Collect. Czech. Chem. Commun. 1987, 52, 2926-2935

Arbuzov rearrangement in the reaction of arylmethylenemalonaldehydes with trimethyl phosphite: Formation of 2-(α-dimethoxyphosphonylbenzyl)-3-methoxyacroleins

Dalimil Dvořák, David Šaman, Miloš Buděšínský and Zdeněk Arnold

Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6


Reaction of arylmethylenemalonaldehydes I with trimethyl phosphite affords substituted methoxyacroleins V. The reaction proceeds via intermediates VII which, according to spectral data, can be described as interconverting dipolar and cyclic structures VIIA and VIIB, respectively. The intermediates VII are easily hydrolyzed to give the substituted malonaldehydes VI. Compounds VI were also obtained by acid-catalyzed hydrolysis of methoxyacroleins V.