Cyanocarboxylic esters

Two procedures for the preparation of a-oxocarboxylic acids via nitrile intermediates have been described. The autoxidation of 3,3-disubstituted 2-cyanocarboxylate ester anions is reported to provide the related a-oxoesters in fair yield a new general procedure for the conversion of aldehydes into the homologous a-oxoacids is based on theoxidationof a-hydroxy-iV-t-butyl-carboxamides (116), prepared by the acid-catalysed alcoholysis of aldehyde cyanohydrins with t-butanol, to the hitherto ui nown -oxocarboxamides, which are in turn readily converted into the parent a-oxoacids on acid-catalysed hydrolysis. 

Potqssiam hydroxide/alcohol Nitriles from a-cyanocarboxylic acid esters... 

Michael addition is one of the most efficient and effective routes to C-C bond formation[127]. This reaction is widely applied in organic synthesis and several new versions of it have been introduced recently. The commonly employed anionic alkyl synthons for Michael addition are those derived from nitroalkanes, ethyl cyanocarboxylates, and malonates, and their limitations have been largely overcome by newer methodologies. However, the newer approaches are by no means devoid of drawbacks such as long reaction times, modest product yields in many cases, and the requirement for excess nitroalkane. Michael addition reactions of Schiff s bases have long been known to constitute a convenient method for functionalizing a-amino esters at the a position and the ratio of Michael addition to cycloaddition product has been found to depend upon the metal ion employed to chelate the enolate produced upon deprotonation (see below). 

Chloroformic acid esters triethylamine Cyanocarboxylic acid esters from dicarboxylic acid monoamides... 

Cyanocarboxylic acid esters. 2-Oximinocyclohexanone dimethyl ketal, trimethyl orthoformate, and a little methanesulfonic acid added at -70° under Ng to liq. SO2, and refluxed 0.5 hr. at ca. -10° methyl 5-cyanopentanoate. Y 97%. -Similarly at 72° Benzil monoxime and triethyl orthoformate -> benzonitrile (Y 95%) and ethyl benzoate (Y 98%). M. M. Rogic et al., J. Org. Chem. 39, 3424 (1974) Beckmann fragmentation with tetrakis(triphenylphosphine)palladium cf. K. Maeda et al., Chem. Commun. 1975, 689. 

Furanone ring from -cyanocarboxylic acid esters and prim, alcohols F ur ano 4,3-6 Jquinoli n-1 (3 )-ones... 

Nitriles from a-cyanocarboxylic acid esters via a-cyanocarboxylic acids s. 16, 136 G(GN)GOOR GHGN... 

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