Rev. Biol. Trop. 50(3/4): 963-967, 2002 www.ucr.ac.cr www.ots.ac.cr www.ots.duke.edu Volatile constituents of the leaves of Siparuna thecaphora (Siparunaceae) from Turrialba, Costa Rica José F. Cicció1* and Jorge Gómez-Laurito2 1 Centro de Investigaciones en Productos Naturales (CIPRONA) and Escuela de Química, Universidad de Costa Rica, 2060 San José, Costa Rica. Fax: (506) 225 9866; [email protected] 2 Centro de Investigaciones en Productos Naturales (CIPRONA) and Escuela de Biología, Universidad de Costa Rica, 2060 San José, Costa Rica. * Corresponding author. Received 6-VIII-2002. Corrected 18-XI-2002. Accepted 26-XI-2002. Abstract: The composition of the essential oil from leaves of Siparuna thecaphora (Poepp. et Endl.) A. DC. collected in Turrialba, Costa Rica, was determined by capillary GC/MS. Seventy-six compounds were identified corresponding to ca. 95% of the oil. The major components were germacrene D (32.7%), a -pinene (16.3%), b- pinene (13.8%) and b-caryophyllene (4.1%). Thirty-one minor compounds were identified for the first time in this genus of plants. Key Words: Siparuna thecaphora, Siparunaceae, essential oil composition, germacrene D, a -pinene, b-pinene, b-caryophyllene. The family Siparunaceae comprises two from southern Mexico throughout Central genera, the monotypic West African genus America to Brazil and Bolivia. It is called col- G l o s s o c a l y x and the Neotropical genus loquially “limoncillo” (little lemon) probably S i p a runa (formerly placed in the family because of the strong lemon-scented fruits. Monimiaceae), which contains about 72 In Panama, the infusion of crushed leaves species of shrubs, straggling shrubs, and trees is used to treat colds and rheumatism (Duke (Renner et al. 1997). Up to now, six species of 1972). In Guatemala, the fresh leaves are S i p a ru n a from Costa Rica have been placed on the forehead to relieve headaches described. (Morton 1980). Siparuna thecaphora (Poepp. et Endl.) A. To the best of our knowledge, no reports DC. is an aromatic shrub or small tree (3-5 m have been made regarding the essential oil tall), with opposite, simple leaves, and unisex- composition from this genus of plants in Costa ual flowers. The fruits are fleshy and reddish Rica. when ripe, with arilate seeds. Due to its highly Early phytochemical studies of the genus variable morphology, a great number of syn- Siparuna revealed the presence of aporphine, onyms are found in the literature (e.g., S. oxoaporphine and morphinandienone alkaloids nicaraguensis, S. andina, S. gilgiana). This (Braz et al. 1976, Chiu et al. 1982, Gerard et plant is a widespread species in Costa Rica. It al. 1986, Lopez et al. 1988, 1990, 1993); cadi- can be found in both Pacific and Caribbean nane sesquiterpenes (El-Seedi et al. 1994) and sides of the Country, from near sea level up to kaempherol glycosides (Leitão et al. 2000). close to 2 000 m elevation. It is distributed Reports of the leaf essential oils constituents 964 REVISTA DE BIOLOGÍATROPICAL obtained from the Panamanian and Brazilian S. ture: 250ºC; detector temperature: 260ºC; ion- guianensis were varied. They range from tho- ization voltage: 70eV; scanning over 38-400 se containing as main constituents curzerenone amu range; split injection 1:20. Integration of and curzerenone derivatives (Antonio et al. the total ion chromatogram, expressed as area 1976), epi-a -bisabolol, spathulenol, selin-11- percent, has been used to obtain quantitative en-4a -ol, elemol, b-eudesmol, atractylone and compositional data. germacrone (Zoghbi et al. 1998) or (E)-neroli- Identification: Identification of the com- dol (Fernandez-Machado et al. 1998). ponents of the oil was performed using the Some chemical studies of S. thecaphora retention indices on a phenyl methyl silicone have been done previously. The oxoaporphine column, and by comparison of their mass alkaloid liriodenine was isolated from the spectra with those published in the literature twigs (under the synonym S. nicaraguensis) (Stenhagen et al. 1974, Swigar and Silverstein (Gerard et al. 1986). The alkaloids liriodenine 1981, McLafferty 1993, Adams 1995, 2001) or and oxonantenine, reported for the first time in those of our own database. the genus, were isolated from the roots (under the synonym S. gilgiana) (Chiu et al. 1982). The volatile oil of the fruits (under the syn- RESULTS onym S. nicaraguensis) was studied previous- ly (Manjarrez and Mendoza 1967). The main The oil is constituted mainly by hydrocar- constituents of the oil were b-elemene, citral bons (89.0%) whereas the oxygenated com- and b-ionone. pounds accounts only for 6.4% (Table 1). Among the 76 compounds identified, sesquiterpenoids represented 56.7% and MATERIALS AND METHODS monoterpenoids 38.7%. Germacrene D (32.7%), a - p i n e n e Plant Material: Leaves of Siparuna the - (16.3%), b-pinene (13.8%) followed by the caphora from Costa Rica, were collected in widespread sesquiterpene b- c a r y o p h y l l e n e Santa Cruz, Turrialba, province of Cartago, in (4.1%) were identified as the main const i t u e n t s 1998. A voucher specimen was deposited in of the oil. Among the oxygenated compounds the Herbarium of the University of Costa Rica a -cadinol (1.6%), epi-a -muurolol (1.0%) and at the School of Biology (USJ 68612). 1,8-cineole (0.8%) were the major ones. Th e Essential Oil Isolation: Fresh leaves other constituents were 69 compounds found in were subjected to hydrodistillation for 3 hr minor or trace amounts. Of these ones, thirty- using a modified Clevenger-type apparatus. one are newly identified compounds in the The distilled oil was collected as a colorless genus Si p a r una (see Table 1). liquid, dried over anhydrous sodium sulfate, and stored at -10ºC [ 0.2% (v/w) yield]. General Analytical Procedures: The oil was analyzed by gas chromatography/mass TABLE 1 spectrometry (GC/MS). The mass spectra were Percentage composition of the Siparuna thecaphora obtained using a Hewlett-Packard G1800A leaf oil from Costa Rica GCMSD System, employing a fused silica aCo m p o u n d bRI Le a v e s dMe t h o d (30im x 0.25 mm) column coated with a 5% phenyl methyl silicone (film thickness a -t h u j e n e * 93 0 0. 3 1, 2 0.25iµm). Operation conditions were: carrier a -p i n e n e 93 9 16 . 3 1, 2, 3 c gas: He (1.0 mL/min); oven temperature pro- a -f e n c h e n e * 95 3 t 1, 2 ca m p h e n e 95 4 0. 4 1, 2 gram: 75ºC (4 min), 75º-200ºC at 3ºC/min, sa b i n e n e * 97 5 1. 3 1, 2 200ºC (8 min); sample injection port tempera- b-p i n e n e 97 9 13 . 8 1, 2, 3 INTERNATIONALJOURNALOF TROPICALBIOLOGYAND CONSERVATION 965 my r c e n e 99 1 2. 5 1, 2 a -c a l a c o r e n e 15 4 6 t 1, 2 a -p h e l l a n d r e n e 10 0 3 t 1, 2 germacrene B 15 6 1 1. 3 1, 2 a -t e r p i n e n e * 10 1 7 0. 1 1, 2 E-n e r o l i d o l 15 6 4 0. 3 1, 2 p-c y m e n e 10 2 5 t 1, 2 b-c a l a c o r e n e * 15 6 6 t 1, 2 li m o n e n e 10 2 9 0. 4 1, 2, 3 germacrene D-4-ol* 15 7 6 0. 1 1, 2 b-p h e l l a n d r e n e 10 3 0 0. 3 1, 2 sp a t h u l e n o l 15 7 8 0. 1 1, 2 1, 8-cineole 10 3 1 0. 8 1, 2, 3 caryophyllene oxide 15 8 3 0. 2 1, 2 (Z)- b-o c i m e n e 10 3 7 1. 0 1, 2 ep i - a - m u u r o l o l * 16 4 0 1. 0 1, 2 (E)- b-o c i m e n e * 10 5 0 0. 2 1, 2 cu b e n o l 16 4 7 0. 3 1, 2 g-t e r p i n e n e 10 6 0 0. 2 1, 2 b-e u d e s m o l 16 5 1 0. 2 1, 2 ci s -sabinene hydrate* 10 7 0 t 1, 2 a -c a d i n o l * 16 5 4 1. 6 1, 2 p-m e n t h a - 3 , 8 - d i e n e * 10 7 3 t 1, 2 mint sulfide* 17 4 1 t 1, 2 te r p i n o l e n e 10 8 9 0. 1 1, 2 Monoterpene hydrocarbons 36 . 9 li n a l o o l 10 9 7 0. 2 1, 2, 3 Oxygenated monoterpenes 1. 8 n-n o n a n a l * 110 1 t 1, 2 Sesquiterpene hydrocarbons 52 . 1 en d o - f e n c h o l * 1117 t 1, 2 Oxygenated sesquiterpenes 4.6 ci s -p-m e n t h - 2 - e n - 1 - o l * 112 2 t 1, 2 al l o - o c i m e n e * 113 2 t 1, 2 a Compounds are listed by elution order in a 5% tr a n s -p i n o c a r v e o l * 113 9 t 1, 2 phenyl methyl silicone column; b RI = Retention tr a n s - p -m e n t h - 2 - e n - 1 - o l * 114 1 0.