COMPOSITION OF ESSENTIAL OIL OF THE LARCH (LARIX) SIBERIAN
© N. V. Chekushkina, N. V. Shatalin, A.A. Efremov
Krasnoyarsk state agricultural university, Mira Ave., 90, Krasnoyarsk, 660049 (Russia)
The method of hromato-mass-spectrometry has investigated component composition of essential oil of needles of larch Siberian, collected in September. It is shown that essential oil contains no more than 59% of monoterpenes, and the structure significantly changes its allocations in the conditions of hydrodistillation eventually.
Keywords: Larix sibirica, hromato-mass-spectrometry, essential oil.
Siberia - the largest forest raw region not only the Russian Federation, but also the whole world as contains 19% of world reserves of wood. In the woods of Siberia plantings of coniferous breeds prevail: more than 83% of the area and 88% of reserve of wood fall to their share. As a part of the woods the larch (52% on the areas and 46% on stock), pine (16 and 20% respectively) and cedar prevails (8 and 12% respectively). The share of fir-tree and fir (together 7 and 10% respectively), and also the soft-wooded broadleaf breeds (13 and 12% with - is responsible) provided mainly by birch is considerable. Thus, in Siberia the main forest richness of the country which involvement in economic use is the major economic task which has to be solved on the basis of the principles of rational and complex environmental management  are concentrated.
Larch Siberian (Larix sibirica.) - the most widespread wood breed in the woods of Asia. The area occupies it huge spaces of the Western and Central Siberia and Mongolia, stretching from Ob, Irtysh to coast of Baikal and from the tundra near Gulf of Ob and the mouth of Yenisei to semi-deserts of Central Asia and Mongolia. The larch Siberian is capable to grow in the conditions of short growing season, using at fast speed heat and moisture. For example, in the conditions of Central Hangaya of Mongolia it successfully grows at the extent of growing season of 2-2,5 months. Is the photophilous culture steady against drought, as defines use it and outside natural distribution.
Essential oils belong to the most important class of biologically active agents of wood greens. Essential oils - difficult mix of the terpenic hydrocarbons and their derivatives produced in the conditions of life activity of the plant. Considering that fact that the needles of larch Siberian form and develop during the summer period, and also that the content of essential oil continuously increases in needles during the entire period of vegetation, can be assumed that the composition of essential oil will change in process of growth of needles. The analysis of the available literary data testifies that the composition of essential oil of larch Siberian is almost not studied or studied not rather fully. Testifies that fact to it that the component structure was studied by earlier chromotographic method with use of stuffed columns on which the analysis of high-boiling components is rather difficult. Really, high-boiling fraction of essential oils coniferous (pine, cedar, fir-tree and larch) is almost not provided from the point of view of component structure. In this regard in this work the exit, physical and chemical characteristics and component composition of essential oil of larch Siberian Krasnoyarsk Krai with use of hromato-mass-spectrometry which allows to define quantitatively and high-boiling components of essential oil, including such connections as karyophyllene, kariofillenoksid, kadinen, kadinol, hamazulen, etc. is studied.
The needles of larch Siberian were collected in the middle of September, 2006 in the Emelyanovsky region of Krasnoyarsk Krai when it was still green. The collected needles from 75 trees were dried up at 20 °C to air-dry state which certain hinge plate (from 1,5 to 2,0 kg) was loaded on grid of metal distillation still at the bottom of which water was located. Essential oil was driven away in the conditions of hydrodistillation, quantitatively gathered in Klevendzher's nozzle. Composition of essential oil determined on the Hewlett-Packard 5890/11c chromatograph by the quadrupole mass-spectrometer HP MSD 5971 as the detector with use of column 30 m long with phase of 5% % diphenyl-95 dimethylsiloxane with internal diameter of 0,25 mm. Chromatographing conditions: the isothermal mode at 50 °C within three minutes, then the programmed rise in temperature with speed of 6 °C/min. up to 250 °C with endurance at final temperature of 30 min. Evaporator temperature - 280 °C, temperature of the ionization camera - 170 °C, ionization energy - 70 ev. The maintenance of components was calculated on the areas of peaks, identification of separate components was carried out comparison of times of keeping and full mass spectrums with the relevant data of components of reference oils and pure connections.
Discussion of results
In the course of experiments it is established that essential oil of larch Siberian is quantitatively driven away from needles during 15-20 h, and has been noticed that the last fractions of distillation have blue coloring (presence, most likely, of azulene derivatives).
The exit of essential oil of needles of larch Siberian in the conditions of hydrodistillation has made 0,41±0,03% of hinge plate of dry raw materials. Density of the received essential oil which is previously dried up over alkali makes 0,883 g/cm3, index of refraction - 1,4786.
For more detailed studying of component composition of essential oil of larch Siberian dynamics of otgonka of oil with stratographic analysis of the received fractions has been investigated. The first fraction gathered within 30 min., the subsequent - in 1,5 h. The index of refraction of separate fractions increases with increase in time of distillation from 1,4712 to 1,4809. It testifies that the component structure of fractions of the received oil changes in process of distillation. The component structure of the received 4 fractions of essential oil of larch Siberian, received with use of hromato-mass spectrometry, is provided in the table.
The analysis of the obtained data shows that essential oil of larch Siberian is provided generally by monoterpenes which contents makes 59%. The main components among monoterpenes are a-pinene, b-pinene, D3 carene, b-phellandrene, terpinolene. Besides, in essential oil of larch rather high content of sequiterpenes - 29% as a part of which dominate kariofil-flax, g-kadinen, b-kadinen, t-murolol, a-kadinol, hamazulen.
It should be noted that the content of bornyl acetate in essential oil of larch Siberian in this case insignificant and makes 1,26%.
The analysis of component structure of separate fractions of essential oil of larch Siberian specifies that the first fractions of essential oil practically do not contain sequiterpenes. In process of increase in time of otgonka the maintenance of the easily boiling components as a part of fractions decreases, and the content of sesquiterpenic hydrocarbons increases. So, for example, b-kadinol, a-kadinen, b-kadinen, kopayen, t-murolol, by a-kadinol and hamazulen are recorded only in the third fraction of essential oil, i.e. in 3,5 h release of oil. At - than the maintenance of the specified components increases in the subsequent fractions (see fraction No. 4).
Component structure of separate fractions and whole essential oil of larch Siberian (masses. % of whole oil)
Maintenance of components, % of masses
Time uder-chewing, min. Component . Fraction 1 Fraction 2 Fraction 3 Fraction 4 Whole oil
4,98 (+) a-pinene 24,84 26,86 17,78 5,44 14,82
5,26 camphene 0,84 0,55 0,40 - 0,72
5,83 b-pinene 4,19 9,11 6,12 2,75 8,04
6,28 myrcene 3,19 2,71 1,96 0,82 2,99
7,07 D3-karen 43,66 47,59 34,86 17,11 22,51
7,26 b-tsimen 3,06 1,49 1,86 0,86 0,93
7,46 b-felandren 4,06 4,08 3,16 2,18 4,21
8,23 g-terpinen - - 1,00 1,20 1,69
9,22 terpinolene - 2,07 2,00 2,85 2,97
11,58 pinokarvon - - 0,78 0,27 0,51
12,21 4-terpineol 0,42 1,82 2,69 3,32 2,88
12,68 menthol 0,85 - 1,02 1,27 1,37
13,05 mentatriyen 0,90 - - - 0,64
13,60 pinokarvon 0,63 - - - 0,44
15,72 bornil azetat 0,21 0,56 1,01 1,32 1,26
18,96 b-burbonen 0,49 - 1,30 1,36 0,54
20,08 karyophyllene - - 2,67 5,28 2,48
22,10 g-кадинен - 1,88 12,13 29,35 11,47
22,57 b-kadinol - - 0,81 2,43 1,10
23,00 a-kadinen - - 0,80 2,65 1,13
23,34 b-kadinen - - 3,03 9,19 7,16
26,30 kopayen - - 0,34 0,22 0,23
26,73 t-murolol - - 0,99 1,97 2,02
27,10 a-kadinol - - 0,98 2,45 2,27
29,15 hamazulen - - 0,67 1,68 1,01
Considering the above, it is possible to claim that for the characteristic of the received essential oil of larch Siberian it is necessary to drive away most fully oil as its characteristics are defined by otgonka time.
Has come to edition on April 22, 2007.
The method of an exhaustive gidroparodistillyation studied process of release of essential oil of a pad of a fir Siberian. The essential oil emitted during 18ch. With an exit of 3,92%, it is presented by 28 components the contents more than 0,1%. The method hromato - mass spectrometry identified all main components of the received oil.
The distillation method with water vapor has studied process of release of essential oil of pad of fir Siberian. The essential oil emitted during 26 h with exit of 5,40% is provided by 30 components with the contents more than 0,1%. The method of hromato-mass-spectrometry has identified all main components of the received oil.
The method of hromato-mass-spectrometry has investigated component composition of essential oil of needles of pine ordinary, collected in September. It is shown that the content of monoterpenes makes no more than 50% and the composition of oil changes in process of its allocation: the maintenance of the easily flying decreases, and the maintenance of the hardly flying increases otgonka eventually.