Biochemical Systematics and Ecology 51 (2013) 240–242

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Biochemical Systematics and Ecology

journal homepage: www.elsevier.com/locate/biochemsyseco

Chemical constituents from Flourensia resinosa S.F. Blake

(Asteraceae)
María Yolanda Rios a, *, Samuel Estrada-Soto b, Virginia Flores-Morales c,
María Isabel Aguilar d
a
Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Avenida Universidad 1001, Col. Chamilpa, 62209
Cuernavaca, Morelos, Mexico
b
Facultad de Farmacia, Universidad Autónoma del Estado de Morelos, Avenida Universidad 1001, Col. Chamilpa, 62209 Cuernavaca,
Morelos, Mexico
c
Unidad Académica de Ciencias Químicas (LSAyB), Universidad Autónoma de Zacatecas Campus Siglo XXI, Carretera
Zacatecas-Guadalajara Km. 6.0, Ejido la Escondida, 98160 Zacatecas, Mexico
d
Facultad de Química, Departamento de Farmacia, Universidad Nacional Autónoma de México, Ciudad Universitaria, México, D.F. 04510,
Mexico

a r t i c l e i n f o a b s t r a c t

Article history: b-eudesmol (1), cryptomeridiol (2), ilicic acid (3), 5,7-dihydroxyflavone (chrysin, 4) and 7-O-
Received 6 May 2013 methyl-chrysin (tectochrysin, 5) were isolated as the major constituents from the acetone
Accepted 21 September 2013 extract of the aerial parts of Flourensia resinosa S.F. Blake (Asteraceae), along with flour-
Available online 8 October 2013
ensiadiol (6), spathulenol (7), p-acetophenol (8), lupeol (9), b-sitosterol (10), triacontanol (11)
and squalene (12). Based on previous studies, this chemical composition for F. resinosa is in
Keywords:
accordance with the chemical profile of other species of Flourensia. The profile of flavonoids,
Flourensia resinosa
sesquiterpenes and benzofurans may have chemotaxonomic significance within this genus.
Flavonoids
Eudesman sesquiterpenes
Ó 2013 Elsevier Ltd. All rights reserved.
Benzofuranes

1. Subject and source

Flourensia genus (Asteraceae) includes about 40 species of resinous shrubs characterized for its leaves surfaces covered
with a characteristic oil-fatty film. These plants grow in arid and semiarid regions throughout the American continent. Plants
belonging to Flourensia genus show important activities, like insecticidal (García et al., 2007), insect antifeedant (Diaz Napal
et al., 2009; Faini et al., 1997a), antibacterial (Joray et al., 2011), antifungal (Jasso de Rodríguez et al., 2012), herbicidal, in-
hibitors on the germination and in growth of plants (Diaz Napal et al., 2009; Silva et al., 2012) and as tyrosinase inhibitors
(Chiari et al., 2010). F. resinosa S.F. Blake (Asteraceae) is a dominant plant at the semi-desertic zone known as “Cerro del Señor”
(20
260 1000 N, 99
050 4200 W, 1915 m above sea level), Ixmiquilpan, Hidalgo, where its aerial parts were collected and identified
in October 27, 2007 by M.C. Ramiro Ríos-Gómez from the Facultad de Estudios Superiores Zaragoza, UNAM, México. A voucher
specimen (number 11839) was deposited at FESZ Herbarium, UNAM.

2. Previous work

F. resinosa is an evergreen shrub up to 2.5 m growing in semiarid environments in central regions of Mexico. As its name
suggests, this plant secretes large amounts of resin, which is deposited on its leaves and aerial parts. This resin contains

* Corresponding author. Tel.: þ52 777 329 7000x6024; fax: þ52 777 329 7997.
E-mail address: myolanda@uaem.mx (M.Y. Rios).

0305-1978/$ – see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.bse.2013.09.005
 M.Y. Rios et al. / Biochemical Systematics and Ecology 51 (2013) 240–242 241

Fig. 1. Chemical contents of the aerial parts from F. resinosa S.F. Blake.

several flavones and flavonols, being 5,7-dihydroxy-flavone (chrysin), 7-O-methyl-chrysin (tectochrysin), 3-methyl-kaemp-
ferol and apigenin its major constituents, while pinobankasin, galangin, 3-methyl-galangin, 7-methyl-galangin, 7-methyl-
apigenin, 40 -methyl-apigenin, 7,40 -dimethyl-apigenin, 3,7-dimethyl-kaempferol, 3,40 -dimethyl-kaempferol and 3,30 -
dimethyl-quercetin were characterized as minor constituents (Wollenweber and Yatskievych, 1985). Angelicate, senecioate
and tiglate flourensianol (benzopyrans), and the acetylenic compound 1,3-tridecadiene-5,7,9,11-tetrayne have also been
characterized from this plant (Bohlmann and Grenz, 1977), as well as the terpenes cryptomeridiol, isocostic acid methyl
esther, lupeol, 11-keto-epilupeol and resinona (3-ceto-lupen-12b-ol) (Rodriguez-Hahn and Rodriguez, 1973).

3. Present study

Compounds were purified by means of open column chromatography (CC) using silica gel 70:230 and flash chromatography
silica gel 230:400 mesh. The isolation procedures and purity of compounds were monitored by thin layer chromatography
(TLC) using silica gel 60 F254 aluminium sheets, visualizing with UV-light and subsequently spraying with (NH4)4Ce(SO4)4 in 2N
H2SO4. Dried aerial parts of F. resinosa (1.14 Kg) were extracted at room temperature with acetone. This solvent was eliminated
to dryness under vacuum to render 84.27 g of extract (7.4% yield). Fractionation of the acetone extract by open CC (silica gel,
100–230 mesh; 12.5 cm i.d.  30 cm) was performed with a step gradient of n-hexane-AcOEt 100:0 to 0:100, collecting 134
fractions of 500 mL. On the basis of TLC analysis, these fractions were pooled into five groups, namely G-1 (fractions 1–5,19.17 g,
n-hexane 100%), G-2 (fractions 6–27, 16.53 g, n-hexane:AcOEt 9:1), G-3 (fractions 28–61, 9.19 g, n-hexane:AcOEt 7:3), G-4
(fractions 62–104, 9.45 g, n-hexane:AcOEt 1:1) and G-5 (fractions 105–134, 10.39 g, AcOEt 100%). G-1 was constituted by fatty
acids, triacontanol (11) and squalene (12). Additional groups were subjected to flash column chromatography: G-2 (silica gel,
230–400 mesh; 6.0 cm i.d.  25 cm, eluent n-hexane 100% to n-hexane:AcOEt 80:20) collecting 141 fractions of 125 mL pooled
into four groups: G-2A affording fatty acids and 12, G-2B to yield b-sitosterol (10) and 11, G-2C to afford b-eudesmol (1, 286 mg,
0.34%), spathulenol (7,19 mg, 0.02%) and 10, and G-2D affording p-acetophenol (8, 34 mg, 0.04%); G-3 (silica gel, 230–400 mesh;
242 M.Y. Rios et al. / Biochemical Systematics and Ecology 51 (2013) 240–242

4.5 cm i.d.  15 cm, eluent n-hexane:AcOEt 90:10 to n-hexane:AcOEt 70:30) collecting 56 fractions of 100 mL to yield 1 (140 mg,
0.16%), tectochrysin (5) (827 mg, 0.98%) and lupeol (9, 36 mg, 0.04%); G-4 (silica gel, 230–400 mesh; 4.5 cm i.d.  15 cm, eluent
n-hexane:AcOEt 80:20 to n-hexane:AcOEt 60:40) collecting 82 fractions of 100 mL to afford chrysin (4) (153 mg, 0.06%), 5
(214.0 mg, 0.25%), and flourensiadiol (6, 22 mg, 0.026%) and G-5 (silica gel, 230–400 mesh; 4.5 cm i.d.  15 cm, eluent n-
hexane:AcOEt 80:20 to n-hexane:AcOEt 60:40) collecting 110 fractions of 100 mL to yield cryptomeridiol (2, 168 mg, 0.20%) and
ilicic acid (3) (76 mg, 0.09%). These compounds were identified by analysis of their polarimetry, IR, 1H and 13C NMR (1D and 2D
experiments) and MS spectra parameters and comparisons with their literature data.

4. Chemotaxonomic significance

From the acetone extract of the aerial parts of F. resinosa, b-eudesmol (1), cryptomeridiol (2), ilicic acid (3), chrysin (4) and
tectochrysin (5) were isolated as its major constituents, along with flourensiadiol (6), spathulenol (7), p-acetophenol (8),
lupeol (9), b-sitosterol (10), triacontanol (11) and squalene (12) (Fig. 1). Several of these compounds have been previously
isolated from species of Flourensia. However compounds 1, 7 and 10–12 were isolated for the first time from F. resinosa.
Species of Flourensia seem to be characterized by the occurrence of eudesman sesquiterpenes, principally costic acid and
alantolactone derivatives. Flavones, flavanones and 8-prenyl-flavonols are also distinctive of Flourensia. Chrysin, galangin,
apigenin, kaempferol, galetin and quercetin derivatives are the most commonly isolated flavones from these species, how-
ever, flavanones, 8-prenyl-flavanones and 8-prenyl-flavonols are also important components. 5-Acetyl-benzofuranes con-
stitutes a third group of compounds commonly found in species of Flourensia.
Eight of the twelve species chemically analyzed include sesquiterpenes. Flourensia heterolepis S.F. Blake is rich in 11,13-
dihydro-costic acid derivatives (Bohlmann and Jakupovic, 1979), while Flourensia thurifera (Molina) DC. and Flourensia
macrophylla S.F. Blake synthesizes costic acid derivatives (Bohlmann et al., 1984; Faini et al., 1997b). On the other hand,
Flourensia macrophylla is also rich in alantolactone derivatives. Sesquiterpene lactones are widespread in the subtribe
Ecliptinae, however, alantolactone, some derivatives and the corresponding related lactones have only been isolated from
Flourensia riparia Griseb. (Uriburu et al., 2004) and Flourensia macrophylla (Bohlmann et al., 1984).
All species of Flourensia synthesize flavonoids. Flavones have been found in Flourensia cernua DC., Flourensia resinosa and
Flourensia thurifera; flavanones in Flourensia oolepis S.F. Blake and Flourensia retinophylla S.F. Blake; and 8-prenyl-flavanones
and 8-prenyl-flavonols in Flourensia fiebrii S.F. Blake, Flourensia macrophylla and Flourensia riparia. At least two types of these
flavonoids are included in Flourensia campestris Griseb., Flourensia heterolepis, Flourensia ilicifolia Brandegee and Flourensia
retinophylla S.F. Blake.
Nine of the twelve species include benzofurans: Flourensia campestris, Flourensia cernua, Flourensia fiebrigii S.F. Blake,
Flourensia heterolepis, Flourensia macrophylla, Flourensia oolepis, Flourensia resinosa, Flourensia riparia, and Flourensia thurifera.
In Flourensia cernua, Flourensia heterolepis, Flourensia macrophylla, Flourensia riparia, and Flourensia thurifera benzofurans co-
occur with benzopyranes. The presence of these aromatic compounds has not been reported in Flourensia ilicifolia and
Flourensia retinophylla. The profile of sesquiterpenes, flavonoids and benzofuranes found in species of Flourensia differ and
may assist differentiate among the species.
Eudesman sesquiterpenes, flavonoids and benzofuranes have been also isolated from Flourensia resinosa (Rodriguez-Hahn
and Rodriguez, 1973; Bohlmann and Grenz, 1977; Wollenweber and Yatskievych, 1985). The chemical composition previously
reported for this species and the isolated metabolites in the present study are in agreement with the metabolic content of the
Flourensia genus.

Acknowledgements

This work was financially supported by CONACyT (Grant number 79584-Q). We are grateful to Enrique Salazar Leyva,
Gabriela Vargas Pineda, Victoria Labastida and María Medina Pastor for technical assistance.

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