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

Abstract

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 LiAlH4 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 CH3OH/H2O (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 HClO4 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 HClO4 or concd HCl, respectively. Importantly, if the DDQ oxidation is quenched with HBr, Br- is oxidized to Br2 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 CH3CN.

Department(s)

Chemistry

Sponsor(s)

American Chemical Society
Petroleum Research Fund
University of Missouri Research Board

International Standard Serial Number (ISSN)

0022-3263

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2000 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jan 2000

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