RU2596031C2 - Herbicide based on fullerene adducts - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. Saturation action herbicide contains aqueous solutions of adducts of N-(phosphonomethyl)-glycine with a mixture of fullerenes with the size of C50-C92 at the following ratio, wt%: adducts of N-(phosphonomethyl)-glycine with a mixture of fullerenes with the size of C50-C92 - 0.01-0.1; rest is water.

EFFECT: invention increases the efficiency of the product.

1 cl, 7 dwg, 2 tbl, 3 ex

Description

The invention relates to organic chemistry and biotechnology and can be used to create water-soluble biologically active preparations for protecting plants from weeds at all stages of their development, as well as water-soluble and alcohol-soluble preparations for the treatment of various plant diseases, in particular highly effective antifungal agents.

The main problem of using a mixture of fullerenes of the C50-C92 fraction to obtain water-soluble compositions of biologically active preparations is their almost complete insolubility in water [Ruoff R.S., Tse D.S., Malhotra R., Lorents D.C. Solubility of fullerene (C60) in a variety of solvents. J. Phys. Chem., 1993; 97: 3379-3383; Bezmelnitsyn V.H., Eletsky A.V., Okun M.V. Fullerenes in solutions. Success physical. Sciences, 1998; 168: 1195-1120], which is unacceptable for drugs that regulate plant growth.

The most effective way to overcome this disadvantage is the synthesis of lyophilic adducts of fullerenes, soluble in water. Thus, there is a known method of forming complexes of fullerenes with hydrophilic substances [Andersson T., Nilsson K., Sundahl M., Westman G., Wennerström O. C60 embedded in γ-cyclodextrin: a water-soluble fullerene. J. Chem. Soc, Chem. Commun., 1992; 604-605], [Piotrovsky LB, Kiselev O.I. Fullerenes in biology. St. Petersburg /: Rostock; 2006]. [Yamakoshi Y.N., Yagami T., Fukuhara K., Sueyoshi S., Miyata N. Solubilization of fullerenes into water with polyvinylpyrrolidone applicable to biological tests. J. Chem. Soc. Chem. Commun., 1994; 517-518; [Nakanishi T., Ariga K., Morita M., Kozai H., Taniguchi N., Murakami H., Sagara T., Nakashima N. Electrochemistry of fullerene C60 embedded in Langmuir-Blodgett films of artificial lipids on electrodes. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2006; 284-285: 607-612]. However, these complexes are not individual substances, do not have sufficient stability during storage and handling, and their stability depends on the environment in which they are located.

The most famous reactions in fullerene chemistry are cycloaddition reactions (Diels-Alder), where C _{60 is} always a dienophile and allows the introduction of a number of functional groups into its core [M. Yurovskaya Methods for the preparation of C ₆₀ fullerene derivatives. Soros Educational Journal, 2000; 5: 26-30; Sidorov L.N., Yurovskaya M.A., Borschevsky A.Ya. Trushkov I.V., Ioffe I.N. Fullerenes (textbook for universities) .- M.: Exam; 2005], single-stage and direct addition reactions of primary and secondary amines, amino acids and dipeptides (Hirsch A., Li Q., Wudl F. Globe-trotting hydrogens on the surface of the fullerene compounds C ₆₀ H ₆ N (CH ₂ CH ₂ ) ₂ O] _6. Angew. Chem. Int. Ed., 1991). (Romanova BC, Tsyryapkin BA, Lyakhovetsky Yu.A., Parnes Z.H., Volpin M.E.) (Bulletin of the Russian Academy of Sciences, ser. Chemical, 1994; 1154-1155). However, these reactions are complex and form by-products of polyaddition.

Also known is a method for producing hydrated n-fullerene amino acids and pharmaceutical compositions based on them (RU 2458046), in which the technical problem is solved in that hydrated fullerene derivatives of amino acids are formed by the interaction of fullerene with a 15-fold molar excess of anhydrous potassium salts of amino acids in an organic medium an aromatic solvent when slowly added to the resulting suspension of an interphase catalyst with stirring and heating to a temperature not exceeding 60-80 ° C until completely discolored I solution and forming a solid precipitate which is then separated, after which the processing is carried out 0.8 M aqueous solutions of potassium salts of fullerene-amino acid 0.1 N solution of organic or mineral acids, followed by centrifugation, washing and drying the precipitate. This method is quite complicated due to the need to use a catalyst and perform step-by-step technological operations in several stages, and the resulting product will also require thorough cleaning of catalyst residues.

The closest known to the described invention (prototype) is a method for producing amino acid and dipeptide derivatives of fullerene (RF Patent No. 2144022, IPC С07К 9/00, 1998), in which sodium or potassium salts of aminocaproic, aminobutyric acid are used for the reaction with fullerene and others in the form of complexes with 18-crown-6, and the system is heterogeneous: o-dichlorobenzene - water and heating at 60 ° C for 6-8 hours, after which the solvents are distilled off, the residue is treated with a saturated solution of potassium chloride and water. The known method of synthesis involves the use of a two-phase system, heating, which is reflected in the low yield of the target product (not more than 5% per fullerene). In addition, in the known method, toxic o-dichlorobenzene is used, which is a narcotic irritant that damages the central nervous system, kidney liver. There is also a high temperature factor, which in the case of optically active compounds (amino acids, peptides, amino sugar) can lead to their racemization. In addition, this method is limited to the use of salts of amino acids and crown ether, which increases the hydrophobicity of amino acids. For compounds where there is no carboxyl group (amino sugar, polyhydroxylamines), this method is not acceptable.

The technical result of the present invention consists in using as a herbicide solutions of the following composition: adducts of N- (phosphonomethyl) -glycine with a mixture of fullerenes of the fraction C50-C92 0.01-0.1 wt. %, water - the rest. The method for the synthesis of water-soluble adducts of a mixture of fullerenes with various herbicides, which are compounds from the class of amino acids, is technological, highly productive, and universal, allows you to expand the range of herbicides for controlling especially perennial weeds, while reducing the herbicidal load on the soil and plants.

The technical problem of the invention is solved in that the water-soluble adducts of N- (phosphonomethyl) -glycine with a mixture of fullerenes of fraction C50-C92 are synthesized as follows:

- Mixed solutions of N- (phosphonomethyl) -glycine (non-selective herbicide-amino acid), a mixture of carbon fullerenes of fraction C ₅₀ -C ₉₂ (component B) and promoter (methylene glycol and / or paraformaldehyde) in appropriate organic solvents

- this mixture of solutions is heated with constant stirring to a reaction temperature of 58-60 ° C and is carried out with a constant return of solvents through a reflux condenser, then a catalyst (concentrated sulfuric acid) is added dropwise to the reaction mixture until gas evolution from the reaction mixture is completely stopped. The end of the reaction is accompanied by a change in the color of the system and the formation of a dark red opaque stable colloidal system of a mixture of synthesis products.

- the isolation of the synthesis products from the obtained colloid is carried out by adding the required amount of distilled water heated to 100 ° C and dividing the resulting system in a separatory funnel into fractions soluble in water and non-polar solvents, respectively.

- the last stage consists in evaporating to a dry residue an aqueous solution of the obtained water-soluble adducts of N- (phosphonomethyl) glycine with C50-C92 fullerenes in a vacuum oven at a temperature of no higher than 40 ° C.

After synthesis, the specified technical problem of the invention is solved by preparing solutions of the selected water-soluble fraction of the following composition, wt.%: Adducts of N- (phosphono-methyl) glycine with C50-C92 fullerenes - 0.01-0.1, water - the rest, and using these solutions both for spraying weed leaves onto the surface and for treating their root system.

Technical solutions of the invention can be illustrated by the following examples:

Example 1. Prepare component A, for which 0.1 g of a mixture of fullerenes C50-C92 is dissolved (fractional composition C ₅₀ -C ₅₈ (14.69%), C ₆₀ (63.12%), C ₆₂ -C ₆₈ (5.88%) , C ₇₀ (13.25%), C ₇₂ -C ₉₂ (3.06%)) in 100 g of methylbenzene with constant stirring at a temperature of 25 ± 5 ° C. Prepare component B, for which 1.2 g of N- (phosphono-methyl) -glycine is dissolved in 400 g of dimethyl ketone with constant stirring at a temperature of 25 ± 5 ° C. Components A and B are mixed in a 1: 1 ratio, heated to a temperature of 40 ± 2 ° C, and a promoter is introduced, in which 0.4 g of methylene glycol is used as an example. The mixture is heated to a temperature of 58-60 ° C and, with continued heating and constant stirring, sulfuric acid with a concentration of 98%, density 1.84 g / ml and a volume of 10 ml is added dropwise until the color of the system changes and the evolution of reaction gases stops completely. Next, the synthesis product is isolated, which is an adduct of N- (phosphonomethyl) glycine with C50-C92 fullerenes, by adding 500 g of distilled water heated to a temperature of 100 ° C to the resulting colloid. The resulting mixture is cooled, placed in a separatory funnel and the aqueous solution of the resulting mixture of synthesis products is drained, which is evaporated to a dry residue in a vacuum oven at a temperature not exceeding 40 ° C.

Example 2. Prepare component A, for which 0.1 g of a mixture of fullerenes C50-C92 is dissolved in 100 g of methylbenzene with constant stirring at a temperature of 25 ± 5 ° C. Prepare component B, for which 1.2 g of N- (phosphono-methyl) -glycine is dissolved in 400 g of dimethyl ketone with constant stirring at a temperature of 25 ± 5 ° C. Components A and B are mixed in a 1: 1 ratio, heated to a temperature of 40 ± 2 ° C and a promoter is introduced, for which, in this example, a mixture consisting of 0.2 g of methylene glycol and 0.2 g of paraformaldehyde is used. The mixture is heated to a temperature of 58-60 ° C and, with continued heating and constant stirring, sulfuric acid with a concentration of 98%, density 1.84 g / ml and a volume of 10 ml is added dropwise until the color of the system changes and the evolution of reaction gases stops completely. Next, the synthesis product is isolated, which is an adduct of N- (phosphonomethyl) glycine with C50-C92 fullerenes, by adding 500 g of distilled water heated to a temperature of 100 ° C to the resulting colloid. The resulting mixture is cooled, placed in a separatory funnel and the aqueous solution of the resulting mixture of synthesis products is drained, which is evaporated to a dry residue in a vacuum oven at a temperature not exceeding 40 ° C.

Example 3. Prepare component A, for which 0.1 g of a mixture of fullerenes C50-C92 is dissolved in 100 g of methylbenzene with constant stirring at a temperature of 25 ± 5 ° C. Prepare component B, for which 1.2 g of N- (phosphono-methyl) -glycine is dissolved in 400 g of dimethyl ketone with constant stirring at a temperature of 25 ± 5 ° C. Components A and B are mixed in a 1: 1 ratio, heated to a temperature of 40 ± 2 ° C, and a promoter is introduced, in which 0.4 g of paraformaldehyde is used as the example. The mixture is heated to a temperature of 58-60 ° C and sulfuric acid (concentration 98%), density 1.84 g / ml, volume 10 ml, is added dropwise with continued heating and constant stirring until the color of the system changes and the evolution of reaction gases stops completely. Next, the synthesis product is isolated, which is an adduct of N- (phosphonomethyl) glycine with C50-C92 fullerenes, by adding 500 g of distilled water heated to a temperature of 100 ° C to the resulting colloid. The resulting mixture is cooled, placed in a separatory funnel and the aqueous solution of the resulting mixture of synthesis products is drained, which is evaporated to a dry residue in a vacuum oven at a temperature not exceeding 40 ° C.

The test results of the obtained herbicide are presented in table 1.

The obtained solutions of products A - F were applied to the leaf surface (by spraying) and to the root system (by dipping) of the test plants, which were considered perennial cereal weeds, in particular Agropyron repens (creeping wheatgrass). After the same time after the beginning of the interaction of the preparations with the plant, the surface structure of the leaves was studied by transmission microscopy. The experiment was carried out in three biological replicates. The results are presented in table 2 (visual observation) and FIG. 1-7 (photographs of observations of a fragment of the reverse side of an Agropyron repens sheet containing a stomatal apparatus by light microscopy at 250X magnification).

In FIG. 1 shows photographs of control samples exposed to distilled water. It was shown that on both sides of the Agropyron repens leaf (wheat grass creeping) there are healthy cells of saturated color, stomatal apparatuses are visible.

In FIG. 2 shows photographs of samples when exposed to product A, at a concentration of 0.28 g / l. It was shown that the cuticle was destroyed on both sides of the leaf, the epidermis was partially damaged, and the stomatal apparatus was destroyed.

In FIG. 3 shows photographs of samples exposed to product B at a concentration of 0.28 g / l. It was shown that the cuticle was destroyed on both sides of the leaf, the epidermis was damaged, the stomatal apparatus was destroyed, and the xylem was partially affected.

In FIG. 4 shows photographs of samples exposed to product C at a concentration of 0.28 g / l. It has been shown that the cuticle is destroyed on both sides of the leaf, the epidermis is damaged, the stomatal apparatus is destroyed, because of the damage the inner layers of the leaf are visible.

In FIG. 5 shows photographs of samples exposed to product D at a concentration of 0.28 g / l. A healthy surface of the lower sheet with a partially damaged cuticle on the upper surface is shown.

In FIG. 6 shows photographs of samples when exposed to product E at a concentration of 0.28 g / l. It is shown that only the cuticle is destroyed, most severely in the upper part of the leaf.

In FIG. 7 shows photographs of samples when exposed to product F at a concentration of 2.8 g / l. It was shown that on both sides of the leaf of the cuticle, the epidermis is damaged, the stomatal apparatus and vascular bundles are destroyed, and the inner layers of the leaf are visible.

Thus, the obtained data indicate that, at the indicated concentration of 0.28 g / l, the effect of all new synthesized products is effective for disrupting the vital functions of the test plant, but at the same time, this concentration is insufficient for the action of an aqueous solution of a simple mixture of hydrated fullerene and N - (phosphonomethyl) -glycine in a ratio of 0.1: 100 and an aqueous solution of N- (phosphonomethyl) -glycine (starting herbicide). Considering that the effective working concentration of N- (phosphonomethyl) -glycine (glyphosate) is from 2.8 to 4.3 g / l, depending on the type of weed being treated, and the minimum effective concentration is not less than 1.4 g / l, then the obtained synthesis products are effective when the content of the active substance is 0.28 g / l, which will reduce the herbicidal load on the cultivated areas from 5 to 10 times.

Claims (1)

A continuous action herbicide based on adducts of N- (phosphonomethyl) -glycine with a mixture of fullerenes of the C50-C92 fraction, characterized in that it contains, wt. %:
N- (phosphonomethyl) -glycine adducts with a mixture of fullerenes fractions C50-C92 0.01-0.1 Water Rest

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