Spectral effects in cyclobutane derivatives : The bathochromic-hypochromic shifts in compounds related to verbenone

The bathochromic-hypochromic spectral shifts, observed in bicyclic enones that contain a 4- or a 3-membered ring, are discussed in molecular-mechanical and molecular-orbital terms. It is proposed that the effect, not only by the cyclopropane but also by the cyclobutane ring, is due to extension of the CCCO chromophore, and not to its mere distortion from “normal” geometry. The high-energy absorption of umbellulone (3), 220 nm in ethanol, is characterized as a second π-π^*. 2-Methylbicyclo3.2.1]oct-2-en-4-one (7) has been synthesized, and its preparation and spectrum are described.