NMR spectroscopic and theoretical study on the isomerism of dimethyl benzodiazepine(diylidene)diacetates.

The isomerism of dimethyl 2,2'-(7,8-dichloro-1H-benzo[b][1,4]diazepine-2,4-(3H,5H)diylidene)diacetate (1a) and dimethyl 2,2'-(7,8-dichloro-3-methyl-1H-benzo[b][1,4]diazepine-2,4-(3H,5H)diylidene)diacetate (1b) was investigated by 1 H, 13 C and 15 N nuclear magnetic resonance (NMR) spectroscopy. In CDCl 3 solution, inversion of the diazepine ring was observed, whereas in (D 6 )DMSO and (D 7 )DMF solution, besides the ring inversion, a partial cleavage of one chelate ring appeared connected with (E/Z) isomerization about one of the exocyclic C=C bonds. Gibbs free energies (ΔG) and free activation energies (ΔG ≠ ) were calculated based on B3PW91-SCRF/ZVP DFT computations. Agreement between NMR data and density functional theory (DFT) computations was found.