Synthesis and reactions of some 3-(2-haloacyl)indoles

The reaction between indole and N-(2-haloacyl)pyridinium salts has been studied. With dioxan as solvent 1-(2-haloacyl)indole (2) was generally the product at low temperatures and 3-(2-haloacyl)indole (1) at high temperatures, as illustrated by the following α-bromopropionylation: Product ratio (1c/2a), 20° (0·01), 40° (0·8) and 60° (8·5). The fact that the a-bromobutyrylation at 60° gave 3-{N-(2-bromobutyryl)-1,4-dihydro-4-pyridyl}indole (6) as the main product, and 3-(2-bromobutyryl)indole (1d) only as a minor product, shows that the 3-acylation is affected by steric hindrance.At high reaction temperature (> 60°) the yield of1 decreased, owing to the formation of 3-indacylpyridinium salts (4).