ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Pyrylium Compounds. XXI. Structure and Tautomerism of Pseudobases of Unsymmetrically Substituted 2,4,6-Triarylpyrylium SaltsHydrolytic ring opening of unsymmetrically substituted 2,4,6-triarylpyrylium salts 11 results in a mixture of two tautomeric pseudobases, the penten-1,5-diones 13 and 14. In crystalline state as a rule one of these tautomers markedly predominates, whereas in solution a rapid equilibrium establishment occurs which can be followed by 1H-n.m.r. and u.v. spectroscopy (equilibrium ratio nearly 1:1). The 1H-n.m.r. spectroscopic structural assignment of the two isomeric forms was supported by u.v. spectroscopic studies using 1:1 mixtures of the chromophoric partial systems ArCOCH=CHPh and ArCOMe or the pseudobases 10 of symmetrically substituted 2,4,6-triarylpyrylium salts 9 as reference systems. From the mass spectra of the pseudobases 10 and 13/14 follows that - if hydrolysis of 11 is performed in media containing H218O - mass spectrometric isotopic analysis of the resulting 18O-labelled pseudobases allows no information to be made about the regioselectivity of the ring opening. - Novel starting pyrylium salts of type 9 and 11 are characterized by u.v./vis data and by transformation into the corresponding pyridine derivatives.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19843260214
