Nonaqueous diazotization of 4-amino-3-arylisothiazole-5-carboxylate esters

4-Amino-3-arylisothiazole-5-carboxylate esters are converted to the corresponding desamino, chloro, bromo, and iodo esters by processes involving nonaqueous diazotization. These related procedures open up the possibility for the conversion of readily available heterocyclic ortho-amino esters and nitriles to related heterocyclic derivatives, which are not easily obtained by alternate routes.     

Secondary deuterium kinetic isotope effects in irreversible additions of allyl reagents to benzaldehyde

The competitive kinetics of additions of allyl to benzaldehyde-h and -d from allyltributyl tin, from diisopropyltartrylallyl boronate, and from allyl bromide and zinc dust in aqueous tetrahydrofuran have inverse secondary deuterium kinetic isotope effects, SDKIEs. These inverse SDKIEs are in contrast to the normal SDKIEs that were obtained with allyl lithium and allyl Grignard, suggesting rate-determining single-electron transfer in these cases. By various MO calculations the transition state for addition of allyl boronate occurs with substantial B-O bond formation and little C-C bond formation. The magnitudes of the SDKIEs with the other two allylating reagents, when compared with reasonable equilibrium isotope effects for the addition, suggest transition states with substantial C-C bond formation.