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The volatiles of six Teucrium species from the iberian peninsula and the balearic islands
Phytochemisrry, Vol. 29, No. 4, pp. 1165 1169, 1990. Printed in Great Britain.
0
THE VOLATILES OF SIX TEUCRIUM SPECIES PENINSULA AND THE BALEARIC
003 l--9422/90 $3.00 +O.oO 1990 Pergamon Press plc
FROM THE IBERIAN ISLANDS
A. VELASCO-NEGUERUELA and M. J. PEREZ-ALONSO Departamento de Biologia Vegetal I (Botinica), Facultad de Biologia, Universidad Complutense, 28040-Madrid, Spain (Received in revised form 18 September 1989)
Key Word Index--Teucrium section Scorodonia; Lamiaceae; essential oils; terpenes; chemotaxonomy.
Abstract-The quantitative composition of the essential oils from six Teucrium species collected on the Iberian Peninsula and the Balearic islands is reported. Sixty-two constituents have been identified. The volatile oil from the hybrid Teucrium scorodonia x T. oxylepis has also been studied.
differences were found in the terpenoid (monoterpene and sesquiterpene) patterns. T. scorodonia x T. oxylepis was only found in one locality. Plant samples are listed in Table 1. The compositions of the essential oils obtained from the plant samples are given in Tables 24. Component concentrations were calculated from GC peak areas without correction factors. Components are arranged in order of GC (OV 1) elution. The Teucrium oxylepis group was characterized by the high content of sesquiterpenes. In T. oxylepis subsp. oxylepis, aristolene, fl-caryophyllene, 8-cadinene, epi-cubenol and a-cadinol were the main components whereas in T. oxylepis subsp. marianum y-cadinene, calamenene, T-cadinol and cr-cadinol were major constituents. Ruiz de la Torre and Ruiz de1 Castillo [4] separated T. oxylepis into two subspecies (oxylepis and marianum) based on morphological grounds. From a chemotaxonomic point of view, our results tend to be in agreement with that proposal.
INTRODUCTION The genus Teucrium comprises some 340 species [l] of which 49 species are found in Europe, mostly in the Mediterranean Basin [2]. Thirty-five species are found in Spain, of which 20 are indigenous [3]. In this work we report on the chemical composition of several samples of volatile oils obtained from six species of Teucrium and of a hybrid Teucrium scorodonia x T. oxylepis. All samples were harvested at flowering.
RESULTS AND DISCUSSION We gathered five populations of Teucrium scorodonia subsp. scorodonia, three populations of T. scorodonia subsp. baeticum and two samples of T. oxylepis subsp. marianum in order to study the differences in composition. Several samples of T. asiaticum, T. salviastrum and T. oxylepis subsp. oxylepis were studied and no significant
Table 1. Collecting sites of Teucrium L. sect. scorodonia (Hill) Schreber Species and subspecies
Place of collection
Teucrium scorodonia L.
Santander Lug0 La Corufia (2 samples) Asturias (Spain) Cgdiz (Spain)
subsp. scorodonia
T. scorodonia
subsp. baeticum (Boiss. et Reuter) Tutin T. oxylepis Font Quer subsp. oxylepis T. oxylepis subsp. marinnum Ruiz de la Torre et Ruiz de1 Castillo T. asiaticum L. T. sahiastrum Schreber T. scorodonia x T. oxylepis
nothosp. nova prov.
1165
Almeria (Spain) Jatn Toledo (Spain) Balearic islands (Spain) Sierra da Estrela (Portugal) Toledo (Spain)
The volatiles of six Teucrium species The hybrid Teucrium scorodonia x T. oxylepis was characterized by higher amounts of aristolene +/?-caryophyllene and by the rare [S, 61 muurol-3-en-9/?-ol-2one only previously reported in the heartwood of Taiwania cryptomedioides. Two unusual components, of M, 236, were tentatively identified by means of their mass spectra [7] as cadin-3-en-9cr-ol-2-one and cadin-3-en-9/Iol-Zone. Linalol was also found as the main monoterpene in these oils. Teucrium asiaticum was shown to contain linalol and linalyl acetate as major monoterpene components while a-muurolene, calamenene and a-calacorene were the main sesquiterpenes and it is worth noting that sesquiterpene alcohols were practically absent. Teucrium saluiastrum, T. scorodonia subsp. scorodonia and T. scorodonia subsp. baeticum showed very similar sesquiterpenoid patterns. These oils were characterized by the high content of aristolene, /I-caryophyllene, a-humulene, alloaromadendrene, caryophyllene epoxide and spathulenol, confirming the close morphological relationships between these species, as other authors have previously suggested [S].
1169
apparatus and submitted to IR spectroscopy. GC-MS analysis was performed with a chromatograph fitted with a Carbowax 20M column (20 m x 0.22 mm i.d.) and FID. Temp. programmed 80-180” at S”/min. Carrier gas He. Flow rate 30 ml/min. The chromatograph was coupled to a mass selective detector at 70 ev. Acknowledgements-We thank Dr J. Perucha (CSIC, Madrid) and Dr Garcia Vallejo from (INIA, Madrid) for the identification of some components and for their help running the mass and IR spectra. This work was supported by the Rectorado de la Universidad Complutense de Madrid (Proyecto Grupo Precompetitive UCP/87). REFERENCES
1. Jackson, B. D. (ed.) (1985) Index Kewensis. Oxonii E Prelo Clarendoniano, U.K. 2. Greuter, W., Burdet, H. M. and Long, G. (1986) MedChecklist Vol. 3. Conservatoire et Jardin Botaniques, GenCve. 3. Valdes-Bermejo, E. and Sanchez Crespo, A. (1978) Acta Bot. Malac. 4, 27.
4. Ruiz de la Torre, J. and Ruiz de Castillo, J. (1975) Bol. Estac. EXPERIMENTAL
Plant material. Samples of each specimen studied (see Table 1) are deposited in the Faculty of Biology Herbarium (MACB). Extraction of essential oils. The aerial parts of each species were steam distilled for 6 hr in a glass still according to the method recommended by the European Pharmacopoeia. The mean yield of the oils was 0.01% based on dry wt of samples. The oils were collected over pentane and dried over sodium sulphate. Identi&ation ofcomponents.Most of the individual components were tentatively identified by comparing their KovLts indices and R,s with those of pure standards available in the author’s laboratory and with those reported in literature [9-121. We also used IR spectroscopy 13C NMR and MS for further identification [13-153. IR spectra were run as liquid films. Analytical GC was carried out with two columns: (i) stainless steeel column 2 m x l/8 in. packed with 5% silicon OV 1 and (ii) stainless steel column, 2 m x l/S in. packed with 10% Carbowax 20M. Detector used dual FID. Carrier gas He. Flow rate 30 ml/min. Temp. programmed 70-225” at 2”/min. Injector temp. 250”. Detector temp. 275”. Injection vol. for all samples 0.10 PI. 13C NMR measurements were performed directly on the essential oil samples as in reference [15]. Prep. GC was performed on a chromatograph fitted with a compact Carbowax 20M column. Components were collected in the outlet of the
Centr. Ecol. 3, 30.
5. Lin, Y. T., Cheng, Y. S. and Kuo, Y. H. (1968) Tetrahedron Letters 36, 3881.
6. Kuo, Y. H., Cheng, Y. S. and Lin, Y. T. (1969) Tetrahedron Letters 28, 2375.
7. Eight Peak Index of Mass Spectra (1974) Vol. I. Mass Spectrometry Data Centre AWRE, Aldermaston, Reading, U.K. 8. Ruiz de la Torre, J. and Ruiz del Castillo, J. (1974) Naturalia Hispanica 1, 7.
9. Schulte-Elte, K. H. and Ohloff, G. (1968) Helu. Chim. Acta 51, 494.
10. Andersen, N. H. and Falcone, M. S. (1969) J. Chromatog. 44, 52. 11. Maurer, B. and Grieder, A. (1977) Helo. Chim. Acta 60,2177. 12. Kaiser, R. and Lamparsky, D. (1983) Helu. Chim. Acta 66, 1843.
13. Jennings, W. and Shibamoto, T. (1980) Qualitative Analysis of Flavor and Fragrance Volatiles by Capillary Gas Chromatography. Academic Press, New York. 14. Swigar, A. and Silverstein, R. M. (1981) Monoterpenes: Infrared, Mass, ‘H NMR and 13C NMR Spectra and Kovbts Indices. Aldrich, Milwaukee, Wisconsin. 15. Formacek, V. and Kubeczka, K.-H. (1982) Essential Oil Analysis by Capillary Gas Chromatography and Carbon-13 NMR Spectroscopy. John Wiley, New York.
0
THE VOLATILES OF SIX TEUCRIUM SPECIES PENINSULA AND THE BALEARIC
003 l--9422/90 $3.00 +O.oO 1990 Pergamon Press plc
FROM THE IBERIAN ISLANDS
A. VELASCO-NEGUERUELA and M. J. PEREZ-ALONSO Departamento de Biologia Vegetal I (Botinica), Facultad de Biologia, Universidad Complutense, 28040-Madrid, Spain (Received in revised form 18 September 1989)
Key Word Index--Teucrium section Scorodonia; Lamiaceae; essential oils; terpenes; chemotaxonomy.
Abstract-The quantitative composition of the essential oils from six Teucrium species collected on the Iberian Peninsula and the Balearic islands is reported. Sixty-two constituents have been identified. The volatile oil from the hybrid Teucrium scorodonia x T. oxylepis has also been studied.
differences were found in the terpenoid (monoterpene and sesquiterpene) patterns. T. scorodonia x T. oxylepis was only found in one locality. Plant samples are listed in Table 1. The compositions of the essential oils obtained from the plant samples are given in Tables 24. Component concentrations were calculated from GC peak areas without correction factors. Components are arranged in order of GC (OV 1) elution. The Teucrium oxylepis group was characterized by the high content of sesquiterpenes. In T. oxylepis subsp. oxylepis, aristolene, fl-caryophyllene, 8-cadinene, epi-cubenol and a-cadinol were the main components whereas in T. oxylepis subsp. marianum y-cadinene, calamenene, T-cadinol and cr-cadinol were major constituents. Ruiz de la Torre and Ruiz de1 Castillo [4] separated T. oxylepis into two subspecies (oxylepis and marianum) based on morphological grounds. From a chemotaxonomic point of view, our results tend to be in agreement with that proposal.
INTRODUCTION The genus Teucrium comprises some 340 species [l] of which 49 species are found in Europe, mostly in the Mediterranean Basin [2]. Thirty-five species are found in Spain, of which 20 are indigenous [3]. In this work we report on the chemical composition of several samples of volatile oils obtained from six species of Teucrium and of a hybrid Teucrium scorodonia x T. oxylepis. All samples were harvested at flowering.
RESULTS AND DISCUSSION We gathered five populations of Teucrium scorodonia subsp. scorodonia, three populations of T. scorodonia subsp. baeticum and two samples of T. oxylepis subsp. marianum in order to study the differences in composition. Several samples of T. asiaticum, T. salviastrum and T. oxylepis subsp. oxylepis were studied and no significant
Table 1. Collecting sites of Teucrium L. sect. scorodonia (Hill) Schreber Species and subspecies
Place of collection
Teucrium scorodonia L.
Santander Lug0 La Corufia (2 samples) Asturias (Spain) Cgdiz (Spain)
subsp. scorodonia
T. scorodonia
subsp. baeticum (Boiss. et Reuter) Tutin T. oxylepis Font Quer subsp. oxylepis T. oxylepis subsp. marinnum Ruiz de la Torre et Ruiz de1 Castillo T. asiaticum L. T. sahiastrum Schreber T. scorodonia x T. oxylepis
nothosp. nova prov.
1165
Almeria (Spain) Jatn Toledo (Spain) Balearic islands (Spain) Sierra da Estrela (Portugal) Toledo (Spain)
The volatiles of six Teucrium species The hybrid Teucrium scorodonia x T. oxylepis was characterized by higher amounts of aristolene +/?-caryophyllene and by the rare [S, 61 muurol-3-en-9/?-ol-2one only previously reported in the heartwood of Taiwania cryptomedioides. Two unusual components, of M, 236, were tentatively identified by means of their mass spectra [7] as cadin-3-en-9cr-ol-2-one and cadin-3-en-9/Iol-Zone. Linalol was also found as the main monoterpene in these oils. Teucrium asiaticum was shown to contain linalol and linalyl acetate as major monoterpene components while a-muurolene, calamenene and a-calacorene were the main sesquiterpenes and it is worth noting that sesquiterpene alcohols were practically absent. Teucrium saluiastrum, T. scorodonia subsp. scorodonia and T. scorodonia subsp. baeticum showed very similar sesquiterpenoid patterns. These oils were characterized by the high content of aristolene, /I-caryophyllene, a-humulene, alloaromadendrene, caryophyllene epoxide and spathulenol, confirming the close morphological relationships between these species, as other authors have previously suggested [S].
1169
apparatus and submitted to IR spectroscopy. GC-MS analysis was performed with a chromatograph fitted with a Carbowax 20M column (20 m x 0.22 mm i.d.) and FID. Temp. programmed 80-180” at S”/min. Carrier gas He. Flow rate 30 ml/min. The chromatograph was coupled to a mass selective detector at 70 ev. Acknowledgements-We thank Dr J. Perucha (CSIC, Madrid) and Dr Garcia Vallejo from (INIA, Madrid) for the identification of some components and for their help running the mass and IR spectra. This work was supported by the Rectorado de la Universidad Complutense de Madrid (Proyecto Grupo Precompetitive UCP/87). REFERENCES
1. Jackson, B. D. (ed.) (1985) Index Kewensis. Oxonii E Prelo Clarendoniano, U.K. 2. Greuter, W., Burdet, H. M. and Long, G. (1986) MedChecklist Vol. 3. Conservatoire et Jardin Botaniques, GenCve. 3. Valdes-Bermejo, E. and Sanchez Crespo, A. (1978) Acta Bot. Malac. 4, 27.
4. Ruiz de la Torre, J. and Ruiz de Castillo, J. (1975) Bol. Estac. EXPERIMENTAL
Plant material. Samples of each specimen studied (see Table 1) are deposited in the Faculty of Biology Herbarium (MACB). Extraction of essential oils. The aerial parts of each species were steam distilled for 6 hr in a glass still according to the method recommended by the European Pharmacopoeia. The mean yield of the oils was 0.01% based on dry wt of samples. The oils were collected over pentane and dried over sodium sulphate. Identi&ation ofcomponents.Most of the individual components were tentatively identified by comparing their KovLts indices and R,s with those of pure standards available in the author’s laboratory and with those reported in literature [9-121. We also used IR spectroscopy 13C NMR and MS for further identification [13-153. IR spectra were run as liquid films. Analytical GC was carried out with two columns: (i) stainless steeel column 2 m x l/8 in. packed with 5% silicon OV 1 and (ii) stainless steel column, 2 m x l/S in. packed with 10% Carbowax 20M. Detector used dual FID. Carrier gas He. Flow rate 30 ml/min. Temp. programmed 70-225” at 2”/min. Injector temp. 250”. Detector temp. 275”. Injection vol. for all samples 0.10 PI. 13C NMR measurements were performed directly on the essential oil samples as in reference [15]. Prep. GC was performed on a chromatograph fitted with a compact Carbowax 20M column. Components were collected in the outlet of the
Centr. Ecol. 3, 30.
5. Lin, Y. T., Cheng, Y. S. and Kuo, Y. H. (1968) Tetrahedron Letters 36, 3881.
6. Kuo, Y. H., Cheng, Y. S. and Lin, Y. T. (1969) Tetrahedron Letters 28, 2375.
7. Eight Peak Index of Mass Spectra (1974) Vol. I. Mass Spectrometry Data Centre AWRE, Aldermaston, Reading, U.K. 8. Ruiz de la Torre, J. and Ruiz del Castillo, J. (1974) Naturalia Hispanica 1, 7.
9. Schulte-Elte, K. H. and Ohloff, G. (1968) Helu. Chim. Acta 51, 494.
10. Andersen, N. H. and Falcone, M. S. (1969) J. Chromatog. 44, 52. 11. Maurer, B. and Grieder, A. (1977) Helo. Chim. Acta 60,2177. 12. Kaiser, R. and Lamparsky, D. (1983) Helu. Chim. Acta 66, 1843.
13. Jennings, W. and Shibamoto, T. (1980) Qualitative Analysis of Flavor and Fragrance Volatiles by Capillary Gas Chromatography. Academic Press, New York. 14. Swigar, A. and Silverstein, R. M. (1981) Monoterpenes: Infrared, Mass, ‘H NMR and 13C NMR Spectra and Kovbts Indices. Aldrich, Milwaukee, Wisconsin. 15. Formacek, V. and Kubeczka, K.-H. (1982) Essential Oil Analysis by Capillary Gas Chromatography and Carbon-13 NMR Spectroscopy. John Wiley, New York.