Oxygen-functionalization of 9-hydroxyphenalenone.

We investigated acyl group transfer in derivatives of 9-hydroxyphenalenone (1,R-H,D). A general scheme for oxygen functionalization of 9-hydroxyphenalenone (1) has proved difficult to achieve, and all previous efforts prepare the acetate (4) have been unsuccessful. The present paper reports the synthesis of 4 and the related compounds 5 and 6 and some of their properties. The mode of preparation allows ready access to O-substituted derivatives of 1 and is likely to be of use in the functionalization of other hydroxyquinones and related compounds where a strong internal hydrogen bond or contact ion-pairs inhibit reactivity. The crystal structure of 9-butoxyphenalenone (6) has been determine and its geometry is compared with that of 1.