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138 Rev. Soc. Quím. Méx. Vol. 47, Núm. 2 (2003) Howard G. Pentes et al. 26: IR 3449, 1752, 1638 cm –1 ; 1 H NMR: δ 5.80 (dd, 1H, C 1 - H, J = 11, 17 Hz); 5.00 (m, 4H, C 2 -Ha,b, C 3 -Ha,b); 4.60 (dd, 1H, C 6 -H, J = 10, 11Hz); 2.20 (d, 1H, C 5 -H, J = 12 Hz); 1.79 (s, 3H, C 15 -CH 3 ); 1.46 (s, 3H, C 13 -CH 3 ); 1.10 (s, 3H, C 14 - CH 3 ); MS m/z (relative intensity) 250 (M + ) (0.3), 204 (M-46 + ) (0.4), 121 (M-129 + ) (3.2). 27: IR 3353, 1770, 1638 cm –1 ; 1 H NMR: 8.68 (s, 1H, OOH); 5.80 (dd, 1H, C 1 -H, J = 11, 17 Hz); 5.00 (m, 4H, C 2 -Ha,b, C 3 - Ha,b); 4.17 (dd, 1H, C 6 -H, J = 11 Hz); 2.32 (d, 1H, C 5 -H, J = 11 Hz); 1.78 (s, 3H, C 15 -CH 3 ); 1.39 (s, 3H, C 13 -CH 3 ); 1.08 (s, 3H, C 14 -CH 3 ); MS m/z (relative intensity) 266 (M + ) (0.5), 216 (M-50 + ) (0.5), 166 M-100 + ) (0.9). 28: IR 3466, 1708, 1638 cm –1 ; 1 H NMR: δ 5.76 (dd, 1H, C 1 -H, J = 11, 17 Hz); 4.90 (m, 4H, C 2 -Ha,b, C 3 -Ha,b); 4.10 (dd, 1H, C 6 -H, J = 11 Hz); 2.25 (s, 3H, C 13 -CH 3 ); 1.78 (s, 3H, C 15 -CH 3 ); 1.04 (s, 3H, C 14 -CH 3 ); MS m/z (relative intensity) 222 (M + ) (2.0), 204 (M-18 + ) (1.5), 189 (M-33 + ) (1.0), 161 (M-61 + ) (3.6). Oxidation of the enolate anion of dihydroparthenolide (4) with (-)-(2S,8aR)-(camphorylsulfonyl)oxaziridine. Dihydroparthenolide (4) (200 mg, 0.8 mmol) dissolved in 5 mL of dry THF was added slowly over 15 min by syringe to a stirred solution of 0.7 mL (1.04 mmol) of LDA in 5 mL of THF under argon at –70 °C. After stirring the solution for an additional 15 min, a THF solution of (-)-(2S,8aR)-(camphorylsulfonyl)oxaziridine (30, 370 mg, 1.6 mmol) was added to the reaction flask by syringe over a 5 min period at –70 °C. After 5 more min, the reaction was quenched with the addition of 5 mL of a saturated aqueous NH 4 Cl solution. The reaction mixture was extracted with diethyl ether (6 × 10 mL). The ether solution was dried over anhydrous Na 2 SO 4 , filtered, and the solvent was evaporated. Attempted precipitation of the unreacted oxaziridine and its reduced form, the imine, at –78 °C in diethyl ether only removed 60-70 % of these reagents. Repeated precipitations did not further purify the product. Dry column (silica gel) chromatography [19] was used to separate the product mixture eluting with DCM/acetone (9:1). The oxaziridine and the imine eluted in the very early fractions. Dihydroparthenolide (4) (58 mg) was recovered and 100 mg (66 %) of 11β-hydroxydihydroparthenolide (6) was isolated. The 1 H NMR data of compound 6 was identical with the data for the product isolated from the reaction of oxygen with the enolate anion of dihydroparthenolide (4). The norsesquiterpene ketone 13 and 11αhydroxydihydroparthenolide (5) were not detected. References 1. Fronczek, F.R.; Vargas, D.; Fischer, N.H.; Hostettmann, K. J. Nat. Prod. 1984, 47, 1036-1039. 2. Vargas, D.; Fronczek, F.R.; Fischer, N.H.; Hostettmann, K. J. Nat. Prod. 1986, 49, 133-138. 3. Hostettmann, K.; Marston, A. "Plants Used in African Traditional Medicines." in Folk Medicine. The Art and the Science, editor R.P. Steiner, 1986, ACS, Wash., D.C. pp. 111-124. 4. Vargas, D.; Younathan, E.S.; Fischer, N.H. Rev. Soc. Quím. Méx. 2001, 45, 159-162. 5. Picman, A.K. Biochem. System. Ecol. 1986, 14, 255-281. 6. Rodriguez, E.; Towers, G.H.N.; Mitchell, J.C. Phytochemistry 1976, 15, 1573-1580. 7. Collado, I.G.; Macías, F.A.; Massanet, G.M.; Molinillo, J.M.G.; R.-Luis, F. J. Org. Chem. 1987, 52, 3323-3326. 8. Davis, F.A.; Hague, M.J.; Ulatowski, T.G.; Towson, J.C. J. Org. Chem. 1986, 51, 2402-2404. 9. Gersmann, H.R.; Bickel, A.F. J. Chem. Soc. (B) 1971, 11, 2230- 2237. 10. Biloski, A.; Ganem, B. Synthesis 1983, 7, 537-538. 11. Bartlett, P.D.; Schaap, A.P. J. Amer. Chem. Soc. 1970, 92, 3223- 3226. 12. Rodriguez, A.A.S.; Garcia, M.; Rabi, J. Phytochemistry 1978, 17, 953-954. 13. Lu, T.; Fischer, N.H. Spectroscopy Letters 1996, 29, 437-448; references therein. 14. Parodi, F.J.; Fronczek, F.R.; Fischer, N.H. J. Nat. Prod. 1989, 52, 554-566. 15. Coll, J.C.; Bowden, B.F. J. Nat. Prod. 1986, 49, 934-936. 16. Lee, I.-Y. "New Sesquiterpene Lactones from the Genera Calea berlandiera (Asteraceae) and the Fragmentation Reactions of 1,3- Dihydroxyeudesmanolide Derivatives." Dissertation, Louisiana State University, 1983. 17. Rao, A.S.; Sadgopal, A.P.; Bhattacharyya, S.C. Tetrahedron 1961, 13, 319. 18. Govindachari, T.R.; Joshi, B.S.; Kamat, V.N. Tetrahedron 1965, 21, 1509-1519. 19. Loev, B.; Goodman, M. M. Chem. and Ind. 1967, 48, 2026-2032. Oxidation of enolate anion of dihydroparthenolide (4) with (+)-(2R,8aS)-(camphorylsulfonyl)oxaziridine. Dihydroparthenolide (4) (200 mg) was oxidized as described above with (+)- (2R,8aS)-(camphorylsulfonyl)oxaziridine 29. The product mixture was separated by dry column (silica gel) chromatography [19] eluting with DCM/acetone (9:1). Dihydroparthenolide (4) (56 mg) was recovered and 110 mg (72 %) of 11β-hydroxydihydroparthenolide (6) was isolated as the only product.
Revista de la Sociedad Química de México, Vol. 47, Núm. 2 (2003) 139-142 Investigación Chemical Composition and Antimicrobial Activity of the Essential Oils from Annona cherimola (Annonaceae) María Yolanda Ríos, 1* Federico Castrejón, 2 Norma Robledo, 2 Ismael León, 1 Gabriela Rojas, 3 and Víctor Navarro 3 1 Centro de Investigaciones Químicas de la Universidad Autónoma del Estado de Morelos. Av. Universidad 1001, Col. Chamilpa, Cuernavaca, Morelos, México, 62210. Phone +52 (777) 329-997 ext. 6024; Fax: +52 (777) 329-7997. E-mail: myolanda@buzon.uaem.mx 2 Centro de Desarrollo de Productos Bióticos del Instituto Politécnico Nacional. Carretera Yautepec-Jojutla Km. 8, Yautepec, Morelos, México, 62731. 3 Centro de Investigación Biomédica del Sur, Instituto Mexicano del Seguro Social. Argentina No. 1, Col. Centro, Xochitepec, Morelos, México, 62790. Recibido el 25 de febrero del 2003; aceptado el 23 de mayo del 2003 This paper is dedicated to Professor Alfonso Romo de Vivar Abstract. The chemical composition of the essential oils obtained by steam distillation of the fresh leaves, flowers and fruits from Annona cherimola was analyzed by means of Gas Chromatography-Mass Spectrometry (GC/MS). Sixty constituents were identified from the oils. While bicyclogermacrene, trans-caryophyllene and δ-amorphene were found to be the major constituents in the oil of the leaves; bicyclogermacrene, α-terpinolene and germacrene D were the major constituents in the oil of the flowers and β-pinene, α-terpinolene, β- fenchyl alcohol and α-pinene were the major constituents in the oil of the fruits. The in vitro antimicrobial activity of the three essential oils and of some of their major constituents against five Gram (±) bacteria and one fungus is reported. Keywords: Annona cherimola, essential oil, Gas Chromatography- Mass Spectrometry, bicyclogermacrene, trans-caryophyllene, α- amorphene, α-copaene, α-terpinolene, germacrene D, linalool, β- fenchyl alcohol, β-pinene, α-pinene. Resumen. La composición química de los aceites esenciales obtenidos por arrastre de vapor de las hojas, flores y frutos frescos de Annona cherimola fue analizada por Cromatografía de Gases-Espectrometría de Masas (GC/MS). Sesenta componentes fueron identificados en los aceites esenciales. Mientras que el biciclogermacreno, el trans-cariofileno y el δ-amorfeno se identificaron como los constituyentes mayoritarios en el aceite esencial de las hojas; el biciclogermacreno, el α-terpinoleno y el germacreno D fueron los constituyentes mayoritarios del aceite esencial de las flores, y el β-pineno, el α-terpinoleno, el alcohol β-fenchílico y el α-pineno fueron los principales componentes del aceite esencial de los frutos. La actividad antimicrobiana in vitro de los tres aceites esenciales y de algunos de sus contituyentes mayoritarios fue evaluada contra cinco bacterias Gram (+), (-) y un hongo. Palabras clave: Annona cherimola, aceite esencial, Cromatografía de Gases-Espectrometría de Masas, biciclogermacreno, trans-cariofileno, α-amorfeno, α-copaeno, α-terpinoleno, germacreno D, linalool, alcohol β-fenchílico, β-pineno, α-pineno. Introduction The Annonaceae family includes 80 genera and about 850 species distributed in tropical and subtropical areas of America, Africa and Asia. Only four genera of this family are of economic importance, and the genus Annona is one of them. Annona cherimola is highly appreciated for its exquisite fruits and for its use in traditional medicine in the treatment of skin diseases [1], tumors and cancer [2], and is reported to have antimicrobial and insecticidal properties [3,4]. Although several reports on the chemical composition of A. cherimola have been published [1-9], to date there are no reports on the chemical analysis of the essential oil of this species. We present here the chemical composition and the antimicrobial activity of the essential oils from the leaves, flowers and fruits of A. cherimola. Results and discussion CG/MS analysis of the three oils led to the identification of sixty constituents, which are listed in Table 1 along with their quantitative data. The identification of each component was based on a comparison of its mass spectrum with those contained in the HP CHEMSTATION-Wiley275.L Library. A high proportion of the essential oils is constituted by four main compounds: more than 40 % of the essential oil from the leaves is composed by bicyclogermacrene (18.20 %), transcaryophyllene (11.50 %), α-amorphene (7.57 %) and α- copaene (5.63 %); similarly, 34.02 % of the essential oil from the flowers corresponds to bicyclogermacrene (11.73 %), α- terpinolene (9.75 %), germacrene D (7.01 %) and linalool (5.53 %); finally, almost 45 % of the essential oil from the fruits corresponds to β-pinene (15.48 %), α-terpinolene (13.59
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Estudio fitoquímico de Salvia urua
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