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Reactions of 1,‐bis(2‐bromopyridinium)alkanes with azide ions: charge effect and intermediates
Author(s) -
da Graças Neves Corrêa Maria,
José Politi Mario,
Hioka Noboru
Publication year - 1999
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199911)12:11<837::aid-poc154>3.0.co;2-t
Subject(s) - chemistry , reactivity (psychology) , azide , pyridinium , methylene , ion , medicinal chemistry , solvent , photochemistry , carbon 13 nmr , organic chemistry , medicine , alternative medicine , pathology
The reaction between 1,ω‐bis(2‐bromopyridinium)alkanes (with 3, 4, 5, 6 and 8 methylene groups) with azide ions was examined to investigate the effects of charge proximity between the aromatic rings upon reactivity. 1 H and 13 C NMR spectra show the formation of a half‐reacted intermediate having bromopyridinium and azidepyridinium extremities. Activation parameters for the reaction, ionic strength and solvent effects were investigated. An increase in reactivity was found with decrease in the methylenic chain length for both reactant and intermediate. The results are rationalized by the favorable formation of sandwich‐type complexes between the pyridinium rings and the azide for the compounds with shorter methylenic spacers. Copyright © 1999 John Wiley & Sons, Ltd.