Studies with Azinylacetonitriles: 2-Pyridylacetonitrile as a Precursor to Functionally Substituted Pyridines

2-Pyridylacetonitrile (1) couples with aromatic diazonium salts to yield arylhydrazones 2a-c, that were shown to exist in the syn-form 2 rather than the anti-form 4. Compounds 2a,c reacted with hydroxylamine in refluxing DMF to yield the interesting 1,2,3-triazolylpyridines 6. Attempts to cyclize 2 to give the corresponding fused pyrazolopyridines 9 failed. On the other hand, compound 1 condensed with dimethylformamide dimethyl acetal to yield enaminonitrile 10 that could be converted into pyrazolylpyridine 11.