CHEMISTRY OF MUCONALDEHYDES OF POSSIBLE RELEVANCE TO THE TOXICOLOGY OF BENZENE

(Z,Z)-Muconaldehyde reacted with primary amines to give N-substituted- 2-(2'-oxoethyl)-pyrroles, which were reduced to N-substituted-2-(2'-hy droxyethyl)-pyrroles by sodium borohydride. The pyrrole-forming reacti on is exhibited by valine and its methyl ester, and is being developed with terminal valine in hemoglobin as a means of dose monitoring (Z,Z )-muconaldehyde, a putative metabolite of benzene. Reactions in aqueou s solution between (Z,Z)-muconaldebyde and adenosine, deoxyadenosine, guanosine, or deoxyguanosine reading to pyrrole-containing adducts are described. The elucidation of the structures of the adducts was assis ted by the study of reactions between (Z,Z)-muconaldehyde and both nuc leoside derivatives and a model compound for guanosine. Reactions of ( Z,Z)-muconaldehyde are complicated by its isomerization to (E,Z)- and (E,E)-muconaldehyde. The kinetics of this process have been studied in benzene, acetonitrile, and dimethylsulfoxide.