LV14276B - Method for obtaining coniferous foliage hydrocarbon extracts not-containing volatile biologically toxic components - Google Patents

Abstract

The present invention relates to the field of forest-chemistry industry and concerns questions about the complex processing of plant material, as the process produces biologically active products with a wide spectrum of uses.Aim of this invention is to develop a method for preparing coniferous foliage hydrocarbon solvent extract, not-containing volatile biologically toxic components.This goal is achieved by before-extraction-blowing through grinded foliage water steam for 2 to 2.5 hours at a temperature of 105 centigrade with a processing intensity rate of 3 to 4 kg of steam per hour calculated to 100 kg of coniferous foliage.

Description

DESCRIPTION OF THE INVENTION

The invention relates to the field of forestry chemistry and concerns the process of complex processing of plant raw materials to obtain biologically active products with a wide range of uses.

Vegetable raw materials are coniferous larvae (needles, non-deciduous shoots): from pine (Pinus sylvestris L.), Siberian cedar pine (Pinus sibirica Du. Tour), spruce (Picea abies (L.) Karst.), Siberian larch ( Abies sibirica Ledeb) and other conifers. Vegetable raw materials produce valuable biologically active products used in pharmaceutical, medical, cosmetic, agricultural, household chemical products.

There is a known process of complex processing of coniferous greenery, in which the raw material is crushed, biologically active substances are extracted from the crushed pulp with organic solvent, the extract is cooled, filtered and the coniferous waxes are extracted, solution and alkaline aqueous solution of organic acid salts. The alkaline solution of the salts of organic acids is precipitated and a mixture of chlorophyllinic acids and fatty acids and resin acids is obtained. Resin acids release insecticide. The neutral substances are distilled in vacuo to yield the isoabienol [1].

It is known to process a complex process of coniferous greenery, whereby the raw material is crushed to a destructurized liquid mass with a moisture content of 45-50% by extraction with a non-polar aliphatic hydrocarbon solvent such as petroleum ether. During the extraction, the mass is stirred at an elevated temperature of 40-45 ° C for 4-4.5 hours, cooled to 20-25 ° C for 20-24 hours. The mass is partitioned between the liquid extract containing the water-hydrocarbon solution and the solid phase. The hydrocarbon solution liberates the natural resinous hydrocarbon solution and the aqueous oligosaccharide solution, while the solid phase liberates the bioflavonoids [5].

There is a known method of isolating natural bioflavonoids from coniferous grass. In the first step of the process, the raw material is comminuted and a liquefied mass is obtained, which is mixed with an aliphatic hydrocarbon emulsion in water. The mass obtained after the first stage is partitioned between the solid phase and the water-hydrocarbon extract. The extract is partitioned between the natural resinous hydrocarbon solution and the aqueous oligosaccharide solution from which the natural resinous and oligosaccharides are released respectively. The solid phase is washed with water and extracted with a low-boiling ether-ethyl alcohol emulsion in water. Dihydro-quercetin flavonoids are released from the alcohol-ether and aqueous phases [7],

There is a known process for the complex processing of coniferous greenery, which involves crushing the raw material, extracting the pulp with gasoline by heating it with indirect steam at a temperature of 60-70 ° C and a pressure of 2-4 atmospheres. Extraction time - 3.5 hours. The mass is then allowed to stand for 1 hour to remove the extract from the needles. The gasoline extract is cooled and left to stand for 24 hours. During precipitation, water is removed from the extract and waxy products fall out. The water is removed and the waxy products are filtered off from the petrol extract. From the filtered petrol extract, distillate the petrol from the resinous substances dissolved in the petrol.

Transfer the resulting resin to a saponification apparatus, add 40% sodium hydroxide solution and hot water, stir for 1 hour at 80-90 ° C. Resin saponification occurs during this process. Chlorophyll carotene paste is obtained, which is a biologically active needle-derived product [12]. Chlorophyll carotene paste has the properties of regenerating the epidermis, has tonic and deodorizing properties, it protects and restores the epithelium, and has bactericidal properties against several simple protozoa [12].

Non-polar or low-polar organic solvents (gasoline, petroleum ether, hexane, "nephrase") are used for the extraction of comminuted greenery in various coniferous complex processing techniques [1-12].

Extraction of the lingonberry mass with non-polar solvents yields specific extracts (resinous substances or lipids) containing fatty acids and resin acids, lipids, pigments (carotene and chlorophyll derivatives). Resinous substances also contain other biologically active compounds - phytosterols, tocopherols, bioflavonoids, oligosaccharides, etc.

Due to the high content of valuable biologically active substances, coniferous extracts and their processing products are widely used in medicine, cosmetics, agriculture and household chemicals. Unfortunately, in the extraction of green grass with non-polar hydrocarbon solvents, toxic volatile compounds [13-15], which limit the use of extracts, dissolve in extracts and their products.

The presence of dissolved volatile active substances in extracts and their processed products may cause toxic effects:

on the eyes (α-pinene, 6 ^3- carrene, limonene, β-pinene, β-humulin, bisabolene, bomylacetate, camphor, isobomeol), on the skin and mucous membrane (b ³ -carene, limonene, β-pinene, β-humulin) , bomilacetāts, camphor, izobomeols), the respiratory tract (α-pinene, 5 ³ -karēns, β-pinene, myrcene, bomilacetāts, izobomeols), the gastrointestinal tract zamu (α-pinene, 5 ³ -karēns, β-pinene , bomyl acetate, camphor).

There is no known method for separating volatile biologically active toxic components from conifer hydrocarbon extracts obtained from the processing of coniferous green grass.

It is an object of the present invention to provide a process for the production of volatile, biologically toxic components containing softwood alfalfa extracts in hydrocarbon solvents.

The objective is achieved by blowing the chopped coniferous lilac prior to extraction with 105 ° C hot water steam for 2 to 2.5 hours at a treatment rate of 3 to 4 kg of steam per hour for 100 kg of coniferous larch, followed by extraction using hydrocarbon solvents.

Execution of the method:

Example 1 (sample 1)

3000 g of pine greenery was crushed, pulverized mass was blown with water steam, steam temperature 105 ± 1 ° C, steam was obtained in laboratory steam generator. The steam treatment was carried out for 2 ± 0.2 hours with a treatment intensity of 4 kg steam per hour per 100 kg of strawberry.

During the steam treatment, volatile toxic compounds were removed from the pulp.

Example 2 (sample 2)

3000 g of fir-grass was chopped, the pulverized mass was blown with water steam, steam temperature 105 ± 1 ° C, steam was obtained in a laboratory steam generator. The steam treatment was carried out for 2 hours with a treatment intensity of 3 kg steam per hour per 100 kg of grass.

During the steam treatment, volatile toxic compounds were removed from the pulp.

l.and sample 2 extraction process

Steam-treated samples of linden (3000 g of pine and 3000 g of fir) were extracted with a non-polar aliphatic hydrocarbon solvent (petroleum ether). Extraction was carried out in a Soxhlet apparatus at a boiling point of the solvent at 40-65 ° C for 6 hours. Both extracts were cooled and analyzed.

Example 3 (Example 3)

3000 g of pine zest were crushed and extracted with a non-polar aliphatic hydrocarbon solvent (petroleum ether) in a Soxhlet apparatus at a boiling point of 40-65 ° C for 6 hours. The extract was cooled and analyzed.

Example 4 (Example 4)

3,000 g of spruce fir were chopped and extracted with a non-polar aliphatic hydrocarbon solvent (petroleum ether) in a Soxhlet apparatus at a boiling point of 40-65 ° C for 6 hours. The extract was cooled and analyzed.

The four coniferous extracts of light petroleum ether obtained were analyzed by gas chromatography.

The volatile matter content of the extracts was determined by gas chromatography (GC-FID). Chromatograph - Agilent 6890N, equipped with a flame ionization detector. Dwell times were compared with authentic samples as measured with DB-IMS and DB-FFAP in a column (30m x 0.25mm internal diameter). The column temperature is programmed as follows: isothermal at 40 ° C for 1 min, then raised to 250 ° C at 6 ° C / min for 4 min; carrier gas - helium, flow rate 1,5 ml / min. The results are noted in Table 1 (% of total extracts).

.table

Name of volatile substances Pine (Examples 1, 3) Spruce (samples 2, 4) Without steam treatment With steam treatment Without steam treatment With steam treatment a-pinene 0.110 signs 0.020 signs β-pinene 0.019 signs 0.007 signs 6 ³ -Caren 0.031 signs 0.017 signs Camphens 0.013 signs 0.024 signs bomyl acetate 0.012 signs 0.020 signs Santene 0.000 0.000 0.001 0.000 limonene 0.021 signs 0.012 signs β-Felandrenene 0.012 signs 0.002 0.000 mircen 0.012 signs 0.003 0.000 longifolene 0.000 0.000 0.002 0.000 β -human 0.000 0.000 0.001 0.000 camphor 0.000 0.000 0.003 signs isobomeol 0.001 0.000 '0.002 0.000 -

Gas chromatographic analyzes of the extracts have shown that the steam treatment of green grass before extraction allows the removal of volatile biologically active components and the extraction of volatile biologically active toxic compounds without the use of hydrocarbon solvents.

Sources of information

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3. Pat. RU 2156785, Cl, 1999, C09F 1/00.

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5. Pat. RU 2252220, Cl, 2005, C07D 311/40, B01 J 20/24.

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12. Pat. RU 2040266, Cl, 1995, A61K 35/78.

13. J.Mann, R. S. Davidson, J. B. Hobbs, D. V. Banthorpe, J. B. Harbone, Natura Products, pp309-311, Addison Wesley Longman Ltd., Harlow, UK, 1994. ISBN 0-582-06009-5.

14. http://russian-chemistrv.ru/chemical agents / details / 4158,

15. http://ru.wikipedia.org/wiki/.

Claims (1)

THE CLAIM A process for producing volatile, biologically non-toxic extracts with hydrocarbon solvents, characterized in that the chopped coniferous grass is blown with 105 ° C hot water vapor for 2 to 2.5 hours at 100 kg / h prior to extraction. kg of coniferous greenery, then extracted using hydrocarbon solvents.