Approaches to the synthesis of triterpenes. V. An unusual acid-catalysed rearrangement of a β,γ-unsaturated ketone
The reaction of 2-keto-1β,4aβ-dimethyl-1α-[2-(3-keto-1,4,4-trimethylcyclohexyl)ethyl]-7-methoxy-1,2,3,4,4a,9-hexahydrophenanthrene 1a and b with p-toluenesulphonic acid in boiling xylene yields the rearranged product, 1,10-dimethyl-2-[2-(3-keto-1,4,4-trimethylcyclohexyl)-ethyl]-7-methoxy-3,4-dihydroanthracene (3). Crystals of 3 are monoclinic, space group P21/c, Z = 4, with a = 7.2684(3), b = 30.942(2), c = 10.5544(7) Å, β = 98.24(1)°. The structure was determined by direct methods from diffractometer data and refined by block-diagonal least-squares to an R of 0.043 for 1810 observed reflections. The molecule exhibits no unusual geometric features, although positional disorder is apparent in the cyclohexanone moiety.A possible route for the formation of 3 from 1a and b is presented.