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Xhmha pacmTe^bHoro cbipba. 2002. № 1. C. 31-36.
COMPOSITION OF ESSENTIAL OIL OF ELSHOLTZIA CILIATA (THUNB.) HYL. FROM THE NOVOSIBIRSK REGION, RUSSIA
© Elena A. Korolyuk,a Wilfried Konig,b Alexey V. Tkachevc*
a Novosibirsk Institute of Organic Chemistry, 630090, Novosibirsk, Russia b University of Hamburg, Hamburg, Germany c Novosibirsk State University, 630090, Novosibirsk, Russia
The research described in this paper was supported in part by The Scientific and Technical Foundation of the Ministry of Education of Russian Federation "Basic Research of the Higher School in Natural Sciences and the Humanities. Universities of Russia" (Grant UR.05.01.036 "Mono- and Sequiterpenoids from Plants: Structural and Chemical Study").
The authors thank Mr. Eugene S. Tatarov, Mr. Sergey N. Bizjaev, Drs. Andrey M. Chibiryaev and Alexander A. Alekseev from the Novosibirsk Institute of Organic Chemistry for their assistance in plant collection and essential oil preparation.
Four samples of essential oil of Elsholtzia ciliata (Thunb.) Hyl. from weed places of the suburb area of Novosibirsk (Russia) were studied by GC-MS. The main components were found to be perillene (2,1-3,9%), elsholtzia ketone (3,3-19,3%), a-dehydro-elsholtzione (2.0-5.7%), dehydro-elsholtzia ketone (66,1-72,4%), and humulene (1,5-3,8%).
Introduction
The genus Elsholtzia Willd. of the family Lamiaceae consists of 20-30 species from Asia and Africa. Several species of this genus are to be found in Europe and Russia, but only one species - annual plant E. Ciliata - has a broad habitat. Elsholtzia ciliata (Thunb.) Hyl. (syn.: E. patrinii (Lepechin) Garke, E. cristata Willd., Sidiritis ciliata Thunb. 1784, Fl. Jap.:245) was described from Japan. E. ciliata represents an adventitious element of European and Russian flora. Usually on the territory of Europe and Russia E. ciliata is a ruderal species or settles on degraded and grazed landscapes as well as on banks of rivers and on pebbles. E. ciliata is also cultivated as spicy and aromatic plant [1] and is often naturalizing [2, 3]. At present E. ciliata is growing wild in the Southern Siberia up to latitude 57° North [4].
There are several publications on chemical composition of essential oil of E. ciliata from natural habitat [59] as well as of samples cultivated in Europe. First the oil was studied in Japan at the beginning of the XX century by I. U. Asahina and I. Murayama and found to contain elsholtzia ketone as the main component [10]. Typical components of the E. ciliata are summarized in table 1. For the first time essential oil of E. ciliata from Siberia was documented in 1932 [11], without mentioning a composition of the oil. Further study demonstrated the composition of the oil from several points of the Tomsk region [12, 13]. So, although E. ciliata is growing on huge territory of the Southern Siberia in different climatic and ecological conditions, composition of the essential is known only for several separated point.
* The author to whom correspondence should be addressed: [email protected]
Materials and methods
Plant Material: Aerial parts of E. ciliata were collected in weed places of the suburb area of Novosibirsk. The species was identified and authenticated by a plant taxonomist. The voucher specimens are deposited at the Herbarium of the Central Siberian Botanical Garden (NS). We have studied 4 samples listed in table 1.
Table 1. Characteristic of the samples of Elsholtzia ciliata (Thunb.) Hyl. studied
Sample name Dates of collection, stages of ontogenesis Yield of the oil, %*
A August 2000, end of flowering - beginning of fruiting 0,3
B August 2001, one axis soot stage 0,2
C August 2001, stage of branching 0,1
D August 2001, end of flowering - beginning of fruiting 0,1
* calculated on a fresh grass.
Chemical analyses: Essential oil was prepared by steam distillation of the fresh grass (7,5 kg) in a field-distillation device made of stainless steel for 1,5 h to give yellowish oil (2,5 ml, d = 0,95 g/cm3, yield 0,035%).
Isolation and Identification of Compounds: GC/MS analysis was made on a quadruple MS (Hewlett-Packard MSD 5971) coupled to a HP 5890/II GC fitted with an HP-5 fused silica column (30 m x 0.25 mm, film thickness 0.25 |am, (5%)-diphenyl-(95%)-dimethylsiloxane copolymer). The carrier gas was He at 1 mL/min constant flow. The column was programmed from 50°C (2 min hold) to 280°C (5 min hold) at 4°C/min, injector and detector (MSD) temperatures were 280°C and 170°C respectively. MSD was operated at 70 ev. Sample injection: 1 |aL of a 1% solution in acetone, split 20 to 1. Mass range: 30 to б50 daltons. Oil components were identified by a combination of retention times and mass spectral data using mass spectra library Wiley275 (275000 records) and reference book [14]. Percentages were calculated from GC peak areas without using a correction factor.
Results and Discussion
The main constitutents of the sample studied were elsholtzia ketone (19%), dehydro-elsholtzia ketone (б8%), perillene (4%), humulene (3%), a-dehydro-elsholtzione (2%). This set of components is quite similar to those found for the Tomsk populations (See table 1, column [13]). The two populations of E. ciliata (from Novosibirsk and Tomsk) are immediate geographical neighbors, and they are regarded by Walter [15] to belong to the same «boreal» phytogeographical zone, although the other authors [1б] rank them to different zones: “boreal cold-temperate zone” (Tomsk population) and “forest-steppe of boreal zone” (Novosibirsk population).
Analysis of the data published by Japanese scientists [9] for composition of the oil for wild plants from natural (original) habitat and those for introduced plants originated from different geographical places but cultivated under the same conditions in Russia [1] allow one to assert that the composition of essential oil of E. ciliata is characteristic for this species and predetermined genetically. According to the data of the Japanese and Russian researchers, transformation of elsholtzia ketone into dehydro-elsholtzia ketone depends on activity of enzymatic system, which might be dependant on ecologo-phytocoenotic conditions [1].
At the moment, there are no enough data to bring to light any dependence of composition of the oil on specific conditions on growth except for dominating of the pair elsholtzia ketone/dehydro-elsholtzia ketone in most of the samples, except for the sample “La Chung” (See table 2, sample [8]) with rosefuran as the main component. Elsholtzia ketone/dehydro-elsholtzia ketone and rosefuran belong to the same structural type and could be related biogenetically. The only quite strange point of the literature data is the composition of essential oil from E. ciliata described in ref. [б] for the sample from Vietnam. As it is obvious from the table 1, this sample contains mainly limonene and geraniol-type compounds, which are only minor components in all the other samples E. ciliata. Probably, the plants material in the reference [б] does not seem to be assigned correctly.
Table 2. Composition of essential oil of the newly studied samples of Elsholtzia ciliata (Thunb.) Hyl. in comparison with the literature data
(The sample names are given in accordance with table 1; components of the newly studied samples are given in the order of increase of the retention time; references are given in square brackets)
New data Literature data
Phytogeographical zone: Forest-steppe Boreal Tropical Mediterranean, subtropical Tropical
Component name A B C D [13]a [13]b [8]c [8]d [9] [1]e [1]f [1]g [l]h [6]
Isovaleric acid 1,3-6
(Z)-3-hexen-l-ol 0,1
(E)-3-hexen-l-ol 0,5 0,1 0,3
1-hexanol 0,1
a-Pinene 0,1 0,1 1,7 0,2 0,5 tr, 0,26 0-0,3
Benz aldehyde tr,
Sabinene tr, 1,2 0-0,5
P-Pinene 0,1 0,1 0,2
Acetyl-methyfuran 3,1 0,2 1,0 0,15 0,25 tr, tr,
l-octen-3-ol 0,2 0,4 1,5 2,3 1,8 tr, 0,5 0,2 1,05 0,18 4,8-6,8
3-octanone tr, 0,1 2,1-2,7
P-Myrcene tr, 0,1
3-octanol 0,5 0,2 0,5 0,8-4,9 0-0,3
a-Phellandrene tr,
P-cymene 1,2 4,3 tr, 0,4 tr, 1,65 0,14 1,3-3,2
Limonene tr, tr, 0,1 0,03 10,9-14,2
P-Phellandrene tr,
1,8-cineol 0,1 1,6 0,3 1,1 4,6 0,8-3,5 tr, tr, 0,06 0,5-2,5
Benzeneacetaldehyde tr,
(E)-P-ocimene 0,3-1,1
y-Terpinene +
Acetophenone 1,9 0,2 0,4 1,2 tr,
Rosefuran (a-naginatene) 84,8 0,01 tr, 0,2 0,41
Linalool 0,1 0-3,5 0,1 0,07 0,33 0,1
Perillene 3,3 2,5 2,1 3,9
P-Naginatel 0,6-2,2 0,78
P-Thujone 1,43 1,06
Camphor 3,6 0,4-1,7
Lavandulol 0,2 0,1 0,2
Terpinen-4-ol 0,1 0-0,2
a-Terpineol 0,3 0-0,2
Ri-1195 0,1 0,1 0,1
Elsholtzia ketone 19,3 5,7 9,4 16,4 6,5 9,8 7,6 26,4-60,6 14,9 13,2 61,8 86
Composition of essential oil of Elsholtzia ciliata (Thunb.) 33
Table 2. (continued)
component name A B C D [13]a [13]b [8]c [8]d [9] [l]e [l]f [l]g [l]h [6]
3-octyl-acetat 0,4-1,7
a-Dehydro-elsholtzione 2,0 2,9 3,5 5,7
Dehydro-elsholtzia ketone 68,1 72,4 69,4 66,1 85 79,6 65,2 0-2,2 80,50 81 30,1 0,5
Methyl chavicol 0,8
Nerol 4,5-6,2
Citronellol 1-7,7
Neral 15,2-20,5
Geraniol 0,18 tr, 0,1 0,19 3,8
Geranial 19,5-26,5
Thymol 1,2
Eugenol 0,1
Neryl acetate 0,4-0,6
Geranyl acetate 0,9 0,35 0,64 0,56 0,1-0,3
P-Bourbonene 0,8 0,1 0,2 0,3
Isocaryophyllene tr,
Caryophyllene 0,5 0,5 0,4 0,2 2,1 1,2 tr, tr, 0,11 1,25 3,7^1,9
Humulene 2,7 3,8 2,5 1,5 0,3 0,45 1,19 7,1 0,4-0,8
(Z)-P-famesene 10,8-11,7
Germacrene D 0,5 0,2 0,2 0,2
Bicyclogennacrene 0,1 0,1
a-Famesene 0,1
P-Bisabolene 0,4-0,6
C15I124 0,9
Myristicine 0,1
8-Cadinene tr,
(Z)-nerolidol 0,6-2,1
(E)-nerolidol 0,2
Caryophyllene oxide tr, 1,2 1 0,4-0,6
Humulene-6,7-epoxide 0,1
Epi-a-cadinol + T-muurolol 0,1
a-Cadinol 0,1
Unidentified lactone 5,3-25,8
Comments:
a growing wild in the Tomsk region; b introduced, originated from the Tomsk population; c sample “La Chung”; d sample “Chung Than”; e introduced, originated from Europe (Leipzig); f introduced, originated from Byelorussia (Minsk); g introduced, originated from Russia (Vladivostok, Russian Far East); h growing wild in Georgia;
34 Elena A. Korolyuk, Wilfried Konig, Alexey V. Tkachev
In general, essential oils of the Asiatic genus Elsholtzia Willd. seem to be poorly investigated. For example, Chinese flora contains at least 33 species and 8 subspecies [17], and only for 11 species we could find the data on composition of essential oils. All these 11 species can be put into several chemo types according to the major constituents of the essential oils (see table 3). Several species (E. cicliata, E. stauntonii, E. splendens, E. strobilifera, E. rugulosa.) are placed to different groups of chemotypes. On the whole, it is not surprisingly because there are many plants demonstrating significant variability in composition of essential oils.
Table 3. Groups of chemotypes of species of the genus Elsholtzia.
Major components of the essential oils, references are given in square brackets
rosefuran, elsholzia keton, dehydroelsholzia keton linalool, geranyl acetat 1,8-cineol, perillen, terpenen-4-ol, caryophyllene oxide thymol
E. flava E. ciliata E. densa [18] [1,5, 7-9, 13, 19] [8]
E. stauntonii E. splendens E. blanda [20,21] [22] [24] [21] [23]
E. fmticosa [8]
E. myositnts E. incisa [25] [8]
E. strobilifera E. rugulosa [26] [271 [26] [271
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Received: September 01, 2001. Accepted: December 01, 2001.
