Studies on Condensed Systems of Aromatic Nitrogenous Series. XIII. : Extension of Malonic Ester Synthesis to the Heterocyclic Series.

Halo‐ and Nitrothiazoles

“…2-Brornothiazole can be used as a substrate in a malonic synthesis (72); starting from phenylacetonitrile the a phenyl-(2-thiazolyl)-acetonitrile is obtained in high yields (84%) (Scheme 11). cl +PhCH,CN -…”

SRN1 mechanism in heteroaromatic nucleophilic substitution. Photostimulation and entrainment of the reaction of lithioacetone with 2-chloroquinoline

“…All yields are of isolated material. 6 Total, including that required to generate the enolate. = DNB (10 mol %, based on 2) added. "…”

“…The use of alkali metals as a source of solvated electrons has been shown to promote the reaction of alkali enolates with halogenated benzenes.2b In the present study, attempted promotion of the SrnI reaction of lithioacetone with 2chloroquinoline by lithium metal resulted in severe competing reactions. For example, addition of 1 equiv of lithium metal to a reaction mixture of 2, 3 equiv of acetone, and 4 equiv of lithium amide in liquid ammonia produced a complex mixture of products consisting of 17.9% recovered 2, 18.0% quinoline, 15.2% 5a, 17.5% 2,3/-biquinoline (6),14 and 7.9% 2-aminoquinoline. The structure of 6 was substantiated by its pmr spectrum.…”