33465-33-7Relevant articles and documents
Development of a one-pot method for the homologation of aldehydes to carboxylic acids
McNulty, James,Das, Priyabrata
experimental part, p. 7794 - 7800 (2009/12/26)
A highly efficient method is described for the one-carbon homologation of aldehydes to carboxylic acid derivatives employing the reaction of a 1,1-bis-dimethylphosphonate derivative with the aldehyde and controlled acid hydrolysis of the derived α-phosphonoenamine intermediate.
α-SUBSTITUIERTE PHOSPHONATE 38. 1-DIMETHYLAMINO-1-CYANO-METHANPHOSPHONSAEUREDIETHYLESTER, EIN NEUES EDUKT ZUR DARSTELLUNG VON CARBONSAEUREN, 1-CYANOENAMINEN UND HOMOENOLATEN.
Costisella, Burkhard,Gross, Hans
, p. 139 - 145 (2007/10/02)
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.
