Crystal structure of (±)-(3aR,5R,8bR)-5-hydroper-oxy-2-phenyl-6-tosyl-4,5,6,8b-tetra-hydro-pyrrolo-[3,4-e]indole-1,3(2H,3aH)-dione.

The title compound, C23H20N2O6S, crystallizes as a racemate in the space group P-1, with an overall L- or J-shape to each mol-ecule. Centrosymmetric pairs of mol-ecules are tandem hydrogen bonded between the hydro-per-oxy H atom and carbonyl O atom. A different centrosymmetric pairing has stacked S-tolyl rings, and a third pairing is L,J-inter-locked by the short leg. Except for stacked tolyl pairs, neighboring π-systems are much closer to orthogonal than coaxial. The title compound is the first example of a hydro-peroxide obtained from the autoxidation of a Diels-Alder adduct of a 2-vinyl-pyrrole.

The heterocyclic ring of 4-substituted-1,8-naphthalimides is NOT inert to nucleophilic attack, contrary to earlier reports.

The heterocyclic ring of N-aryl-4-chloro-1,8-naphthalimides, reported to be resistant to nucleophilic attack, reacts with primary amine nucleophiles at room temperature to give 4-chloro-N-alkyl-1,8-naphthalimides. The reaction is first order in the naphthalimide. The Hammett plot is linear (R(2) 0.996) with a large positive slope (+3.0), consistent with substantial negative charge development at nitrogen in the activated complex.