I. Lunga et al./Chem.J.Mold. 2008, 3 (1), 89-93Table 113C NMR spectral data (150 MHz, CD 3OD) <strong>of</strong> saponins (1-3)Carbon 1 2 31 37.9 37.9 37.92 30.4 30.2 30.03 78.9 79.1 79.14 34.9 35.1 35.05 45.8 45.8 45.96 32.9 32.9 29.57 34.6 34.6 32.98 36.0 36.0 34.79 55.2 55.2 56.110 36.5 36.4 35.711 21.5 21.5 21.312 40.5 40.5 35.713 41.8 41.8 47.214 57.5 57.5 57.315 32.3 32.3 32.916 82.1 82.2 147.017 63.7 63.7 156.418 16.7 16.7 15.719 12.5 12.6 12.220 42.6 42.6 199.321 14.2 14.2 26.822 110.5 110.523 32.2 32.124 29.1 29.125 31.2 31.226 67.7 67.727 16.7 16.71' 103,5 103,2 102.92' 72,9 78,1 72.93' 80,7 82.5 75.34' 70,5 71,7 80.25' 75,6 75,4 77.86' 60,3 60,1 60.41'' 105,0 104,9 104.52'' 75,5 75,5 84.73'' 78,3 78,0 77.84'' 71,2 71,2 71.45'' 78,9 78,9 78.66'' 63,1 62,9 62.51''' 105,1 105.12''' 75,5 75.53''' 78,3 78.24''' 71,7 71.35''' 78,1 78.96''' 63,1 63.1ExperimentalThe seeds <strong>of</strong> Hyoscyamus niger L. has been collected in the scientific research field <strong>of</strong> Institute <strong>of</strong> ScientificResearches and Technological Constructions for Tobacco and Tobacco Products <strong>of</strong> Moldova in November 2001 year.The voucher specimen has been deposited in Laboratory <strong>of</strong> selection under direction <strong>of</strong> Doctor in Biology KalkeiE.D.Dry powdered seeds (500 g) were extracted three times in 50°C with n-buthanol saturated with water.The received n-butanol-water extract was evaporated and then purified with chlor<strong>of</strong>orm. After purification it wascrystallised in acetone. The residue was dried in vacuum at 40°C and the sum <strong>of</strong> steroidal saponins has been obtainedas yellow powder in 3.7% yield. 3g <strong>of</strong> extract has been chromatographied on silica gel column (30-500mm, 60-100m,91
I. Lunga et al./Chem.J.Mold. 2008, 3 (1), 89-93Merck). The column was eluted with system chlor<strong>of</strong>orm-methanol-water (8:2:020:10:1) and 4ml fractions werecollected. Fractions showing identical characteristics [TLC, silica gel, chlor<strong>of</strong>orm-methanol (4:1)] were combined. Twosubfractions, (A) and (B) were obtained, which were further separated on a C 18column (7,8x300mm, LiChroprep RP18,25-40m, XTerra Waters) using a H 2O/MeOH (60-80% MeOH) isocratic. Ten single compounds were isolated.NMR experiments were performed on a Bruker DRX-600 spectrometer (Bruker BioSpin GmBH, Rheinstetten,Germany) at 300 K dissolving all the samples in CD 3OD (Carlo Erba, 99.8 %). The standard pulse sequence andphase cycling were used for DQF-COSY, HSQC and HMBC spectra. The NMR data were processed using UXNMRs<strong>of</strong>tware.ESI-MS in the positive ion mode was performed using a Finnigan LCQ Deca ion trap instrument from ThermoFinnigan (San Jose, CA) equipped with Xcalibur s<strong>of</strong>tware.HPLC separations were carried out on a Waters 590 system equipped with a Waters R401 refractive indexdetector, a Waters XTerra Prep MSC 18column (300 x 7.8 mm i.d.) and a Rheodyne injector.Column chromatography was performed over Silica gel (0.1-0.06 mm, Merck). TLC was performed on silica gelplates (Merck precoated silica gel 60 F 254). All solvents for chromatographic separation were <strong>of</strong> analytical grade fromCarlo Erba (Rodano, Italy). HPLC grade water (18 m) was prepared using a Millipore Milli-Q purification system(Millipore Corp., Bedford, MA).1. HRMS m/z 741.452[calculated for C 39H 64O 13(M) + ]; 579.3 [M-162] + ; 1 H NMR (aglycon) 4.41 (1H, m,H-16), 3.68 (1H, m, H-3), 3.46 (1H, m, H-26a), 3.33 (1H, m, H-26b), 0.88 (3H, s, Me-19), 0.81 (3H, s, Me-18), 0.98(3H, d, Me-21), 1.10 (3H, d, Me-27). (sugars) 4.38 (d, J=7.4 Hz, H-1Gal), 3.51 (dd, J=7.4 and 9.0 Hz, H-2Gal), 3.76(dd, J=4.0 and 9.0 Hz, H-3Gal), 3.85 (dd, J=2.5 and 4.0 Hz, H-4Gal), 3.58 (ddd, J=2.5, 2.5 and 4.5 Hz, H-5Gal), 3.63(dd, J=4.5 and 12.0 Hz, H-6aGal), 3.90 (dd, J=2.5 and 12.0 Hz, H-6bGal), 4.53 (d, J=7.5 Hz, H-1Glc), 3.29 (dd, J=7.5and 9.0 Hz, H-2Glc), 3.39 (dd, J=9.0 and 9.0 Hz, H-3Glc), 3.24 (dd, J=9.0 and 9.0 Hz, H-4Glc), 3.31 (ddd, J=2.5, 4.5and 9.0 Hz, H-5Glc), 3.62 (dd, J=4.5 and 11.5 Hz, H-6aGlc), 3.93 (dd, J=2.5 and 11.5 Hz, H-6bGlc). For 13 C NMRsee Table 1.2. HRMS, m/z 903.443 [calculated for C 45H 74O 18(M) + ]; 741.6 [M-162] + ; 579 [M-2x162] + ; 1 H NMR (aglycon) 4.40 (1H, m, H-16), 3.69 (1H, m, H-3), 3.47 (1H, m, H-26a), 3.34 (1H, m, H-26b), 0.89 (3H, s, Me-19), 0.82 (3H, s,Me-18), 0.99 (3H, d, Me-21), 1.27(3H, d, Me-27). (sugars) 4.39 (d, J=7.4 Hz, H-1Gal), 3.84 (dd, J=7.4 and 9.0 Hz,H-2Gal), 3.78 (dd, J=4.0 and 9.0 Hz, H-3Gal), 4.02 (dd, J=2.5 and 4.0 Hz, H-4Gal), 3.69 (ddd, J=2.5, 2.5 and 4.5 Hz,H-5Gal), 3.62 (dd, J=4.5 and 12.0 Hz, H-6aGal), 3.95 (dd, J=2.5 and 12.0 Hz, H-6bGal), 4.56 (d, J=7.5 Hz, H-1Glc),3.30 (dd, J=7.5 and 9.0 Hz, H-2Glc), 3.60 (dd, J=9.0 and 9.0 Hz, H-3Glc), 3.35 (dd, J=9.0 and 9.0 Hz, H-4Glc), 3.25(ddd, J=2.5, 4.5 and 9.0 Hz, H-5Glc), 3.60 (dd, J=4.5 and 11.5 Hz, H-6aGlc), 3.93 (dd, J=2.5 and 11.5 Hz, H-6bGlc),4.69 (d, J=7.5 Hz, H-1GlcI), 3.29 (dd, J=7.5 and 9.0 Hz, H-2GlcI), 3.36 (dd, J=9.0 and 9.0 Hz, H-3GlcI), 3.40 (dd,J=9.0 and 9.0 Hz, H-4GlcI), 3.42 (ddd, J=2.5, 4.5 and 9.0 Hz, H-5GlcI), 3.69 (dd, J=4.5 and 11.5 Hz, H-6aGlcI), 3.82(dd, J=2.5 and 11.5 Hz, H-6bGlcI). For 13 C NMR see Table 1.3. HRMS, m/z [calculated for C 39H 50O 20(M) + ]; 676.8 [M-162] + ; 1 H NMR (aglycon) 6.91 (1H, m, H-16), 3.69(1H, m, H-3), 0.90 (3H, s, Me-19), 0.91 (3H, s, Me-18), 2.28 (3H, d, H-21). (sugars) 4.40 (d, J=7.4 Hz, H-1Gal), 3.61(dd, J=7.4 and 9.0 Hz, H-2Gal), 3.54 (dd, J=4.0 and 9.0 Hz, H-3Gal), 4.03 (dd, J=2.5 and 4.0 Hz, H-4Gal), 3.60 (ddd,J=2.5, 2.5 and 4.5 Hz, H-5Gal), 3.58 (dd, J=4.5 and 12.0 Hz, H-6aGal), 3.93 (dd, J=2.5 and 12.0 Hz, H-6bGal), 4.56(d, J=7.5 Hz, H-1Glc), 3.59 (dd, J=7.5 and 9.0 Hz, H-2Glc), 3.61 (dd, J=9.0 and 9.0 Hz, H-3Glc), 3.36 (dd, J=9.0 and9.0 Hz, H-4Glc), 3.26 (ddd, J=2.5, 4.5 and 9.0 Hz, H-5Glc), 3.61 (dd, J=4.5 and 11.5 Hz, H-6aGlc), 3.94 (dd, J=2.5and 11.5 Hz, H-6bGlc), 4.69 (d, J=7.5 Hz, H-1GlcI), 3.29 (dd, J=7.5 and 9.0 Hz, H-2GlcI), 3.37 (dd, J=9.0 and 9.0 Hz,H-3GlcI), 3.41 (dd, J=9.0 and 9.0 Hz, H-4GlcI), 3.41 (ddd, J=2.5, 4.5 and 9.0 Hz, H-5GlcI), 3.83 (dd, J=4.5 and 11.5Hz, H-6aGlcI), 3.69 (dd, J=2.5 and 11.5 Hz, H-6bGlcI). For 13 C NMR see Table 1.ConclusionThree new compounds, hyoscyamosides B (1), C (2) and C 2(3), together with seven known steroidal saponins(4-10) have been isolated from the seeds <strong>of</strong> Hyoscyamus niger L. for the first time. The structures <strong>of</strong> hyoscyamosidesB (1), C (2) and C 2(3) were elucidated as 3-O--D-glucopyranosyl- (13) - -D- galactopyranoside - (25 R)-5spirostan- 3-ol, 3--{[-D-glucopyranosyl-(12)]-[-D- glucopyranosyl-(13)]--D-galactopyranoside}-(25-R)-5-spirostan-3-ol and 3-O-D-glucopyranosyl (12)- -D-glucopyranosyl-(14)- -D-galactopyranosyl-5-pregn-16-en-20-one-3-ol, respectively by means <strong>of</strong> physico-chemical methods.92
- Page 7:
Chemistry Journal of Moldova. Gener
- Page 10:
Chemistry Journal of Moldova. Gener
- Page 14 and 15:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 16 and 17:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 20 and 21:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 22 and 23:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 24 and 25:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 26 and 27:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 28 and 29:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 30 and 31:
Gh. Duca et al./Chem.J. Mold.. 2008
- Page 32 and 33:
Chemistry Journal of Moldova. Ion D
- Page 34 and 35:
Ion Dranca/Chem.J. Mold. 2008, 3 (1
- Page 36 and 37:
Ion Dranca/Chem.J. Mold. 2008, 3 (1
- Page 38 and 39:
Ion Dranca/Chem.J. Mold. 2008, 3 (1
- Page 40 and 41:
Ion Dranca/Chem.J. Mold. 2008, 3 (1
- Page 42 and 43: Ion Dranca/Chem.J. Mold. 2008, 3 (1
- Page 44 and 45: Ion Dranca/Chem.J. Mold. 2008, 3 (1
- Page 46 and 47: M. Revenco et al./Chem.J. Mold. 200
- Page 48 and 49: M. Revenco et al./Chem.J. Mold. 200
- Page 50 and 51: Gh. Zgherea/Chem.J. Mold. 2008, 3 (
- Page 52 and 53: Gh. Zgherea/Chem.J. Mold. 2008, 3 (
- Page 54 and 55: Gh. Zgherea/Chem.J. Mold. 2008, 3 (
- Page 56 and 57: Gh. Zgherea/Chem.J. Mold. 2008, 3 (
- Page 58 and 59: G. Vasile et al./Chem.J. Mold. 2008
- Page 60 and 61: G. Vasile et al./Chem.J. Mold. 2008
- Page 62 and 63: G. Vasile et al./Chem.J. Mold. 2008
- Page 64 and 65: V. Mukhin et al./Chem.J.Mold. 2008,
- Page 66 and 67: V. Mukhin et al./Chem.J.Mold. 2008,
- Page 68 and 69: Chemistry Journal of Moldova. N. Ku
- Page 70 and 71: N. Kulikov et al./Chem.J.Mold. 2008
- Page 72 and 73: V. Gladchi et al./Chem.J.Mold. 2008
- Page 74 and 75: V. Gladchi et al./Chem.J.Mold. 2008
- Page 76 and 77: V. Gladchi et al./Chem.J.Mold. 2008
- Page 78 and 79: Chemistry Journal of Moldova. R. St
- Page 80 and 81: R. Sturza et al./Chem.J.Mold. 2008,
- Page 82 and 83: R. Sturza et al./Chem.J.Mold. 2008,
- Page 84 and 85: R. Sturza et al./Chem.J.Mold. 2008,
- Page 86 and 87: Chemistry Journal of Moldova. V. Bo
- Page 88 and 89: V. Boldescu et al./Chem.J.Mold. 200
- Page 90 and 91: Chemistry Journal of Moldova. I. Lu
- Page 94 and 95: I. Lunga et al./Chem.J.Mold. 2008,
- Page 96 and 97: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 98 and 99: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 100 and 101: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 102 and 103: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 104 and 105: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 106 and 107: Chemistry Journal of Moldova. N.Gor
- Page 108 and 109: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 110 and 111: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 112 and 113: N.Gorinchoy et al./Chem.J.Mold. 200
- Page 114 and 115: I. Ogurtsov, A. Tihonovschi / Chem.
- Page 116 and 117: I. Ogurtsov, A. Tihonovschi / Chem.
- Page 118 and 119: I. Ogurtsov, A. Tihonovschi / Chem.
- Page 120 and 121: M. Gonta et al./Chem.J.Mold. 2008,
- Page 122 and 123: M. Gonta et al./Chem.J.Mold. 2008,
- Page 124 and 125: M. Gonta et al./Chem.J.Mold. 2008,
- Page 126 and 127: M. Gonta et al./Chem.J.Mold. 2008,
- Page 128 and 129: Chemistry Journal of Moldova. N. Se
- Page 130 and 131: Chemistry Journal of Moldova. D. Ba
- Page 132 and 133: D. Batîr/Chem.J.Mold. 2008, 3 (1),
- Page 134 and 135: CHEMISTRY JOURNAL OF MOLDOVA.Genera
- Page 136 and 137: CHEMISTRY JOURNAL OF MOLDOVA.Genera
- Page 138: CHEMISTRY JOURNAL OF MOLDOVA.Genera