A Convenient Synthesis and Spectroscopic Characterization of N,N ‘ -Bis(2-propenyl)-2,7-diazapyrenium Quaternary Salts

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The Journal of Organic Chemistry, ISSN: 0022-3263, Vol: 65, Issue: 19, Page: 6017-6023

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Chariklia Sotiriou-Leventis; Zhan Mao; Abdel-Monem M. Rawashdeh
American Chemical Society (ACS)
article description
N,N'-Bis(2-propenyl)-2,7-diazapyrenium salts are synthesized in good yield from the reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride with allylamine, followed by LiAlH reduction and subsequent oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The nature of the counteranion depends on the solvent system used for recrystallization of the crude product from the final DDQ-oxidation step. X-ray analysis shows that if recrystallization is carried out in boiling CHOH/HO (1:1, v/v), the counteranion in the resulting deep-red crystals is always the alkoxy anion of 2-cyano-5,6-dichloro-3-hydroxy-1,4-benzoquinone, whether the final DDQ oxidation ends with addition of HClO or HCl; on the other hand, if recrystallization is carried out with anhydrous acetonitrile, the product is N,N'-bis(2-propenyl)-2,7-diazapyrenium diperchlorate or dichloride depending on whether the DDQ oxidation is followed by addition of concd HClO or concd HCl, respectively. Importantly, if the DDQ oxidation is quenched with HBr, Br is oxidized to Br by unreacted DDQ, and the resulting product is N,N'-bis(2,3-dibromopropyl)-2,7-diazapyrenium dibromide. Comparative absorption and time-resolved emission studies provide evidence for possible dimerization of N,N'-bis(2-propenyl)-2,7-diazapyrenium diperchlorate in CHCN.