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26Journal of Siberian Federal University. Chemistry 4 (2014 7) 487-493
УДК 547.913:582.099
Chemical Composition of the Essential Oil from Fruits of Heracleum dissectum L. Growing in Krasnoyarsk Krai
Alina M. Shushenacheva and Aleksandr A. Efremov*
Siberian Federal University 79 Svobodny, Krasnoyarsk, 660041 Russia
Received 06.10.2014, received in revised form 21.10.2014, accepted 16.12.2014
The constituents of the essential oil from fruits of Heracleum dissectum L. obtained by steam distillation were determined by GS-MS method. It was found that the essential oil from fruits of Heracleum dissectum L. growing in Krasnoyarsk region of Russia contains more than 47 compounds; 44 compounds representing 98.6 % of the oil were identified. The major constituents of the oil were vinylcyclohexane (4.52 %), octyl acetate (58.5 %), 2-methyloctyl propanoate (10.81 %) and ^-alanine (9,47 %). Five fractions of the essential oil were obtained. It was found that compositions of all five fractions are different.
Keywords: essential oil, GS, GS-MS, Heracleum, composition.
Компонентный состав эфирного масла корней борщевика рассеченного, произрастающего в Красноярском крае
А.М. Шушеначева, А.А. Ефремов
Сибирский федеральный университет Россия, 660041, Красноярск, пр. Свободный, 79
Методом хромато-масс-спектрометрии определены компоненты эфирного масла плодов борщевика рассеченного, полученного методом перегонки с паром. Обнаружено, что в эфирном масле из плодов борщевика рассеченного, произрастающего в Красноярском крае, содержится более 47 компонентов, 44 из которых, представляющих собой 98,6 % от цельного масла, были
© Siberian Federal University. All rights reserved Corresponding author E-mail address: chuchic1@yandex.ru
идентифицированы. Основными компонентами эфирного масла являются винилциклогексан (4,52 %), октилацетат (58,5 %), 2-метилоктил пропаноат (10,81 %) и бета-аланин (9,47 %). Также были получены пять различных фракций эфирного масла. Установлено, что все пять фракций эфирного масла имеют различный состав.
Ключевые слова: эфирное масло, ГХ, ГХ-МС, борщевик, компонентный состав.
Introduction
The genus Heracleum includes approximately 70 species and most of them can be found in Russia. Heracleum species growing in Siberia, such as Heracleum dissectum Ledeb are edible plants. Heracleum dissectum L. grows in broken forests, in forest glades and in the meadows of Siberia, Central Asia and Far East. It is spread in all areas of forest zone and the neighbouring forest-steppe and steppe zones. In the north of Krasnoyarsk Region of Russia areal reaches 700 of north latitude. In the west, areal border within forest zone lies along Irtysh and Ob rivers (1-3).
Fruits of Heracleum species contain 1-10 % of essential oil. The essential oil from fruits of Heracleum dissectum L. contains a-pinene, p-pinene, octanol, octyl acetate, octyl butyrate, octanal, hexyl butyrate; coumarines: umbelliferone, sphondin, xanthotoxin, izopimpinellin, bergapten, angelicin, isobergapten, pimpinellin, imperatorin, ostol, scopoletin, biakangelicin, heraclesol, marmezin, fellopterin (4-9).
Composition of the essential oils depends on the habitat of plants and maturity of fruits (10-12). A literature survey showed that composition of the essential oil of Heracleum dissectum, growing in Siberia haven't been investigated. Therefore the objective of this study was to identify the individual components of the essential oil of Heracleum dissectum from Central Siberia (Krasnoyarsk region of Russia) and to compare the data with literature.
Experimental
Isolation of the essential oil
Mature fruits of Heracleum dissectum L. were collected in July-August 2011 in Krasnoyarsk Region of Russia. The essential oil of air-dried fruits of Heracleum dissectum L. was extracted by steam distillation using Clevenger-type apparatus for 53 hours.
Analysis of the essential oil
The essential oil was analyzed with Agilent Technologies 7890 GC system coupled with Agilent Technologies 5975 C quadrupole mass spectrometer as detector equipped with 30 m capillary column (ID=0.25 mm) coated with 5 % diphenyl-95 % dimethylsiloxane. Chromatographic conditions: isothermal mode at 50 °C for 2 min, then temperature programmed mode from 50 to 280°C at 4°C/ min and isothermal mode at 280°C for 20 min. Evaporator temperature 280 °C, ionization chamber temperature - 230 ° C, ionization energy - 70 eV. The oil components were identified by comparison of their linear retention indices and full mass spectra with the library of mass spectrometric data Wiley 275 and literature (13-15).
Results and discussion
It was found that the essential oil from fruits of Heracleum dissectum L. quantitatively distils within 53 hours. The essential oil is a light-blue liquid with a specific strong odour.
It was shown by GC and GC-MS method that the essential oil from fruits of Heracleum dissectum L. growing in Krasnoyarsk region contains more than 47 compounds, 43 of which were identified (in an amount exceeding 0.1 % of the whole oil). In the first fraction of the essential oil 29 constituents were identified, in the second fraction - 31, in the third- 33, in the fourth - 30, in the fifth- 33 constituents.
The data on distillation dynamics of the essential oil from fruits of Heracleum dissectum L. are shown in Fig. 1. As it can be seen from Table 1, refraction indices of all five fractions are different and refraction indices increase from the first to the fifth fraction (except for the second).
The composition of the essential oil from fruits of Heracleum dissectum L. is shown in Table 2.
As it can be seen from Table 2, the essential oil from fruits of Heracleum dissectum L. contains three compounds with concentration more than 5 %, five compounds with concentration from 1 to
120
Time, Ei
Fig. 1. Yield of the essential oil during extraction
Table 1. Distillation dynamics and refraction indices of the essential oil from fruits of Heracleum dissectum L.
Fraction Time of distillation (h) Yield (% by weight) Refraction index
1 4.83 27.39 1.4246
2 14.67 42.62 1.4244
3 5.50 9.13 1.4269
4 18.00 16.90 1.4280
5 10.00 3.96 1.4317
whole 53.00 100.00 1.4254
Table 2. Composition of the essential oil from fruits of Heracleum dissectum L.
№ RT RI Compound % Composition
1 fr 2 fr. 3 fr. 4 fr. 5 fr. whole
1 7.96 1003 octanal 2.14 0.45 0.25 - - 1.31
2 8.08 1008 isobutyl 3-methylbutanoate 0.42 0.24 0.21 - - 0.46
3 8.73 1026 limonene 0.51 - - - - 0.24
4 8.97 1034 benzyl alcohol 1.56 2.75 1.33 1.48 1.33 1.51
5 9.97 1063 (Z)-5-octene-1-ol 0.30 0.10 - - - 0.10
6 10.25 1072 n-octanol - 2.57 2.06 1.84 1.73 1. 80
7 10.53 1080 Isobutyl 3-methyl-2-butenoate 0.32 0.17 - - - 0.21
8 11.38 1105 2-methyl-3-methylbutyl butanoate 0.14 0.38 0.35 0.27 0.16 0.20
9 11.44 1107 Isopentyl 3-methylbutanoate 0.33 - - - - 0.25
10 11.53 1109 3-methyl-2-methylbutyl butanoate 0.29 0.21 0.16 - - 0.10
11 12.94 1150 n-hexyl isobutanoate 0.47 0.31 0.26 0.20 0.12 0.32
12 14.19 1186 pentyl 3-methyl-2-butenoate 0.25 0.18 - - - 0.10
13 14.49 1194 hexyl butanoate 0.77 0.81 0.83 0.57 0.56 0.75
14 14.72 1201 vinylcyclohexane 5.02 3.71 2.85 2.19 1.12 4.52
15 14.96 1208 decanal 0.59 0.53 0.40 0.33 0.23 0.55
16 15.45 1222 octyl acetate 64.73 57.08 46.73 39.36 25.80 58.50
17 16.03 1240 2-methylhexyl butanoate 0.33 0.38 0.39 0.37 0.32 0.37
18 16.20 1244 3-methylhexyl butanoate 0.71 0.73 0.68 0.62 0.51 0.76
19 17.59 1285 (-)-bornyl acetate - - - - 0.13 0.10
20 18.82 1322 3-methylhexyl 2-butenoate 0.25 0.22 0.26 0.23 0.16 0.22
21 19.63 1347 octyl-2-methyl propanoate 0.69 0.83 0.94 0.92 0.89 0.77
22 20.63 1377 1-ethenylhexyl butanoate 0.49 0.62 0.83 1.12 1.24 1.03
23 21.14 1393 2-methyloctyl propanoate 12.91 18.87 14.21 4.25 - 10.18
24 21.22 1395 1,5-cyclodecadiene 0.29 0.33 0.60 0.62 0.27 0.50
25 21.33 1399 2,6-dimethyl bicyclooctane - 0.15 0.38 0.15 0.17 0.17
26 21.65 1408 tetradecanal - - 0.22 0.25 0.29 0.15
27 21.73 1411 decyl acetate 0.33 0.41 0.55 0.69 0.68 0.40
28 21.88 1416 trans-caryophyllene 0.27 0.13 0.14 0.16 0.24 0.22
29 22.19 1426 cyclodecene 0.16 0.15 0.22 0.24 0.28 0.17
30 22.45 1435 n-octyl-2-methyl butanoate 0.31 0.32 0.50 0.55 0.60 0.21
31 22.60 1440 3-methyloctyl butanoate 0.66 0.64 0.92 0.99 1.06 0.36
32 23.80 1477 germacrene D 0.36 - - - - 0.16
33 25.12 1521 S-cadinene - 0.26 0.46 0.54 0.78 0.38
34 25.90 1548 octyl hexanoate 0.33 0.24 0.49 0.67 0.88 0.25
35 26.40 1565 (E)-nerolidol - - 0.18 0.24 0.36 0.21
36 26.58 1570 4-ethyl-3-ethylydene cyclohexene - - 0.20 0.28 0.41 0.23
37 26.98 1585 ß-alanine - 4.80 5.09 13.77 19.61 9.47
38 27.14 1590 decyl butanoate - - 0.38 0.53 0.82 0.40
39 28.54 1639 T-cadinol - - - - 0.23 0.10
40 28.90 1652 a-cadinol - - - - 0.33 0.10
41 29.73 1681 cis-azarone - - 0.61 0.81 1.47 0.62
42 30.92 1725 chamazulene - - 0.28 0.42 0.80 0.34
43 32.31 1778 octyl octanoate - 0.33 0.34 0.89 3.31 1.55
44 36.92 1954 dibutyl phthalate - - 0.31 0.31 0.82 0.21
Total 98.54
RI - experimental linear retention indices calculated against a C8-C20 n-alkanes mixture
5 % and 36 compounds with concentration from 0.1 to 1 %. Mainly constituents are esters, alcohols and aldehydes. Sesquiterpenes and terpenes content is low (less than 3 %). The major constituents of the oil are vinylcyclohexane (4,52 %), octyl acetate (58,5 %), 2-methyloctyl propanoate (10,18 %) and P-alanine (9,47 %). It was found that the essential oil from fruits of Heracleum dissectum L. growing in Krasnoyarsk Region of Russia contains chamazulene (0,34 %).
As it is seen, first fractions of the essential oil contain highly volatile components and during the distillation process the content of semi-volatile compounds grows up slowing down the distillation process. So, in the first fraction one of the major constituents is octanal, whis was not found in the fourth and fifth fractions.
It was made a comparison of the essential oil from fruits of Heracleum dissectum L. growing in Krasnoyarsk region of Russia with the essential oils from plants growing in other places obtained by steam distillation (5,6,16).
As it is seen from Table 3, the composition of the essential oil from fruits of Heracleum dissectum L. depends on the habitat. The main constituent of the essential oils from fruits of plants growing in Krasnoyarsk and Leningrad regions of Russia and Mongolia (Mongolia2) is octyacetate, but its content is different. The largest amount of octylacetate is contained in the essential oil from fruits of Heracleum dissectum L. growing in Krasnoyarsk region.
It is known that the essential oils from plants of Heracleum dissectum L. growing in natural environment does not contain terpenes [5], but they were found in small amounts in the essential oil from fruits of plant growing in Krasnoyarsk region.
There is a difference in composition of the essential oils from fruits of Heracleum dissectum L. gathered in different years in Mongolia. The essential oil from fruits gathered in 1980 (Mongolia^ does not contain octylacetate, but it is the main constituent of the essential oil from fruits gathered later (Mongolia2). The area of growth Heracleum dissectum L. includes Central Asia, so Heracleum dissectum grows in natural environment. Despite this the main constituents of one of the essential oils from fruits of Heracleum dissectum L. growing in Mongolia (Mongolia^ are terpenes.
Table 3. Some constituents of the essential oils from fruits of Heracleum dissectum L. growing in different places
Component Leningrad Region, Russia* Mongolia1 Krasnoyarsk Region, Russia Mongolia2
a - pinene 1.1 22.17 - 0.48
myrcene - 10.91 - 9.49
ß - pinene 2.4 1.31 - -
octanal 9.2 - 1.31 -
limonene - 2.82 0.24 2.81
benzyl alcohol - - 1.51 -
n-octanol 6.2 - 1. 80 4.82
hexyl butanoate 2.1 - 0.75 -
vinylcyclohexane - - 4.52 -
octylacetate 45.1 - 58.50 46.92
octylbutyrate 22.7 - - 11.21
(-)-bornyl acetate - 1.58 0.10 -
2-methyloctyl propanoate - - 10.18 -
trans-caryophyllene 0.17 0.22 -
germacrene D - 0.43 0.16 -
S-cadinene - 0.15 0.38 -
(E)-nerolidol 1.72 0.21 -
ß-alanine - - 9.47 -
chamazulene - - 0.34 -
1- V.P. Papageorgiou, G. Ochir, O. Motl, N. Argyriadou and H. Dunkel, Composition of the essential oil from Heracleum dissectum. J. Nat. Prod., 48, 851-853 (1985).
2-S. Shatar, Sh. Altantsetseg, J. Irekhbayar, D. Suran, L.D. Radnayeva, S.V. Jigjitjapova, Chemical composition of essential oil from fruits of Heracleum dissectum Ledeb. of Mongolian flora (Khimicheskii sostav efirnogo masla plodov Heracleum dissectum Ledeb. flory Mongolii). Bulleten VSNC SO RAMN, 2 (66), 316-317 (2009). * - introduced plant
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