116

ORGANIC REACTIONS Decomposition of Malonic Acid Derivatives

A method of synthesis of ketoketenes which is closely related to the pyrolysis described in the preceding section consists in the thermal decomposition of disubstituted malonic anhydrides, of either the simple or mixed types.

R \ R 0

C=C=O + C02

R R COOCOR' \ / R \ C=C=O + R'COOCOR' + CO2

c / \

R COOCOR' R Monosubstituted malonic anhydrides have not yielded aldoketenes,108 but malonic acid itself yields carbon suboxide when heated with phosphorus pentoxide.38 The disubstituted malonic anhydrides can be prepared from the corresponding malonic acids and acetic anhydride in the presence of a little sulfuric acid, with neutralization of the mineral acid by treatment with barium carbonate and removal of acetic acid and acetic anhydride by distillation.109 The residual malonic anhydride is decomposed by heating under low pressure. This method appears to have been used only for dimethylketene (80% yield), diethylketene (55% yield), methylethylketene (65% yield), and dipropyl- and diisopropyl-ketenes (50% yields). A more common method involves the decomposition of mixed anhydrides, nearly all of which have been obtained by treating the dialkylmalonic acid, dissolved in dry ether, with diphenylketene. The resulting mixed anhydrides, derived from the malonic acids and diphenylacetic acid, are nearly insoluble in ether and separate in almost quantitative yields. They are decomposed by heating under diminished pressure until
108 109

Staudinger, Anthes, and Schneider, Ber., 46, 3539 (1913). Staudinger, Helv. Chim. Ada, 8, 306 (1925).