Photocycloadditions of Chloranil to Homobenzvalene, Norbornadiene, and Quadricyclane

Abstract

Solutions of chloranil (CA) in toluene or benzene have been irradiated in the presence of the C7H8 valence isomers homobenzvalene (HB), norbornadiene (N), and quadricyclane (Q). In the case of HB, the adducts 3–6 were obtained, all of them having a rearranged structure. By a separate irradiation it was shown that 4 is a consecutive product of 3. The structure of 4 was established by X-ray diffraction analysis. These reactions are most probably initiated by an electron transfer (ET) from HB to 3CA, continue by bond formation between the radical ions to give the zwitterion 14, which undergoes Wagner–Meerwein rearrangements, and are completed by ring-closure between the charged centres of the resulting zwitterions. The oxidation potential of N is not larger than that of HB and the products 8–10 may well be formed through an ET to 3CA. However, the pathway leading to product 3 most probably involves diradical intermediates. This should also be the case for the adducts 11 and 12, which were produced upon irradiation of methyl phenylglyoxylate (PG) in the presence of N. In the case of Q, an ET to 3CA is again highly likely, followed by a combination of the radical ions to generate the zwitterion 29, which eventually collapses to produce the oxetane 8 as the sole identifiable product. The photoreactions of CA with N and Q proceeded much less efficiently in acetonitrile solution.