Computer-aided design of promising photochemical alkoxy radical precursors

A computer-aided design of alkoxyl radical precursors is performed. The new precursors should combine the advantages of N-alkoxypyridine-2(1H)thiones (less reactive radicals) and N-alkoxythiazole-2(3H)thiones (stable with respect to daylight). Additionally, the radical liberation process should be initiated by light with a wavelength of around 350 nm. To find promising compounds, 18 test candidates were obtained by a systematic variation of the parent compound N-alkoxythiazole-2(3H)thione. The properties of the test molecules were computed by a protocol that was already successfully used to rationalize the photochemical behavior of N-alkoxypyridine-2(1H)thiones and N-alkoxythiazole-2(3H)thiones. The computations identify two promising new compounds. For N-methoxy-(1,3)dihydro-[1,3]azaphosphole-2-thione (6a), they predict that the fragmentation process will be initiated by an absorption at 348 nm. An analysis of its fragmentation process indicates that the free excess energy of the resulting radicals should more resemble the situation found for N-alkoxypyridine-2(1H)thiones. For N-methoxy-(1,3)dihydro-pyrrole-2-thione (3a), the excitation energy is somewhat higher (330 nm), but the computed fragmentation paths again indicate that the remaining excess energy of the released radicals is quite favorable. The test molecules also contained the experimentally well-known N-methoxypyridine-2(1H)one (1b). For this molecule, our computed data rationalizes nicely the experimental findings.