FLAVOUR AND FRAGRANCE JOURNAL

Flavour Fragr. J. 2001; 16: 201203

DOI: 10.1002/ffj.978
Essential oils of Hypericum olympicum L. and Hypericum
perforatum L.
Branislav Gud zi c,
1
Sini sa Dordevi c,
2
Radosav Pali c
3
and Gordana Stojanovi c
3
*
1
D. D. Zdravlje Pharmaceutical and Chemical Company, 16 000 Leskovac, Yugoslavia
2
Faculty of Technology, 124 Bulevar Oslobodenja, 16 000 Leskovac, Yugoslavia
3
Department of Chemistry, Faculty of Science, 2

Cirila and Metodija, 18 000 Ni s, Yugoslavia
Received 22 June 2000
Revised 6 November 2000
Accepted 14 November 2000
ABSTRACT: The essential oil of Hypericum olympicum L. was analysed for the rst time and was compared
to the essential oil of Hypericum perforatum L. from the same location. Eighteen components were common for
both species. The main components of H. olympicim oil were (E)-anethole (30.7%) and -farnesene (12.4%), and
for H. perforatum oil they were -caryophyllene (14.2%) and 2-methyl-octane (13.1%). Copyright 2001 John
Wiley & Sons, Ltd.
KEY WORDS: Hypericum olympicum L.; Hypericum perforatum L.; Hypericaceae; essential oil composition
Introduction
Herbs belonging to the genus Hypericum L. are very sig-
nicant in pharmacology, particularly H. perforatum.
1
The oil maceration extract of H. perforatum owers was
described in the rst London pharmacopoeia (Pharma-
copoeia Londonesis, 1618). A great number of stud-
ies refer to the biologically active components isolated
from H. perforatum: hypericin,
25
pseudohypericin,
3,4
hyperforin,
6
adhyperforin,
7
procyandins,
8
xantones
9,10
and avonoids.
11
The essential oils are not used inde-
pendently in medicine. This is probably the reason
for the smaller number of studies on the composi-
tion of the essential oil of species belonging to this
genus. The distribution area of H. olympicum L. is lim-
ited to the Balkan
12
where it grows in sparse popula-
tions on dry spots and rocky grounds. H. perforatum
is widely spread in Europe, Asia, North Africa, New
Zealand and America.
13
Particularly rich deposits of this
herbal species are found in Germany, Ukraine and the
Balkan.
The aim of this paper was to determine the composi-
tion of the essential oil of wild-growing H. olympicum
for the rst time and to compare it with the com-
position of H. perforatum essential oil from the same
location.
*Correspondence to: G. Stojanovi c, Department of Chemistry, Faculty
of Science, 2

Cirila and Metodija, 18 000 Ni s, Yugoslavia. E-mail:
goca@lfak.lfak.ni.ac.yu
Experimental
The plant material was collected in 1998 on the Rujan
mountain, south-east Serbia, and dried for 10 days in a
cool place. Voucher specimens are deposited in Herbar-
ium Moesicum Doljevac (HMD; H. perforatum, No. 45;
H. olympicum, No. 49). Dried and ground drug was
hydrodistilled for 2.5 h using a Clevenger-type appara-
tus. The oil was extracted from the distillate with ether,
and then dried with anhydrous Na
2
SO
4
. The solvent was
removed by distillation at atmosphere pressure, and the
pure oil was kept at 4

C until analysis.
Identication Procedure
A Varian model 3700 Gas Chromatograph, equipped
with a 60 m 0.32 mm fused silica capillary column,
with a 0.3 m lm thickness of PTE-5 and FID was
used for GC measurements. The operating conditions
were as follows: temperature programme 60285

C at
4.3

Cmin and an injector and detector temperature of

250

C; the carrier gas was H

2
(2 ml/min). GCMS anal-
yses were performed on a Finigan Mat, model 8230,
equipped with fused silica PTE-5 capillary column,
30 m 0.25 mm, lm thickness 0.25 m. The carrier
gas was H
2
(2.5 ml/min) with the same temperature
programme as for analytical GC. Constituents were iden-
tied by comparison of their mass spectra to those
from MS libraries (Adams89, Nist92 and Amdis32) and
the results obtained were correlated with calculated and
Copyright 2001 John Wiley & Sons, Ltd.
202 B. GUD

ZI

C ET AL.
Table 1. Chemical composition of the H. olympicum
L. essential oil
Component Percentage Calculated RI

KI
15
Tricyclene 0.7 928 926
2,5,6-trimethyl-hepta-1,3,6-
triene
0.2 953
-Pinene 0.3 982 980
Myrcene 0.1 993 991
-Phellandrene t 1008 1005
-Terpinene t 1020 1018
p-Cymene t 1027 1026
Limonene 0.3 1033 1031
Ocimene 0.2 1050 1050
Fenchone 0.5 1090 1087
Undecane 0.3 1100 1100
-Terpineol t 1178 1177
Estragole 0.5 1195 1195
Carvone 4.2 1245 1242
(E)-Anethole 30.7 1285 1283
-Cubebene 1.3 1353 1351
-Ylangene 0.6 1373 1372
-Copaene 2.7 1378 1376
-Bourbonene 0.1 1387 1384
-Cubebene 0.7 1389 1390
-Gurjunene 0.1 1411 1409
-Caryophyllene 2.1 1419 1418
-Gurjunene 1.1 1431 1432
Patchoulene 0.5 1440 1456
Bicyclosesquiphellandrene 1.8 1448
-Caryophyllene 0.3 1456 1454
-Farnesene 12.4 1461 1458
-Muurolene 7.5 1475 1477
Germacrene D 4.3 1481 1480
Eremophyllene 0.7 1490 1491
-Muurolene 1.5 1450 1499
-Farnesene 0.5 1511 1508
-Cadinene 4.2 1515 1513
-Bisabolene t 1520 1515
Calamenene 0.4 1522 1521
-Cadinene 8.7 1525 1524
Cadina-3,9-diene 0.7 1529
Cadina-1,4-diene 0.7 1535 1532
Muurola-4,9-diene 0.7 1540
-Calacorene 0.3 1546 1542
Germacrene B 0.7 1560 1556
-Calacorene t 1565 1563
Spathulenol 0.4 1580 1576
(1-epi)-Cubenol 0.1 1630 1627
-Elemene t 1635
(epi -)-Cadinol 0.2 1642 1640
(epi --Muurolol t 1645 1641
-Cadinol 0.5 1658 1653
-Bisabolol 0.2 1690 1683

Determined from curve logarithm of corrected retenton timeretention

index.
t, less than 0.1%.
Adams retention indices.
14,15
Area percent was obtained
electronically from the GCFID response without the
use of an internal standard or correction factors.
Results
The oil content of the aerial dried parts of H. olympicum
was 0.45% and for H. perforatum 0.32%. Both oils iso-
lated were yellow, with a specic odour. The previously
determined content of the H. perforatum
16
oil was the
Table 2. Chemical composition of the H. perforatum
L. essential oil
Component Percentage Calculated RI

KI
15
2-Methyl-octane 13.1 858
n-Nonane 1.4 900 900
-Pinene 2.2 982 980
-Myrcene 0.3 993 991
n-Decane 0.2 1000 1000
p-Cymene 0.8 1024 1022
(E)--Ocimene 0.3 1041 1040
2-Methyl-decane 7.9 1062
p-Cymenene 0.2 1090 1089
n-Undecane 3.9 1100 1100
Campholenal 0.1 1126 1125
iso-Nonanol 0.4 1173 1171
(E)-Pinocarveol 0.4 1139 1139
Pinocarvone 0.1 1164 1162
4-Terpineol 0.5 1180 1177
p-Cumen-8-ol 0.2 1185 1183
-Terpineol 0.3 1191 1189
Myrtenol t 1195 1194
Carvone 0.1 1243 1242
Geraniol t 1257 1255
2-Methyl-dodecane 4.5 1267
(E)-Anethole 0.1 1285 1283
n-Tridecane 1.3 1300 1300
-Longipinene 0.4 1352 1351
-Copaene 0.2 1380 1376
-Bourbonene 0.2 1386 1384
-Caryophylene 14.2 1424 1418
-Gurjunene 0.2 1436 1432
-Himachalene 0.4 1450 1447
-Caryophyllene 0.4 1456 1454
-Farnesene 3.2 1462 1458
-Muurolene 3.5 1480 1477
-Farnesene 0.1 1510 1508
-Cadinene 0.5 1518 1513
-Cadinene 0.5 1530 1524
Nerolidol 0.8 1570 1564
3-(Z)-Hexenyl-benzoate 0.5 1572 1570
Spathulenol 4.5 1580 1576
Humulene-epoxide 4.2 1610 1606
1-epi-Cubenol 0.7 1631 1627
n-Tetradecanol 4.1 1680 1676
Benzyl benzoate 0.1 1768 1762
n-Hexadecanol 0.4 1882 1879
n-Nonadecane 0.2 1900 1900

Determined from curve logarithm of corrected retenton timeretention

index.
t, Less than 0.1%.
same as for the H. perforatum sample examined and
was very close to content of the leaf essential oil of
H. perforatum from India.
17
Results of GC and GC-MS are given in Tables 1
and 2. Forty-nine components of H. olympicum oil
were identied, representing 94% of the oil. The four
most abundant components [(E)-anethole, -farnesene,
-cadinene and -muurolene] represented 59.3% of the
oil. The component with the highest content in H. olyim-
picum was anethole (30.7%). It was not registered in
the previously examined H. perforatum oil.
16
We have
found it in a very low level in our H. perforatum
oil (0.1%).
Forty-four components of H. perforatum oil were
identied, representing 90.7% of the oil. Most of the
Copyright 2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 201203
ESSENTIAL OILS OF HYPERICUM SPP. 203
components were represented in small approximate per-
centages in the oil. Signicant amounts of alkanes,
2-methyl-octane (13.1%) and 2-methyl-decane (7.9%),
were observed. -Caryophyllene was the main compo-
nent in the previously examined oil of H. perforatum
16
(48.5%), while it was considerably lower in our H. per-
foratum oil (14.2%) and in H. olympicum (2.1%).
The contents of -farnesene in the oils of H. olym-
picum L. and H. perforatum L. previously examined
were similar (12.4% and 12.1%), while in our H. per-
foratum sample it was considerably lower (3.2%).
There were 18 common components for the H. olym-
picum L. and H. perforatum L oils. Comparing the
composition of the leaf essential oil of H. perforatum
from India
17
and the examined essential oil of the aerial
parts of H. perforatum (leaves, owers and stems), it can
be seen that:
-Pinene was the main component in the oil from
India (67.3%), which was not registered in the oil
from Serbia.
-Caryophyllene was the main component (14.2%) in
the oil from Serbia, while its content in the leaf oil
from India was considerably lower (5.2%).
There were 15 common components from the oils
from India and Serbia.
The observed differences in the composition of the
examined essential oils of H. olympicum and H. per-
foratum from the same location are very likely geneti-
cally determined. On the other hand, there are signicant
differences in the composition of oils originating from
different populations of the same species.
16
Further investigations of the composition and bio-
logical activity of essential oils of a larger number of
different populations of the same species, along with
more data about different species of the genus Hyper-
icum, could be helpful in chemotaxonomy and might
possibly be considered for eventual medical use.
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Copyright 2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 201203