STEREOCHEMISTRY OF THERMOLYTIC BASE-CATALYZED DECARBOXYLATION TO FORM CONJUGATED DIENE-ACIDS - SYNTHESIS USING ETHYLIDENEMALONIC ESTER CONDENSATION

• Published in: J. Chem. Soc., Perkin Trans. 1 no. 10; pp. 1267 - 1274
• Main Authors: CROMBIE, L, CROMBIE, WML
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 1994; Royal Society of Chemistry
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Noncondensed benzenic compounds; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; Pyrolysis; Base catalysis; Isotope labelling; Isomerization; Temperature effect; Stereoselectivity; Pyridine; Carboxylic acid; Decarboxylation; Conjugated dienic compound; Quinoline; Benzenic compound; Dicarboxylic acid
• ISSN: 0300-922X; 2050-8255; 1364-5463
• DOI: 10.1039/p19940001267

The condensation of aromatic aldehydes with ethylidenemalonic ester in the presence of benzyltrimethylammonium hydroxide leads to 2(E),4(E)-half-esters. which are decarboxylated in refluxing pyridine to 2(E),4(E)-esters. When decarboxylated by thermolysis in quinoline at 130 degrees C cinnamyl-idenemalonic acid gives almost pure 5-phenylpenta-2(Z),4(E)-dienoic acid which slowly stereo-mutates, but on continued heating at 170 degrees C it passes over to give almost pure 2(E),4(E)-acid. In pyridine near its boiling point, however, the malonic acid is converted into a 64:36 mixture of 2(Z),4(E)-:2(E),4(E)-acids, the composition of wh ich does not change on continued refluxing. The use of carboxy-labelled dideuteriomalonic acid in the pyridine reaction leads to 5-phenylpenta-2(Z),4(E)-dienoic acid and its 2(E),4(E)-stereoisomer, each having similar similar to 2:1 alpha/gamma deuterium labelling. The latter stereoisomer does not arise by stereomutation, and a dual pathway originating from a common deuteriated lactone is proposed. Decarboxylation of the deuteriomalonic acid in quinoline at 130 degrees C, giving almost pure 2(Z),4(E)-dienoic acid with similar to 2:1 alpha/gamma labelling, involves only one of the pathways. The ethylidenemalonic acid method is suitable for the preparation of 2(E),4(E)-half-esters and 5-phenylpenta-2(Z),4(E)-dienoic acids having both electron-withdrawing as well as electron-releasing aryl substituents. 2(Z),4(E)-Sorbic acid can also be made from the corresponding malonic acid by quinoline-catalysed decarboxylation, whereas the classical pyridine-catalysed Doebner reaction forms almost entirely 2(E),4(E)-sorbic acid.