Pyridine labile” adducts from dimethyl

The ultraviolet absorption spectra have been used to distinguish between the tautomers obtained by addition of dimethyl acetylene-dicarboxylate to pyridines. The 4/f-quinolizines show a band around 265 mfi. which is missing from the spectra of the 9a/f-quinolizines. Acheson and Taylor26 have successfully used this information to settle the constitution of the stable and labile adducts obtained by the action of acetylenedicarboxylic esters on pyridines. The ultraviolet spectra of the stable adducts formed by the above methods show... 

Pyridine, and its monomethyl and 3,5-dimethyl derivatives " combine exothermically with dimethyl acetylenedicarboxylate in ether yielding some ether soluble materials, including trimethyl pyrrocoline-1,2,3-tricarboxylate (Section III,F,3) and deep red ether-insoluble gums. A number of crystalline compounds have been isolated from these gums by fractional crystallizations and will now be considered in detail. In the case of pyridine, Diels et al. ° isolated a red labile 1 2 molar adduct, which they formulated as (75), which isomerized rapidly on standing to a yellow stable adduct (76). These formulations are no longer accepted. Diels and Alder also suggested that the acetylenic ester first dimerized to the diradical (74) which then combined with the pyridine. 

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