Esters from Ferula samarcandica
In continuation of research on terpenoid plants of the Ferula L. genus (Apiaceae), we studied components of the roots of Samarkand ferula ( Ferula samarcandica Korov.) collected in Tashkent district. The terpenoid coumarins samarcandin and samarcandone were isolated previously from Samarkand ferula [1]. Later, a study of Samarkand ferula misidentified as mogoltav ferula ( F. mogoltavica Lipsky ex Korov.) isolated the terpenoid coumarins samarcandin, samarcandone, mogoltadone, gummosin, and farnesiferol A [2-4]. Air-dried ground roots were extracted with ethanol. The alcohol extract was evaporated, diluted with water (1:2), and treated with ethylacetate. The combined ethylacetate extract was distilled to produce a thick extract that was placed on a col umn of KSK silica gel (d = 3 cm, h = 80 cm) and eluted by benzine:ethylacetate (9:1) with a subsequent increase of ethylace tate concentration. Fractions of 100 mL were collected. The separation of the total terpenoids was monitored using TLC (hydrocarbons:ethylacetate, 4:1; developer, 1% vanillin in conc. H 2SO4). Four terpenoid esters were isolated: 1, C17H22O3, mp 155-156°C; 2, C18H24O4, mp 84-85°C; 3, C18H24O4, [α]D 22 -30 (c 0.5, ethanol); 4, C22H28O5, mp 129-130°C. Comparison of the PMR, UV, IR, and mass spectra of 1 and 2 with those in the literature identified them as tschimgin and tschimganin [5]. The IR spectrum (KBr, ν, cm) of 3 exhibited absorption bands typical of hydroxyl (3534), ester carbonyl (1693), and an aromatic ring (1598, 1514) [6]. The mass spectrum of 3 was similar to that of esters of monoterpene alcohols and had peaks for ions with m/z 304 [M]+, 168 (C8H8O4), 148, 123, 95, 93. The PMR spectrum (100 MHz, DMSO-d 6, δ, ppm, J/Hz) of 3 exhibited signals at 0.70, 0.80, and 1.02 (each 3H, s), 3.65 (3H, s, OCH 3), 7.10 (1H, d, J = 9.0, H-3 ′), 7.72 (1H, d, J = 2, H-6 ′), 7.75 (1H, q, J 1 = 9.0, J2 = 2, H-2′), 4.90 (1H, d, J1 = J2 = 7.5) and 5.15 (1H, br.d, J = 10). The two signals at 4.90 and 5.15 ppm in the range of geminal protons indicate that 3 is a natural mixture of tschimganin and iso-tschimganin. Similar mixtures of tschimgin/ iso-tschimgin and tschimganin/ isotschimganin were isolated from F. dshizakensis Korov. and F. angreni Korov. [7, 8]. The neutral part of the hydrolysate from base hydrolysis of 3 by aqueous KOH (5%) afforded a monoterpene alcohol of composition C10H18O with mp 201-202 °C that was identified as borneol [5]. Comparison of the PMR, IR, and mass spectra of 4 with those of known carotane esters showed that this compound was lancerodiol p-hydroxybenzoate, which was isolated earlier from F. lancerottensis [9]. Thus, it is found for the first time that Samarkand ferula contains esters of terpenoid alcohols in addition to terpenoid coumarins.
Carotane sesquiterpenes from Ferula lancerottensis
Abstract Six new carotane sesquiterpenes, the p -hydroxybenzoate of epoxyjaeschkeanadiol the p -methoxybenzoate and p -hydroxybenzoate of lancerodiol, lancerodiol, the p -hydroxybenzoate of lancerotriol and the p -methoxybenzoate of linkitriol, and the already known p -hydroxybenzoate of jaeschkeanadiol have been isolated from Ferula lancerottensis .
Eight carotane sesquiterpenes from Ferula linkii
Abstract Six new carotane sesquiterpenes, the p -methoxybenzoate-, isovalerate- and veratrate of epoxyjaesckeanadiol, the 1-acetate, 5-isovalerate of ferulinkiol, the 1-acetate, 5-isovalerate of lapiferol and the 1-acetate of lapiferol, and the already known p -methoxybenzoate of jaesckeanadiol and lapiferin have been isolated from Ferula linkii .