Unexpected conversion of a polycyclic thiophene to a macrocyclic anhydride

Oxygenation of 2,5,9,12-tetra(tert-butyl)diacenaphtho[1,2-b:1′,2′-d]-thiophene (1, C₄₀H₄₄S) by peracids gave the cyclic sulfonic ester 4 (2,7,10,13-tetra(tert-butyl)diacenaphtho[1,2-c:1′,2′-e]oxathiin 5,5-dioxide, C₄₀H₄₄O₃S) which, when heated in nitrobenzene, is converted into a complex, macrocyclic anhydride 3 (C₈₀H₈₈O₃), which is derived from two molecules of 4. Further investigation found a likely intermediate in this reaction, 4,4′,7,7′-tetra(tert-butyl)-1,1′-biacenaphthylenylidene-2,2′-dione (5, C₄₀H₄₄O₂), apparently formed from 4 by additional oxidation. Anhydride 3 plausibly arises by Diels-Alder reaction of 4 and 5 followed by several ring fragmentations. The structures of 3, 4, and 5 were unambiguously established by X-ray crystallography.