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FLAVOUR AND FRAGRANCE JOURNALFlavour Fragr. J. 2003; 18: 3638Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/ffj.1147

Essential oil composition of Achillea santolina L. andAchillea biebersteinii Afan. collected in Jordan

Ammar Bader,1 Guido Flamini,2* Pier Luigi Cioni2 and Ivano Morelli2

1 Faculty of Pharmacy, Al-Zaytoonah University of Jordan, PO Box 130 (11733), Amman, Jordan2 Dipartimento di Chimica Bioorganica e Biofarmacia, Via Bonanno 33, 56126 Pisa, Italy

Received 4 January 2002

Revised 15 May 2002

Accepted 10 June 2002

ABSTRACT: The essential oils of Achillea santolina L. and A. biebersteinii Afan., collected in Jordan, have

been studied. The former has never been previously investigated, while the latter evidenced from a literature

survey a high variability. The two oils were quite different: A. santolina oil showed mainly 1,8-cineole, camphor,

4-terpineol and trans-carveol, while A. biebersteinii oil contained cis-ascaridole, p-cymene, carvenone oxide andcamphor among its principal constituents. This is the second report of carvenone oxide from a natural source.

Copyright 2002 John Wiley & Sons, Ltd.

KEY WORDS: Achillea santolina; Achillea biebersteinii ; Asteraceae; 1,8-cineole; camphor; cis-ascaridole; p-

cymene; carvenone oxide

Introduction

Achillea santolina L. and Achillea biebersteinii Afan.,

are two species typical of arid environments of Jordan,

but they are also able to colonize Euro-Asiatic habitats

with a more humid and cold climate.1A. santolina is a perennial herb, 1530 cm high,

woolly-canescent, with stems erect to ascending, sim-

ple or branched, leafy up to the inflorescence; the leaves

are narrow, linear, green, pinnatisect into minute trans-

versely and rather loosely imbricate segments, each

segment divided into three ovate-orbicular spinulose-

denticulate lobules; The heads are radiate, in compound

corymbs; the flowering period is MarchApril and the

plant grows on the edge of cultivated lands.

A. biebersteinii is a perennial herb, 3060 cm high;

villose, stems erect, simple or branched from the base;

leaves up to 10 cm, oblong-lanceolate in outline, pinna-tisect into numerous narrow segments, segments divided

into minute linear-lanceolate mucronate lobes; the heads

are radiate, in large dense compound corymbs; involucre

4 5 mm, oblong-ovoid; flowering period, April May;

grows on clay soils.

In Jordan and Iraq infusions of the leaves of A.

santolina are used for intestinal colics, dysentery and

as a carminative;2 the plant is also considered to be

insect-repellent2,3 and its essential oil has insecticide

* Correspondence to: Guido Flamini, Dipartimento di Chimica Bioor-ganica e Biofarmacia, Via Bonanno 33, 56126 Pisa, Italy.

E-mail: flamini@farm.unipi.itIn memory of Professor Serena Catalano (19452002).

properties.4 A. biebersteinii is used in Jordan because

of its carminative properties,2 while in Turkey the plant

is also used for abdominal pain, stomach-ache and for

wound healing.5

Many previous phytochemical studies have identified

in the aerial parts of A. santolina flavonoids6 9 andsesquiterpene lactones.1012 Moreover, this species also

produces alkaloids, saponins, tannins, resins, sterols, car-

bohydrates and an unidentified volatile oil.13 Pharmaco-

logical studies of A. santolina showed its antimicrobial2

and antiflammatory14 activities. Many sesquiterpene lac-

tones have been reported from A. biebersteinii,10,1517

while only one paper reported the presence of four

flavonols, a hydrocarbon, a ketone and an alcohol.17

Rustaiyan et al.18 studied the essential oil obtained from

the leaves and flowers of Iranian plants of A. bieber-

steinii, which contained mainly ascaridole 37%), piperi-

tone (17%) and camphor (12%). Plants collected intwo stations in Turkey19 showed different compositions

of their essential oils: near Ankara the principal con-

stituent was piperitone (49.9%), while near Erzurum

1,8-cineole (29.9%) and camphor (17.3%) were the main

constituents. Again in Turkey, Chialva et al.20 identi-

fied, as principal constituents of the essential oil of A.

biebersteinii, 1,8-cineole (46.2%), camphor (17.6%), -

terpineol (8.2%) and borneol (3.4%). Abbassoglu and

Kuesmenoglu21 demonstrated the antibacterial and anti-

fungal properties of the essential oil of A. biebersteinii.

Recently, another study on this species collected in

Iran showed piperitone (45.9%) and 1,8-cineole (17.6%)among the main constituents of the essential oil.29

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ESSENTIAL OIL OF ACHILLEA SPP. 37

Since the composition of the essential oil of A.

santolina has never been previously investigated and

several publications revealed a high variability of the

essential oil of A. biebersteinii, we have studied these

two species, collected in the same habitat in Jor-

dan, to contribute to the chemical knowledge of this

genus.

Materials and Methods

The flowering aerial parts of A. santolina L. and A.

biebersteinii Afan. were collected in Naur (Jordan) at

the end of April 1999 in a Mediterranean climate.

Voucher specimens have been deposited in the Herbar-

ium of the University of Jordan under Accessiar Nos

J21 and J22, respectively. The plant material was driedin air and in the shade until constant weight was

attached and two samples (100 g each), coarsely ground,

were hydrodistilled in a Clevenger-like apparatus for

2 h.

GC analyses were accomplished with a HP-5890

Series II instrument equipped with HP-WAX and HP-

5 capillary columns (30 m 0.25 mm, 0.25 m film

thickness), working with the following temperature pro-

gram: 60 C for 10 min, rising at 5 C/min to 220 C;

injector and detector temperatures, 250 C; carrier gas,

nitrogen (2 ml/min); detector, dual FID; split ratio,

1 : 30; injection of 0.5 l). The identification of the

components was performed, for both the columns, by

comparison of their retention times with those of pure

authentic samples and by means of their linear retention

indices (LRIs) relative to the series of n-hydrocarbons.

The relative proportions of the essential oil constituents

were percentages obtained by FID peak-area normaliza-

tion, all relative response factors being taken as 1.

GC EI MS analyses were performed with a Var-

ian CP-3800 gas chromatograph equipped with a DB-5

capillary column (30 m 0.25 mm; coating thickness

0.25 m) and a Varian Saturn 2000 ion trap mass detec-

tor. Analytical conditions: injector and transfer line tem-

peratures, 220 and 240 C, respectively; oven temper-ature programmed from 60 C to 240 C a t 3 C/min;

carrier gas, helium at 1 ml/min; injection of 0.2 l (10%

hexane solution); split ratio, 1 : 30. Identification of the

constituents was based on comparison of the reten-

tion times with those of authentic samples, comparing

their linear retention indices relative to the series of

n-hydrocarbons, and on computer matching against com-

mercial (NIST 98 and ADAMS) and home-made library

mass spectra built up from pure substances and compo-

nents of known oils and MS literature data. 2227 More-

over, the molecular weights of all the identified sub-

stances were confirmed by GCCIMS, using MeOHas CI ionizing gas.

Results and Discussion

The essential oil yields of A. santolina and A. bieber-

steinii were 0.18% and 0.20% (w/w), respectively, and

their compositions are reported in Table 1. Fifty-three

compounds were identified, accounting for 85.1% and

95.4%, respectively, of the total essences. The missing

Table 1. Essential oil composition of Achillea santolinaand A. biebersteinii

Constituents K.I. A. santolina A. biebersteinii

(E)-2-Hexenal 854 0.1Isopentyl acetate 876 0.1 2-Methylbutyl acetate 880 0.2 Santolina triene 909 1.3 -Thujene 932 0.9 0.2-Pinene 940 0.6 0.4Camphene 954 1.2 1.2

Sabinene 977 0.9 0.1-Pinene 981 0.4 0.12,3-Dehydro-1,8-cineole 992 0.5 Yomogi alcohol 1000 0.3 -Phellandrene 1006 0.1-Terpinene 1019 1.2 1.8p-Cymene 1027 3.5 31.6Limonene 1032 1.1 0.11,8-Cineole 1034 17.6 0.8-Terpinene 1063 2.1 0.3cis-Sabinene hydrate 1070 2.1 0.1Artemisia alcohol 1084 0.1 Terpinolene 1090 0.6 tra

p-Cymenene 1091 0.1Linalool 1100 1.0 0.2trans-Sabinene hydrate 1101 2.7

Isopentyl isovalerate 1105 0.6 cis-p-Menth-2-en-1-ol 1123 0.7 2.0trans-p-Menth-2-en-1-ol 1142 0.5 1.2Camphor 1145 17.5 4.7Borneol 1168 1.0 1.04-Terpineol 1179 7.0 0.8p-Cymen-8-ol 1185 0.6-Terpineol 1191 2.5 trans-Piperitol 1208 0.2 0.6trans-Carveol 1220 4.8 0.1cis-Ascaridole 1239 36.2Carvone 1245 1.4 Piperitone oxide 1253 1.2Carvenone oxide 1261 6.4Isobornyl acetate 1287 0.4Lavandulyl acetate 1289 1.4 Thymol 1292 0.8 0.8

Carvacrol 1300 1.3trans-Carvyl acetate 1338 0.9 Methyl-p-anisate 1373 0.2 -Caryophyllene 1420 0.4 Germacrene D 1482 0.6 0.5-Selinene 1487 0.2 0.1Bicyclogermacrene 1496 0.3 0.1-Bisabolene 1510 0.2 -Cadinene 1525 0.3 Spathulenol 1578 1.1 0.1Caryophyllene oxide 1583 1.1 T-cadinol 1642 0.6 -Eudesmol 1650 1.6 -Bisabolol 1685 0.8

Total 85.1 95.4

Yield (w/w) 0.18 0.20

a tr, trace amounts (

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38 A. BADER ET AL.

15% for A. santolina was distributed on more than 25

minor peaks (only three peaks comprised 1.11.5%).

The main constituents of the essential oil of A. san-

tolina (Table 1) were 1,8-cineole (17.6%) and camphor

(17.5%), followed by 4-terpineol (7.0%), trans-carveol

(4.8%), p-cymene (3.5%), trans-sabinene hydrate (2.7%)

and -terpineol (2.5%). Other monoterpenes and ses-

quiterpenes, either hydrocarbons or oxygenated, were

present in smaller amounts.

From a literature survey, a high variability of the

essential oil composition of A. biebersteinii was evi-

denced.1618,29 However, all the main constituents were

more or less oxygenated p-menthane or camphane deri-

vatives. The geographic origin of the plant seems to be

irrelevant for the essential oil composition, so different

chemotypes could be hypothesized, all based on different

combinations of ascaridol, piperitone, camphor and 1,8-

cineole.The essential oil of A. biebersteinii from Jordan was

found to be rich in ascaridol (36.2%), p-cymene (31.6%),

carvenone oxide (6.4%) and camphor (4.7%). Because

the high amounts of ascaridol, its composition was

found to be fairly similar to that obtained from one

of the Iranian samples,18 but it also contained a high

percentage of p-cymene, totally absent in the Iranian

oil; moreover, it did not contain piperitone at all. The

essential oil contained also piperitone oxide and its

rare isomer carvenone oxide (3,4-epoxy-p-menth-2-one).

This is the second report of the presence in nature of

the latter compound, identified until now only in theessential oil of Ledum palustre var. nipponicum.28

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Copyright 2002 John Wiley & Sons, Ltd. Flavour Fragr. J. 2003; 18: 3638