ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Pyrylium Compounds. XXII. 1H-N.M.R. and U.V. Spectroscopic Investigations on the Isomerization of Pseudobases of Unsymmetrically Substituted 2, 4, 6-Triarylpyrylium SaltsThe kinetics and mechanism of the isomerization of the title compounds, the pentene 1,5-diones 2 and 3, were studied by 1H-n.m.r. and u.v. spectroscopy. The equilibrium constants measured vary little near 1, indicating the small influence of substituents on the equilibrium position. The mutual rearrangement 2⇄3 proved to be a base-catalized reaction which is characterized by strictly linear Hammett correlation between 1g k and Σσp. The results obtained suggest resonance-stabilized anions of type4 as intermediates. - Pseudobases of 3-alkyl-2, 4, 6-triarylsubstituted pyrylium salts do not undergo a reversible isomerization.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19843260418
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