Photocyclization of 2,4,6-triethylbenzophenones in the solid state

Abstract

Photocyclization of 2,4,6-triethylbenzophenones (TEBPs) into ( E)- or ( Z)-benzocyclobutenols (( E)- or ( Z)-CBs) is E-selective in solution. By contrast, upon solid-state photolysis, TEBP-3,4-diCl and especially TEBP-4- t-Bu gave ( Z)-CB relative to ( E)-CB with a much higher proportion than that in solution. For TEBP-4- t-Bu, the most major product in the solid state is an indanol derivative (Inol) ( E/ Z/Inol=1:3.9:10.3 at 9% conversion). On the basis of the X-ray crystallographic analysis, Inol and ( Z)-CB are both topochemical products. Notably, the relative proportion of ( E)-CB increased with increased conversion, namely with increased disruption of the crystal lattice. The DFT calculation of highly hindered 2,6-diisopropylbenzophenone (DIBP) was also conducted. These results in conjunction with the previous results on 2,4,6-triisopropylbenzophenones (TIBPs) indicate that CB is formed either via trans-enol followed by its conrotatory ring-closure (paths a and d) or through direct cyclization of biradical (BR) (path b) as shown in Scheme 1. Normally the former route is faster. However, in the crystalline state or in the case of sterically hindered phenyl ketones, path b tends to be adopted.