Synthesen von 2‐Pyronen aus α, β‐ungesättigten Säurechloriden und tertiären Aminen

Abstract

AbstractA new synthesis of 2‐pyrones has been developed. Two molecules of α, β‐unsaturated acid chlorides (8, 12 and 18) condense, with loss of two molecules hydrogen chloride, to pairs of substituted 2‐pyrones (9 and 10, 13 and 14, 19 and 20) when treated with triethyl amine in chloroform or methylene chloride at room temperature. In the case of 18, two additional products were obtained, namely the resorcinol derivative 21 and traces of the 1, 3‐cyclobutanedione derivative 22. Under the same conditions the α, β‐unsaturated acid chlorides 8, 15, 18 and 41 were condensed with trichloroacetyl chloride to give 6‐trichloromethyl‐2‐pyrones (42, 43, 44 and 46). These 2‐pyrones are valuable intermediates for the synthesis of 6‐carboxy‐2‐pyrones and 6‐methyl‐2‐pyrones.A methyl group in β‐position of the α, β‐unsaturated acid chloride appears to be essential for the described condensations, for the acid chlorides 16 and 17 did not yield defined products and the acid chloride 40 reacted with trichloroacetyl chloride in a very low yield. It is considered that the described reactions proceed via the 1, 4‐addition of an acid chloride to a vinyl ketene or through the acylation of an intermediate anion by an acyl derivative as outlined in reaction scheme 1. The structures of the 2‐pyrones were confirmed by their spectroscopic properties, summarized in table 3, and by some of their chemical transformations.