82518-40-9

Upstream product

• 82518-32-9 diethyl α-cyano-α-dimethylaminomethylphosphonate 
• 100-52-7 benzaldehyde 
• 127780-70-5 α-dimethylamino-α(trimethylsilyl)acetonitrile 

Relevant academic research and scientific papers

An effective synthesis of α-cyanoenamines by Peterson olefination

A convenient and gentle method for the synthesis of α-cyanoenamines based on the Peterson olefination has been developed. For these sensitive, highly functionalized olefins, the present method is superior to the Horner-Emmons condensation, as manifested by the higher yields and broader scope.

CATHODIC PROMOTION OF HORNER REACTION

It has been established that the electrolysis of α-substituted phosphonates (I) on Pt or glassy carbon cathodes involves the cleavage of activated C-H bond with the formation of the carbanion (II) which further reacts with the carbonyl compounds (III) to form olefines (IV) in satisfactory yields.

α-SUBSTITUIERTE PHOSPHONATE 38. 1-DIMETHYLAMINO-1-CYANO-METHANPHOSPHONSAEUREDIETHYLESTER, EIN NEUES EDUKT ZUR DARSTELLUNG VON CARBONSAEUREN, 1-CYANOENAMINEN UND HOMOENOLATEN.

Alkylation of 1-dimethylamino-1-cyanomethanephosphonic acid diethyl ester (8), easily obtainable from diethyl phosphite and the O,N-acetal 9, yields 1-alkyl derivatives 14.Elimination of HCN converts 14 into 1-phosphonoenamines 6.Carbonyl compounds react with 8 to give 1-cyanoenamines 15 which may be hydrolyzed to form the homologous carboxylic acid.Alternatively, deprotonation of 15 yields the homoenolate anions 17 which can be alkylated or hydroxyalkylated, permitting chain extension of carbonyl compounds through introduction of an α-carboxyl and a β-alkyl group.Acid catalyzed hydrolysis of 8 results in the cleavage of the P-C bond, leading to the corresponding α-dimethylamino alkanoic acids.A phosphonic acid 11 can be obtained from 8 by application of the silylester method.An unambigous assignment of E/Z-isomers of cyanoenamines 15 has been derived from 13C-NMR spectroscopy.