Polatoglu ˘ et al.
The Essential Oil Composition of Tanacetum densum (Labill.) Heywood ssp. sivasicum Hub.-Mor. & Grierson from Turkey† Kaan Polatoglu* ˘ and Nezhun Gören, Department of Biology, Faculty of Science and Arts, Yıldız Technical University Davutpa¸sa Campus No:127 Merter 34010 Istanbul, Turkey; Tel: +90-212-449-17-64; Fax: +90-212-449-15-14; Email:
[email protected],
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K. Hüsnü Can Baser ¸ and Betül Demirci, Department of Pharmacognosy, Faculty of Pharmacy, Anadolu University, 26470 Eskisehir, Turkey Tel: +90-222-335-05-80; Fax: +90-222-335-07-50; Email:
[email protected],
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Abstract Water-distilled essential oils from the aerial parts of Tanacetum densum (L.) Heywood ssp. sivasicum Hub.-Mor. et Grierson from Turkey were analyzed by GC and GC/MS. Tanacetum densum ssp. sivasicum flower and stem oils were characterized with 1,8-cineole (21.1% and 28.3%, respectively), camphor (19.2% and 16.4%, respectively), and borneol (5.8% and 6.4%, respectively). Key Word Index Tanacetum densum ssp. sivasicum, Compositae, essential oil composition, 1,8-cineole, camphor.
Introduction Genus Tanacetum is represented by 45 species and altogether 60 taxon in Turkey. Tanacetum densum has four subspecies, T. densum (Labill.) Heywood ssp. sivasicum Hub.-Mor. et Grierson, ssp. amani Heywood, ssp. eginense Heywood, and ssp. laxum Grierson, which are endemic to Turkey (1). Previous reports on T. densum ssp. sivasicum from the same location present some known sesquiterpene lactones as well as a new sesquiterpene lactone sivasinolide having antibacterial activity (2). In a further investigation, a new germacranolide, isotanargyrolide, was isolated (3) from the same plant, in addition to two new farnesol derivatives (4). Tanacetum densum ssp. eginense from the same location yielded a new sesquiterpene lactone eginensolide (5). The previous reports on the essential oil composition of Tanacetum species growing in Turkey were on T. armenum, T. balsamita, T. chiliophyllum var. chiliophyllum, T. haradjani (6), T. argyrophyllum var. argyrophyllum, T. argenteum ssp. canum var. canum, T. praeteritum ssp. praeter† Partly presented at 36th International Sympossium on Essential Oils, September 4–7, 2005 in Budapest, Hungary
itum and T. praeteritum ssp. massicyticum (7). The main oil components of the Tanacetum species from Turkey which have been reported until now were a-thujone, camphor, 1,8-cineole, borneol and camphene (8). Also, the major oil components of T. densum ssp. amani were reported as b-patchoulene (17.5%), camphor (15.6%), and 1,8-cineole (11.5%) (9). Tanacetum densum ssp. sivasicum is an endemic species to Turkey, and to the best of our knowledge, there is no previous report on its oil composition. This report presents the oil composition of T. densum ssp. sivasicum.
Experimental Plant materials: Plant materials were collected during the flowering period in July 2002 from the Bög˘ rüdelik village of Sivas city at 1800 m altitude. Voucher specimens have been deposited at the Herbarium of the Faculty of Science, Istanbul University in Istanbul (Voucher no. ISTE 80539), Turkey. Plant materials were identified by Dr. Kerim Alpınar. Isolation of the essential oils: Flowers and stems (100 g each) of the plants were separately subjected to hydrodistillation
Received: June 2006
*Address for correspondence
Revised: September 2006 1041-2905/09/0003-0200$14.00/0—© 2009 Allured Business Media 200/Journal of Essential Oil Research
Accepted: October 2006 Vol. 21, May/June 2009
T. densum
for 4 h using a Clevenger-type apparatus to produce the oils. The oil yields of the flower and stem oils were 0.25% and 0.1%, respectively. Essential oil analysis: The oils were analyzed by GC using a Hewlett Packard 6890 system. An HP-Innowax FSC column (60 m × 0.25 mm, 0.25 mm film thickness) was used with N2 as carrier gas (1 mL/min). The oven temperature was kept at 60°C for 10 min and programmed to 220°C at a rate of 4°C/min, then kept constant at 220°C for 10 min and programmed to 240°C at a rate of 1°C/min. The injector temperature was set at 250°C. The percentage composition of the individual components was obtained from electronic integration mea-
surements using flame ionization detection (FID, 250°C). n-Alkanes were used as reference points in the calculation of relative retention indices (RRI). Relative percentages of the characterized components were as cited in Table I. GC/MS analysis was performed with a Hewlett-Packard GCD system. Innowax FSC column (60 m × 0.25 mm, 0.25 mm film thickness) was used with He as carrier gas. GC oven temperature conditions were as described above. Split flow was adjusted at 50:1. The injector temperature was 250°C. Mass spectra were recorded at 70 eV. Mass range was from m/z 35 to 425. Library search was carried out using the in-house “Ba s¸ er Library of Essential Oil Constituents.”
Table I. Composition (%) of the flower and stem oils of Tanacetum densum (Labill.) Heywood ssp. sivasicum Hub.-Mor. et Grierson RRI
Compound
1014 1032 1043 1076 1118 1132 1138 1176 1188 1195 1203 1213 1244 1255 1280 1290 1296 1299 1386 1400 1439 1445 1452 1474 1482 1497 1499 1522 1532 1553 1556 1568 1586 1590 1611 1638 1648 1657 1670 1682 1683 1706 1719 1726 1758 1764
tricyclene a-pinene santolinatriene camphene b-pinene sabinene butylbenzene a-phellandrene a-terpinene dehydro-1,8-cineole limonene 1,8-cineole 2-pentylfuran g-terpinene p-cymene terpinolene octanal 2-methylbutyl isovalerate 1-octenyl acetate nonanal g-campholene aldehyde filifolene 1-octen-3-ol trans-sabinene hydrate longipinene a-copaene a-campholene aldehyde chrysanthenone camphor linalool cis-sabinene hydrate 1-methyl-4-acetylcyclohex-1-ene pinocarvone bornyl acetate terpinen-4-ol cis-p-menth-2-en-1-ol myrtenal umbellulone trans-pinocarveol d-terpineol trans-verbenol a-terpineol borneol germacrene D cis-piperitol cis-chrysanthenol
Flower oil 0.1 2.3 3.5 2.5 2.2 0.2 0.1 tr 0.3 0.2 0.1 21.1 tr 0.6 0.9 0.1 0.1 0.1 - 0.1 0.1 0.2 0.1 - 0.2 0.1 0.3 0.4 19.2 0.2 - 0.9 0.8 1.1 2.3 0.2 0.4 0.1 0.8 0.4 0.5 0.7 5.8 1.0 - 0.7
Stem oil 0.1 3.3 0.9 1.5 2.3 0.1 0.1 0.2 0.1 0.2 28.3 0.4 1.5 0.1 tr tr tr tr tr 0.2 0.1 0.1 0.3 0.7 16.4 0.9 1.7 1.6 1.2 2.1 0.3 0.5 1.5 0.3 2.0 0.3 6.4 0.4 0.2 0.2
RRI
Compound
Flower oil
d-cadinene tr myrtenol 0.8 (E,E)-2,4-decadienal - (E)-b-damascenone 0.1 trans-carveol 0.2 isopiperitenone - methyl hydrocinnamate 0.1 geranylacetone - cis-carveol 0.2 myrtanol - ethyl 3-phenylpropionate 0.1 a-calacorene tr 1,5-epoxy-salvial(4)14-ene 0.1 (E)-b-ionone - unknown I 1.2 caryophyllene oxide 0.8 perillylalcohol 0.1 pentadecanal 0.1 unknown II 0.6 p-mentha-1,4-dien-7-ol 0.4 b-oplopenone 0.2 cuminyl alcohol - spathulenol 0.5 unknown III 1.1 thymol - a-bisabolol - carvacrol - a-cadinol tr 1,4-dimethyl azulene 0.8 tricosane 0.2 caryophylla-2(12),6(13)-dien-5b-ol (= caryophylladienol-I) 0.2 2324 caryophylla-2(12),6(13)-dien-5a-ol (= caryophylladienol-II) 1.1 2392 caryophylla-2(12),6-dien-5b-ol (= caryophyllenol-II) - 2500 pentacosane 0.5 2571 eicosanal tr 2700 heptacosane - Monoterpene hydrocarbons 12.8 Oxygenated monoterpenes 57.4 Sesquiterpene hydrocarbons 1.3 Oxygenated sesquiterpenes 2.9 Diterpenes - Others 3.1 Total 77.5 1773 1804 1827 1838 1845 1865 1866 1868 1882 1889 1904 1941 1945 1958 1977 2008 2029 2041 2045 2073 2092 2113 2144 2166 2198 2232 2239 2255 2291 2300 2316
Stem oil 0.7 tr 0.2 0.2 0.1 0.1 tr 0.1 0.1 0.1 0.8 0.9 0.3 0.1 0.6 1.0 0.1 0.2 0.2 0.4 1.1 0.4 tr 0.1 10.6 65.4 0.4 3.7 2.1 82.2
RRI = Relative retention indices; tr = trace (< 0.1%); Unknown I: EIMS, 70 eV, m/z (rel. int.): 218(11), 203(3), 175(9), 161(7), 132(57), 125(31), 119(28), 107(100), 105(32), 91(32), 77(18), 67(9), 55(14); Unknown II: EIMS, 70 eV, m/z (rel. int.): 262(2), 220(5), 202(35), 187(30), 159(50), 145(48), 132(100), 119(97), 105(52), 91(43), 79(24), 69(19), 55(62); Unknown III: EIMS, 70 eV, m/z (rel. int.): 220(16), 205(6), 187(13), 159(28), 145(33), 132(100), 119(93), 107(89), 91(65), 79(35), 67(21), 55(28).
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Polatoglu ˘ et al.
Results and Discussion Water-distilled essential oils from herbal parts of T. densum ssp. sivasicum were analyzed by GC and GC/MS. The compounds identified are given in Table I with their percentages. Sixty-four and 61 compounds were identified in the oils of T. densum ssp. sivasicum, representing 77.5% and 82.2% of the flower and stem oils, respectively. 1,8-Cineole (21.1% (flower) and 28.3% (stem)) was the main constituent of the oils. Camphor (19.2% (flower) and 16.4% (stem)) and borneol (5.8% (flower) and 6.4% (stem)) were also present in the oils of T. densum ssp. sivasicum. Previously, Tanacetum species with 1,8-cineole, camphor, borneol and camphene as main constituents were reported from Turkey (6), the Netherlands (10), and Iran (11–15). Except for the reported occurrence of b-patchoulene in the oil of T. densum ssp. amani (9), the main components were similar with T. densum ssp. sivasicum oil. The oils of this species were dominated by oxygenated monoterpenes: 57.4% (flower) and 65.4% (stem). References 1. A. Güner, N. Özhatay, T. Ekim and K.H.C. Ba¸ser, Flora of Turkey and the East Aegean Islands. 10, 159–160, University Press, Edinburgh, UK (2001). 2. N. Gören, C. Bozok-Johansson, J. Jakupovic, L.J. Lin, H.L. Shieh, G.A. Cordell and N. Çelik, Sesquiterpene Lactones with Antibacterial Activity from Tanacetum densum subsp. sivasicum. Phytochemistry, 31, 101–104 (1992). 3. N. Gören, P. Cai, L. Scott, Tianosoa-Ramomonjyl and J.K. Synder, A New Germacranolide from Tanacetum densum subsp. sivasicum (Compositae). Tetrahedron, 51, 4627–4634 (1995).
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4. N. Gören, Two Farnesol Derivatives from Tanacetum densum subsp. sivasicum. Phytochemistry, 34, 743–745 (1993). 5. N. Gören and E. Tahtasakal, Constituents of Tanacetum densum subsp. eginense. Phytochemistry, 36, 1281–1282 (1994). 6. K.H.C. Ba¸ser, B. Demirci, N. Tabanca, T. Özek and N. Gören, Composition of the Essential Oils of Tanacetum armenum (DC.) Schultz Bip., T. balsamita L., T. chiliophyllum (Fisch. & Mey.) Schultz Bip. var. chiliophyllum and T. haradjani (Rech. Fil.) Grierson and the Enantiomeric Distribution of Camphor and Carvone. Flav. Fragr. J., 16, 195–200 (2001). 7. K.H.C. Ba¸ser, N. Gören and B. Demirci, Composition of the Essential Oils of Tanacetum ssp. from Turkey. Flav. Fragr. J., 16, 191–194 (2001). 8. K. Polato˘glu, K.H.C. Ba¸ser, B. Demirci and N. Gören, Distrubution of Volatile Compounds in Tanacetum Species of Turkey. pp. 92, 36th International Symposium on Essential Oils, Budapest, Hungary (2005). 9. H.C. Özen, Z. Toker and S.A. Ertekin, Composition of the Essential Oil of Tanacetum densum (Lab.) Schultz Bip. subsp. amani Heywood. AFS, Adv. Food Sci., 25(4), 159–161 (2003). 10. H. Hendriks, D.J.D. van der Elst, F.M.S. van Puten and R. Bos, The Essential Oil of Dutch Tansy (Tanacetum vulgare L.). J. Essent. Oil Res., 2, 155–162 (1990). 11. P. Weyerstahl, H. Marschall, K. Thefeld and A. Rustaiyan, Constituents of the Essential Oil of Tanacetum (syn. Chrysanthemum) fruticulosum Ledeb. From Iran. Flav. Fragr. J., 14, 112–120 (1999). 12. D.N. Shargh, H. Norouzi-Arasi, M. Mirza, K. Jaimand and S. Mohammadi, Chemical Composition of the Essential Oils of Tanacetum polycephalum (Schultz Bip. ssp. heterophyllum). Flav. Fragr. J., 14, 105–106 (1999). 13. A. Rustaiyan, F. Mojob and M. Salsali, Composition of the Essential Oil of Tanacetum polycephalum Schultz Bip. J. Essent. Oil Res., 11, 497–498 (1999). 14. T. Majed-Jabari, H. Vatanpoor, S. Masoudi and A. Monfared, Composition of the Essential Oil of Tanacetum khorassanicum (Krasch.) Parsa. A New Species From Iran. J. Essent. Oil Res., 14, 380–381 (2002). 15. A. Monfared, S.S.H. Davarani, A. Rustaiyan and S. Masoudi, Composition of the Essential Oil of Tanacetum balsamita L. Balsamitoides (Schultz Bip.) Grierson from Iran. J. Essent. Oil Res., 14, 1–2 (2002).
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