D. R. Kodirova, K. Rasulova, N. Abdullaev
Dec 10, 2011
Citations
1
Influential Citations
3
Citations
Journal
Chemistry of Natural Compounds
Abstract
Alkaloids from plants of the genus Haplophyllum (Rutaceae) exert a calming action on the central nervous system and have low toxicity [1]. Several of the alkaloids exhibit analgesic, anticonvulsive, soporific, sedative [2, 3], and estrogenic [4, 5] in addition to anticancer activity [6]. Furthermore, alkaloids of this genus are used in folk medicine to treat animals for helminths, diseases of the gastrointestinal tract, and respiratory organs of animals and humans. Rational use of pastures with incorporation of Haplophyllum species can facilitate the revitalization of animals and increase the production of the herd [7]. This all indicates that studies of plants of the genus Haplophyllum are promising. H. griffithianum Boiss. is a perennial herbaceous plant indigenous to mountainous regions of Central Asia (southwest Pamir-Alai) and Afghanistan [8]. We studied for the first time the alkaloid composition of the previously unstudied plant H. griffithianum collected during flowering in Surkhandarin Oblast (Nilu village). Ground air-dried roots (370 g) and aerial part (580 g) were extracted with MeOH. The MeOH extracts were condensed. Basic, acidic, and neutral fractions were separated by the known procedure to afford CHCl3 total alkaloids from the aerial part (2.32 g, 0.4% of dry aerial part mass) and roots (2.15 g, 0.58% of dry root mass). Total alkaloids from the aerial part were worked up with acetone to isolate dubinine (1, 0.32 g). The dubinine mother liquor was chromatographed over a column of silica gel to isolate dubinine (1), dictamnine (2), skimmianine (3), dubinidine (4), dubamine (5), and N-methylhaplofoline (6). Chromatographic separation of total alkaloids from roots of H. griffithianum over a column of silica gel isolated dictamnine and skimmianine. Alkaloids 2, 3, and 4 were identified based on TLC and mixtures with authentic samples obtained previously from H. perforatum [10]. Pure compounds 1, 5, and 6 were identified based on UV, IR, PMR, 13C NMR, and DEPT data as dubinine, dubamine, and N-methylhaplofoline. Dubinine (1), mp 185–186°C (EtOH), C17H19NO5. UV spectrum (EtOH, max, nm): 229, 282, 302 (log 4.86, 4.12, 4.00). IR spectrum (mineral oil, max, cm –1): 3262 (OH), 1719 (OCOCH3), 1627, 1584, 1516 (aromatic). PMR spectrum (400 MHz, CDCl3, , ppm, J/Hz, 0 = HMDS): 1.24 (3H, s, CH3), 2.08 (3H, s, CH3COO), 4.10 (3H, s, 4-OCH3), 3.83 (1H, dd, J = 15.3, 6.9, H-3a), 3.49 (1H, dd, J = 15.3, 9.3, H-3b), 4.39 and 4.44 (1H each, d, J = 11.0, CH2–O), 4.86 (1H, dd, J = 9.3, 6.9, H-2), 5.68 (1H, br.s, OH), 7.02 (1H, td, J = 8.3, 1.3, H-7), 7.31 (1H, td, J = 8.3, 1.3, H-6), 7.43 (1H, d, J = 8.3, H-8), 7.56 (1H, dd, J = 8.3, 1.3, H-5). 13C NMR spectrum (100 MHz, CDCl3, , ppm): 171.28 (CO), 168.81 (C-2), 158.91 (C-4), 146.55 (C-8a), 129.57 (C-7), 125.74 (C-6), 122.12 (C-5), 123.28 (C-8), 119.66 (C-4a), 101.42 (C-3), 83.52 (C-2a), 72.81 (C-9), 68.78 (C-10), 58.35 (4-OCH3), 28.44 (C-3a), 21.34 (COCH3), 20.88 (C-11). Dubamine (5), mp 93–95°C (EtOH), C16H11NO2. UV spectrum (EtOH, max, nm): 221, 226, 337, 308 (log 4.35, 5.34, 3.18, 4.84). Changed upon adding acid. PMR spectrum (400 MHz, CDCl3, , ppm, J/Hz): 8.10 (1H, d, J = 8.6, H-4), 8.05 (1H, d, J = 8.2, H-5), 7.72 (1H, d, J = 8.6, H-3), 7.64 (1H, td, J = 8.2, 1.5, H-6), 7.44 (1H, td, J = 8.2, 1.2, H-7), 7.74 (1H, dd, J = 8.2, 1.5, H-8), 7.67 (1H, d, J = 1.7, H-2 ), 6.88 (1H, d, J = 8.2, H-5 ), 7.59 (1H, dd, J = 8.2, 1.7, H-6 ), 5.97 (2H, s, OCH2O).