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As a subspecies of sea buckthorn, Hippophae rhamnoides L. subsp. turkestanica (Fam. Elaeagnaceae) is a deciduous shrub and is distributed widely throughout many regions of Central Asia (Xinjiang of China, northwest of India, Pakistan, Uzbekistan, etc.) [1]. The fruits of H. rhamnoides L. subsp. turkestanica were collected in October 2011 from Wushi, Xinjiang,China and identified by Prof. Guanmian Shen (Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences).
Air-dried and powdered fruits (12 kg) were extracted with MeOH (8 L × 5) at room temperature. Then the methanol extracts were combined, evaporated, and suspended in 10 L of water. The suspension was partitioned with petroleum ether, EtOAc, and n-BuOH. Both the EtOAc and n-BuOH fractions were purified by column chromatography on silica gel and Sephadex LH-20, and preparative HPLC to yield compounds 1–21.
Compounds 1–7 were isolated from the Elaeagnaceae family for the first time. Compounds 8–14 were obtained from the species Hippophae rhamnoides L. subsp. turkestanica for the first time. Moreover, the structure of compound 4 was only postulated from the MS and 1H NMR spectrum in the literature [5]. Here, compound 4 was identified as 1-n-propyl-6-hydroxyl, 2,3,4-tetrahydro-β-carboline by 1D and 2D NMR in combination with MS spectral data for the first time.
cis - p -Cinnamic acid-4- O -β-D-glucopyranoside (1), yellow amorphous powder. C15H18O8. MS spectrum (ESI) m/z 327 [M + H]+. 1H NMR (600 MHz, DMSO-d6, δ, ppm, J/Hz): 7.66 (2H, d, J = 8.4, H-2, 6), 6.99 (2H, d, J = 8.4, H-3, 5), 5.84 (1H, d, J = 12.6, H-α), 6.69 (1H, d, J = 12.6, H-β), 4.90 (1H, d, J = 7.2, H-1′). 13C NMR (150 MHz, DMSO-d6, δ, ppm): 128.8 (C-1), 131.3 (C-2, 6), 115.6 (C-3, 5), 157.6 (C-4), 120.7 (C-α), 138.0 (C-β), 168.4 (COOH), 100.1 (C-1′), 73.2 (C-2′), 76.6 (C-3′), 69.7 (C-4′), 77.0 (C-5′), 60.7 (C-6′) [2].
trans - p -Cinnamic acid-4- O -β-D-glucopyranoside (2), yellow amorphous powder. C15H18O8. MS spectrum (ESI) m/z 349 [M + Na]+. 1H NMR (400 MHz, D2O, δ, ppm, J/Hz): 7.34 (2H, d, J = 7.6, H-2, 6), 6.90 (2H, d, J = 7.6, H-3, 5), 6.15 (1H, d, J = 15.6, H-α), 7.20 (1H, d, J = 15.6, H-β), 4.94 (1H, d, J = 6.4, H-1′). 13C NMR (100 MHz, D2O, δ, ppm): 128.9 (C-1), 129.9 (C-2, 6), 116.5 (C-3, 5), 158.1 (C-4), 117.0 (C-α), 144.6 (C-β), 171.9 (COOH), 99.5 (C-1′), 72.8 (C-2′), 75.4 (C-3′), 69.3 (C-4′), 76.0 (C-5′), 60.4 (C-6′) [3].
1-Methyl-6-hydroxy-l,2,3,4-tetrahydro-β-carboline (3), yellow amorphous powder. C12H14N2O. MS spectrum (ESI) m/z 203 [M + H]+. 1H NMR (600 MHz, DMSO-d6, δ, ppm, J/Hz): 10.70 (1H, s, NH-9), 8.33 (1H, s, OH), 7.11 (1H, d, J = 7.2, H-8), 6.72 (1H, s, H-5), 6.59 (1H, d, J = 7.2, H-7), 4.50 (1H, m, H-1), 3.61 and 3.13 (1H, m, H-3), 2.74 (2H, m, H-4), 1.54 (3H, t, J = 7.2, Me). 13C NMR (150 MHz, DMSO-d6, δ, ppm): 150.6 (C-6), 133.6 (C-4b), 130.3 (C-9a), 126.9 (C-8a), 111.5 (C-7), 111.3 (C-8), 104.8 (C-4a), 102.0 (C-5), 48.1 (C-1), 40.5 (C-3), 19.3 (C-4), 18.0 (Me) [4].
1- n -Propyl-6-hydroxy-l,2,3,4-tetrahydro-β-carboline (4), yellow amorphous powder. C14H18N2O, MS spectrum (ESI) m/z 231 [M + H]+. 1H NMR (400 MHz, CD3OD, δ, ppm, J/Hz): 8.47 (1H, s, OH), 7.18 (1H, d, J = 8.4, H-8), 6.83 (1H, d, J = 2.4, H-5), 6.71 (1H, dd, J = 8.4, 2.4, H-7), 4.64 (1H, m, H-1), 3.71 and 3.42 (1H, m, H-3), 2.98 (2H, m, H-4), 2.19 and 1.91 (1H, m, H-1′), 1.60 (2H, m, H-2′), 1.08 (3H, t, J = 7.2, H-3′). 13C NMR (100 MHz, CD3OD, δ, ppm): 152.1 (C-6), 133.8 (C-4b), 131.1 (C-9a), 128.3 (C-8a), 113.5 (C-7), 113.0 (C-8), 106.6 (C-4a), 103.5 (C-5), 55.0 (C-1), 43.3 (C-3), 35.6 (C-1′), 19.7 (C-4), 19.6 (C-2′), 14.3 (C-3′) [5].
Quercetin-3- O -[α-L-rhamnopyranosyl-(1 → 2)]-[α-L-rhamnopyranosyl-(1 → 6)]-β-D-glucopyranoside (5), yellow amorphous powder. C33H40O20. MS spectrum (ESI) m/z 755 [M – H]–. 1H NMR (600 MHz, DMSO-d6, δ, ppm, J/Hz): 7.55 (1H, dd, J = 7.2, 1.8, H-6′), 7.50 (1H, d, J = 1.8, H-2′), 6.86 (1H, d, J = 7.8, H-5′), 6.40 (1H, s, H-8), 6.20 (1H, s, H-6), 5.55 (1H, d, J = 7.8, H-1′′), 5.09 (1H, s, H-1′′′), 4.37 (1H, s, H-1′′′′), 0.99 and 0.83 (3H, d, J = 6.6, Me) [6].
Quercetin-3- O -β- D-sophoroside-7- O -α-L-rhamnoside (6), yellow amorphous powder. C33H40O21. MS spectrum (ESI) m/z 771 [M – H]–. 1H NMR (600 MHz, DMSO-d6, δ, ppm, J/Hz): 7.65 (1H, dd, J = 8.4, 2.4, H-6′), 7.61 (1H, d, J = 1.8, H-2′), 6.88 (1H, d, J = 8.4, H-5′), 6.78 (1H, s, H-8), 6.43 (1H, s, H-6), 5.72 (1H, d, J = 7.8, H-1′′), 5.56 (1H, s, H-1′′′′), 4.63 (1H, d, J = 7.8, H-1′′′), 1.16 (3H, d, J = 5.4, Me). 13C NMR (150 MHz, DMSO-d6, δ, ppm): 177.6, 161.5, 160.9, 156.1, 155.8, 148.6, 145.0, 133.3, 122.0, 120.6, 116.1, 115.4, 105.6, 104.6, 99.4, 98.4, 98.0, 94.1, 82.8, 77.6, 76.8, 76.6, 76.5, 74.4, 71.6,\ 70.2, 70.1, 69.8, 69.5, 69.5, 60.7, 60.6, 17.9 [7].
Fumaric acid monomethyl ester (7), white amorphous powder. C5H6O4. MS spectrum (ESI) m/z 131 [M + H]+. 1H NMR (400 MHz, pyridine-d5, δ, ppm, J/Hz): 6.58 (1H, s, H-3), 6.53 (1H, s, H-2), 3.86 (3H, s, Me). 13C NMR (100 MHz, pyridine- d5, δ, ppm): 166.4 (C-4), 164.4 (C-1), 97.1 (C-3), 94.8 (C-2), 52.6 (Me) [8].
Isorhamnetin-3- O -β- D-sophoroside-7- O -α-L-rhamnoside (8), yellow amorphous powder. C34H42O21. MS spectrum (ESI) m/z 785 [M – H]–. The 1H NMR and 13C NMR data agreed with those reported in the literature [9].
Isorhamnetin-3- O -β-D-glucopyranoside-7- O -α-L-rhamnoside (9), yellow amorphous powder. C28H32O16. MS spectrum (ESI) m/z 623 [M – H]–. The MS and NMR data agreed with those reported in the literature [9].
Isorhamnetin-3- O -β-D-glucopyranoside (10), yellow amorphous powder. C22H22O12. MS spectrum (ESI) m/z 479 [M + H]+. The MS and NMR data agreed with those reported in the literature [10].
Quercetin-3- O -β-D-glucopyranoside (11), yellow amorphous powder. C21H20O12. MS spectrum (ESI) m/z 463 [M – H]–. The MS and NMR data agreed with those reported in the literature [10].
Quercetin-7- O -β-D-glucopyranoside (12), yellow amorphous powder. C21H20O12. MS spectrum (ESI) m/z 463 [M – H]–. The MS and NMR data agreed with those reported in the literature [10].
Ethyl -β-D-glucopyranoside (13), white needles, mp 78–79C. C8H16O6. MS spectrum (ESI) m/z 207 [M – H]–. The NMR data agreed with those reported in the literature [11].
Isorhamnetin-3- O -rutinoside (14), yellow needle crystals, mp 181–183C. C28H32O16. MS spectrum (ESI) m/z: 625 [M + H]+, 647 [M + Na]+. The NMR and MS data were in agreement with those reported in the literature [10].
Kaempferol (15), yellow needle crystals, mp 275–279C. The compound was compared with a standard sample by HPLC.
Isorhamnetin (16), yellow amorphous powder, mp 306–307C. C16H12O7. MS spectrum (ESI) m/z 315 [M – H]–. The NMR and MS data were in agreement with those reported in the literature [12].
Protocatechuic acid (17), white needle crystals, decompose at 194–197C. C7H6O4. MS spectrum (ESI) m/z 153 [M – H]–. The MS and NMR data agreed with those reported in the literature [12].
Rutin (18), yellow needle crystals, mp 176–178C. C27H30O16. MS spectrum (ESI) m/z 609 [M – H]–. The MS and NMR data agreed with those reported in the literature [12].
Quinic acid (19), white needle crystals, mp 161–162C. C7H12O6. MS spectrum (ESI) m/z 191 [M – H]–. The MS and NMR data agreed with those reported in the literature [12].
Oleanic acid (20), white amorphous powder. The NMR data agreed with those reported in the literature [12].
Daucosterol (21), white amorphous powder, mp 276–280C. The NMR and MS data were in agreement with those reported in the literature [12].
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Acknowledgement
This work was supported by the National Natural Science Funds of China (No. 31110103908) and the Key Projects in the National Science & Technology Pillar Program (2010DAE00390) and the National Science Foundation for Distinguished Young Scholars of China (No. 30925045).
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Published in Khimiya Prirodnykh Soedinenii, No. 2, March–April, 2014, pp. 307–308.
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Li, Y., Yili, A., Liu, Y. et al. Chemical Constituents of Hippophae rhamnoides subsp. turkestanica Fruits. Chem Nat Compd 50, 352–354 (2014). https://doi.org/10.1007/s10600-014-0951-7
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DOI: https://doi.org/10.1007/s10600-014-0951-7