RU2488999C2 - Herbicidal composition and method of weed control in crops of cultivated plants - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. The herbicidal composition comprises as active ingredient an effective combination N-(2,6-difluorophenyl)-8-fluorine-5- methoxy[1,2,4]triazole[1,5-c]pyrimidine-2-sulfonamide (florasulam) (1) or a salt thereof and a herbicide of sulfonylureas series, which is a methyl ester 2-[[[[(4-methoxy-6-methyl-1,3,5-triazine-2-il)methylamine]carbonyl]amino]sulfonyl]of benzoic acid (tribenuron-methyl) (II) or its salt. The weight ratio of the components I:II is from 1:5 to 5:1. The composition also comprises a solid carrier or liquid solvent and a surfactant. When processing at an early stage of development of crop plants the herbicidal composition destroys or inhibits a wide variety of monocot and dicot weeds.

EFFECT: invention enables to improve the efficiency of processing.

8 cl, 4 tbl, 8 ex

Description

The invention relates to plant protection products that can be used in crops of cultivated plants, and more particularly, to a herbicidal composition based on two herbicides from the class of ALS inhibitors and to a method for controlling weeds in crops of cultivated plants based on this herbicidal composition.

One of the means for weed control in crops of cultivated plants of maize and wheat is the active substance of floraasulam (I)

N- (2,6-difluorophenyl) -8-fluoro-5-methoxy [1,2,4] triazolo [1,5-c] pyrimidin-2-sulfone amide, known from the patents EP 343752 and EP 537611.

Industrial preparations of the Dau Agrosaenses company are known both on the basis of one florasulam in the form of a suspension concentrate - Boxer, CK (50 g / l florasulam), and a number of two-component preparations in the form of suspoemulsions containing fluroxypyr methylheptyl ether - GF- preparations 184, SE (100 g / l of fluroxypyr methylheptyl ester + 2.5 g / l of flurasulam), Hiker, SE (100 g / l of fluroxypyr methylheptyl ether + 1 g / l of florasulam), Starane XL, SE (144 g / l of methylheptyl fluroxypyr ester + 2.5 g / l florasulam) or 2-ethylg 2,4-D acid xyl ester - Prima preparation, SE (300 g / l 2,4-D to-you + 6.25 g / l florasulam), as well as the preparation CJSC “August” Balerina, SE (410 g / l 2,4-D acid + 7.4 g / l florasulam). The preparations in the form of suspoemulsions Prima and Ballerina are registered in the "State catalog of pesticides and agrochemicals approved for use in the Russian Federation", Moscow, 2011.

Active ingredient tribenuron-methyl (II)

2 - [[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl) methylamino] carbonyl] amino] sulfonyl] benzoic acid methyl ester is known from patent EP 202830 and exhibits high activity against broad spectrum of weed plants. Tribenuron-methyl-based preparations are commercially in demand and are widely used in agriculture to protect crops. In the Russian Federation, in the “State catalog of pesticides and agrochemicals approved for use on the territory of the Russian Federation” for 2011, DuPont products are registered both on the basis of tribenuron-methyl - Granstar, STS (750 g / kg tribenuron-methyl) and in as a mixture with other sulfonylureas: Granstar Ultra, EDC (500 g / kg tribenuron-methyl + 250 g / kg chlorosulfuron); Allay Light, VDG (391 g / kg metsulfuron-methyl + 261 g / kg tribenuron-methyl); Caliber, VDG (500 g / kg of tifensulfuron-methyl and 250 g / kg of tribenuron-methyl).

In the claims of the Bayer Crop Science patents, combinations of a number of ALS inhibitors from the sulfonylurea group with many other substances, including florasulam, are patented. For example, patented two-component combinations based on amidosulfuron patent - EP 1418812, mesosulfuron or iodosulfuron-methyl - patent RU 2344601 and three-component combinations based on amidosulfuron and iodosulfuron-methyl - patent EA 6816 or mesosulfuron and iodosulfuron-EA 6816.

The materials of the company Dau Agrosaenses (http://www.dowagro.com/uk/cereal/faq.htm) give a general recommendation that preparations based on florasulam in some cases can be used sequentially or in the form of a tank mixture with other drugs on based on ALS sulfonylurea inhibitors, including with tribenuron-methyl based drugs. The materials of ZAO Avgust Firm (http://www.firm-august.ru/product/?countrv=rf&drug_type=71&drug_id=2704&part=reglament) also give a general recommendation on the use of Ballerina, SE in a mixture with tribenuron-based drugs -methyl. DuPont Brief Communication No. 3, published in North Central Weed Science Society Proceedings v. 62, 2007 (http://www.ncwss.org/proceed/2007/Abstracts/003.pdf) also mentioned the possibility of joint application in the form of a tank mixture of different preparations based on 2,4-D ester of acid, florasulam and tribenuron-methyl.

In all of the above sources of information, there is no information about the finished formulation (herbicidal composition) based on a two-component mixture of florasulam and tribenuron-methyl or any direct indications of the advisability of creating such a formulation and its composition.

Keeping in mind the practical interest from combining the two active substances in one preparation, the aim of the present invention was to provide such a herbicidal composition. The problem was solved by the development of a herbicidal composition containing, as active substances, a combination of N- (2,6-difluorophenyl) -8-fluoro-5-methoxy [1,2,4] triazolo [1,5-c] pyrimidin-2- sulfonamide (florasulam) (I) or a salt thereof and another sulfonylurea herbicide, wherein the other sulfonylurea herbicide is methyl ester 2 - [[[[(4-methoxy-6-methyl-1,3,5 -triazin-2-yl) methylamino] carbonyl] amino] sulfonyl] benzoic acid (tribenuron-methyl) (II) or a salt thereof. Such a composition also contains a solid carrier or a liquid solvent and a surfactant. It was unexpectedly found that in the range of weight ratios of two substances in the range from 1: 5 to 5: 1, a synergistic effect is manifested, i.e. found the range of ratios of active substances, in which such a composition is synergistically effective.

The proposed herbicidal composition exhibits excellent herbicidal action against a wide range of monocotyledonous and dicotyledonous weeds, including perennial root shoots.

The action of the proposed herbicidal composition extends to such monocotyledonous weeds such as oats, oatmeal, foxtail, dewdrop, chaff, wheat grass, blackberry, millet, bluegrass, bristle, including perennials such as porcupine, sorghum, gumai, creeping wheat grass, raw others.

In dicotyledonous weeds, the effect extends to species such as shiritsa, gauze, bedstraws, morning glory, cochia, cassock, purple bindweed, highlander, sid, mustard, nightshade, asterisk, veronica, violet, gingerbread, creeper, mallow. such as field bindweed, sow thistle yellow and sow thistle pink, sorrel, wormwood and others.

The herbicidal composition in accordance with the present invention can be applied immediately after sowing before plant emergence, however, post-emergence application at an early stage of development of weeds and cultivated plants is preferred. Herbicidal action occurs, as a rule, quickly: there is a characteristic cessation of growth or death after a certain time. At the same time, cultivated plants remain intact.

Suitable for this combination of herbicides are, for example, such formulations as water-soluble and wettable powders, granules, including water-soluble and water-dispersible, and liquid formulations in the form of water-glycol and aqueous solutions.

Oxyethylated or propoxyethylated alkyl phenols, polyoxyethylated alcohols or amines, ethoxy-propoxy block copolymers, sulfates or phosphates of polyoxyethylated alcohols or their salts, ethoxylated tristyrylphenyl or propoxylated or propoxylated sulfates or phosphates can be used as surfactants in the formulation. their salts, alkyl sulfates or aryl sulfates or their salts, alkyl sulfonates or aryl sulfonates or their salts, lignosulfonates, condens th e alkylnaphthalene sulfonates, including compounds such as 2,2-dinaphthylmethane-6,6-disulfonate, sodium dibutylnaphthalenesulfonate, salts of polycarboxylates, sulfosuccinate derivatives.

Wettable powders are uniformly dispersible in water preparations, which, along with the active substances, contain a solid carrier (inert substance, for example, kaolin, bentonite, alkaline or alkaline-earth metal carbonate, sodium sulfate, calcium stearate, trisodium phosphate, lactose or other natural sugar) and a surfactant that acts as a wetting agent and / or dispersant.

Water-dispersible and water-soluble granules can be obtained by a variety of known granulation methods from a mixture consisting of a mixture of active substances with inert carriers (for example, noted above), surfactants listed above, if necessary adding antifoam and other auxiliary substances.

The herbicidal composition in the form of a wettable or water-soluble powder or water-soluble or water-dispersible granules has the following ratio of its constituent components in wt.%:

Florasulam or its salt (acid equivalent) 3-70% tribenuron-methyl or its salt (acid equivalent) 10-60% surfactant or mixture thereof 5-25% antifoam 0-0.2% carrier up to 100%

Aqueous-glycolic and aqueous solutions are prepared from preformed amine salts or alkali metal salts of flurasulam and tribenuron-methyl, preferably in aqueous or aqueous-organic solutions.

The herbicidal composition in the form of an aqueous or water-glycol solution containing the constituents in its composition in the following amounts, in wt.%:

Florosulam salt (acid equivalent) 10-30% tribenuron-methyl salt (acid equivalent) 10-30% surfactant or mixture thereof 5-25% antifoam 0,0,2% triethylene glycol 0-15% water up to 100%

Another object of the invention is a method for controlling weeds in crops of cultivated plants, which consists in applying the herbicidal composition based on florasulam and tribenuron-methyl in effective amounts to weeds to be destroyed or their habitat.

The following are examples of the preparation of various preparative forms, their compositions (table No. 1) and characteristics (table No. 2), as well as the results of the biological effectiveness of a number of preparative forms (tables No. 3 and 4). The following examples illustrate but do not limit the present invention.

Example No. 1.

Obtaining wettable powders (SP).

A mixture of tribenuron-methyl and florasulam, the calculated amounts of surfactants (wetting agent and dispersant), a carrier and, if necessary, an antifoam are loaded into the mixer. The mixture is thoroughly mixed, then ground in a mill to a fineness of at least 85% of particles with a size of less than 10 microns.

Example No. 2.

Obtaining a water-soluble powder (GRP)

150 g of tribenuron-methyl and 30 g of florasulam are loaded into the mixer, 10 g of trisodium phosphate are added, the calculated amounts of surfactants (wetting agent and dispersant), antifoam are mixed thoroughly and then milled to a particle size of at least 85% of particles with a size of less than 10 microns.

Example No. 3.

Obtaining water-dispersible granules (VDG).

A granulation mixture is prepared in the mixer consisting of tribenuron-methyl and florasulam in the selected ratio, an inert carrier, surfactants (wetting agent, dispersant), antifoam, thoroughly homogenize, grind and add the required amount of water to a total moisture content of 8-22%, obtained the mass is sent to a granulator where granulation is carried out by any of the known methods. The obtained granulate is dried to a moisture content of not more than 2%, if necessary, additionally crushed and dispersed on sieves to isolate the desired fraction of the granules.

Example No. 4.

Obtaining water-soluble granules (VRG)

400 grams of tribenuron-methyl and 200 grams of florasulam, 8 grams of trisodium phosphate are loaded into the mixer, surfactants (wetting agent and dispersant) and antifoam are added, thoroughly homogenized, the required amount of water is added to a total moisture content of 5-16%, the resulting mass is sent and the granulator where granulation is carried out by any of the known methods.

Example No. 5.

Obtaining water-glycol (AGR) and aqueous solutions (BP)

The calculated amount of the corresponding amine or alkali solution, water and glycol (for water-glycol solutions) are placed in the reactor, and tribenuron-methyl and florasulam are gradually sprinkled in the selected ratio. After the dissolution of the active substances is completed, the required amounts of surfactants and, if necessary, an antifoam are loaded into the solution.

Example No. 6.

Assessment of the physico-chemical characteristics of the resulting formulations was carried out in accordance with international tests presented below:

1. Stability test of a 0.1% aqueous suspension of the preparation (CIPAC MT 168 and MT 15.1 methods).

2. Test for moisture content according to Fisher (method CIPAC MT 30).

3. Dispersibility test (CIPAC MT 167 methodology).

4. Test for determining the pH value (method CIPAC MT 75).

From the physico-chemical characteristics given in table 2, it follows that the evaluated formulations comply with the requirements of GOST R 51247-99 “Pesticides. General specifications. "

Biological tests

Example No. 7.

Tests in the artificial climate laboratory

The initial assessment of the herbicidal activity of mixtures of florosulam with tribenuron-methyl in order to select the optimal ratio of substances was carried out in an artificial climate laboratory under the following camera operating conditions: day duration - 16 hours, night - 8 hours, illumination in the daytime - 15000 Lx, air temperature - 20 ° C, relative humidity - 75%, the duration of the experiment - 30 days.

As models of weeds, white gauze (Chenopodium album) and a common sod (Xanthium strumarium) were used.

Samples of the herbicidal test compositions were prepared by dissolving mixtures of florasulam and tribenuron-methyl in predetermined proportions in a neutral organic solvent with the addition of a nonionic surfactant and subsequent dilution with water to the desired concentration.

For the treatment of test plants, an experimental sprayer was used that was configured as close as possible to the production mode according to the following indicators: rate of flow of the working fluid, uniformity of its distribution on the treated area, degree of dispersion of the droplets.

Test plants were treated with a working fluid flow rate of 400 l / ha, the average droplet size of 180 ± 20 microns (see "Chemistry in Agriculture", 1985, No. 7).

The processing of test plants was carried out in the phase of 3-6 leaves, the repetition of experiments was 3 times. Accounting was carried out 40 days after treatment in comparison with the control.

Synergism was calculated using the Colby formula (see S.R. Colby, Weeds. “Calculating Synergistic and Antagonistic response of herbicide combination”, v.15, pp.20-22, 1967):

E = ά + β- (ά × β): 100, where

ά -% inhibition by component A;

β -% inhibition by component B;

E - expected (estimated) efficiency. The results are presented in table 3.

Example No. 8.

Field Tests

Tests of the herbicidal activity of preparations based on florasulam and tribenuron-methyl in the field were carried out on winter wheat crops.

Boxer, CK (50 g / l Florasulam), manufactured by Dow Agrosciences, and Granstar, CTC (750 g / kg tribenuron-methyl), manufactured by DuPont, were used as a reference.

The size of the plots is 0.75 ha, the number of replications is 3 for each option. The phase of development of corn plants at the time of processing is 5-6 true leaves. Vegetative plants were sprayed using a POM-63 sprayer. The flow rate of the working fluid is 300 l / ha. Accounting for weeds was carried out before treatment, 30 days after treatment.

The crops under study were littered with weeds such as wild oats, chicken millet, bristle, neglected mallow, one-year-old purse, overgrown beetle, white gauze, yellow sow thistle, pink thistle, walnut, mountaineer buddy, asterisk, veronica, violet, confinement, field bindweed and others.

During spraying, weeds had from 4 to 6 true leaves, perennial leaves had a rosette of 8-12 cm in diameter.

All tested compounds have a wide spectrum of action on weeds and are not toxic to wheat in this growth phase. The average results of evaluating the sensitivity of various types of weeds to drugs are presented in table 4.

Table 1 The composition of the preparative forms of the herbicidal composition. Component Name The composition of the drug, wt.% GRP Joint venture EDC VRG Joint venture AGR BP Joint venture EDC Sample Number No. one 2 3 four 5 6 7 8 9 The ratio of active substances (tribenuron-methyl: florasulam) 5: 1 4: 1 3: 1 2: 1 1: 1 1: 2 1: 3 1: 4 1: 5 one Tribenuron methyl fifteen 60 56.1 40 36 12 CE * 10 CE * fifteen 12.8 2 Floralsulam 3 fifteen 18.7 twenty 36 24 CE * 30 CE * 60 64 3 Aryl (alkyl) sulfonate (sulfate) salt 2 1,5 - 3 - - - - - four Polyoxyethylene alcohol - - - - - 5 - - - 5 Oxy (propoxy) ethylphenyl alkyl phenol four - - - - - - - - 6 Sulfate (phosphate) of polyoxyethylated alcohol or their salts 5 7 Dialkyl sulfosuccinate - - - - 2 - - - 2 8 Polycarboxylate Salt 5 - - 12 - - 6 - 9 Condensed Alkyl Naphthalenesulfonate - 6 5 - - - - - 10 10 Lignosulfonate - 5 - - 7.5 - 9 - eleven Ethoxylated Tristyrylphenol - - - - - 2 - - - 12 Sulfate (phosphate) - - - - - - - - - ethoxylated tristyrylphenol or their salts 13 Ethoxy propoxy block copolymer - - - - - - 5 - four fourteen Antifoam agent 0.1 0.1 0.15 0.15 - 0.15 - 0.1 0.1 fifteen Bentonite - - - - 5 - - up to 100% - 16 Kaolin - up to 100% - - - - - - - 17 Alkaline or alkaline earth carbonate 5 3 - - - - - -

Continuation of table 1. eighteen Lactose or other natural sugars - - up to 100% up to 100% - - - - up to 100% 19 Sodium sulfate up to 100% - - - up to 100% - - - - twenty Trisodium phosphate 10 5 - 8 4,5 - - - - 21 Water - - - - - up to 100% up to 100% - - 22 Calcium stearate - - 0.2 0.15 - - - - 0.1 23 Triethylene glycol - - - - - fifteen - - 0.1 * CE - acid equivalent

table 2 Physico-chemical properties of the obtained samples. Sample Number physical and chemical indicators Appearance Stability 0.1% - ion according to the preparation of an aqueous suspension (solution),% The activity index of hydrogen ions of 1% aqueous suspension (solution) of the preparation, pH Mass fraction of water,% Dispersibility% one Beige powder one hundred 7.3 1.85 100.0 2 Beige powder 89.5 6.5 0.8 89.0 3 Beige granules 90.5 7.1 0.95 94.0 four Beige granules 99.3 7.8 1.3 100.0 5 Beige powder 90.5 6.9 1.75 93.5 6 Transparent yellow liquid without delamination - 7.8 - - 7 Transparent yellow liquid without delamination - 7.2 - - 8 Beige powder 89 6.55 1.7 85.3 9 Beige granules 93.5 6.35 1.65 93

Table 3 Test results of the herbicidal activity of the compositions on test plants in a greenhouse. No. The ratio of tribenuron-methyl and florasulam Application rate, g / ha Inhibition of the growth of test plants of the fruit cock, in% of control Synergism Inhibition of growth of test plants marie white, in% of control Synergism tribenuron methyl floresulam Fact. Calc. Fact. Calc. one 2 3 four 5 6 7 8 9 10 5 5 75 72.5 +2.5 61 47.5 +13.5 one 1: 1 9 9 90 82.5 +7.5 82 68.5 +13.5 12 12 98 88.5 +9.5 96 91 +5.0 2 2: 1 12 6 90 79.3 + 10.7 76 62,2 +13.8 eighteen 9 99 89.5 +9.5 92 79.8 +12.2 3 3: 1 fifteen 5 92 82.5 +9.5 77 61.5 +15.5 eighteen 6 99 86.5 +12.5 90 71.7 +18.3 four 4: 1 12 3 81.2 70.1 +11.1 67 53,2 +13.8 twenty 5 one hundred 87.5 +12.5 82 72.0 +10.0 5 5: 1 fifteen 3 92 77.3 +14.7 69 57.1 +11.9 twenty four 99 85.8 +13.2 86 70.0 +16.0 6 1: 2 6 12 95 86.5 +8.5 96.4 88.9 +7.5 7 1: 3 5 fifteen 98 91.8 + 6.2 one hundred 96.3 +3.7 8 1: 4 3 12 94 83.8 +10.2 96 88 +8.0 9 1: 5 3 fifteen 99 90.3 +8.7 one hundred 96 +4.0

Continuation of table 3. one 2 3 four 5 6 7 8 9 10 3 - 35 - - twenty - - 5 - 45 - - 25 - - 6 - 46 - - 26 - - 9 - fifty - - thirty - - 12 - 54 - - 40 - - Tribenuron methyl fifteen - 65 - - 45 - - eighteen - 70 - - 55 - - twenty - 75 - - 60 - - 24 - 80 - - 65 - - thirty one hundred 70 3 35 22 four 43 25 - - 5 fifty thirty Floralsulam - 6 55 - - 37 - - - 9 65 - - 55 - - 10 68 - - 58 - - - 12 75 - - 85 - - - fifteen 85 - - 95 - -

Table 4 The sensitivity of various types of weeds to herbicides (accounting before harvesting). Sample number, ratio Application rate g / ha Reduction of weediness,% of control tribenuron methyl floresulam Millet Chicken Gray bristles Rosichka blood red Shiritsa thrown back Leaf Ambrosia Portulak garden Sample 1 1: 1 5 5 71.3 73,2 76.5 99.1 84.5 88.9 Sample 3 3: 1 fifteen 5 96.4 97.1 96.8 99.1 92.3 94.8 Sample 5 5: 1 fifteen 3 93.8 94.5 95.1 one hundred 88.7 91.5 Boxer, CK 5 94.5 91.6 90.3 one hundred 11,4 78.6 Granstar, STS 10 0.7 0 0 98.4 one hundred 87.2 Control ^* 53,4 42.3 21,2 32,4 28,2 17.1 In control - the number of weeds pcs / m ²

Claims (8)

1. A herbicidal composition containing, as active substances, an effective combination of N- (2,6-difluorophenyl) -8-fluoro-5-methoxy [1,2,4] triazolo [1,5-c] pyrimidin-2-sulfonamide ( Florasulam) (I) or its salt and another sulfonylurea herbicide, wherein the other sulfonylurea herbicide is methyl ester 2 - [[[((4-methoxy-6-methyl-1,3,5-triazine -2-yl) methylamino] carbonyl] amino] sulfonyl] benzoic acid (tribenuron methyl) (II) or its salt, the weight ratio of components I: II can vary from 1: 5 to 5: 1, as well as tv A solid carrier or liquid solvent and surfactant. 2. The herbicidal composition according to claim 1, characterized in that the active substances are taken in synergistically effective amounts. 3. The herbicidal composition according to claim 1, characterized in that it further comprises other target additives. 4. The herbicidal composition according to any one of claims 1 to 3, characterized in that it can be used in the form of a formulation selected from the group of: wettable or water-soluble powders, water-soluble or water-dispersible granules, aqueous or water-glycol solutions. 5. The herbicidal composition according to claim 1, characterized in that the composition contains a compound selected from the group: hydroxyethylated or propoxyethylated alkyl phenol, polyoxyethylated alcohol or amine, ethoxypropoxyblock copolymer, polyoxyethylated alcohol sulfate or phosphate or their salts, ethoxylated tristyrylphenol , sulfate or phosphate of ethoxylated or propoxylated tristyrylphenol or their salts, alkyl sulfate or aryl sulfate or their salts, alkyl sulfonate or aryl sulfonate and whether their salts, lignosulfonate or a salt thereof, condensed alkylnaphthalene sulfonate, a polycarboxylate salt, a sulfosuccinate derivative, or mixtures thereof. 6. The herbicidal composition according to claim 1 in the form of a wettable or water-soluble powder or water-soluble or water-dispersible granules, characterized in that it contains as a solid carrier a substance selected from the group: kaolin, bentonite, alkaline or alkaline-earth metal carbonate, lactose , natural sugars, sodium sulfate, calcium stearate, trisodium phosphate in the following ratio, wt.%:
Florasulam or its salt (acid equivalent) 3-70 tribenuron-methyl or its salt (acid equivalent) 10-60 surfactant or mixture thereof 5-25 antifoam 0-0.2 carrier up to 100 7. The herbicidal composition according to claim 1 in the form of an aqueous or aqueous glycol solution containing the constituent components in the following amounts, wt.%:
Florosulam salt (acid equivalent) 10-30 tribenuron-methyl salt (acid equivalent) 10-30 surfactant or mixture thereof 5-25 antifoam 0-0.2 triethylene glycol 0-15 water up to 100 8. A method of combating weeds in crops of cultivated plants by treating them with herbicides containing florausulam and tribenuron-methyl as active substances, characterized in that an effective amount of the herbicidal composition according to any one of claims is applied to the weeds to be destroyed or their habitat. 1-7.