Synthesis, molecular structure, and chemical reactivity of azuleno[1,2-a]acenaphthylene

The azuleno[1,2-a]acenaphthylene (1a) was prepared from 1-pyrrolidinylacenaphthylene (5) and 2H-cyclohepta[b]furan-2-one (6) by the method of the Takase-Yasunami azulene synthesis. Its ¹H and ¹³C NMR spectra indicate that 1a comprises azulene and naphthalene rather than acenaphtylene and heptafulvene in accordance with speculation drawn from a previous study of the DEPE calculations. The solid-state structure of 1a was elucidated by X-ray crystallographical analysis, indicating that 1a is nearly planar and exhibits little bond alternation as seen in the optimized structure at the MB3LYP/6-311G* level of theory. All bond lengths observed by the X-ray analysis are in good agreement within 0.024Å with those calculated. Under pyrolytic conditions 1a underwent azulene-naphthalene rearrangement to give 9 and 10. The electrophilic substitution of 1a was observed at the 7-position and the second reaction at the 3-position. The cycloaddition reaction of 1a with dimethyl acetylenedicarboxylate (DMAD) yielded the 1:1 cycloadduct with a heptalene skeleton 16a and the 1:2 cycloadduct 19, along with the substitution product 17. The X-ray structural analysis of the cycloadducts 16a and 19 is also described.