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

Abstract

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.

Shaken Not Stirred: Perfluoropyridine-Polyalkylether Prepolymers

“…Perfluoropyridine (PFP), a heteroaromatic, affords an avenue for regioselectivity in nucleophilic aromatic substitution (SNAr) reactions . Some notable examples by others recently exploit the versatility of PFP as a robust protecting group under mild conditions, nucleophilic fluorinated agent for alkyl halides, and deoxyfluorination reagent of carboxylic acids in addition to demonstrating site-selective metal-catalyzed defluorination and halogen exchange. , According to Fuhrer et al, the highest occupied molecular orbital (HOMO) of perfluoropyridine provides the rationale as to why the nucleophile will first attack the 4-position or para -carbon of perfluoropyridine.…”

Synthetic Advantages of Defluorinative C−F Bond Functionalization

“…The content is organized by the type of carbon framework the fluorine is attached to, as summarized in Scheme 1. The coverage does not include applications to material sciences, [14] defluorination for environmental remediation, [15] reactions with biomolecules [16] or common-place defluorinative processes of commercial reagents (e.g., difluorocarbene generation from TMSCF 3 ; TMS = trimethylsilyl). [17] The goal of this review is to highlight the main challenges, advances and applications for each type of CÀ F bond to guide synthetic chemists and to motivate researchers to devise new CÀ F functionalization methods.…”

Site-selective nucleophilic substitution reactions of pentafluoropyridine with hydroxybenzaldehydes: synthesis of triarylmethanes comprising perfluoropyridine moieties

“…40 PFP is also used widely as a building block for the production of new fluorinated pyridines which are of immense importance in the areas of organic synthesis, medicinal- and materials chemistry, as well as agrochemicals. 41 The PFP nucleus is highly electrophilic due to the high electron deficiency caused by the fluorines attached to it and hence readily reacts with nitrogen, 41 a , e ,42 oxygen, 38 e ,41 e ,43 sulfur, 41 e ,44 and carbanion nucleophiles. 41 e ,45 Though all five fluorines can be practically replaced by nucleophiles, their participation in nucleophilic substitution reactions takes place in a stepwise manner, and functionalization occurs at C–4, C–2, and C–3 positions, respectively.…”