (1), perfluoropyrimidine (2), and perfluoropyridazine (3) are immediately attractive targets for chemical modeling (Figure 1) [18][19][20][21]. These molecules have been of increasing significance in the literature over the last several decades [22].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Prediction and Explanation of Reaction Site Selectivity in the Addition of a Phenoxy Group to Perfluoropyrimidine, Perfluoropyridazine, and Perfluoropyrazine

et al. 2021

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Perfluoroaromatics, such as perfluoropyridine and perfluorobenzene, are privileged synthetic scaffolds in organofluorine methodology, undergoing a series of regioselective substitution reactions with a variety of nucleophiles. This unique chemical behavior allows for the synthesis of many perfluoroaromatic derived molecules with unique and diverse architectures. Recently, it has been demonstrated that perfluoropyridine and perfluorobenzene can be utilized as precursors for a variety of materials, ranging from high performance polyaryl ethers to promising drug scaffolds. In this work, using density functional theory, we investigate the possibility of perfluoropyrimidine, perfluoropyridazine, and perfluoropyrazine participating in similar substitution reactions. We have found that the first nucleophilic addition of a phenoxide group substitution on perfluoropyrimidine and on perfluoropyridazine would happen at a site para to one of the nitrogen atoms. While previous literature points to mesomeric effects as the primary cause of this phenomenon, our work demonstrates that this effect is enhanced by the fact that the transition states for these reactions result in bond angles that allow the phenoxide to π-complex with the electron-deficient diazine ring. The second substitution on perfluoropyrimidine and on perfluoropyridazine is most likely to happen at the site para to the other nitrogen. The second substitution on perfluoropyrazine is most likely to happen at the site para to the first substitution. The activation energies for these reactions are in line with those reported for perfluoropyridine and suggest that these platforms may also be worth investigation in the lab as possible monomers for high performance polymers.

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Utilizing the regioselectivity of perfluoropyridine towards the preparation of phenyoxyacetylene precursors for partially fluorinated polymers of diverse architecture

Cited by 23 publications

References 20 publications

Perfluoropyridine: Discovery, Chemistry, and Applications in Polymers and Material Science

Perfluoropyridine: Discovery, Chemistry, and Applications in Polymers and Material Science

Synthesis of complex unnatural fluorine-containing amino acids

Theoretical Prediction and Explanation of Reaction Site Selectivity in the Addition of a Phenoxy Group to Perfluoropyrimidine, Perfluoropyridazine, and Perfluoropyrazine

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