- Email: [email protected]
Comparative chemical composition of the resinous exudates from Haplopappus foliosus and H. uncinatus
Biochemical Systematics and Ecology 28 (2000) 491}493
Comparative chemical composition of the resinous exudates from Haplopappus foliosus and H. uncinatus Alejandro UrzuH a*, Luz Andrade, Francisco Jara Laboratorio de Qun& mica Ecolo& gica, Facultad de Qun& mica y Biologn& a, Universidad de Santiago de Chile, Casilla 40, Correo-33, Santiago, Chile Received 5 May 1999; received in revised form 18 June 1999; accepted 2 August 1999
Keywords: Haplopappus foliosus; H. uncinatus; Asteraceae; Resinous exudates; Monoterpenes; Sesquiterpenes; Straight-chain hydrocarbons; Phenyl propanoids; Miscellaneous compounds; GC/EI-MS
1. Subject and source The large genus Haplopappus Cass. is represented in Chile by about 60 species (Marticorena and Quezada, 1985). Most show the presence of glandular and nonglandular trichomes on the surface of leaves and stems (Marticorena and Quezada, 1985). Aerial parts of Haplopappus foliosus D.C. (SGO-108837) were collected during the #owering season, December 1997, between Zapallar and Papudo (V RegioH n, Chile, 323 30@S, 713 30@W), and aerial parts of Haplopappus uncinatus Phil. (SGO-111557) were collected during the #owering season, September 1997, between Santiago and Farellones (RegioH n Metropolitana, Chile, 333 21@S, 703 21@W). Voucher specimens have been deposited in the Herbarium of the National History Museum, Santiago, Chile.
2. Previous work The constituents of H. foliosus have received attention; the compounds isolated including sesquiterpenes, diterpenes, #avonoids and a simple coumarin. From the
* Corresponding author. E-mail address: [email protected] (A. UrzuH a). 0305-1978/00/$ - see front matter ( 2000 Elsevier Science Ltd. All rights reserved. PII: S 0 3 0 5 - 1 9 7 8 ( 9 9 ) 0 0 0 8 0 - 0
492
A. Urzu& a et al. / Biochemical Systematics and Ecology 28 (2000) 491}493
dried and powdered aerial parts, the clerodane diterpene ent-3,13-clerodadien-15,18dioic acid (haplopappic acid) was isolated (Silva and Sammes, 1973). Flavonoid glycosides, #avonoid aglycones, and a simple coumarin were reported using a procedure speci"c for the isolation of #avonoids (Ulubelen et al., 1982), and from the dried and milled roots a benzoylated #avonoid was also reported (Tschesche et al., 1985). A recent communication reports the isolation of two #avonoid aglycones, and two clerodane diterpenoids. These compounds were identi"ed in the extract obtained after maceration of the fresh aereal parts of H. foliosus with CH2 Cl2 for 30 min (Torres et al., 1997). Also, three guaianes sesquiterpenes were isolated after maceration with MeOH of the CH2 Cl2 extracted material (Torres et al., 1997). No work has been reported on H. uncinatus.
3. Present study The resinous exudates of H. uncinatus (1.6 kg) and H. foliosus (125 g) were obtained by dipping fresh plant material in cold CH2 Cl2 for 15}20 s. The extracts were concentrated to solid residues (68.9 g from H. uncinatus, and 2.2 g from H. foliosus). The resinous exudate of H. uncinatus was fractioned by CC on silica gel, using pentane containing increasing amounts of CH2 Cl2 . The resinous exudates, and the fraction of the minor components of H. uncinatus were analyzed by GC/EI-MS using a FISONS MD-800, equipped with an HP Ultra-2 capillary column (12 m]0.20 mm). The temperature of the injector was 2703C, and the temperature of the column was progammed to start at 803C, for 2 min, followed by a rise to 3203C at 203C min~1. Helium was the carrier gas at 7 lb psi. The identi"cation of the compounds was achieved by comparison of the retention times with available standards, and by comparison of the MS data with the NIST library. Identity was accepted only when the correlation index was larger than 96%. From the resinous exudate of H. foliosus the following compounds were identi"ed. Monoterpenes: thujane; (Z)-a-ocimene; b-pinene; a-terpinene; m-cymene; triciclene; (E)-p-menth-2-en-1-ol; (Z)-p-menth-2-en-1-ol and (R)-p-menth-2-en-4-ol. Sesquiterpenes: d-ambrinol; and 1,2,3,4,5,6,7,8-octahydro-1,4-dimethyl-7-(1-methylethylidene)-azulene. Straight-chain hydrocarbons: C23 H48 ;C24 H50 ;C25 H52 ;C26 H54 ; C27 H56 ;C28 H58 ;C29 H60 ;C30 H62 ;C31 H64 ;C32 H66 and C33 H68 . Phenyl propanoids: (E)-cinnamic acid and (E)-cinnamic acid benzyl ester. Miscellaneous compounds: 2,3-dihydrobenzofuran and 2-isopropylphenol. In addition, compounds of: M` 164 (one compound); M` 218 (three compounds); M` 220 (one compound); M` 236 (one compound) and M` 302 (two compounds) were not identi"ed. From the resinous exudate of H. uncinatus two clerodane diterpenes of M` 362, and M` 378 were observed and not identi"ed. From the fraction of the minor components of the resinous exudate of H. uncinatus the following compounds were identi"ed. Sesquiterpenes: 4(15)-cubebene; a-copaene; 3,3,7,7-tetramethyl-5-(2-methyl-1-propenyl)-tricyclo[4,1,02,4]heptane and 4-isopropyl-1,6-dimethylnaphthalene. Straightchain hydrocarbons: C25 H52 ; C27 H56 ; C29 H60 ; C31 H64 and C33 H68 .
A. Urzu& a et al. / Biochemical Systematics and Ecology 28 (2000) 491}493
493
4. Chemotaxonomic and ecological signi5cance The structure of trichomes and the chemical composition of its exudates as well as the ultrastructure of the epicuticular wax layers, and also their chemical composition, constitute the "rst line of resistance (physical and chemical) of a plant against microorganisms and insects. In addition, volatile compounds a!ect the behaviour of some insects that can perceive them as kairomones or allomones and employ them to discriminate between host and non-host plants (Schoonhoven et al., 1998). These results indicate considerable di!erences between the chemical composition of the resinous exudates of H. foliosus and H. uncinatus. In H. uncinatus the exudate appeared quite simple and the important compounds were the two clerodane diterpenes of M` 362 and M` 378. In H. foliosus around 40 compounds show chromatographic peaks with relatively high intensities.
Acknowledgements This work was supported by FONDECYT(Chile) No 1990209 and by DICYT (Universidad de Santiago de Chile).
References Marticorena, C., Quezada, M., 1985. Gayana 42, 33. Schoonhoven, L. M., Jeremy, T., van Loon, J.J.A., 1998. Insect-Plant Biology from Physiology to Evolution. Chapman & Hall, London, p. 31}82. Silva, M., Sammes, P.G., 1973. Phytochemistry 12, 1755. Torres, R., Delle-Monache, F., Carbonell, P., Coll, J., LabbeH , C., Faini, F., 1997. XXI Symposium of Chilean Society of Chemistry, Osorno, Chile, p. 324. Tschesche, R., Dalhui, M., Sepulveda, S., Zilliken, F., Kirkel, A., Will, G., 1985. Liebigs Ann. Chem. 2465. Ulubelen, A., Ayonglu, E., Clark, E., Brown, G., Mabry, T., 1982. J. Nat. Prod. 45, 363.
Comparative chemical composition of the resinous exudates from Haplopappus foliosus and H. uncinatus Alejandro UrzuH a*, Luz Andrade, Francisco Jara Laboratorio de Qun& mica Ecolo& gica, Facultad de Qun& mica y Biologn& a, Universidad de Santiago de Chile, Casilla 40, Correo-33, Santiago, Chile Received 5 May 1999; received in revised form 18 June 1999; accepted 2 August 1999
Keywords: Haplopappus foliosus; H. uncinatus; Asteraceae; Resinous exudates; Monoterpenes; Sesquiterpenes; Straight-chain hydrocarbons; Phenyl propanoids; Miscellaneous compounds; GC/EI-MS
1. Subject and source The large genus Haplopappus Cass. is represented in Chile by about 60 species (Marticorena and Quezada, 1985). Most show the presence of glandular and nonglandular trichomes on the surface of leaves and stems (Marticorena and Quezada, 1985). Aerial parts of Haplopappus foliosus D.C. (SGO-108837) were collected during the #owering season, December 1997, between Zapallar and Papudo (V RegioH n, Chile, 323 30@S, 713 30@W), and aerial parts of Haplopappus uncinatus Phil. (SGO-111557) were collected during the #owering season, September 1997, between Santiago and Farellones (RegioH n Metropolitana, Chile, 333 21@S, 703 21@W). Voucher specimens have been deposited in the Herbarium of the National History Museum, Santiago, Chile.
2. Previous work The constituents of H. foliosus have received attention; the compounds isolated including sesquiterpenes, diterpenes, #avonoids and a simple coumarin. From the
* Corresponding author. E-mail address: [email protected] (A. UrzuH a). 0305-1978/00/$ - see front matter ( 2000 Elsevier Science Ltd. All rights reserved. PII: S 0 3 0 5 - 1 9 7 8 ( 9 9 ) 0 0 0 8 0 - 0
492
A. Urzu& a et al. / Biochemical Systematics and Ecology 28 (2000) 491}493
dried and powdered aerial parts, the clerodane diterpene ent-3,13-clerodadien-15,18dioic acid (haplopappic acid) was isolated (Silva and Sammes, 1973). Flavonoid glycosides, #avonoid aglycones, and a simple coumarin were reported using a procedure speci"c for the isolation of #avonoids (Ulubelen et al., 1982), and from the dried and milled roots a benzoylated #avonoid was also reported (Tschesche et al., 1985). A recent communication reports the isolation of two #avonoid aglycones, and two clerodane diterpenoids. These compounds were identi"ed in the extract obtained after maceration of the fresh aereal parts of H. foliosus with CH2 Cl2 for 30 min (Torres et al., 1997). Also, three guaianes sesquiterpenes were isolated after maceration with MeOH of the CH2 Cl2 extracted material (Torres et al., 1997). No work has been reported on H. uncinatus.
3. Present study The resinous exudates of H. uncinatus (1.6 kg) and H. foliosus (125 g) were obtained by dipping fresh plant material in cold CH2 Cl2 for 15}20 s. The extracts were concentrated to solid residues (68.9 g from H. uncinatus, and 2.2 g from H. foliosus). The resinous exudate of H. uncinatus was fractioned by CC on silica gel, using pentane containing increasing amounts of CH2 Cl2 . The resinous exudates, and the fraction of the minor components of H. uncinatus were analyzed by GC/EI-MS using a FISONS MD-800, equipped with an HP Ultra-2 capillary column (12 m]0.20 mm). The temperature of the injector was 2703C, and the temperature of the column was progammed to start at 803C, for 2 min, followed by a rise to 3203C at 203C min~1. Helium was the carrier gas at 7 lb psi. The identi"cation of the compounds was achieved by comparison of the retention times with available standards, and by comparison of the MS data with the NIST library. Identity was accepted only when the correlation index was larger than 96%. From the resinous exudate of H. foliosus the following compounds were identi"ed. Monoterpenes: thujane; (Z)-a-ocimene; b-pinene; a-terpinene; m-cymene; triciclene; (E)-p-menth-2-en-1-ol; (Z)-p-menth-2-en-1-ol and (R)-p-menth-2-en-4-ol. Sesquiterpenes: d-ambrinol; and 1,2,3,4,5,6,7,8-octahydro-1,4-dimethyl-7-(1-methylethylidene)-azulene. Straight-chain hydrocarbons: C23 H48 ;C24 H50 ;C25 H52 ;C26 H54 ; C27 H56 ;C28 H58 ;C29 H60 ;C30 H62 ;C31 H64 ;C32 H66 and C33 H68 . Phenyl propanoids: (E)-cinnamic acid and (E)-cinnamic acid benzyl ester. Miscellaneous compounds: 2,3-dihydrobenzofuran and 2-isopropylphenol. In addition, compounds of: M` 164 (one compound); M` 218 (three compounds); M` 220 (one compound); M` 236 (one compound) and M` 302 (two compounds) were not identi"ed. From the resinous exudate of H. uncinatus two clerodane diterpenes of M` 362, and M` 378 were observed and not identi"ed. From the fraction of the minor components of the resinous exudate of H. uncinatus the following compounds were identi"ed. Sesquiterpenes: 4(15)-cubebene; a-copaene; 3,3,7,7-tetramethyl-5-(2-methyl-1-propenyl)-tricyclo[4,1,02,4]heptane and 4-isopropyl-1,6-dimethylnaphthalene. Straightchain hydrocarbons: C25 H52 ; C27 H56 ; C29 H60 ; C31 H64 and C33 H68 .
A. Urzu& a et al. / Biochemical Systematics and Ecology 28 (2000) 491}493
493
4. Chemotaxonomic and ecological signi5cance The structure of trichomes and the chemical composition of its exudates as well as the ultrastructure of the epicuticular wax layers, and also their chemical composition, constitute the "rst line of resistance (physical and chemical) of a plant against microorganisms and insects. In addition, volatile compounds a!ect the behaviour of some insects that can perceive them as kairomones or allomones and employ them to discriminate between host and non-host plants (Schoonhoven et al., 1998). These results indicate considerable di!erences between the chemical composition of the resinous exudates of H. foliosus and H. uncinatus. In H. uncinatus the exudate appeared quite simple and the important compounds were the two clerodane diterpenes of M` 362 and M` 378. In H. foliosus around 40 compounds show chromatographic peaks with relatively high intensities.
Acknowledgements This work was supported by FONDECYT(Chile) No 1990209 and by DICYT (Universidad de Santiago de Chile).
References Marticorena, C., Quezada, M., 1985. Gayana 42, 33. Schoonhoven, L. M., Jeremy, T., van Loon, J.J.A., 1998. Insect-Plant Biology from Physiology to Evolution. Chapman & Hall, London, p. 31}82. Silva, M., Sammes, P.G., 1973. Phytochemistry 12, 1755. Torres, R., Delle-Monache, F., Carbonell, P., Coll, J., LabbeH , C., Faini, F., 1997. XXI Symposium of Chilean Society of Chemistry, Osorno, Chile, p. 324. Tschesche, R., Dalhui, M., Sepulveda, S., Zilliken, F., Kirkel, A., Will, G., 1985. Liebigs Ann. Chem. 2465. Ulubelen, A., Ayonglu, E., Clark, E., Brown, G., Mabry, T., 1982. J. Nat. Prod. 45, 363.