Chemistry and spectroscopy of cross-conjugated and pseudo-cross-conjugated quinolinium-ethynyl-benzoate mesomeric betaines

Abstract

Abstract The three isomers 1-methylquinolinium-2-, 3-, and 4-ethynyl(phenyl-4-carboxylates) belong to two distinct types of heterocyclic mesomeric betaines. The quinolinium substituted in position 3 is a cross-conjugated mesomeric betaine (CCMB), whereas the quinolinium derivatives substituted in positions 2 and 4 are members of the class of pseudo-cross-conjugated mesomeric betaines (PCCMBs). While the charges are strictly separated within the common π-electron system of the CCMB according to the canonical formulae, the charges are effectively but not exclusively delocalized in the PCCMBs because cumulenoid resonance forms including electron sextet structures without external octet stabilization can be formed in accordance with the definition of PCCMBs. As a consequence, despite being closely related structures, the three isomers differ in their chemical and spectroscopic behaviors. Thus, on trying to hydrolyze the ester group of the methyl quinolinium-2-ethynyl-benzoate into the corresponding acid by subsequent treatment with sodium hydroxide in methanol and aqueous hydrochloric acid at pH 3, the acetal methyl 1,1-dimethoxy-2-(quinolinium-ylidene)ethyl]benzoate and the corresponding β-enamino carbonyl compound were formed, respectively. The corresponding acids of the 2- and 4-substituted quinolinium-ethynyl-benzoates were obtained by a modified procedure. On deprotonation, the resulting cross-conjugated quinolinium-3-ethynyl-benzoate betaine proved to be stable, whereas the corresponding pseudo-cross-conjugated quinolinium-2- and -4-ethynyl-benzoate betaines decomposed. Frontier orbital profiles were calculated, and IR and Raman spectra of the starting materials were measured and calculated to analyze the differences of CCMBs and PCCMBs of mesomeric betaines possessing triple bonds. A higher contribution of the cumulenoid resonance forms to the overall structure of the PCCMBs was determined.