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Optimizing the preparation of bromo phthalonitriles and piloting them to peripherally brominated boron subphthalocyanines

Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario, Canada M5S 3E5, Canada

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and

Timothy P. Bender

Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario, Canada M5S 3E5, Canada

Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6, Canada

Department of Materials Science and Engineering, University of Toronto, 184 College Street, Toronto, Ontario, Canada M5S 3E4, Canada

E-mail Address: tim.bender@utoronto.ca

Corresponding author.

SPP full member in good standing.

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https://doi.org/10.1142/S1088424624500366Cited by:0 (Source: Crossref)

Abstract

Boron subphthalocyanines (BsubPcs) are versatile molecules with advantageous properties for applications. The BsubPcs are synthesized by the cyclotrimerization of a phthalonitrile and are composed of three isoindole subunits bound by three aza-/imine-bridging nitrogens. There are a variety of BsubPc derivatives shown within the literature due to the differentiation of a phthalonitrile precursor. The differentiation of a phthalonitrile enables the peripheral functional groups. The BsubPcs can be derivatized in two steps: First step is the cyclotrimerization of a phthalonitrile in the presence of a strong Lewis Acid, typically a boron trihalide (BX3) and enables a remaining axial substituent that is a B-X $_{a}$ bond; second step is optional, the B-X $_{a}$ bond can react with a nucleophile and results in B-X $_{b}$ . If the starting phthalonitrile is asymmetric, it will result in a combination of isomers. For this study, our approach is to have bromine substituents and to study their physical properties to see if applicable to organic electronic applications; chlorine and fluorine have been in past studies as halogens are unique and variations may present useful tools as they are known for electronegativities. The general phthalonitrile with no substitutions is produced in industry from $o$ -xylene. There are a variety of ways to synthesize other phthalonitriles with halogens. However, phthalonitriles can also be made by a method that has the most versatility with its substituents and can start with phthalic acid and go to phthalic anhydride to phthalimide to phthalamide and final to phthalonitrile; it is also possible to synthesize a phthalimide directly from phthalic acid, and this is part of this study as we were focusing on bromination, we also wanted to optimize the synthetic pathways to brominated phthalonitriles, and we took an engineering perspective and for this study, we wish to show you.

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