SHORT REPORT Rec. Nat. Prod. 6:1 (2012) 80-83 Composition of the Essential oil of Endemic Haplophyllum megalanthum Bornm. from Turkey Nehir Ünver-Somer*1, Gülen rem Kaya1, Buket Sarıkaya1, Mustafa Ali Önür1, Canan Özdemir2, Betül Demirci3 and Kemal Hüsnü Can Ba er3 1 2 3 Department of Pharmacognosy, Faculty of Pharmacy, Ege University, Izmir, Türkiye Department of Biology, Faculty of Art and Science, Celal Bayar University, Manisa, Türkiye Department of Pharmacognosy, Faculty of Pharmacy, Anadolu University, Eski ehir, Türkiye (Received December 18, 2010; Revised April 1, 2011; Accepted April 3, 2011) Abstract: The composition of the essential oil produced from the flowering aerial parts of Haplophyllum megalanthum Bornm. (Rutaceae), endemic to Turkey, was analyzed by GC and GC-MS. Among the fifty-eight compounds constituting about 91.7 % of the essential oil, the main components were characterized as palmito-γlactone (45.8 %), octadecatrienoic acid (10.7 %), linoleic acid (6.5 %), octadecatetraenoic acid (6.3 %) and nonacosane (4.8 %). Keywords: Haplophyllum megalanthum; essential oil composition; palmito-γ-lactone; octadecatrienoic acid; linoleic acid; octadecatetraenoic acid; nonacosane. 1. Plant Source Haplophyllum A. Juss. (Rutaceae) is a genus, comprising of about 70 species distributed from the Mediterranean to eastern Siberia [1]. It is represented by 14 species in the Flora of Turkey [2]. The aerial parts of H. megalanthum Bornm. were collected during the flowering period from Manisa. The plant was identified by one of the authors (M.A.O.) and a voucher specimen (No: 1350) is deposited in the Herbarium of the Department of Pharmacognosy, Faculty of Pharmacy, Ege University. * Corresponding author: E- Mail: nehir.somer@ege.edu.tr The article was published by Academy of Chemistry of Globe Publications www.acgpubs.org/RNP © Published 08 /05/2011 EISSN: 1307-6167 81 Ünver-Somer et al., Rec. Nat. Prod. (2012) 6:1 80-83 2. Previous Studies Haplophyllum species have been shown to possess alkaloids [3-7], lignans [5-7], coumarins [5], flavonoids [7] and volatile constituents [8-11] with important biological activities [3,4,6,11]. To the best of our knowledge, there is no report found in the literature on the chemical and biological properties of H. megalanthum, an endemic species of Turkey. In the present study, the chemical composition of the essential oil of this plant is reported for the first time. 3. Present Study Aerial parts (100 g) were subjected to hydrodistillation for 3 hours using a Clevenger-type apparatus to provide the essential oil. Yellow colored oil was obtained in 0.1 % (v/w) yield. The GC-MS analysis was carried out with an Agilent 5975 GC-MSD system. Innowax FSC column (60 m x 0.25 mm, 0.25 µm film thickness) was used with helium as carrier gas (0.8 ml/min). GC oven temperature was kept at 60°C for 10 min and programmed to 220°C at a rate of 4°C/min, and kept constant at 220°C for 10 min and then programmed to 240°C at a rate of 1°C/min. Split ratio was adjusted at 40:1. The injector temperature was set at 250°C. Mass spectra were recorded at 70 eV. Mass range was from m/z 35 to 450. The GC analysis was carried out using an Agilent 6890N GC system. FID detector temperature was 300°C. To obtain the same elution order with GC/MS, simultaneous autoinjection was done on a duplicate of the same column applying the same operational conditions. Relative percentage amounts of the separated compounds were calculated from FID chromatograms. The result of analysis is shown in Table 1. Identification of the essential oil components were carried out by comparison of their relative retention times with those of authentic samples or by comparison of their relative retention indices (RRI) to series of n-alkanes. Computer matching against commercial (Wiley GC-MS Library, Adams Library, MassFinder 3 Library) [12,13] and in-house “Ba er Library of Essential Oil Constituents” built up by genuine compounds and components of known oils, as well as MS literature data [14,15] were used for the identification. Fifty eight compounds were characterized representing 91.7 % of the oil (Table 1). Fatty acids and their derivatives were found in large quantities. Palmito-γ-lactone was detected as the major component constituting 45.8 % of the essential oil. Other significant compounds were octadecatrienoic acid (10.7 %), linoleic acid (6.5 %), octadecatetraenoic acid (6.3 %) and nonacosane (4.8 %) followed by dodecanoic acid (2.5 %) and hexadecanoic acid (2.3 %). Previous studies on the chemical compositions of the oils obtained from Haplophyllum species growing in different countries showed that members of this genus possess essential oils with different compositions. For example, essential oils of H. glabrrimum Bge. ex Boiss. [16], H. robustum Bge. [17], H. tuberculatum (Forssk.) A. Juss. [11], H. linifolium (L.) G. Don. fil. [18] contained monoterpenes as the main constituents. Elemol and β-eudesmol were reported as the major components of H. furfuraceum Bge. ex Boiss. essential oil whereas H. virgatum Spach. essential oil was found to be rich in aliphatic ketones namely, 2-nonanone and 2-undecanone [19]. Major constituents of H. lissonotum C. Town. essential oil were detected as caryophyllene oxide, βcaryophyllene, humulene oxide II, α-humulene and caryophylla-4(14),8(15)-dien-5β-ol while the essential oil of H. buxbaumii (Poir.) G. Don. subsp. mesopotamicum (Boiss.) C. Town. was found to possess hexadecanoic acid, ethyl linolenate, phytol and caryophyllene oxide as the main compounds [10]. 82 Essential oil of Haplophyllum megalanthum Table 1. Composition of the essential oil of H. megalanthum RI 1032 1093 1174 1203 1218 1220 1225 1244 1246 1253 1266 1400 1460 1505 1535 1553 1589 1591 1597 1612 1638 1655 1661 1694 1704 1726 1740 Compound (%) RI α-Pinene 0.5 t 0.1 t 0.1 0.1 0.3 t 0.1 0.1 0.1 0.2 t 1773 1760 1827 1857 1868 1900 1957 1958 2037 2050 2100 2131 2144 0.1 0.4 0.4 0.1 0.1 0.1 t t t 0.4 0.1 0.1 2179 2209 2210 2278 2300 2369 2500 2503 2622 2857 2900 2931 1.1 t 3061 3290 Hexanal Myrcene Limonene β-Phellandrene cis-Anhydrolinalool oxide (Z)-3-Hexenal 2-Pentyl furan (Z)-β-Ocimene trans-Anhydrolinalool oxide (E)-β-Ocimene Nonanal 2,6-Dimethyl-1,3(E),5(E),7octatetraene Dihydroedulane II β-Bourbonene Linalool β-Ylangene Bornyl acetate β-Copaene β-Caryophyllene β-Cyclocitral (E)-2-Decenal Alloaromadendrene Neral γ-Muurolene Germacrene D α-Muurolene Compound (%) δ-Cadinene isodihydrocarveol (E,E)-2,4-Decadienal Geraniol (E)-Geranyl acetone epi-Cubebol Cubebol (E)-β-Ionone Salvial-4(14)-en-1-one (E)-Nerolidol Heneicosane Hexahydrofarnesyl acetone Spathulenol 0.2 0.3 0.2 0.2 0.3 t 0.1 0.1 0.2 0.4 0.1 0.1 0.3 3,4-Dimethyl-5-pentylidene-2(5H)-furanone T-Muurolol Copaborneol torilenol Tricosane Eudesma-4(15),7-dien-1β-ol Pentacosane Dodecanoic acid Phytol Palmito-γ-lactone (=4-Hexadecanolide) Nonacosane Hexadecanoic acid 0.2 0.4 0.4 0.2 1.5 0.3 0.4 2.5 1.3 45.8 4.8 2.3 Stearolactone (=4-Octadecanolide)* Linoleic acid (=(Z,Z)-9,12-octadecadienoic acid) 1742 Geranial 0.2 3157 Octadecatrienoic acid* 1755 Bicyclogermacrene t 3274 Octadecatetraenoic acid* Total RI: Relative retention indices calculated against n-alkanes; %: calculated from FID data; t: trace (< 0.1 %); *Tentatively identified : Stearolactone: EIMS, 70 eV, C18H34O2, m/z (rel.int.): 282[M]+, 264(9), 246(7), 220(11), 195(3), 166(5), 151(6), 137(5), 123(9), 111(14), 97(30), 85(100), 69(28), 55 (36), 41(29). Octadecatrienoic acid: EIMS, 70 eV, C18H30O2, m/z (rel.int.): 278[M]+ (3), 235(2), 218(4), 205(5), 193(5), 149(10), 136(33), 121(29), 107(28), 93(52), 79(89), 67(100), 55(49), 41(49). Octadecatetraenoic acid: EIMS, 70 eV, C18H28O2, m/z (rel.int.): 276[M]+ (2), 220(1), 189(3), 175(2), 161(5), 147(19), 133(11), 119(16), 105(22), 93(51), 79(100), 67(58), 55(25), 41(33). 0.9 6.5 10.7 6.3 91.7 Considering the Turkish Haplophyllum species, only Haplophyllum myrtifolium Boiss., an endemic species to Turkey, has been investigated for its essential oil composition [8]. Moreover, in another study, volatile fractions of the petroleum ether and alkaloid extracts of the same species were analyzed by GC-MS [9]. Linalool (12.8 %), β-caryophyllene (10.3 %) and methyleugenol (5.9 %) were identifed as the major components of the essential oil of H. myrtifolium [8]. However, in our study, the amount of linalool was found to be 0.4 % in the oil of H. megalanthum, whereas βcaryophyllene was detected in trace amount. Methyleugenol was not detected in the oil of H. megalanthum. In conclusion, the composition of H. megalanthum oil, with a very high content of fatty acids and their derivatives, differ significantly from the compositions of other oils of Haplophyllum species. 83 Ünver-Somer et al., Rec. Nat. Prod. (2012) 6:1 80-83 References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] J.C. Willis (1980). A Dictionary of Flowering Plants and Ferns. 8th ed, revised by Airy H. K. Shaw, Cambridge University Press, Cambridge, p. 532. C.C. Townsend (1967). Haplophyllum A. Juss., In: The Flora of Turkey and the East Aegean Islands, ed: P.H. Davis, Vol 2, Edinburgh University Press, Edinburgh, pp. 496-506. P. Varamini, K. Javidnia, M. Soltani, A.R. Mehdipour and A. Ghaderi (2009). Cytotoxic activity and cell cycle analysis of quinoline alkaloids from Haplophyllum canaliculatum Boiss. Planta Med, 75, 15091516. D. Staerk, J.R. Kesting, M. Sairafianpour, M. Witt, J. Asili, S.A. Emami and J.W. Jaroszewski (2009). Accelerated dereplication of crude extracts using HPLC-PDA-MS-SPE-NMR: quinoline alkaloids of Haplophyllum acutifolium, Phytochemistry, 70, 1055-1061. A. Ulubelen and M. Öztürk (2008). Alkaloids, coumarins and lignans from Haplophyllum species, Rec. Nat. Prod. 2:3, 54-69. C.L. Cantrell, K.K. Schrader, L.K. Mamanov, G.T. Sitpaeva, T.S. Kustova, C. Dunbar and D.E. Wedge (2005). Isolation and identification of antifungal and antialgal alkaloids from Haplophyllum sieversii, J. Agric. Food Chem. 53, 7741-7748. H. Sa lam, T. Gözler and B. Gözler (2003). A new prenylated arylnaphthalene lignan from Haplophyllum myrtifolium, Fitoterapia, 74, 564-569. H. Sa lam, T. Gözler, B. Kıvçak, B. Demirci and K.H.C. Ba er (2001). Composition of the essential oil of Haplophyllum myrtifolium, Chem Nat. Comp. 37, 439-441. H. Sa lam, T. Gözler, B. Kıvçak, B. Demirci and K.H.C. Ba er (2001). Volatile compounds from Haplophyllum myrtifolium, Chem. Nat. Comp. 37, 442-444. K. Javidnia, R. Miri, M. Soltani and P. Varamini (2009). Volatile constituents of two species of Haplophyllum A. Juss from Iran [H. lissonotum C. Town. and H. buxbaumii (Poir.) G. Don. subsp. mesopotamicum (Boiss.) C. Town.], J. Essent. Oil Res. 21, 48-51. S.K.S. Al-Burtamani, M.O. Fatope, R.G. Marwah, A.K.Onifade and S.H.Al-Saidi (2005). Chemical composition, antibacterial and antifungal activities of the essential oil of Haplophyllum tuberculatum from Oman, J. Ethnopharm. 96, 107-112. F.W. Mclafferty and D.B. Stauffer (1989). The Wiley/NBS registry of mass spectral data. J. Wiley and Sons, New York. W.A. Koenig, D. Joulain, D.H. Hochmuth (2004). Terpenoids and related constituents of essential oils. Mass Finder 3, In: Convenient and Rapid Analysis of GCMS, ed: D.H. Hochmuth, Hamburg, Germany. D. Joulain, W.A. König (1998). The atlas of spectra data of sesquiterpene hydrocarbons. EB-verlag, Hamburg. ESO 2000 (1999). The Complete Database of Essential Oils, Boelens Aroma Chemical Information Service, The Netherlands. A. Bamoniri, B.B. F. Mirjalili, A. Mazoochi, H. Naeimi, H. Golchin and H. Batooli (2010). Study of the bioactive and fragrant constituents extracted from leaves and aerial parts of Haplophyllum glabrrimum Bge. ex Boiss. Central Iran by nanoscale injection, Dig. J. Nanomater. Bios. 5, 169-172. M. Rahimi-Nasrabadi, M.B. Gholivand and H. Batooli (2009). Chemical composition of the essential oil from leaves and flowering aerial parts of Haplophyllum robustum Bge. (Rutaceae), Dig. J. Nanomater. Bios. 4, 819-822. K.H. Kubeczka, W. Schultze, P. Torres and M. Grande (2003). Essential oil of Haplophyllum linifolium (L.) G. Don. fil. (Rutaceae), J. Essent. Oil Res. 15, 41-43. T. Biniyaz, Z. Habibi, S. Masoudi and A. Rustaiyan (2007). Composition of the essential oils of Haplophyllum furfuraceum Bge. ex Boiss. and Haplophyllum virgatum Spach. from Iran, J. Essent. Oil Res. 19, 49-51. © 2011 Reproduction is free for scientific studies View publication stats