New pyrazolium-carboxylates as structural analogues of the pseudo-cross-conjugated betainic alkaloid nigellicine.
Pyrazolium-3-carboxylates were examined as relatives of the betainic alkaloid Nigellicine and as new examples of the sparsely populated class 16 of heterocyclic pseudo-cross-conjugated mesomeric betaines (PCCMB). The title compounds were prepared in a 4-step procedure starting from beta-diketo compounds 8 which were cyclized with substituted hydrazines. The resulting isomeric pyrazole esters 9 and 10 were separated and subsequently quaternized with dimethyl sulfate in the presence of nitrobenzene to pyrazolium esters 11 and 12. Saponification was best accomplished in diluted sulfuric acid, which resulted in the formation of the pseudo-cross-conjugated mesomeric betaines 13 and 14 in one step. Protonation to the corresponding carboxylic acids required the treatment of the betaines with tetrafluoroboric acid in dichloromethane. The effect of negative solvatochromism proves the charge separation in the ground state of the molecules. X-ray crystallographic analyses, semiempirical calculations, and ESI mass spectrometric measurements were performed to gain knowledge about the phenomenon of pseudo-cross-conjugation.
Schmidt
Andreas
A
Technical University of Clausthal, Institute of Organic Chemistry, Leibnizstrasse 6, D-38678 Clausthal-Zellerfeld, Germany. schmidt@ioc.tu-clausthal.de
Habeck
Tobias
T
Kindermann
Markus Karl
MK
Nieger
Martin
M
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D002264:Carboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D007202:Indicators and Reagents; D008958:Models, Molecular; D031881:Nigella sativa; D010936:Plant Extracts / Q000737:chemistry* / Q000302:isolation & purification; D011720:Pyrazoles / Q000138:chemical synthesis* / Q000737:chemistry; D013329:Structure-Activity Relationship; D062367:ortho-Aminobenzoates / Q000737:chemistry*
D000470:Alkaloids; D002264:Carboxylic Acids; D007202:Indicators and Reagents; D010936:Plant Extracts; D011720:Pyrazoles; D062367:ortho-Aminobenzoates; C018499:damascenine