[P-075]

[P-075] VOLATILE COMPOUNDS OF TWO MEMBERS OF Inula verbascifolia GROUP:
I. verbascifolia subsp. parnassica AND I. verbascifolia subsp. methanea

Olga TZAKOU¹, Alexandra PETROPOULOU¹,
Theophanis CONSTANTINIDIS² and Catherine HARVALA¹
¹Department of Pharmacognosy, School of Pharmacy, University of Athens, Athens 15771, Greece
²Institute of Botany, Department of Biology, University of Patras, Gr-26500, Patras

ABSTRACT

Hydrodistilled oils from aerial parts of two Greek Inula species (I. verbascifolia subsp. parnassica and I. verbascifolia subsp. methanea) were subjected to GC/MS analyses. More than 90 compounds were identified from the oils. The major oil constituents were found to be methyl salicylate (23.4%) and cis-chrysanthenol (17.3%) for I. verbascifolia subsp. parnassica. The oil of I. verbascifolia subsp. methanea was made up mainly of sesquiterpenoids of which epi-a-cadinol (19.5%) and (Z)-nuciferol (16.6%) were the main constituents.

INTRODUCTION

The genus Inula, from the tribe Inulae, has often been chemically investigated. Sesquiterpene lactones and flavonoids are typical in the genus (Harborne 1977).

The chemical composition of the oils of some Inula species, especially I. helenium have been investigated [Perez-Alonso et al. (1996), Bourrel et al. (1993)].

Our present contribution deals with the volatile compounds of two Greek endemic taxa: I. verbascifolia subsp. parnassica (Boiss. & Heldr.) Tutin (= I. parnassica Boiss. & Heldr.) and I. verbascifolia subsp. methanea (Hausskn.) Tutin (= I. methanea Hausskn.).

Both taxa are distributed in Peloponnisos and Sterea Ellas, while I. verbascifolia subsp. parnassica is also found on the island of Evia. The main morphological characters that are used to distinguish between them include leaf indumentum, number and shape of upper bracts and involucral bracts and also, size of ligules (Ball and Tutin 1976).

MATERIALS AND METHODS

Plant material

Wild growing Inula verbascifolia plants were collected during anthesis. Specimens were identified by Dr.Th.Constantinidis. Voucher specimens have been deposited at the Herbarium of the Institut of Botany, University of Patras (UPA).

Inula verbascifolia subsp. parnassica : A= Mt. Parnassos, County Biotia, 1100 m (July 1999).

Inula verbascifolia subsp. methanea: B= Mt. Parnes, County Attiki, 800 m (June 1998).

Sample Analysis

Dried aerial parts from each population were cut into small pieces just before subjected to hydrodistillation for 3h using a Clevenger-type apparatus. Yields were 0.25% (v/w) for I. verbascifolia subsp. parnassica and 0.16% (v/w) for I. verbascifolia subsp. methanea.

The oils were analyised by GC/MS using a Hewlett Packard 6890/5973 system operating in EI mode, fitted with a HP-5MS capillary column. GC oven initial temperature was 60°C and programmed to 280°C at a rate of 3°C/min. Library search was carried out using Wiley, NIST/NBS MS libraries and from the best match of their mass spectra with those of the literature (Adams 1995).

RESULTS AND DISCUSSION

The list of constituents identified in the aerial parts of I. verbascifolia subsp. parnassica and I. verbascifolia subsp. methanea is shown in Table 1. The results show that there are interesting differences in the composition among the subspecies studied. These dissimilarities can be of high chemotaxonomic importance.

The oil of I. verbascifolia subsp. parnassica was characterized by the presence of high concentration of esters, with methyl salicylate being the major component (23.4%). Oxygenated sesquiterpenes constitued only 3.3% of the oil. In the sesquiterpene hydrocarbons fraction the main component was (E)-caryophyllene (13.2%). cis-Chrysanthenol (17.3%) and linalool (7.1%) were the monoterpenes which were present in appreciable amounts.

In the oil of I. verbascifolia subsp. methanea linalool (21.2%), epi-a-cadinol (19.5%) and (Z)-nuciferol (16.6%) were the major representatives of monoterpenes the first and sesquiterpenes the others. In esters fraction the main component was (Z)-3-hexenyl benzoate (6.4%).

Table 1. Percentage composition of the oils of Inula verbascifolia subsp. parnassica
and I. verbascifolia subsp. Methanea

Components	KI	Sample A	Sample B
(E,E)-2,4-heptadienal	988	t	-
p-cymene	1011	-	t
limonene	1015	-	t
1,8-cineole	1018	-	t
Benzene acetaldehyde	1029	t	0.7
(E)-b-ocimene	1033	-	t
g-terpinene	1044	t	-
(Z)-linalool oxide	1058	-	t
(E)-linalool oxide	1073	-	0.7
terpinolene	1078	t	-
linalool	1088	7.1	21.2
nonanal	1091	1.2	0.5
p-menth-3-en-8-ol	1134	t	-
(Z)-2-nonenal	1145	t	-
chrysanthenol	1149	17.3	-
ethyl benzoate	1156	t	-
terpin-4-ol	1163	0.9	-
octanoic acid	1170	t	-
a-terpineol	1175	t	1.9
methyl salicylate	1178	23.4	t
dodecane	1185	t	-
decanal	1191	1.1	0.8
b-cyclocitral	1205	t	t
nerol	1213	-	t
cis-3-hexenyl-2-methyl butyrate	1220	-	t
neral	1224	-	t
geraniol	1238	t	1.8
geranial	1244	-	t
nonanoic acid	1257	-	t
thymol	1276	-
(E,Z)-2,4 decadienal	1277	t	t
carvacrol	1288	-	t
undecanal	1290	1.2	-
(E,E)-2,4-decadienal	1299	t	t
(Z)-3-hexenyl tiglate	1307	t	-
butyl benzoate	1310	2.5	-
hexyl tiglate	1314	t	-
(Z)-3-hexenyl hexanoate	1323	-	t
(Z)-methylpropyl octanoate	1331	t	-
eugenol	1339	t	t
2-dodecen-1-al	1346	t	t
cyclosativene	1348	t	t
decanoic acid	1355	t	t
a-copaene	1358	t	t
(E)- b-damascenone	1367	2.1	t
(E,Z)-nepetalactone	1370	-	t
(E)-jasmanone	1374	-	t
(Z)-jasmanone	1381	t	t
iso-italicene	1385	-	t
methyl eugenol	1388	t	t
dodecanal	1392	1.0	-
(E)-b-damascone	1396	-	t
(E)-caryophyllene	1400	13.2	t
b-gurjunene	1411	t	-
2-methyl butyl benzoate	1420	t	-
aromadendrene	1426	t	-
geranyl acetone	1435	-	t
a-humulene	1435	1.9	0.8
allo-aromadendrene	1442	t	1.6
a-acoradiene	1448	-	t
g-gurjunene	1455	-	t
g-muurolene	1458	t	t
g-curcumene	1462	-	1.3
germacrene D	1463	3.8	-
ar-curcumene	1465	-	1.3
(E)-b-ionone	1468	4.4	t
epi-cubebol	1476	-	t
bicyclogermacrene	1478	0.9	-
a-muurolene	1482	t	t
tridecanal	1494	5.3	-
g-cadinene	1495	t	2.5
d-cadinene	1504	2.6	2.9
a-calacorene	1524	t	t
(E)-nerolidol	1547	t	-
(Z)-3-hexenyl benzoate	1552	4.4	6.4
Germacrene D-4-ol	1556	t	-
Hexyl benzoate	1558	2.4	t
caryophyllene oxide	1563	3.3	2.8
guaiol	1581	-	2.6
10-epi-g-eudesmol	1599	-	t
a-acorenol	1607	-	t
g-eudesmol	1611	-	t
epi-a-cadinol	1624	-	19.5
hinesol	1625	-	t
epi-a-muurolol	1626	t	-
a-muurolol	1632	t	9.4
b-eudesmol	1636	t	-
a-cadinol	1640	t	4.7
14-hydroxy-9-epi-(E)-caryophyllene	1673	t	-
(Z)-nuciferol	1711	-	16.6
(E)-nuciferol	1734	-	t
benzyl benzoate	1747	t	t
tetradecanoic acid	1749	t	-
pentacosane	2500	t	-
Total		100	100

t=trace<0.01%
LITERATURE

Adams R.P.(1995): Identification of Essential Oil Components by Gas Chromatography and Mass Spectrometry, Allured Publ. Corp., Carol Stream, IL, USA.
Ball P.W. and Tutin T.G. (1976): Inula L. In: Flora Europaea. Edits., Tutin T.G., Heywood V.H., Burges N.A., Moore D.M., Valentine D.H., Walters S.M. and Webb D.A., vol. 4. pp 133-136, Cambridge University Press, Cambridge.
Bourrel C., Vilarem G. and Perineau F. (1993): Chemical analysis, bacteriostatic and fungistatic properties of the essential oil of Elecampane (Inula helenium L.), J.Essent.Oil Res., 5, 411-417.
Harborne J.B.(1977): In: The Biology and Chemistry of the Compositae. Edits., Heywood V.H.,. Harborne J.B and Turner B.L., p. 603, Academic Press, London.
Perez-Alonso M.J., Velasco-Negueruela A., Duru M.E., Harmandar M. and Garcia Vallejo M.C. (1996): Composition of volatile oil from the aerial parts of Inula viscosa (L.) Aiton., Flav. Fragr. J., 11, 349-351.

[P-075]