The conformational equilibria and preferences in dibenzo[c,h] [1,6]diazecines have been investigated by 1H DNMR measurements and X-ray crystallography. It has been found that restricted rotation about the exocyclic N-S bond in 6,13-ditosyl-6,7,13,14-tetrahydro-5H,12H-dibenzo[c,h][1,6] diazecine 2 becomes slow on the NMR timescale in the temperature range 200-300 K. The free energy of activation was determined to be 43.5 ± 0.5 kJ mol-1 for this dynamic process. Steric hindrance at the transition state is deemed to be the most important contribution to the N,S barrier. From X-ray crystal structure analyses, it appears that the influence of the N-inversion on this barrier is negligible. The conformation in the solid state is also the preferred one in solution. The X-ray structure illustrates the spatial vicinity of the tosyl groups relative to the annelated benzene moieties of the 10-membered ring. Consistent with these results are high field shifts and corresponding splittings in the aromatic part of the 1H NMR spectrum of compound 2.

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Journal Journal of the Chemical Society. Perkin Transactions 2
Citation
Lehmann, S. (Silke), Buchanan, G.W, Bensimon, C. (Corinne), Hartmann, J. (Jens), & Schroth, W. (Werner). (1996). 1H dynamic NMR and x-ray crystal structure studies of conformational preferences in dibenzo [c,h] [1,6] diazecines. Journal of the Chemical Society. Perkin Transactions 2, 3, 467–470.