Ethyl isopropylidene cyanoacetate

The formation of ethyl isopropylidene cyanoacetate is an example of the Knoevenagel reaction (see Discussion before Section IV,123). With higher ketones a mixture of ammonium acetate and acetic acid is an effective catalyst the water formed is removed by azeotropic distillation with benzene. The essential step in the reaction with aqueous potassium cyanide is the addition of the cyanide ion to the p-end of the ap-double bond ... 

The treatment of isopropylidene phenylaminomethylenemalonates (1319) with ethyl cyanoacetate or malononitrile in the presence of potassium hydroxide in DMF at 90°C afforded the potassium salts of derivatives of Meldrum s acid in 74% yields, which were converted without isolation to pyridones (1320) in 91% yield on the action of aqueous hydrochloric acid [78ZN(B)1550]. 

D-mcn/io-heptonic acid, and its 6-epimer has been effected from the cyanohydrins of 1,2 3,4-di-O-isopropylidene-D- a/flcto-dialdose (see Chapter 8), and treatment of 5,6-anhydro-l,3 2,4-di-O-ethylidene-D-glucitol with the anion of ethyl acetoacetate led to the octonic acid -lactones (7). Ethyl cyanoacetate afforded related products that dimerized on hydrolysis. ... 

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