Insecticidal composition and method of combating insects


(57) Abstract:

Describes the insecticidal composition comprising, in wt.%: cypermethrin 1.8 to 6.3 and fipronil of 0.8-2.5 at a weight ratio of from 1.5:1 to 4.5:1; modified white carbon 4,0-12,0 and Aerosil 1,3-4,0 when the weight ratio between the two last from 3:1 to 6:1; ethylendiaminetetraacetic acid 2,0-10,0 and potassium carbonate and 0.8 to 8.0 when the weight ratio between the last two from 1.1:1 to 2:1, and urea - rest. Describes the method of controlling insects by treating the plants an effective amount of the composition. The technical result is an increase in the activity of the composition, enhancing the stability of working, improved particle size distribution. 2 c.p. f-crystals, 12 tab.

The present invention relates to a combined insecticidal compositions containing two active substances, in particular insecticidal compositions containing as active ingredient a mixture of cypermethrin and fipronil in synergistic active ratio of components.

This composition is designed for controlling insects on green plants, mostly from the Colorado potato beetle. To control Colorado potato beetle last 10-15 is Trina-3-phenoxyphenyl--lanmeter-3-(2,2 - dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate. The advantage of cypermethrin are high insecticidal activity, a wide range and duration of protective actions (N. N. Melnikov. Pesticides and plant growth regulators. The Handbook. M.: Chemistry, 1995, S. 196).

Along with this, it is known that cypermethrin, like other pyrethroids, decompose when stored and used under the action of oxidizing agents and UV radiation, which leads to the decrease of its activity and duration of action. To improve the efficiency and duration of action of pyrethroids in the composition containing products add or so called "true synergists, for example, piperonylbutoxide or other insecticides, as well as antioxidants and absorbers of UV radiation. (See patents of the Russian Federation N 1466635, N 2097971, N. N. Melnikov. Chemistry and technology of pesticides. M.: Chemistry, 1987, S. 220.)

Known solid insecticide designed on the basis of cypermethrin INTA-VIR", containing a sorption medium Aerosil, as surface-active substances-sulfonic acid as a stabilizer suspension - lignosulfonate or concentrate sulphite yeast brew, and as filler - urea. INTA-VIR comes in the form of tablets of a certain weight and recommended to combat insect is permethrin eventually decomposes under the action of various oxidizing agents and UV radiation.

In addition, the long and often excessive use of PYRETHROID preparations against the Colorado potato beetle has led to the development of resistance of this pest to pyrethroids (See. Amirkhanov nutrient content, and other Features of estimation of the level of resistance of Colorado potato beetle to pyrethroids. In Proc. of "the State of the problem of resistance of pests to HSR and its overcoming", Riga, 1998). INTA-VIR has all the above disadvantages. In this regard, there is a need to create a new, more efficient and stable preparation containing as active ingredient the same cypermethrin so that a new drug can be applied not only against the Colorado potato beetle, but against other insect pests of green plants, which use INTA-VIR.

One way to overcome the resistance of Colorado potato beetle to pyrethroids may be adding to the PYRETHROID insecticide drug active against this pest and belonging to a new group of compounds, resistance to which is to be formed did not have time. One of these drugs is insecticidal drug company rhône-Poulenc "Regent", the active ingredient is fipronil.

Fipronil-5-amino-3-CIPW N 0295117 from 12.06.87,, publ.14.12.88 as a drug effective against arthropod, plant nematode, protozoa and other pests.

In the International application 095/22902 described synergistic termiticidal composition containing as active ingredients derived 3-cyano-1-phenylpyrazoles, including fipronil, and PYRETHROID compounds, including cypermethrin. In the claims the claimed relationship between PYRETHROID and fipronil from 0.1 to 10, preferably from 0.5 to 5. The composition used for termite control, treating effective amount of the composition of the soil or material in which the termites live or which they eat.

It is known that fipronil shows high activity against the Colorado potato beetle, therefore the study of mixtures of cypermethrin with fipronil in order to enhance the toxicity of cypermethrin against the Colorado potato beetle seemed promising.

A significant drawback of fipronil is its phytotoxicity. Even in small concentrations, this drug has a very hard effect on plants, which limits the potential for its use to control insect pests of green plants.

The other half is the country to ensure its competitiveness as a means to control insect pests of green plants used including personal subsidiary plots.

The object of the present invention is an insecticidal composition containing as active ingredients cypermethrin and fipronil in synergistic effective amounts to control insect pests of green plants, mostly from the Colorado potato beetle in combination with suitable for the manufacture of solid formulations of carriers, fillers, surfactants and other additives.

Another object of the invention is a method of combating insect pests of green plants using this composition.

The effect of mixtures of cypermethrin and fipronil most extensively studied in the Colorado potato beetle, used those populations that have already acquired a certain resistance to cypermethrin. According to laboratory experiments, the application of a mixture of cypermethrin and fipronil in the ratio of 2.5:1 toxic effect increases 1.68 times. When moving into the field, this effect persists for the ratio of components cypermethrin:fipronil from 1.5:1 to 4.5: 1, although quantitatively changed under the influence of various notarisii of 1.8:1 in comparison with the standard INTA-VIR showed that trial medication maintains high efficiency even by the 15th day of the survey (over 96%), while the benchmark in a similar consumption rate caused the death of the pest, close to full, only the first three days, to the end of the study (15 days) efficiency dropped to 69%.

In addition to the Colorado potato beetle conducted experiments on pests, which, unlike the Colorado potato beetle, fipronil does not have a high efficiency. In laboratory experiments on rice weevil and field experiments on the cabbage butterflies also observed a slight increase in toxicity, that is, the drug can be used to combat these pests.

Test the phytotoxicity of the mixture, cypermethrin and fipronil (1,8:1) for model plants in laboratory conditions showed that the risk of fipronil for green plants when applied in mixture with cypermethrin significantly reduced, i.e. the application of a mixture safer for plants than the use of fipronil. Study the possibility of replacing part of the imported data on white soot domestic production (also based on SiO2) has shown that the required quality characteristics of the tablets can be provided, elegantula substances during storage and under the action of UV radiation is achieved by adding to the formulation of the drug mixture ethylendiaminetetraacetic acid and potassium carbonate in a ratio of from 1.1:1 to 2:1. This mixture also works well as an opener. (See table. N 9, 10, 11.) Ethylenediaminetetraacetate acid and its salts previously to increase the stability and improve the performance of drugs were not used. It is known the use of complexes of ethylendiaminetetraacetic acid with iron to combat chlorosis, i.e. as a source of micronutrients in plant nutrition (N. M. Dyatlova and other Chelating agents. M.: Chemistry, 1970, S. 360).

In the patent of Russian Federation N 2028053 describes the use of zinc complex ethylendiaminetetraacetic acid as an additive for removing the negative impact of chlorsulfuron on the content of essential amino acids in the grain.

As the main filler in the composition as well as in the preparation of INTA-VIR is urea, which is both environmentally friendly binder material for forming tablets, providing durability without adding any polymer components. Urea is highly soluble in water, which creates conditions for dissolution of the tablet and the formation of a continuous and homogeneous working suspension.

As the surfactant may be any of anionic surfactants, including the phenols and fatty acids, and as stabilizers suspension - high molecular weight anionic surfactants, for example ligno - sulfonates of alkali metals and calcium concentrate sulphite yeast brew, etc.

Selected fillers, surfactants and adjuvants in combination provide excellent performance characteristics, and chemical and physical stability while maintaining high efficiency claimed insecticidal composition.

This is followed by examples illustrating the invention.

Example 1. Obtaining products based on mixtures of cypermethrin and financila

1.1. In the mixer load of 6 g of the modified white black*and 2 g of Aerosil**. The mixture is heated to 30 - 35oC and through the nozzle add 2,98 g (94%) (0,006 m) cypermethrin heated to 50 - 60oC. the Mixture is stirred for 30 minutes, keeping the temperature between 30 and 35oC (mixture No. 1).

Note:*mark BS-120, GOST 18307-78;

**import 200 mark.

1.2. In the apparatus load of 75 g of sulfonic acid and 25 g (80%) of fipronil, stirred for 30 minutes at 20 - 25oC (batch No. 2).

1.3. In a mixer with the charge N 1 (10,98 g) load of 7.5 g (0,0034 m) charge N 2, stirred for 30 minutes at 20 - 25oC, then load 2 UB>), 6 g of sulfonic acid and 64,52 g of urea. The mixture is stirred for 30 minutes.

To obtain tablets charge additional ground in a pin mill and pressed into tablets weighing from 4 to 12,

Similarly receive other samples whose composition is given in table No. 1, including the sample No. 10, which does not contain EDUC and K2CO3.

Example 2. Evaluation of the insecticidal activity of the mixture of cypermethrin and fipronil

Insecticidal activity was studied in laboratory conditions on adult beetle rice weevil.

Cups with insects were treated with solutions of several successive concentrations of the mixture of fipronil and cypermethrin in the ratio of 1:1.8 and current substance in triplicate (mean values). As standards used cypermethrin and fipronil in the same concentrations. The counts were made at 48 hours after treatment. The results of the tests are presented in table No. 2.

Example 3. Evaluation of synergistic effect in laboratory experiments

The experiments were conducted on the Colorado potato beetle Leptinotarsa decem - lineata say, the order Coleoptera. In the laboratory used the population of larvae of the beetle 2-3 age, collected on atively solutions of insecticides with progressively decreasing the concentration of active substances. The account of the destruction carried out after 24 hours. The coefficient of synergy (COP) was calculated on the basis of the additivity formula:

< / BR>
where SC-50 and IC-50B - concentration, which killed 50% of the test insects;

%A - % the death of insects under the action of the component;

%B - % the death of insects under the action of the component B.

The results of the tests are presented in table N-3. According to laboratory experiments, the toxic effect of the mixture is increased to 1.68 times.

Example 4. Assessment of efficacy under field conditions

Small-plot field experiments were carried out in the Moscow region, where Colorado potato beetle acquired partial resistance to pyrethroids due to frequent use to combat this pest. Processing was performed using Castelfranco sprayer "quasar". Accounting for mortality was performed after 24 hours. The concentration of the studied drugs and ratio of components in the mixtures were calculated according to the active substances. The magnitude of the norms of consumption of drugs was adopted standards, it is recommended for use in personal subsidiary plots against the Colorado potato beetle. For cypermethrin is 300 mg of nutrient content per 10 liters of water, i.e., 0,003% D. C., for fipronil 160 mg of nutrient content per 10 litres, i.e. 0,0016% D. C. tx2">

As can be seen from the experiments, 1/4 + 1/4 consumption rates of the two components causes a higher percentage loss than 1/2 the rates of consumption of each component.

Example 5. Tests for acute phytotoxicity

The tests were carried out in laboratory conditions on the cucumber seedlings of the cultivar "April" in the first stage of this sheet. The plants were treated by spraying and left after processing in the bathroom on a shelf at a temperature of 17 - 24oC. the test Results are presented in table No. 5 (given the mean values of 3 experiments).

As the table shows, the danger of fipronil in a mixture with cypermethrin when applying for green plants is significantly reduced.

Example 6. Evaluation of biological efficacy and synergistic effects of insecticidal compounds in field experiments

Evaluation of the biological activity of insecticidal compositions were performed in small-plot field experiments on potato against Colorado potato beetle larvae. As standards used drug INTA-VIR (D. C. cypermethrin) and drug Regent-800 C., (D. C. fipronil). The area of the experimental plots 10 m2repeated three times. Surveys were conducted on model bushes (3 hive on the plot). Each sample ISPR next day precipitation was absent. Processing of data was performed by hand sprayer, accounting for 24 hours after treatment. Take into account the living, the sick and the dead larvae, and one half of the patients were referred to the living, and the other for the dead (K. A. Gard. Methods for testing the toxicity and efficacy of insecticides. M: Selhozizdat, 1963). Statistical processing of data was performed using the computer program a one-way ANOVA.

A synergistic effect was calculated by the Colby formula


where Enthe observed % of the deaths of insects;

Eaboutexpected % of the deaths of insects, and

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where X % of the deaths of insects from the component I;

Y - % the death of the insects from the component II.

The results are given in table No. 6.

Example 7. Field trials insecticidal compositions against the Colorado potato beetle on potatoes. The study duration of protective action

The tests were carried out on the allotment in Ostrogozhsk district, Voronezh region on potato varieties Lorch between 14.06 on 29.06.99, the plot Size of 25 m2the placing step four, the number of replications - 4.

The plants were sprayed with the solution obtained by dissolving in water R>
The calculation of the pests spent 14.06 (before processing) 17.06, 21.06, 29.06. The period of the protective action of the pesticide 15 days. Date of harvest 30.08.99, as the standard used well-known drug INTA-VIR based on cypermethrin (see U.S. Pat. RF N 2093027).

Negative impact on the growth and development of potato spraying the test drug did not.

During the testing period the larvae 1-3 ages 1-generation Colorado potato beetle constitute more than 90% of the total population of the pest. The results of the tests are presented in table N-7. Shown here are averages of 4 replicates. The tested drugs within the first week after treatment provided 100% mortality of the pest, and by the 15th day counts its effectiveness remained high and was more than 96%. At the same time standard in a similar consumption rate caused the death of the pest, close to full (98.2 per cent), only the first three days, the seventh day of the efficiency standard is reduced to 84%, and by the end of observations (15 days) - up to 69%.

Half the consumption rate of the test product (4 g/10 l of water) showed high efficiency (100% mortality) for 7 days, then the death of the pest began to decline and to 15 days was 81%. Etal is 1,5 - 603%).

Thus, the test drug effectiveness significantly outperforms the benchmark.

Harvest in the variant with the test drug is 88% higher than in the control and significantly higher than in the variant with the standard.

By the end of the census percent while feeding shrubs of Colorado potato beetle in the untreated control exceeded 90% in the variant with standard (8 g / 10 l)- 60%, and in the variant with the test drug (8 g / 10 l) did not exceed 5%.

Example 8. To study the efficacy of drugs against cabbage moth on cabbage

The effectiveness of the drug (sample No. 10) against the larvae of 2-3 ages cabbage butterfly Pieris brassicae L. was studied in field plot experiments on the cabbage varieties "Glory 1305". The consumption rate of the drug 8 g per 10 l of water. The flow rate of the working fluid 10 l 100 m2planting cabbage. The size of plots 24 m2replicates-3. Standards - INTA-VIR (D. C. cypermethrin) and Regent 800 C. D., (D. C. fipronil).

The number of caterpillars on the plants were counted before treatment and 24 hours after treatment. The percentage mortality was calculated taking into account the mortality of larvae in the control. The results are given in table No. 8.

The table shows that when the joint vzaimnoe strengthening their actions. Despite the low efficacy of fipronil against this object, the effectiveness of the mixed product containing fewer cypermethrin, even slightly higher than the efficiency of standard INTA-VIR containing cypermethrin at higher concentrations.

Example 9. The study of the stability of active substances under conditions of accelerated aging and under the action of UV radiation

The study of the stability of active substances was carried out on two samples, one of which (sample 10) did not contain in its composition ethylendiaminetetraacetic acid and potassium carbonate. Both samples immediately after preparation was analyzed for content of cypermethrin and fipronil. Samples in polyethylene bottles were placed in a thermostat and kept at 40oC for 120 days, which corresponds to 15 months of storage under normal conditions (instruction P-42-2-82). Spent three parallel experience and determined the average values, the method of analysis liquid chromatography.

To assess the stability of existing substances under conditions of UV irradiation, the samples were kept for 24 hours at 30 - 34oC under the action of a source of UV radiation.

The results presented in tables 9 and 10 indicate tlno improves the stability of active ingredients during storage and under the action of UV radiation.

For comparison, the test results of the drug INTA-VIR conducted under the same conditions.

Table 11 shows the operational characteristics of the tablets made according to the method described in example 1. The stability of the suspension was determined according to GOST 14189-81, sieve residue - OST 113-04-2-91 p. 3, granulometric composition - granulometry brand Alcatel-850.

Table 12 characteristics of the tablets based on the ratio of the sorption fillers in the charge.

As shown in tables N 9-12 results, in addition to improving chemical stability, introduction to composition white black and mixtures ethylendiaminetetraacetic acid and potash can significantly improve the performance characteristics of tablets compared to tablets INTA-VIR", namely: to reduce the disintegration time of the tablets about 2 times, to increase the stability of the suspension is about 1.5 times, to improve its granulometric composition that allows for the uniform distribution of the drug on the treated surface to ensure its high biological efficiency.

1. Insecticidal composition containing cypermethrin, Aerosil, mocheotdelenie cypermethrin to fipronil is 1.5:1 to 4.5: 1, modified white carbon with mass ratio white black to the aerosol from 3:1 to 6:1 and the mixture ethylendiaminetetraacetic acid and potassium carbonate at a mass ratio of between 1.1:1 to 2:1, in the following ratio of components, wt.%:

Cypermethrin - 1,8 - 6,3

Fipronil - 0,8 - 2,5

Modified white soot - 4,0 - 12,0

Aerosil - 1,3 - 4,0

Sodium lignosulphonate - 1,3 - 4,0

The sulfonic acid - 4,0 - 12,0

Ethylenediaminetetraacetate acid - 2,0 - 10,0

Potassium carbonate and 0.8 to 8.0

Urea - Rest

2. Method of controlling insects by treating the plants with an insecticidal preparation, characterized in that the treatment is carried out effective amount of the composition under item 1.


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in whichmeans simple or double bond, and the index and the substituents have the following meanings:

n means 0, 1 or 2;

m means 0, 1 or 2 and the substituents R2may be different if m is greater than 1;

X represents a direct bond, O or NRa;

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R2means nitro, halogen, C1-C4alkyl, C1-C4halogenated or1-C4alkoxycarbonyl;

R3means optionally substituted alkyl, optionally substituted saturated cycle or optionally substituted single or dual core aromatic radical, which together with the carbon atoms may contain as members of the cycle from one to four nitrogen atoms;

R4means hydrogen, optionally substituted alkyl;

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EFFECT: mixture for effective selective weed controlling in cultural plant, particularly in maize and grain cultures.

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SUBSTANCE: invention relates to compounds of formula I

, wherein R1 and R2 are hydrogen or C1-C4-alkyl; X is C3-C8-cycloalkyl, phenyl or styryl, as well as method for production thereof and fungicide composition containing the same. Compounds of present invention have fungicide activity and are useful in effective controlling of deleterious fungi.

EFFECT: compounds and fungicide composition with improved effectiveness.

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