Studies On The Chemical Constituents From The Bulbs Of Scilla Scilloides

Objective：Scilla bulbus is collected from the bulb or whole plant of Scilla scilloides(Lindl.) Druce and usually used as a folk medicine for promoting blood circulation, asan antiinflammatory agent, and as an analgesic. To understand the chemicalcompositions of this plant, a systematically chemical investigation was conductedincluding the separation, purification and structural identification of the chemicalconstituents, and the qualitative and quantitative analyses based on HPLC andUPLC-orbitrap-MS.Methods: The fresh bulbs of S. scilloides were extracted with95%EtOH,70%EtOHand50%EtOH, respectively. The95%EtOH extraction was suspended in H2O andextracted with EtOAc. The aqueous fraction was passed through a HPD-100columnchromatography eluted by water,30%EtOH,50%EtOH and95%EtOH in turn. TheEtOAC extract and95%eluate contained the similar major constituents based on thepreliminary TLC and HPLC analyses and both were combined. The combined fractionwas subjected to repeated column chromatography on silica gel, Sephadex LH-20andODS, as well as semi-preparative HPLC. The structures of the isolated compounds wereidentified on the basis of the spectroscopic data including UV, NMR, MS, and chemicalreactions. The qualitative HPLC and UPLC-MS were employed for the identification ofhomoisoflavnoids and stilbenes in the bulbs of S. scilloides, collected from the differentgrowing regions. Sequently, the quantitaficaiton of six homoisoflavoids and twostilbenes in four batches of bulbs and two batches of leaves of this plant, was carried outby HPLC.Results: Twenty-nine compounds were isolated and their structures were determined asfollows:15homoisoflavovoids:2-hydroxy-7-methoxyscillascillin (11), scillascillin (12),5,7-dihydroxy-3’,4’-dimethoxyspiro{2H-1-benzopyran-7’-bicyclo[4.2.0]octa[1,3,5]-trien}-4-one (14), socialinone(15),3-(4-hydroxy)-5,7-dihydroxy-9-hydroxychroman-4-one (17), scillavone A (20),3,9-dihydroeucomnalin (21),3-(3-hydroxy-4-methoxybenzyl)-5,7-dihydroxychroman-4-one (22),3 (3R)-5,7,3’-trihydroxy-4’-methoxyspiro{2H-1-benzopyran-7’-bicyclo[4,2,0]octa[1,3,5]-trien}-4-one (23),2-hydroxyscillascillin (25),3-(4-hydroxybenzyl)-5,7-dihydroxychroman-4-one (26),3-(4-hydroxybenzylidene)-5,7-dihydroxychroman-4-one (27),3-(4-hydroxybenzyl)-5-hydroxy-7,8-dimethoxychroman-4-one (28),3-(4-hydroxybenzyl)-5-hydroxy-6,8-dimethoxychroman-4-one (29),3-(4-hydroxybenzyl)-5,8-hydroxy-7-dimethoxychroman-4-one (30); elevennortriterpene or nortriterpene glycosides:(23S)-3β-[(O-β-D-apiofuranosyl-(1â†'2)-[β-D-glucopyranosyl-(1â†'3)]-O-β-D-glucopyranosyl-(1â†'2)-O-α-L-arabinopyranosyl-(1â†'6)-O-β-D-glucopyranosyl)oxy]-17α,23-epoxy-28,29-dihydroxy-27-norlanost-8-en-24-one (1), scillasclloside E-3(2), scillascllosideG-1(3), scillanostaside C (4), scillasclloside E-1(5), scillasclloside E-5(6),3β-[(O-α-L-rhamopyranosyl-(1â†'2)-[O-β-D-galactopyranosyl-(1â†'2)-O-β-D-glucopyranosyl-(1â†'3)]-O-β-D-glucopyranosyl-(1â†'2)-O-α-L-arabinopyranosyl-(1â†'6)-O-β-D-glucopyranosyl)oxy]-17α,23-epoxy-28-hydroxy-27-norlanost-8-en-24-one (7),3β-[(O-β-D-apiofuranosyl-(1â†'2)-O-[β-D-glucopyranosyl-(1â†'3)]-O-β-D-glucopyranosyl-(1â†'2)-O-α-L-arabinopyranosyl-(1â†'6)-O-β-D-glucopyranosyl)oxy]-17,23-epoxy-28-dihydroxy-27-norlanost-8,22-dien-24-one (8),15-deoxoeucosterol (9), scillascllosideD-1(10),24-hydroxy-15-deoxoeucosterol (16).Three stilbenes:4-methylresveratrol (18),(E)-resveratrol (19), scillabene A (24). Among them, four compounds (7,8,16,17) werenew compounds. Nine compounds (1,14,15,22,24,26,28,29,30) were isolated forthe first time from this plants. Based on the retention time, on-line ultraviolet spectraand the fragmentation patterns of reference compounds,28homoisoflavoids andstilbenes were identified form the ethanol extract of fresh bulb of S. scilloides, amongwhich10compounds were detected for the first time from this plant. The quantitativeanalysis indicated that the content of homoisoflavovoids and stilbenes in the samplescollected from different parts and different growing regions were rather various.Conclusion:29compounds were isolated from the fresh bulbs of S. Scilloides,including a new homoisoflavoid, a new nortriterpene and two nortriterpene glycosidesas well as9first-reported constituents. The qualitative and quantitative analyses byHPLC and UPLC-MS further indicated the relative and absolute amounts ofhomosioflavoids and stilbenes in the bulbs and leaves of S. scilloides. The presentinvestigation provides some evidences for the development and utilization of the resource of this plant.