Estrogens and congeners from spent hops (Humulus lupulus).
Estrogenicity-directed fractionation of a methanol extract of the strobiles of Humulus lupulus that had been extracted previously with supercritical CO(2), known as "spent hops", led to the isolation and identification of 22 compounds including 12 prenylated chalcones (1-8, 10-13), five prenylflavanones (14-17), 4-hydroxybenzaldehyde (18), sitosterol-3-O-beta-glucopyranoside (19), humulinone (20), and cohumulinone (21). In addition, the prenylated chalcone xanthohumol C (9a) was obtained as a 6:1 mixture along with its 1' ',2' '-dihydro derivative (9b). Three new chalcones (4, 11, 12) and four previously unreported constituents of hops (5, 6, 9b, 13) are reported. The structures of the new compounds were determined through a combination of spectrometric techniques including 1D and 2D NMR, HRESIMS, and ESIMS-MS. Full 1H NMR spin system analyses were performed to characterize the higher-order glucopyranosyl, prenyl, and chalcone B-ring spectra of the isolates. The principle estrogen 8-prenylnaringenin (15) from hops is an artifact formed along with its positional isomer 6-prenylnaringenin (16) through the spontaneous isomerization of the pro-estrogenic chalcone DMX (7).
Chadwick
Lucas R
LR
UIC/NIH Center for Botanical Dietary Supplements Research, Department of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, University of Illinois at Chicago, Chicago, Illinois 60612, USA.
Nikolic
Dejan
D
Burdette
Joanna E
JE
Overk
Cassia R
CR
Bolton
Judy L
JL
van Breemen
Richard B
RB
Fröhlich
Roland
R
Fong
Harry H S
HH
Farnsworth
Norman R
NR
Pauli
Guido F
GF
D000469:Alkaline Phosphatase / Q000378:metabolism; D004968:Estrogens, Non-Steroidal / Q000737:chemistry / Q000302:isolation & purification* / Q000494:pharmacology; D005419:Flavonoids / Q000737:chemistry / Q000302:isolation & purification* / Q000494:pharmacology; D006801:Humans; D027582:Humulus / Q000737:chemistry*; D008968:Molecular Conformation; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D048789:Phytoestrogens; D014407:Tumor Cells, Cultured
D004968:Estrogens, Non-Steroidal; D005419:Flavonoids; D048789:Phytoestrogens; D000469:Alkaline Phosphatase