Structure Identification: |
Journal of Labelled Compounds & Radiopharmaceuticals, 1985, 22(11):1175-9. | Synthesis of malondialdehyde-1-2H and malondialdehyde-1,3-2H2[Reference: WebLink] | Two synthetic routes for deuterium labelling of 1,1,3,3-Tetraethoxypropane, the precursor of the ubiquitous natural compound malondialdehyde, are described. METHODS AND RESULTS: In one scheme, deuterium is incorporated in ethyl vinyl ether by metalation with t-butyllithium followed by quenching with 2H2O. The conversion of the deuterated ether to monodeuterated Tetraethoxypropane, however, proceeds with an overall yield of only ˜5%. As an alternative route, we have metalated the bis-1,3-propylene dithioacetal of malondialdehyde which undergoes excellent deuterium incorporation (92%). In addition, the latter method allows isotopic labelling of either one or two deuterium(s) /molecule. Hydrolysis of the deuterated dithioacetal to the corresponding Tetraethoxypropane can be best effected by refluxing with HgO(red) /HgCl2/BF3. etherate in the presence of CH(OC2H5)3/C2H5OH. The overall yield of the method is 48%. |
|