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 quaternary 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).
Pabuccuoglu
V
V
Medicinal Chemistry Section, LAC, NIDDK, National Institutes of Health, Bethesda, Maryland 20892.
Rozwadowska
M D
MD
Brossi
A
A
Clark
A
A
Hufford
C D
CD
George
C
C
Flippen-Anderson
J L
JL
D000470:Alkaloids / Q000138:chemical synthesis* / Q000494:pharmacology; D000935:Antifungal Agents / Q000138:chemical synthesis* / Q000494:pharmacology; D001060:Aporphines / Q000138:chemical synthesis* / Q000494:pharmacology; D002176:Candida albicans / Q000187:drug effects; D008826:Microbial Sensitivity Tests
D000470:Alkaloids; D000935:Antifungal Agents; D001060:Aporphines; C069090:lysicamine; C069092:liriodendronine 2-O-methyl ether; C069091:liriodendronine