Preparation comprising water-soluble triterpenic acid salts and method for its preparing

FIELD: organic chemistry, chemical technology, agriculture.

SUBSTANCE: invention relates to a method for preparing the preparation comprising triterpenic acid water-soluble salts and additionally added protein-containing product and vegetable raw, the source of triterpenic acids taken in the following ratio of components, wt.-%: protein-containing product, 10-17; triterpenic acid sodium salts, 4-5, and vegetable raw, the balance. Method involves mixing triterpenic acid-containing vegetable raw with the protein-containing product taken in the ratio = (9-11):(1-2), mechanical-chemical treatment of this mixture in activator device, mixing of prepared semi-finished product with sodium carbonate or sodium hydrocarbonate taken in the ratio = (92-97):(3.5-8.3) and repeated treatment in the activator device. Method involves applying flow-type ball vibration-centrifugal or ellipse-centrifugal mills as the activator device that provide the acceleration of milling bodies up to 170-250 m/c² and time for treatment for 1.5-3 min. Invention provides simplifying the process and the complex processing waste in lumber industry.

EFFECT: improved preparing method.

6 cl, 1 tbl, 6 ex

The invention relates to the production of bark and wood green fir, timber industry waste, biologically active agents, active substances which are water-soluble salt forms of triterpene acids. The drug can be used in agriculture to increase the productivity of plants.

There is a method of isolating biologically active amounts of acid from the Abies needles, including chopping wood green fir, obtaining salts of acids directly processing the crushed material with a moisture content of 45% or less aqueous alkali solution with a concentration of 0.5 to 50% or 1.0-50%aqueous solution of a carbonate of an alkali metal, the separation of the solid part of the wood green from the resulting salt solution, acidification of an aqueous alkaline solution or an aqueous solution of a carbonate of an alkali metal to pH 2-3, extracted triterpene acids with an organic solvent, followed by removing the solvent and obtaining the target product [1. Pat. Of the Russian Federation No. 2161149, class C 07 C 57/26, And 61 To 35/07, publ. 27.12.2000,].

The disadvantage of this method is that the extraction is carried out with alkali or carbonate of an alkali metal directly from plant material, resulting in the final product may be contaminated polyphenolic compounds that inhibit development the plants. If re-extraction of triterpene acids with an organic solvent together with triterpene acids extracts and polyphenolic compounds, which remain in the final product after the distillation of the organic solvent and drying.

The closest technical solution chosen for the prototype is the method of obtaining biologically active amounts of salts triterpene acids from the dried and crushed the Abies needles by its extraction with an organic solvent is a mixture of petroleum ether (nefras) and ethyl acetate, treatment of the extract with alkali, separating the aqueous solution in which the aqueous solution is separated from the organic phase after its spontaneous neutralization to pH 7-8 and dried to powder [2. Pat. Of the Russian Federation No. 2108107, class a 61 K 35/78, publ. 10.04.98,].

This technical solution polyphenolic compounds remain in the organic phase, and salt triterpene acids in aqueous solution, that is, the product is practically not contaminated polyphenolic compounds.

A disadvantage of the known technical solution is the use of large quantities of flammable and explosive organic solvents, the method is quite complicated, multi-stage.

For the prototype of the proposed drug selected product obtained according to a known method [2], which represents the gray-green the hydrated powder, containing about 50% sodium salts of triterpene acids and about 50% sodium acetate.

The disadvantage of this product is its high cost, because when it is received using a large number of expensive organic solvents, and drying it to produce at a high temperature under vacuum.

The problem solved by the claimed technical solution is to create a new environmentally safe and technologically simple method of obtaining a cheap and effective drug, which triterpene acids are biologically active early, and polyphenolic compounds are bound form and have no inhibitory effect on the growth of plants.

The problem is solved due to the fact that the claimed drug to increase the productivity of plants containing water-soluble salts of triterpene acids, represents a powdery composite containing additional protein-containing product, and plant raw materials containing triterpene acid, in the following ratio, wt.%:

Protein-containing product,

rich in protein 10-17

Sodium salt of triterpene acids 4-5

Plant raw materials containing

triterpene acids - rest

Preferably, as the protein-containing product is that the product contains dry soy milk.

Preferably, as the protein-containing product the product contains nedobity waste from the leather industry.

Preferably, as the protein-containing product the product contains gelatin.

The inventive solution has novelty. Get drug cheap enough, relative to the selected prototype has the following major differences:

- additionally contains a protein-containing product;

- additionally contains crushed plant material containing triterpene acids;

- the drug has the above-mentioned ratio of the components.

As a protein-containing product may be used dry soy milk, soy beans, which does not exclude the use of other protein-containing foods, such as gelatin or redoubling tannery wastes.

The problem is solved by the claimed method of producing drug for increasing the productivity of plants containing salt triterpene acids, due to the fact that plant material containing triterpene acid, is mixed with the protein-containing product in the ratio of 9-11:1-2, the resulting mixture is subjected to mechanochemical treatment in the activator, the resulting intermediate is mixed with carbonate or sodium bicarbonate in a ratio of 92-97:3,5 to 8,3 and re-experience the t processing in the activator.

Preferably, the activator is used running the ball or vibratory centrifugal elliptocytosis mills, providing faster grinding media 170-250 m/s²and the residence time in the treatment zone of 1.5-3 minutes.

Preliminary mechanochemical processing of plant raw materials containing triterpene acid, in the presence of dry soy milk, soy or other protein-containing foods rich in proteins, allows you to associate polyphenolic compounds.

The obtained semi-product is again subjected to mechanochemical treatment in the presence of carbonate or bicarbonate of sodium, you get a powdery composite containing a soluble salt forms of triterpene acids.

The main features of the proposed method are:

plant raw materials containing triterpene acid, is mixed with the protein-containing product in the ratio of 9-11:1-2, respectively;

- the resulting mixture is subjected to mechanochemical activation;

- obtained intermediate is mixed with carbonate or sodium bicarbonate in a ratio of 92-97:3,5 to 8,3;

the mixture is subjected to repeated mechanical activation.

The method is as follows.

Example 1.

The bark of the fir pre-dried to a water content of 2-5 wt.%, crushed to the size of the and particles 1,0-2,0 mm The resulting mass is mixed with dry soy milk or soy beans in the ratio of 9:2. A mixture of mechanochemical processes in flow activator type TSEM or VCM, providing faster grinding media 170-250 m/s²and the residence time in the treatment zone of 1.5-3 minutes. The resulting intermediate is mixed until a homogeneous mass with sodium carbonate in the ratio of intermediate - sodium carbonate 96:3,8. The mixture mechanochemical process in terms of obtaining intermediate. The resulting product is a fine powder light brown in color and has a distribution of particles of 5-25 μm 60-80%, 20-50 μm 15-19%. The target product can be used for inlays of wheat seeds to improve their germination and to ensure the formation of a strong root system.

The target product is characterized by the fact that the 20-minute infusion in water with stirring or agitation releases into solution more than 80% triterpene acids contained in the original plant material. Extracted with ethyl acetate triterpene acids from the filtered water infusion, which before extraction was acidified 12%sulfuric acid to a pH of 2-3, have a maximum in the UV region 236-239 nm. The chromatogram of the acid obtained by HPLC according to [Aggrogant and others, identifying the components of the acidic part of the pine extract PI is you Siberian using preparative microcolumn HPLC, NMR spectroscopy and mass spectrometry. / / Chemistry for sustainable development 8 (2000) 699], corresponds to the chromatogram amount of triterpene acids exuded by a known method.

Example 2.

Carried out under conditions of claim 1, in feedstock use the green wood of fir, which is mixed with dry soy milk in the ratio of 11:1. Obtained from this mixture the product is a fine powder brown-green color and has a distribution of particles 10-40 μm 60-80%, 40-55 µm 15-19%. The target product can be used for inlays wheat seeds, with the aim of increasing their germination and to ensure the formation of a strong root system.

The target product is characterized by the fact that the 20-minute infusion in water with stirring or agitation releases into solution more than 75% triterpene acids contained in the original plant material. Extracted with ethyl acetate triterpene acids from the filtered water infusion, which before extraction was acidified 12%sulfuric acid to a pH of 2-3, have a maximum in the UV region 236-239 nm. The chromatogram of the acid obtained by HPLC according to [Aggrogant and others, identifying the components of the acidic part of the extract of Siberian fir needles using preparative microcolumn HPLC, NMR spectroscopy and mass spectrome the Rhee // Chemistry for sustainable development, 8 (2000) 699], corresponds to the chromatogram amount of triterpene acids exuded by a known method.

Example 3.

Carried out under conditions of claim 1. The resulting product is soaked in water under stirring at a temperature of 15-25°s, water ratio 6-10. The solid residue is separated by centrifugation or filtration, followed by extraction of the solid residue through filtrating. The resulting aqueous infusion of light brown color contains water-soluble sodium salt of triterpene acids in concentrations of 0.25 to 0.35 wt.%.

Example 4.

Is 2. The resulting product is soaked in water under stirring at a temperature of 15-25°s, water ratio 6-10. The solid residue is separated by centrifugation or filtration, followed by extraction of the solid residue through filtrating. The resulting aqueous infusion of greenish-brown color contains water-soluble sodium salt of triterpene acids at a concentration of 0.6-0.8 wt.%. Received on p.3 and p.4 products can be used through irrigation of crops.

Example 5.

Carried out under conditions of claim 1. As the alkaline reagent is used sodium bicarbonate, which take in double the amount with respect to sodium carbonate according to claim 1.

Example 6.

Carried out under conditions of claim 1. As a binder polyphenols used in the t nedobity waste from the leather industry.

Example 6.

Carried out under conditions of claim 1. As a binder polyphenols use gelatin.

The specified ratio of the concentrations of the components of mechanochemical treated mixture and settings mechanochemical processing (the residence time in the zone of influence of the grinding bodies, the acceleration of the grinding bodies, the number and geometrical characteristics of the particles loaded into the mechanochemical activator) depend on the characteristics of the original plant material - moisture content of triterpene acids, resinous components and polyphenolic compounds.

Content in the mixture of protein-containing product should provide binding 90-95% polyphenolic compounds. To find the optimum content of the protein-containing product determine the total amount of polyphenols before and after mechanochemical treatment according to the method [Haze-active protein and polyphenols in apple juice assessed by turbidimetry / Siebert, Karl J., Lynn, Penelope Y. // J.Food Sci. - 1997. - Vol.62. - N1. - C.79-84].

The minimum content of the alkaline agent depends on the kinetics of mechanochemical process (rate of transfer of components during mechanochemical treatment) and on the content of triterpene acids in plant material. The amount of added alkaline agent must ensure full neutralization of triterpene acids, but should not be less than 3%, because otherwise lie the mechanochemical processing required for complete neutralization of the acids is increased to technologically unacceptable values.

In relation to the prototype of the proposed method has the following advantages:

- ready-to-use product is obtained by two-stage waste technology;

the technology eliminates the use of organic solvents;

- the inventive method is simple and allows us to solve the complex issues of waste timber production.

Tested the effectiveness of the drug, obtained by the proposed method (4), in comparison with the product obtained by a known method (prototype). Found a stimulating effect of the drug obtained by the claimed solution. Seed treatment with the drug increases the germination and leads to the formation of strong, well foliated and well-rooted seedlings. The results of the tests are presented in table 1.

1. The drug is to increase the productivity of plants containing water-soluble salts of triterpene acids, characterized in that it is a powdery composite containing additional protein-containing product and plant raw materials containing triterpene acid, in the following ratio, wt.%:

2. The preparation according to claim 1, characterized in that as the protein-containing product it contains dry soy milk.

3. The preparation according to claim 1, characterized in that as the protein-containing product it contains nedobity waste from the leather industry.

4. The preparation according to claim 1, characterized in that as the protein-containing product it contains gelatine.

5. The method of producing drug for increasing the productivity of plants containing water-soluble salts of triterpene acids from the dried and powdered plant materials containing triterpene acid, wherein the plant material containing triterpene acid, is mixed with the protein-containing product in the ratio of 9-11:1-2, the resulting mixture is subjected to mechanochemical treatment in the activator, the resulting intermediate is mixed with carbonate or sodium bicarbonate in a ratio of 92-97:3,5 to 8,3 and re-processed in the activator.

6. The method according to claim 3, characterized in that the activator is used running the ball or vibratory centrifugal elliptocytosis mill, provide the state of acceleration of the grinding bodies 170-250 m/s ²and the residence time in the treatment zone of 1.5-3 minutes