Thermal Decomposition of Geminal Diazidomalonic Acid Derivatives. An Intermolecular Process

Article abstract of DOI:10.1021/jo00220a007

Thermal decomposition of a 1:1 mixture of (CH3OCO)2C(N3)2 and (CD3OCO)2C(N3)2 to yield 1-methyl-5-carbomethoxytetrazole-d_x proceeds with crossover of the isotope label, indicating an intermolecular pathway for this reaction.A chain mechanism involving tetrazolium nucleophiles is proposed.The thermal decomposition of diazidomalonamide (14) and N,N'-dimethyldiazidomalonamide (16) occurs analogously yielding 5-carbamoyltetrazole (15) and 5-(methylcarbamoyl)tetrazole (17), respectively.In order to test the mechanistic possibility that a tetrazolium intermediate plays a role in these decompositions, lithio-5-carbomethoxytetrazole was added in 10percent molar concentration to dimethyl diazidomalonate (1) in dodecane.A similar experiment was carried out with diazidomalonamide (14).In both cases the reaction occured at lower temperatures, and in each case the same products were observed as those obtained in the normal thermolysis.