RU2244426C1 - Preparation comprising water-soluble triterpenic acid salts and method for its preparing - Google Patents

Abstract

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

Description

The invention relates to the production of fir from bark and woody greens, waste from the woodworking industry, a biologically active preparation, the active substances of which are water-soluble salt forms of triterpene acids. The drug can be used in agriculture to increase plant productivity.

There is a method of isolating a biologically active amount of acid from fir green wood, including grinding fir green wood, obtaining acid salts directly by processing chopped raw materials with a moisture content of 45% or less with an aqueous alkali solution with a concentration of 0.5-50% or 1.0-50% aqueous solution of alkali metal carbonate, separation of the solid part of woody green from the resulting salt solution, acidification of an aqueous alkali solution or an aqueous solution of alkali metal carbonate to pH 2-3, extraction of triterpene acids with organic solvent, the subsequent removal of the solvent and obtain the target product [1. Pat. RF №2161149, class C 07 C 57/26, A 61 K 35/07, publ. December 27, 2000].

The disadvantage of this method is that the extraction is carried out with an alkali solution or alkali metal carbonate directly from plant materials, as a result of which the final product may be contaminated with polyphenolic compounds that inhibit the development of plants. When the triterpenic acids are re-extracted with an organic solvent, the polyphenolic compounds are extracted along with the triterpene acids, which remain in the final product after distillation of the organic solvent and drying.

The closest technical solution chosen for the prototype is a method of obtaining a biologically active amount of salts of triterpenic acids from dried and ground wood green fir by extracting it with an organic solvent - a mixture of petroleum ether (nefras) and ethyl acetate, treating the extract with alkali, separating an aqueous solution in which aqueous the solution is separated from the organic phase after spontaneous neutralization to a pH of 7-8 and dried to a powder [2. Pat. RF №2108107, cl. A 61 K 35/78, publ. 04/10/98].

In this technical solution, the polyphenolic compounds remain in the organic phase, and the salts of triterpene acids remain in the aqueous solution, that is, the product is practically not contaminated with polyphenolic compounds.

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

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

The disadvantage of this product is its high cost, since a large number of expensive organic solvents are used in its preparation, and it is dried at elevated temperature under vacuum.

The problem solved by the claimed technical solution is to create a new environmentally safe and technologically simple way to obtain a cheap and effective drug, in which triterpene acids are a biologically active active principle, and polyphenolic compounds are in a bound form and do not have an inhibitory effect on plant development.

The problem is solved due to the fact that the claimed preparation for increasing plant productivity, containing water-soluble salts of triterpene acids, is a powder composite containing an additional protein-containing product, and plant material containing triterpene acids, in the following ratio, wt.%:

Protein-containing product

high in protein 10-17

Sodium salts of triterpenic acids 4-5

Plant material containing

triterpene acids - the rest

Preferably, as a protein-containing product, the preparation contains dried soy milk.

Preferably, as a protein-containing product, the preparation contains underexposed leather wastes.

Preferably, the preparation comprises a gelatin as a protein-containing product.

The claimed solution has novelty. The resulting preparation is quite cheap, with respect to the selected prototype it has the following significant differences:

- additionally contains a protein-containing product;

- additionally contains crushed plant material containing triterpene acids;

- the drug has the above ratio of components.

As a protein-containing product, it is possible to use soy milk powder, soybeans, which does not exclude the possibility of using other protein-containing products, for example, gelatin or untreated leather products.

The problem is solved by the claimed method of obtaining a preparation for increasing the productivity of plants containing salts of triterpene acids, due to the fact that plant materials containing triterpene acids are mixed with a protein-containing product in a ratio of 9-11: 1-2, the resulting mixture is subjected to mechanochemical treatment in an activator, the resulting intermediate is mixed with sodium carbonate or bicarbonate in a ratio of 92-97: 3.5-8.3 and re-treated in the activator.

Preferably, as an activator, flow ball vibrocentrifugal or ellipsocentrifugal mills are used, which accelerate grinding media 170-250 m / s ² and the residence time in the treatment zone is 1.5-3 minutes.

Preliminary mechanochemical treatment of plant materials containing triterpene acids in the presence of soy milk powder, soy beans or other protein-rich protein-containing products allows polyphenolic compounds to be bound.

The resulting intermediate is re-subjected to mechanochemical treatment in the presence of sodium carbonate or sodium bicarbonate, and a powdery composite is obtained containing soluble salt forms of triterpene acids.

Salient features of the proposed method are:

- vegetable raw materials containing triterpenic acids are mixed with a protein-containing product in a ratio of 9-11: 1-2, respectively;

- the resulting mixture is subjected to mechanochemical activation;

- the resulting intermediate is mixed with sodium carbonate or sodium bicarbonate in a ratio of 92-97: 3.5-8.3;

- the mixture is subjected to repeated mechanochemical activation.

The method is as follows.

Example 1

The bark of fir, previously dried to a water content of 2-5 wt.%, Is crushed to a particle size of 1.0-2.0 mm The resulting mass is mixed with dried soy milk or soybeans in a ratio of 9: 2. The mixture is mechanochemically treated in a flow activator of the TsEM or VTSM type, providing acceleration of grinding media 170-250 m / s ² and a residence time in the treatment zone of 1.5-3 minutes. The resulting intermediate is mixed to obtain a homogeneous mass with sodium carbonate in the ratio of intermediate - sodium carbonate 96: 3,8. The mixture is mechanochemically treated under the conditions of obtaining an intermediate. The resulting product is a fine powder of light brown color and has a particle distribution of 5-25 microns 60-80%, 20-50 microns 15-19%. The target product can be used to inlaid wheat seeds in order to increase their germination and to ensure the formation of a strong root system.

The target product is characterized by the fact that with a 20-minute infusion in water with stirring or shaking, it releases into solution more than 80% of triterpene acids contained in the initial plant material. The triterpenic acids extracted from ethyl acetate from a filtered aqueous infusion, which was acidified before extraction with 12% sulfuric acid to pH 2-3, have a maximum in the UV region of 236-239 nm. Chromatogram of acids obtained by HPLC according to [A.G. Druganov et al., Identification of the components of the acidic part of Siberian fir needle extract using preparative microcolumn HPLC, NMR and mass spectrometry // Chemistry for Sustainable Development, 8 (2000) 699 ], corresponds to the chromatogram of the sum of triterpenic acids isolated by a known method.

Example 2

It is carried out in the conditions of claim 1, as the source of raw materials use wood green fir, which is mixed with dried soy milk in a ratio of 11: 1. The product obtained from this mixture is a finely divided powder of brown-green color and has a particle distribution of 10-40 microns 60-80%, 40-55 microns 15-19%. The target product can be used to inlaid wheat seeds, in order to increase their germination and to ensure the formation of a strong root system.

The target product is characterized by the fact that with a 20-minute infusion in water with stirring or shaking, it releases more than 75% of triterpenic acids contained in the initial plant material into the solution. The triterpenic acids extracted from ethyl acetate from a filtered aqueous infusion, which was acidified before extraction with 12% sulfuric acid to pH 2-3, have a maximum in the UV region of 236-239 nm. Chromatogram of acids obtained by HPLC according to [A.G. Druganov et al., Identification of the components of the acidic part of Siberian fir needle extract using preparative microcolumn HPLC, NMR and mass spectrometry // Chemistry for Sustainable Development, 8 (2000) 699 ], corresponds to the chromatogram of the sum of triterpenic acids isolated by a known method.

Example 3

It is carried out in the conditions of claim 1. The resulting product is infused in water with stirring at a temperature of 15-25 ° C, a water module of 6-10. The solid residue is separated by centrifugation or filtration, followed by extraction of the solid residue through a filter cloth. The resulting light brown water infusion contains water-soluble sodium salts of triterpene acids in a concentration of 0.25-0.35 wt.%.

Example 4

It is carried out in the conditions of paragraph 2. The resulting product is infused in water with stirring at a temperature of 15-25 ° C, a water module of 6-10. The solid residue is separated by centrifugation or filtration, followed by extraction of the solid residue through a filter cloth. The resulting greenish-brown aqueous tincture contains water-soluble sodium salts of triterpene acids in a concentration of 0.6-0.8 wt.%. Obtained according to claim 3 and claim 4 products can be used by irrigation of crops.

Example 5

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

Example 6

It is carried out in the conditions of claim 1. As a binder, polyphenols use underexposed wastes of leather production.

Example 6

It is carried out in the conditions of claim 1. Gelatin is used as a binder polyphenols.

The indicated ratios of the concentrations of the components of the mechanochemically processed mixture and the parameters of the mechanochemical treatment (the time spent in the zone of influence of the grinding media, acceleration of the grinding media, the number and geometric characteristics of the grinding media loaded into the mechanochemical activator) depend on the characteristics of the initial plant material — humidity, triterpene acids, resinous components and polyphenolic compounds.

The content of the protein-containing product in the mixture should ensure the binding of 90-95% of polyphenolic compounds. To find the optimal protein-containing product content, the total amount of polyphenols before and after mechanochemical processing is determined according to the method of [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 alkaline agent content depends on the kinetics of the mechanochemical process (component transfer rate during mechanochemical processing) and on the content of triterpene acids in plant materials. The amount of alkaline agent introduced should ensure the complete neutralization of triterpenic acids, but should not be less than 3%, because otherwise the mechanochemical treatment time necessary for the complete neutralization of acids increases to technologically unacceptable values.

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

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

- technology eliminates the use of organic solvents;

- the inventive method is simple and allows you to solve the issues of integrated processing of waste from forestry production.

Checked the effectiveness of the drug obtained by the proposed method (p. 4), in comparison with the drug obtained by the known method (prototype). The stimulating effect of the drug obtained by the claimed solution was found. Treatment of seeds with the drug increases germination and leads to the formation of strong, well-leafy and well-rooted seedlings. The test results are presented in table 1.

Table 1 The influence of the preparations on the germination of seeds of wheat of the Novosibirsk 89 variety. No. A drug, 4 day experience 11 day experience Germination,% Triterpene concentration Shoot height Root length Shoot height Root length acids, mg / liter mm % mm % mm % mm % 1 Control, 0 16 100 22 100 105 100 45 100 90 2 The drug according to a known method, 1.0 thirteen 81 19 86 114 109 47 104 93 3 Water infusion according to claim 4, 1,0 14 88 24 109 124 118 58 129 99

Claims (6)

1. A preparation for increasing plant productivity containing water-soluble salts of triterpene acids, characterized in that it is a powder composite containing an additional protein-containing product and plant material containing triterpene acids, in the following ratio, wt.%: Protein-containing product 10-17 Sodium salts of triterpenic acids 4-5 Plant materials containing triterpene acids Rest 2. The drug according to claim 1, characterized in that as a protein-containing product, it contains dried soy milk. 3. The drug according to claim 1, characterized in that as a protein-containing product, it contains underexposed wastes of leather production. 4. The drug according to claim 1, characterized in that as a protein-containing product, it contains gelatin. 5. A method of obtaining a preparation for increasing the productivity of plants containing water-soluble salts of triterpene acids from dried and ground plant materials containing triterpene acids, characterized in that the plant material containing triterpene acids is mixed with a protein-containing product in a ratio of 9-11: 1-2 , the resulting mixture is subjected to mechanochemical treatment in the activator, the resulting intermediate is mixed with sodium carbonate or bicarbonate in a ratio of 92-97: 3.5-8.3 and re-subjected Otke in the activator. 6. The method according to claim 3, characterized in that as an activator, flow ball vibrocentrifugal or ellipsocentrifugal mills are used, which accelerate grinding media 170-250 m / s ² and the residence time in the treatment zone is 1.5-3 minutes.