Alternative method for the synthesis of triazenes from aryl diazonium salts

An alternative mild method for access to 1-aryl-3,3-dimethyl alkyl triazenes is described. This protocol employs the dropwise addition of a methanolic solution of a carboxylate (RCO2M) or carbonate (CO32-) to a gently heated DMF solution containing an aryl diazonium salt (ArN2+), that had been previously isolated. Presumably homolysis of the weak N-O bond of diazo ether adducts formed in this operation initiates radical pathways that lead to the generation of triazene product. DMF serves as not only a one-electron donor to the diazonium salts employed in this process, but also as a source of dimethylamine radicals that act as a nucleophilic coupling partner. The reaction provides modest yields (ca. 20-40%) across an array of aryl diazonium salts that contain various substitution. Furthermore this unique approach to triazenes contrasts with traditional methods that employ dimethyl amine in reagent form which directly couples with diazonium salts. Seemingly, only one other example employing somewhat similar reaction conditions to this current investigation en route to triazenes has been reported, albeit with lower yields and for one representative example furnished as a side-product. The current work here improves upon the efficiency of this reported result, and further expands the reaction scope. Published by Elsevier Ltd.

Automated summary

An alternative mild method for synthesizing 1-aryl-3,3-dimethyl alkyl triazenes has been described, utilizing radical pathways initiated by homolysis of weak N-O bonds in diazo ether adducts. This method provides modest yields (ca. 20-40%) across a range of aryl diazonium salts. The use of DMF as both an electron donor and a source of dimethylamine radicals sets this approach apart from traditional methods.