OXOAPORPHINE ALKALOIDS - CONVERSION OF LYSICAMINE INTO LIRIODENDRONINE AND ITS 2-O-METHYL ETHER, AND ANTIFUNGAL ACTIVITY

Pschorr reaction of diazonium salt 7 in aqueous methanolic sulfuric acid afforded, besides lysicamine 2, the orange colored sulfate of oxodibenzopyrrocoline (8). The structure is fully supported by an X-ray analysis of its picrate salt. Selective ether cleavage of lysicamine (2) with 48% HBr afforded a hydrobromide of 9, and free betaine 9 on treatment with pyridine-water. Both compounds methylated on treatment with etherial diazomethane on nitrogen to give the known 2-O,N-dimethylliriodendronine (11). Liriodendronine (10) was obtained from lysicamine (2) on heating with pyridine.HBr at 189-degrees-C, and treatment with pyridine-water, as a dark violet betaine. Betaine 12 was obtained by heating 11.HCl to 200-degrees-C. The quatemary salts of lysicamine, lysicamine methiodide (3) and lysicamine methosulfate (4) were comparable in anticandidal activity to liriodenine (1), but were not as active as liriodenine methiodide (13).