THERMAL REARRANGEMENT OF PYRIDYLNITRAMINES

N-Methyl-N-pyridylnitramines form corresponding methylamino-nitropyrid ines in 74-90 % yield when heated (120-130 degrees C) in chlorobenzene without an acidic catalyst. N-(P-Pyridyl) nitramine behaves analogous ly while remaining primary pyridylnitramines rather decompose than rea rrange. The rearrangement can he carried out in the anisole or m-xylen e solutions without cross-nitration, hence migration of the nitro grou p must have an intramolecular character. Some analogies in the thermal and acid-catalyzed rearrangements have been observed. Various ortho/p ara ratios can be explained assuming different mechanisms of hydrogen transfer in the intermediary sigma-complexes.