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Synthesis of malondialdehyde‐1‐ 2 H and malondialdehyde‐1,3‐ 2 H 2
Author(s) -
Basu Ashis K.,
Marnett Lawrence J.
Publication year - 1985
Publication title -
journal of labelled compounds and radiopharmaceuticals
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.432
H-Index - 47
eISSN - 1099-1344
pISSN - 0362-4803
DOI - 10.1002/jlcr.2580221111
Subject(s) - chemistry , deuterium , malondialdehyde , ether , yield (engineering) , metalation , hydrolysis , medicinal chemistry , kinetic isotope effect , nuclear chemistry , organic chemistry , physics , materials science , quantum mechanics , metallurgy , antioxidant
Abstract Two synthetic routes for deuterium labelling of 1,1,3,3‐tetraethoxypropane, the precursor of the ubiquitous natural compound malondialdehyde, are described. In one scheme, deuterium is incorporated in ethyl vinyl ether by metalation with t‐butyllithium followed by quenching with 2 H 2 O. 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 H g O(red) /HgCl 2 /BF 3 . etherate in the presence of CH(OC 2 H 5 ) 3 /C 2 H 5 OH. The overall yield of the method is 48%.