Abstract
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.
Highlights
Perfluoroaromatics are a privileged scaffold in organofluorine chemistry, often used in the production of various drugs, agrochemicals, and high-performance fluoropolymers [1,2,3]
The chemistry of selected systems such as perfluoropyridine is well established by experiment and supported by theory, demonstrating that these systems can undergo a series of regioselective substitution reactions with a variety of nucleophiles owing to its unique electronic structure [14]
This work demonstrates an in-depth study of simulated regio-selective additions of phenoxide additions to perfluoroaromatics 1–3 and their relative activation energies as potentially attractive scaffolds for the preparation of molecules of complex architectures
Summary
Perfluoroaromatics are a privileged scaffold in organofluorine chemistry, often used in the production of various drugs, agrochemicals, and high-performance fluoropolymers [1,2,3]. 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 liter2atouf r9e over the last several decades [22]. This work demonstrates an in-depth study of simulated regio-selective additions of phenoxide additions to perfluoroaromatics 1–3 and their relative activation energies as potentially attractive scaffolds for the preparation of molecules of complex architectures
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