Composition of the Essential Oils from Galls and Aerial Parts of Pistacia lentiscus L. 1

Transcription

1 /. Essen. Oil Res., 12, 1923 (Jan/Feb 2000) Composiion of he Essenial Oils from Galls and Aerial Pars of Pisacia leniscus L. 1 Ana Fernandez,* Ana Camacho, b Carlos Fernandez* and Joaquin Alarejos c * "Deparamenos de Biologia Animal, Vegeal y Ecologia h Ciencias de la Salud c Quimica Inorgdnica y Orgdnica Faculad de Ciencias Experimenalesy de la Salud, Universidad dejaen, Jaen, Spain Pilar Perez Desilaciones Garcia de la FueneUniversal Fragrances SA, Apdo. Correos no. 69, Granada, Spain Absrac The chemical composiion of he essenial oils obained from he galls and he aerial pars of Pisacia leniscus L. (Anacardiaceae) was analyzed by GC/MS. Among he 58 consiuens idenified (represening 82.8% of he oil composiion) sesquierpene hydrocarbons predominaed (ca. 47%), J3caryophyllene (13.1%), 6cadinene (8.1%) and Germacrene D (6.8%) being he major componens. Alhough galls and oils of he aerial pars were similar from a qualiaive viewpoin, he laer oil was somewha more complex (73 componens idenified, accouning for 85.4% of he oil) and he monoerpene hydrocarbons fracion (ca. 35%) was now dominan in he oil, apinene (13.0%), Pcaryophyllene (6.9%), limonene and pphellandrene (5.4%), {3pinene (4.9%) and pcymene (4.7%) being he main componens. Key Word Index Pisacia leniscus, Anacardiaceae, galls, essenial oil composiion, pcaryophyllene, apinene. Inroducion Pisacia leniscus L. (Anacardiaceae) is an evergreen shrub or small ree naive o he Medierranean region and Middle Eas (1). I is commonly found in almos he whole Iberian Peninsula in dry open woods, pine fores and as a par of he scrub, and is flowering and frucificaion periods are during he spring and he auumn, respecively (2). The lenisco (Spanish common name) is valued because i is he source of masic gum, an exudae which has been widely used in folk medicine o srenghen gums, deodorize breah, comba diarrhea and uberculosis, ec. (2,3), and more receniy o flavor alcoholic beverages, pharmaceuicals, chewing gum and radiional food (4,5). In addiion, lenisco leaves and fruis have been used in a variey of ways by rural inhabians of he areas where he plan grows wild (2,3,6). Wih regard o he composiion of volailes from differen pars of he plan, he leaves (711), fruis (4,7,9) and masic gum (7,12,13) have been he subjec of previous research. However, in spie of all his work, nohing is known abou he chemical composiion of he galls, a eraologic srucure Address for correspondence Received: Ocober 1998 x Par of his work was presened as a poser (Absracs, p 37) a he Xllh Inernaional Revised: February 1999 Conference on Aromas and Essenial Oils, Seville, Spain, Ocober 1923, 1997 Acceped: April 1999 l04l2905/00/000100l9$06.00/ Allured Publishing Corp.

2 20 FERNANDEZ ET AL. Table I. Percenage composiion 0 of he oils of Pisacia leniscus L. Rl a Compound 15 A d B e (E)2Hexenal (Z)3Hexenol Hexanol Tricyclene apinene Camphene Sabinene ppinene Myrcene aphellandrene 83Carene 1,4Cineole aterpinene pcymene Limonene + pphellandrene (Z)pOcimene (E)pOcimene Isoamyl buyrae yterpinene Terpinolene + 2Nonanone Linalool + acampholenic aldehyde Isoamyl isovalerae Isoamyl valerae ranspinocarveol pmenhariene Pinocarvone Borneol Carvoanaceone Terpinen4ol pcymen8ol aterpineol Myrenal cissabinol" 1 " Verbenone ciscarveol (Z)3Hexenyl 2mehylbuyrae (Z)3Hexenyl isovalerae Cuminaldehyde Carvone Isoamyl hexanoae Bornyl aceae 2Undecanone 2,4,6Trimehylbenzaldehyde acubebene 2,4,5Trimehylbenzaldehyde (Z)3Hexenyl hexanoae acopaene pbourbonene PCubebene + pelemene pcaryophyllene. " " f

3 PlSTACIA LENTISCUS 21 Table I. Coninued Rl a Compound 5 A d B Isoamyl benzoae 1 " Isoamyl ocanoae Geranyl aceone ahumulene Aromadendrene aamorphene Germacrene D amuurolene PBisabolene ycadinene 5Cadinene Cadina1,4diene Elemicin (Z)3Hexenyl benzoae Spahulenol Caryophyllene oxide 10epiyEudesmol 1 ' TMuurolol acadinol isomer* Bisabolol* Myrisic acid Benzyl benzoae "Temperaureprogrammed reenion indices referred o nalkanes, deermined on DB5 column according o reference 19; "Consiuens lised in eluion order from a 30 m DB5 capillary column. Unidenified peaks wih a presence in he oil of % or higher have been included. Mass specra daa of unknown compounds and hose wih a f are included in Table II; 'Percenage values less han % are denoed as (races); d A = Pisacia leniscus galls; *B = Pisacia leniscus aerial pars; 'Peak value corresponding o erpinolene alone; g Peak value corresponding o linalool alone. enaively idenified; *Correc isomer no deermined of his plan which appears in he leaves as a response o he parasiic acion of he insec Aploneura ' lenisci (2). Therefore, here we repor on he oil composiion of P. leniscus galls (14), and also ha from he aerial pars of he plan. Experimenal Plan Maerial. The P. leniscus samples were colleced in Ocober 1996 during he frucificaion period near he Cabra del Sano Criso village (30S VG7783) in he Province of Jaen (Spain). Voucher specimens have been deposied a he Herbarium of he Universiy of Jaen. The plan maerial consised in he whole aerial pars formed by leaves and erminal sems (sample B in Table I) and galls (sample A in Table I). Airdried aerial pars (135.4 g) were ground and hydrodisilled for 8 h using a Clevengerype apparaus (15). The oil was dried over anhydrous sodium sulfae and sored under refrigeraion C4 C) in he dark (335 mg, 5%). In he same manner he galls sample (56.8 g) yielded he

4 22 FERNANDEZ ET AL. Table II. Mass specra daa of unknown and enaively idenified componens of Pisacia leniscus oil Rl a Compound m/z (rel. in.) cissabinol Isoamyl benzoae 1 oepiyeudesmol acadinol isomer 152 [M + ](3), 134(28), 119(19), 109(20), 92(100), 91(87), 81(45), 79(37), 65(17), 41(41) [M + ]?, 161(21), 133(5), 123(22), 105(100), 77(49), 70(55), 55(23), 41(17) 204[M + ](27), 189(5), 161(100), 133(13), 119(45), 105(81), 91(34), 81(35), 69(12), 55(14), 41(27) 204[M + ](32), 189(14), 161(100), 133(17), 119(30), 105(46), 91(23), 81(29), 69(7), 55(9), 41(18) 204[M + ](21), 189(3), 161(100), 133(16), 119(35), 105(53), 91(45), 79(20), 67(9), 55(13), 41(25) 220[M + ](10), 205(8), 202(10), 187(11), 177(15), 159(42), 146(30), 131(62), 123(83), 105(72), 91(87), 79(81), 67(44), 55(57), 41(100) 220[M + ](6), 205(8), 202(7), 187(13), 177(14), 159(38), 145(33), 131(44), 119(32), 105(60), 91(64), 79(53), 67(75), 55(51), 41(100) 222[M + ](11), 204(40), 189(17), 179(25), 161(42), 149(17), 135(33), 121(23), 109(100), 93(47), 81(51), 67(40), 55(44), 41(67) [M + ]?, 204(42), 189(38), 179(19), 161(79), 147(52), 135(7), 119(100), 105(46), 95(28), 81(28), 69(21), 55(33), 43(40) 222 [M + ](7), 204(67), 189(100), 161(87), 149(21), 133(49), 119(19), 107(35), 105(33), 91(46), 81(35), 67(19), 59(51), 43(37), 41(38) 222[M + ](), 204(29), 189(8), 177(6), 161(100), 147(8), 133(13), 119(64), 105(47), 95(43), 79(37), 67(19), 55(23), 43(72) 222[M + ](4), 204(39), 189(9), 177(4), 161(40), 149(9), 137(14), 121(70), 105(33), 95(100), 79(39), 71(28), 55(23), 43(94) Temperaureprogrammed reenion indices (see Table I) corresponding essenial oil (49 mg, 0.09%). GC/MS: Analyses were done on a HewlePackard gas chromaograph (model 5890) coupled o a HewlePackard mass specromeer (model 5970 B). Gas chromaograph uni: DB5 30 m x 5 mm fused silica capillary column, film hickness 5 Jim; carrier gas He (30 cm/s); iniial emperaure 50 C; final emperaure 220 C; final ime 30 min; rae 3 C/min; "spli mode" raio 1:60; injecor emperaure 240 C, C. Mass specromeer uni: ion source emperaure 230 C; ionizing volage 70 ev; scan range from m/z 35 o m/z 300. Mos componens were idenified wih he use of a builin NBS peak maching library searchsysem. Reenion indices, auhenic sandards and/or daa repored in he lieraure (16,17) were also used for furher idenificaion. Quaniaive daa were direcdy obained from he oal ion chromaogram, carried ou under he condiions specified before. Resuls and Discussion Table I shows he composiion of he oils obained from galls and aerial pars of P. leniscus. Consiuens are lised in order of heir eluion from a DB5 capillary column and were idenified by GC/MS analysis in combinaion wih reenion indices. The oil conen in galls (0.09%) was lower han in he whole plan (5%) as i can be direcly appreciaed by he resinouspoorer aspec of his ipycal formaions if compared, for insance, wih hose from he close relaed species P. erebinhus (18). Examinaion of he galls oil showed he presence of a leas 80 componens, 58 of which were idenified (Table I) accouning for 83% of he oil. I was mainly composed of {3caryophyllene (13.1%), 6cadinene (8.1%) and Germacrene D (6.8%) and of somewha lesser amouns of ocpinene (4.4%), an acadinol isomer (4.3%), Tmuurolol (38%), 10epiyeudesmol (3.5%); he las hree componens idenified

5 i PlSTACIA LENTISCVS 23 according only o heir mass specra. The oil was dominaed by sesquierpene hydrocarbons (ca. 47%), oxygenaed sesquierpenes (ca. 14%) and monoerpene hydrocarbons (ca. 12%), he cadinane, caryophyllane, germacrane and pinane being he mos represenaive skelea found. Comparing his oil wih ha obained from he whole aerial pars of he plan (Table I, column B), which was colleced on he same dae, i can be deduced ha boh oils were similar from a qualiaive viewpoin. However, in his second oil he major componens were apinene (13.0%), Pcaryophyllene (6.9%), limonene plus J3phellandrene (5.4%), Ppinene (4.9 %) and pcymene (4.7%), he monoerpene hydrocarbons fracion (ca. 35%) being now predominan in he oil versus he sesquierpene hydrocarbons one (ca. 25%). Fuhermore, some compounds found as minor or race componens in he whole plan oil, such as pcymen8ol, pmenhariene, ranspinocarveol, isoamyl isovalerae, verbenone, carvone and ohers could no be deeced in he galls oil. In conras, he galls conained 10epiyeudesmol, 2,4,5rimehylbenzaldehyde and myrisic acid, while he whole plan oil did no. References 1. T. G. Tuin, Pisacia L. In: Flora Europaea. Edis., T. G. Tuin, V. H. Heywood, N. A. Burges, D. M. Moore, D. H. Valenine, S. M. Walers and D. A. Webb, Vol 2, p 237, Cambridge Universiy Press, Cambridge (1968). 2. P. Fon Quer, Lenisco. In: PlanasMedicinales: El Dioscorides Renovado. pp , Labor, Barcelona (1978). 3. G. Lopez, Pisacia leniscusl. In: La Guia Incafo de los Arbolesy Arbusos de la Peninsula Iberica. pp , Incafo, Madrid (1982). 4. S. G. Wyllie, J. J. Brophy, V. Sarafis and M. Hobbs, Volaile componens of hefrui of Pisacia leniscus. J. Food Sci., 55, (1990). 5. B. M. Lawrence, Masic gum oil. In: Essenial Oils Edi., Naural Flavor and Fragrance Maerials "Perfumer & Flavoris", p 6, Allured Publ. Corp., Carol Sream, IL (1979). 6. A. M. FemandezOcana, I. OrunoMoya, A. I. MarosGilaber and C. FernandezLopez, Sabery Uilizacion de Planas en la Provincia defaen. Campana de 1993 Bol. Ins. Es. Giennenses, 161, (1996). 7. M. H. Boelens and R. Jimenez, Chemical composiion of he essenial oils from gum and from various pars of Pisacia leniscusl. Flav. Fragr. J., 6, (1991). 8. V. Picci, A. Scoi, M. Mariani and E. Colombo, Composiion of he volaile oil of Pisacia leniscusl. In: Flavour Science and Technology. Edis., M. Marens, G. A. Dalen and H. Russwurm, pp , J. Wiley & Sons Ld., New York (1987). 9. Z. Fleisher and A. Fleisher, Aromaic plans of he Holy Land and he Sinai. ParX. Volailes of he Masic ree Pisacia leniscusl.). Essen. Oil Res., 4, (1992). 10. H. L. DePooer, N. M. Schamp, E. A. Abouabl, S. F. El Tohamy and S. L. Doss, Essenial oils from he leaves of hree Pisacia species grown in Egyp. Flav. Fragr. J., 6, (1991). 11. V. Casola, A. Bighelli, F. Tomi and J. Casanova, Analyse de I'huile essenielle de Pisachier Lenisque de Corse parrmndu carbone13. Riv. Ial. EPPOS, 7, (1996). 12. S. Kasiois and N. G. Oikonomou, Qualiaive and quaniaive GLC analysis of he essenial oil of Pisacia leniscus (Masix)from differen disrics of he Chios Island. Pharm. Del., Episem. Ekdosis, 10,1728 (1984); Chem. Absr., 103, 42382b (1985). 13. V. P. Papageorgiou, A. S. Mellidis andn. Argyriadou, The chemical composiion ofhe essenial oil of Masic gum. J. Essen. Oil Res., 3, (1991). 14. A. Fernandez, A. Camacho, C. Fernandez, J. Alarejos and P. Perez, Composiion of an essenial oil of Pisacia leniscus galls. Paper No. 7, XLTh Inernaional Conference on Aromas and Essenial Oils, Seville, Spain (1997). 15 R. P. Adams, Cedarwood oilanalyses and properies. In: Modern Mehods of Plan Analysis. Essenial Oils and Waxes. Edis., H. F. Linskens and J. F. Jackson, pp , SpringerVerlag, Berlin (1991). 16. W. Jennings and T. Shibamoo, Qualiaive Analysis of Flavor and Fragrance Volailes by Glass Capillary Gas Chromaography. Academic Press, New York (1980). 17. R. P. Adams, Idenificaion of Essenial Oils by Ion Trap Mass Specromery. Academic Press, San Diego (1989). 18. P. Monaco, R. Capuo, G. Palumbo and L. Mangoni, Neural rierpenes from he galls of Pisacia erebinhus. Phyochemisry, 12, (1973). 19. H. Vandendool and P. D. Kraz, A generalizaion ofhe reenion index sysem including Linear Temperaure Programmed GasLiquid Pariion Chromaography.]. Chromaogr., 11, (1963).