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Isolation and Structure Elucidation of Pyridine Alkaloids from the Aerial

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Isolation and Structure Elucidation of Pyridine Alkaloids from the Aerial www.nature.com/scientificreports OPEN Isolation and structure elucidation of pyridine alkaloids from the aerial parts of the Mongolian medicinal plant Caryopteris mongolica Bunge Dumaa Mishig1,2,3, Margit Gruner1, Tilo Lübken1, Chunsriimyatav Ganbaatar1,2, Duger Regdel2 & Hans‑Joachim Knölker1* The seven pyridine alkaloids 1–7, the favonoid acacetin (8), and L‑proline anhydride (9) have been isolated from the aerial parts of the Mongolian medicinal plant Caryopteris mongolica Bunge. The structures of the natural products 1–9 have been assigned by MS, as well as IR, 1D NMR (1H, 13C, DEPT), and 2D NMR (COSY, HSQC, HMBC, NOESY) spectroscopic methods. The compounds 2 and 4–7 represent new chemical structures. Acacetin (8) and L‑proline anhydride (9) have been obtained from C. mongolica for the frst time. Caryopteris mongolica Bunge is a deciduous shrub and belongs to the Verbenaceae family. C. mongolica which is widely distributed in the mountainous and Gobi regions of Mongolia (Khentei, Khangai, Mongol-Daurian, Mid- dle Khalkha, Mongolian Altai, East Mongolia Valley of Lakes, Govi-Altai, East Govi, Trans-Altai Gobi, Gobi and Alashan Gobi)1. In fact only this species of Caryopteris is growing in Mongolia, whereas about 16 species of this genus occur all over the world. In traditional Mongolian medicine, the aerial parts of this plant have been prepared as decoction and used for haemorrhage, increasing muscle strength, urinary excretion, pulmonary windy oedema and chronic bronchitis2. In Chinese folk medicine, Caryopteris ternifora has been used as anti- pyretic, detoxifying, expectorant, and anti-infammatory agent and for the treatment of cold, tuberculosis and rheumatism3. Previous chemical investigations of Caryopteris mongolica showed the presence of mono- and sesquiterpenoids4, hypolaetin-7-glucoside5, iridoid glucosides and steroids6. From the roots of this plant, the abietane ortho-quinone caryopteron A and derivatives were isolated 7. In our previous phytochemical investiga- tion of the aerial parts of C. mongolica, we have identifed some phenolic compounds such as acacetin, apigenin, luteolin, and cafeic acid 8. From other species of Caryopteris steroidal and iridoid glucosides, phenylethanoids, diterpenoids, α-caryopterone, a new pyranojuglone, clandonoside and its acetylated derivatives, favonoids and sterols have been isolated 9–13. In the present paper, we describe the isolation of pyridine monoterpene alkaloids, isoquinoline alkaloids, a dipyrrolopyrazine, and a favonoid (acacetin) from the aerial parts of C. mongolica and their structure elucidation using MS, as well as IR, 1H NMR, 13C NMR, and 2D NMR spectroscopic methods. Experimental section General experimental procedures. Flash column chromatography (FCC) was performed using silica gel 200–300 mesh from Acros Organics occasionally on a Büchi Sepacore system equipped with a UV moni- tor. For thin layer chromatography (TLC), silica gel plates Merck 60 F 254 were used. Spots detected on the TLC plates under the UV lamp at 254 or 365 nm were visualized by spraying Dragendorf’s reagent. Te EI-MS were recorded on a Finnigan MAT-95 mass spectrometer (70 eV) and the ESI-MS on an Bruker Esquire LC with an ion trap detector. Positive and negative ions were detected. ESI-HRMS were recorded on a Waters Xevo G2-XS QTOF mass spectrometer. Te 1D and 2D NMR spectra (600 MHz 1H NMR and 150 MHz 13C NMR) were measured on a Bruker AVANCE III 600 MHz spectrometer using CDCl3 or CD3OD as solvents. Te chemi- cal shifs δ are reported in ppm using either CHCl 3/CDCl3 (δH = 7.25, δC = 77.0) or CH3OH/CD3OD (δH = 3.31, δC = 49.0 ppm) as internal standard relative to TMS. Coupling constants J are given in Hz. Te complete assign- 1Fakultät Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany. 2Institute of Chemistry and Chemical Technology, Mongolian Academy of Sciences, Ulaanbaatar 210351, Mongolia. 3New Medical University, Sonsgolon road – 5/2, Ulaanbaatar, Mongolia. *email: [email protected] Scientifc Reports | (2021) 11:13740 | https://doi.org/10.1038/s41598-021-93010-4 1 Vol.:(0123456789) www.nature.com/scientificreports/ OH 4 OH O 4a 4 4 3 5 4a 5 4a 3 3 5 6 6 6 N 7 7 10 8 N N 8 7 1 8 11 1 O 1 9 H 9 H 9 123 O O 4 4 O 4a 7 3 5 H 4a 5 H 6 3 6 6a 6 H 5a 5a 8 OH 5a N 7 N O 5 11b 11a 11b 11a 14 7 10b O N 12 4a 4 1 7a 1 10a 13 11 13 10 11 7a 13 11 10a O 10a 8 3 8 11a 14 N 10 9 10 9 1 14 HO 456 O 3' 4 4' OCH 5 2' 3 O 4a 6 3 1 3 12 8 1' 4 OH HO 9 O N 5 N 11a 2 11b 6a 6b 7 7 2 1 N 6 3 13 11 8 10 1 10a 5 4 14 N O 10 OH O 789 Figure 1. Structures of the compounds 1–9 isolated from the aerial parts of C. mongolica. ment of 1H and 13C NMR signals was confrmed by 2D NMR spectroscopic methods (COSY, HSQC, HMBC and NOESY). Plant material. Te aerial parts of Caryopteris mongolica Bunge were collected at Baruun kharaa of Selenge province Bayantsogt Mountain, during the fowering period in July 2014. Te plant was identifed by Prof. E. Ganbold and Dr. B. Mandahk, Institute of Botany, MAS, and voucher specimen were deposited at the Herbarium of Laboratory of Natural Products Chemistry, ICCT, Research Institute of the Mongolian Academy of Sciences, in Ulaanbaatar (voucher numbers: UBA-0004020 and UBA-0004021). Te authors confrm that the present study complies with the IUCN Policy Statement on Research Involving Species at Risk of Extinction and the Convention on the Trade in Endangered Species of Wild Fauna and Flora. Extraction and isolation of compounds. Te air-dried and powdered aerial parts (12.5 kg) of Cary- opteris mongolica were extracted three times at room temperature with 95% aqueous ethanol. Te ethanol was removed and the residue treated with 2.5% HCl (pH = 1–2). Te aqueous acidic solution was extracted succes- sively with n-hexane and chloroform. Ten, the residual aqueous solution was adjusted to pH = 9–10 by addition of aqueous NH 4OH (25%), extracted with CHCl 3 and dried over Na 2SO4. Finally, CHCl 3 was evaporated under reduced pressure to give 12.02 g of crude total alkaloid extract (0.096%). Te crude total alkaloid extract (12.02 g) isolated from C. mongolica was purifed by FCC (fash column chromatography on silica gel, 200–300 mesh from Acros Organics) (175 g silica gel). Te elution with CHCl 3, CHCl3–CH3OH mixtures ranging from 90:10, 85:15, 80:20, 75:25, and 50:50 (1000–1500 mL), and pure CH3OH aforded 11 sub-fractions from A to K: A (108 mg), B (69.6 mg), C (1.50 g), D (851 mg), E and F (218 mg), G (399 mg), H (1.34 g), I (161 mg), J (274 mg), and K (85.0 mg). Te fractions were monitored by TLC, compounds detected as described by Dragendorf’s reagent, and checked by ESI-MS. Fraction C (1.50 g) was subjected to FCC (25 g silica gel), and eluted with CHCl 3–CH3OH mixtures ranging from 99:1 to 95:5 to aford seven fractions from A1 to G1: A1 (8.7 mg), B1 (46.0 mg), C1 (55.0 mg), D 1 (46.9 mg), 14, 15 E1/F1 (234 mg), and G1 (183 mg). From fraction B1, compound 3 (aucubinine B) (13.2 mg) was isolated (Fig. 1). Te compounds 1 (7-methylene-6,7-dihydro-5H-cyclopenta[c]pyridin-5-ol)13 (20.1 mg) and 2 (10.1 mg, + ESI-MS: m/z = 194.2 [M + H] ) have been obtained from fraction G1. Fraction C1 provided by crystallization from 8, 16–19 CHCl3 colorless needles which were identifed as compound 8 (acacetin) (23.6 mg). Te purifed fraction + E1/F1 aforded a mixture of the compounds 4 and 5 (30.8 mg, ESI-MS: m/z = 296.2 [M + ­H] ). Finally, we have combined all fractions (139 mg) exhibiting in their ESI–MS a peak at m/z = 296.2 [M + ­H]+, subjected them to Scientifc Reports | (2021) 11:13740 | https://doi.org/10.1038/s41598-021-93010-4 2 Vol:.(1234567890) www.nature.com/scientificreports/ 1 2 3 Atom δH (J) δC δH (J) δC δH (J) δC 1 8.70 s 143.04 8.54 s 145.34 8.96 s 149.2 2(N) – – – – – – 3 8.42 d (5.0) 148.65 8.52 d (5.0) 149.33 8.69 d (5.0) 148.5 4 7.39 d (5.0) 120.00 7.39 d (5.0) 119.90 7.53 dd (5.0, 1.0) 116.2 4a – 155.18 – 153.50 – 142.6 5 5.27 dd (7.5, 4.8) 72.69 5.03 dd (6.4, 4.8) 72.35 – 206.0 3.18 br dd (16.8, 7.5) 2.37 dd (13.5, 6.4) 2.98 dd (19.4, 7.5) 6 42.25 48.03 45.3 2.67 br dd (16.8, 4.8) 2.31 dd (13.5, 4.8) 2.31 dd (19.4, 3.6) 7 – 143.72 – 83.00 3.56 qdd (7.1, 7.5, 3.6) 31.5 8 – 135.88 – 140.78 – 152.5 5.61 br s 9 106.35 1.53 s 24.56 1.46 d (7.1) 21.2 5.18 br s 10 – – 3.32 q (7.0) 58.64 – – 11 – – 1.11 t (7.0) 15.80 – – 1 13 Table 1.
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