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Primary steps of thermolysis of the promising high‐energy compound 1,1‐diamino‐2,2‐dinitroethylene (DADNE or FOX‐7) were studied by the quantum‐chemical methods using the PBE0 hybrid functional in the cc‐pVDZ basis set and the coupled‐cluster method at the CCSD/aug‐cc‐pVDZ level. A series of thermal decomposition reactions were studied. The reactions proceeding via hydrogen transfer from the amino group to carbon, along with four variants of transformations of the aci form of DADNE insufficiently studied earlier, are shown to be the most energetically favorable channels of the DADNE thermal decomposition. The activation enthalpies ΔHa of all these channels are close to the most reliable experimental values which are in the range of 190–200 kJ mol−1.

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The thermolysis mechanism of two members of the 2-alkoxydiazene-1-oxide class of compounds -1-methyl-2-methoxydiazene-1-oxide (1) and 2-methoxy-1-neopentyldiazene-1-oxide (2) was studied by quantum chemical methods. Calculations were performed using coupled clusters method at the CCSD and CCSD(T) level using the aug-cc-pVDZ and aug-cc-pVTZ basis sets. It was shown that the mechanism of thermal decomposition of compounds 1 and 2 is similar and occurs via two competing channelsvia homolytic N-OCH 3 bond cleavage and via intramolecular nucleophilic substitution at the methoxyl carbon atom. The calculated values of the activation enthalpies for both compounds are close (ΔН а ‡ is in the range of 200-210 kJ/mol) and practically coincide with the experimental activation energies obtained earlier. The main thermolysis products predicted theoretically correspond to the thermal decomposition products of compounds 1 and 2 that have been observedexperimentally.

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