9-Oxobenzomorphans. IV. 9-Oxo-5-[3″-(1″-hydroxypropyl)]- and 9-oxo-5-[3″-(1″-sulfidrylpropyl)]-6,7-benzomorphans as cyclic hemiketals and hemithioketals

Abstract

The syntheses of 9-oxobenzomorphans 10 and 12 are described. Both products exist in the cyclic forms 11 and 13 respectively. Hydrobromide and oxalate salts of the 9-oxobenzomorphan 1 when crystallized from methanol form stable methylhemiketals 4 and 5. Bromination of 5 yielded benzomorphan 8 which on treatment with sodium hydroxide produced, via 10, the cyclic hemiketal 11. Reaction of 8 with sodium hydrogen sulfide afforded, via 12, the cyclic hemithioketals 13.