Orcacetophcnone monomethyl ether has been condensed with ethyl acetate, ethyl propionate and ethyl butyrate in presence of metallic sodium.; instead of the expected \(\beta\)-diketones other products are obtained to which the structures of 4-hydroxy-7-methoxy-4 :5-dimethyl-, -3 :4:5-trimethyl-, and -3-ethyl-4 :5-dimethyl-3 :4-dihydrocoumarin respectively, have been tentatively assigned. Molecular rearrangement of orcacetophenone diacetate in presence of metallic sodium gives 7-hydroxy-4-acetome­thyl-5-methylconmarin instead of the isomeric chromone. The formation of coumarin derivatives in the above reactions has not been observed before. Similar rearrangement of orcacetophenone dibenzoate gives the expected 7-hydroxy-5-methylflavone.