HU190843B - Synergic combinations of insecticide compositions containing 2,2-dichloro-vinyl-dimethyl-phosphate and 2-chloro-vinyl-dimethyl-phosphate - Google Patents

Abstract

Insecticide or combined insecticide and acaricide and/or fungicide prepns., pref. ready-to-use insect-killers contain 0.5-100.0 wt.%, 2,2-dichloro-vinyldimethyl-phosphate and 0.0-50.0 wt.% other insecticide cpds., pref. 1-naphthylmethyl-carbamate and/or RS-alpha-cyano-3 (phenoxy)-benzyl-RS- cis, trans-3-(2,2-dichloro-vin yl) -2,2-dimethyl-cyclopropane-carboxylate, 0.0-50.0 wt.% acaricide and/or fungicide cpds., pref. 4-chloro-phenyl-2,4,5 trichloro-phenyl-sulphonate and/or 0-6-(ethoxy-carbonyl)-5. methyl-pyrazolo-(1,5-alpha)- pyrimidin-2-yl-O,O-diethyl phosphoro-thioate and/or 5-butyl-2-(ethyl-amino) 6-methylpyrimidin-4-ol and opt. additives. - The prepns. contain apart from 2,2-dichloro-vinyl- dimethyl-phosphate also 2-30 wt.% of the synergistic 2-chloro-vinyl- dimethyl-phosphate.

Description

The present invention relates to synergistic insecticidal compositions containing 2,2-dichloro-vinyl-dimethyl-phosphate and 2-chloro-vinyl-dimethyl-phosphate, and combinations thereof, which may also contain organic phosphoric acid ester derivatives and / or pyrethroid derivatives.

It is known that 2,2-dichloro-vinyl-dimethyl-phosphate (dichlorphos) has excellent insecticidal properties, so that compositions containing this compound as active ingredient are currently widely used both in plant protection and in the control of warehousing and health insects.

It is a well-known disadvantage that 2,2-dichloro-vinyl-dimethyl phosphate-containing pesticides, when used indoors, require high concentrations of the active ingredient due to its volatility, otherwise, in the presence of a small amount of active ingredient, the active ingredient would evaporate, before it can sufficiently exert its insecticidal effect.

Particularly in the case of small volume volumetric (LV and ULV) formulations containing 2,2-dichloro-vinyldimethyl phosphate, the evaporation loss can be significant, since the small droplet size (15-110 pm) produced by the two spraying technologies greatly increases the evaporation surface. The loss of airborne droplets in the air for a relatively long period of time can only increase the loss of airborne ULV treatments, so only spraying a very high active ingredient formulation can produce any results at all. For example, to date, only compositions containing more than 70% by weight of 2,2-dichloro-vinyl-dimethyl phosphate have been used to control ULV aircraft mosquitoes, with moderate success.

The high concentration of 2,2-dichloro-vinyl-dimethyl phosphate required in the formulations also limits the possibility of combining this active ingredient with other compounds which also act as insecticides.

It is an object of the present invention to provide a composition with increased activity in which the concentration of 2,2-dichloro-vinyl-dimethyl phosphate can be reduced, thus eliminating the difficulties of use with known formulations.

It has been found that the drawbacks associated with known insecticidal compositions containing 2,2-dichloro-vinyl-dimethyl-phosphate can be overcome and the above object can be achieved by a composition which, in addition to 2,2-dichloro-vinyl-dimethyl-phosphate, contains 2-chloro-vinyldimethyl-phosphate. also included.

The present invention is based on the discovery that the insecticidal activity of 2,2-dichloro-vinyl-dimethyl-phosphate is significantly increased in the presence of 2-chloro-vinyl-dimethyl-phosphate and consequently the insecticidal effect of the known compositions is reduced.

2.2-dichloro-vinyl-dimethyl phosphate, or a

Significantly higher insecticidal activity can be achieved with known formulations while maintaining the amount of 2,2-dichloro-vinyl dimethyl phosphate.

It is surprising to those skilled in the art that 2-chloro-vinyl-dimethyl-phosphate synergizes the insecticidal activity of 2,2-dichloro-vinyldimethyl-phosphate, as other insecticides, including organic phosphoric esters and

No synergism has been observed with combinations of 2-chloro-vinyl-dimethyl-phosphate.

The surprising observation that 2-chloro-vinyldimethyl-phosphate significantly increases the insecticidal activity of 2,2-dichloro-vinyl-dimethyl-phosphate, allows to reduce the amount of the latter in the formulation.

Examination: It was also found that the proportion of the two components in the preparations containing 2,2-dichloro-vinyl-dimethyl-phosphate and 2-chloro-vinyl-dimethyl-phosphate is not at least insensitive to the color effect. Thus, if less than 2% by weight of 2-chlorovinyldimethyl phosphate is present in the composition, based on dichlorophosphate, the increase in activity resulting from synergism is not yet significant, with a content of 2-chlorovinyldimethylphosphate greater than 30% by weight. and the increase in activity due to synergism is otherwise barely offset by the active component,

Reduction in the proportion of 2,2-dichloro-vinyl dimethyl phosphate in the mixture.

Synergism was investigated for mixtures of the two substances in different ratios as follows. 2-Chloro-vinyl-dimethyl-phosphate, 2,2-dichloro-vinyl-dimethyl-phosphate and different concentrations of the active compound were used as inert solvents, or different component ratios were made by mixing the two. The labeling and composition of the sample solutions thus prepared are summarized in Table 1.

Thus, sample series IA-IX.A is an isopropyl myristate solution containing from 1 to 50% by weight of 2-chlorovinyldimethyl phosphate (isopropyl myristate inert solvent), and sample series IB-IX.B is 99 to 50% by weight. isopropyl myristate solution containing% 2,2-dichloro-vinyl-dimethyl-phosphate and finally

I.C-IX.C Sample Series A mixture of 2-chloro-vinyl-dimethyl-phosphate and 2,2-dichloro-vinyl-dimethyl-phosphate (1: 99) to (50: 50).

The samples were then diluted with 0.04% (w / v) methyl ethyl ketone. 0.5-0.5 microliters of the solutions were added dropwise to a total of 120 stomoxis clacitrans (Surfopy Stallion Fly) thoracic anesthesia per sample, and dead insects were counted after 24 hours. The insecticidal activity of each sample is characterized by the percentage of dead insects (% mortality) that were exposed to each sample. In the studies, the control group was treated with methyl ethyl ketone (control) and methyl ethyl ketone (control) containing 0.04% v / v isopropyl myristate.

The results,% mortality per sample, are summarized in Table 2.

From the% mortality data for samples I.A-IX.A and I.B-IX.B, the Colby method was used to calculate the% mortality values for mixtures (I.C-IX.C) and the difference between observed and expected values [S. A. Colby: Weeds 75, 20-22 (1967) II. formula]. These last two series of data are shown in the last two columns of Table 2.

A synergistic effect was observed for active compound mixtures where the difference between the measured and expected% mortality was + 10%,

190,843, i.e., 70-98% by weight of 2,2-dichloro-vinyl-dimethyl-phosphate and 2-30% by weight of 2-chloro-vinyl-dimethylphosphate.

Table 1

A

C

I H 1 2 99 98 1 2 + + 99 98 III. 5 95 5 + 95 ARC. 7 93 7 + 93 V 10 90 10 + 90 VI. 20 80 20 + 80 VII. 30 70 30 + 70 VIII. 40 60 40 + 60 IX. 50 50 50 + 50

Second spreadsheet THE B c the pattern because because because expected THE% Indication morta- stability is % morta- stability is % morta- stability is % morta- stability is % I 0 71 65 71 -6 II. 0 67 81 67 + 14 III. 0 67 100 67 + 33 ARC. 2 68 100 69 + 31st V 5 65 97 67 + 30 VI. 13 63 84 68 + 16 VII. '18 58 78 66 + 12 VIII. 20 53 71 67 + 4 IX. 32 31 51 53 -2 controls, 0 0 - - It controls; - - 0 - -

From the data obtained, it can be concluded that the mixtures of 2,2-dichloro-vinyl-dimethyl-phosphate and 2-chloro-vinyl-dimethyl-phosphate have a well detectable excess insecticidal activity which is 2 - 30% by weight of 2-chloro-vinyl-dimethyl- up to the phosphate content is significant from a practical point of view. The overactivity reaches a maximum at 5% to 7% by weight of 2-chloro-vinyldimethyl phosphate.

To determine the degree of synergism, the insect toxicity of 2,2-dichloro-vinyl-dimethyl-phosphate containing 1% (sample A) and 7% (sample B) of synergist was determined and compared as follows.

Serial dilutions of 0.04% (v / v) solutions of both samples were made with methyl ethyl ketone. 0.5-0.5 μ 0,5 of each dilution was applied to the throat of 60-60 female domestic flies (Musca domestica) under carbon dioxide anesthesia and the 24-hour mortality was determined for each dilution of the two samples as described in the previous study. we expressed.

Values corrected for control mortality - - at various concentrations of the samples from the data ram ⁵ percent mortality was calculated for the two samples LD _J0 Rf together with confidence intervals for the significance level of 5% [PJ Finney, Probit Analysis, 3rd Edition, Cambridge, 1971],

The following results were obtained:

Sample A: LD ₅₀ = 18.7 x 10 ³ (10.2-32.9) pg / insect

Sample B: LD ₅₀ = 7.2x10 ³ (3.1-12.1) pg / insect

While sample A from insect A required 18.7 x 1 (T ³ pg% 15) per insect to kill 50% of the treated population,

7.2 x 10 ~ ³ pg proved to be sufficient, so the degree of synergism was found to be 2.6 times.

Synergistic insecticidal composition of the present invention as an active ingredient 0.5 to 95% by weight of ^{2,2-di-chloro-20-vinyl} dimethyl phosphate, 2 to 30 parts by weight calculated on the amount of active synergists% 2-vinyl dimethyl phosphate, and a stabilizer, preferably l-chloro-2,3-epoxypropane, optionally liquid carriers, preferably odorless petrolatum and isopropanol or octyl alcohol and paraffin oil or xylene, propellants, preferably carbon dioxide or trichlorofluoromethane and dichlorodifluoromethane, emulsifiers; , preferably polyethylene glycol sorbitol hexaoleate and polyethylene glycol lauryl ether, and a solid support, preferably polyester resin.

The stabilizers and, optionally, solid or liquid carriers, propellants and emulsifiers used in the compositions of the present invention may be conventional excipients in insecticidal compositions.

Preferred types of the composition of the present invention are insecticide or aerosol, evaporator sheet, small volume (LV or ULV) formulation and emulsifiable concentrate.

The composition may contain one or more excipients and may also contain one or more excipients of each type.

The solid carrier is, for example, a plastic such as polyvinyl chloride or polyester, the carrier is, for example, paraffin oil, alkanol or aromatic hydrocarbon, the emulsifier or wetting agent is an anionic, cationic or nonionic surfactant and the stabilizer is, for example, epichlorohydrin. In aerosol formulations, the propellant is a halogenated hydrocarbon or a mixture of halogenated hydrocarbons, carbon dioxide, isobutane and the like. may.

In our experiments with the synergized 2,2-dichloro-vinyldimethyl phosphate according to the invention, we have found that the control of pests that have many generations per year, such as the house fly, results in a relatively rapid loss of sensitivity. As a result, subsequent generations of pests can only be killed with significantly increased amount of pesticides. A decrease in susceptibility leads to the development of resistance over time, in which case the pests can no longer be controlled by the synergized 2,2-dichloro-vinyldimethyl phosphate.

so la. example composition in stables

-3190 843 initially provided effective ventilation at 8-12 mg / m ³ , but by the end of year 2 we had to use 20-25 mg / m ³ to kill more than 99% of the flies.

However, as a result of the fact that the 2-chloro-vinyl-dimethyl-phosphate synergist present in the present invention significantly increases the insecticidal activity of 2,2-dichloro-vinyldimethyl-phosphate, and thus the latter can be reduced in the composition, for the simultaneous administration of the preparation, which delay or eliminate the occurrence of a decrease in sensitivity or resistance.

Organic phosphoric acid esters and pyrethroids have been found to be advantageous for this purpose, in particular the following: S-6-chloro-2,3-dihydro-2-oxooxazolo [4,5-b] pyridin-3-ylmethyl-0 , O-dimethyl phosphorothioate (azamethiphos), (E) -O-2- (isopropoxycarbonyl) -1-methylvinyl-methyl-ethyl-phosphoramidothioate (propetamphos), (S) -alpha-cyano-3 - phenoxybenzyl (1R, 3R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin),

3,4,5,6-Tetrahydrophthalimidomethyl- (1RS) -cis, trans-chrysanthemate (tetramethrin) and RS-alpha-cyano-3-phenoxybenzyl- (1 RS) -cis, trans-3 ( 2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (cypermethrin).

The above phosphoric acid esters and pyrethroids containing lb., le., P. and formulations 2 and 2 in similar conditions as Example 1a. We found that even after 2 years of use, the effective dose required to kill the flies did not change.

Therefore, the composition according to the invention may optionally also contain one or more organic phosphoric acid esters and / or one or more pyrethroids in a total amount of 0-50% by weight, preferably azamethiphos and / or propetamphos and / or deltamethrin and / or tetramethrin and / or cypermethrin .

The composition of the invention is prepared in a manner known per se, generally by mixing the components. When used as an aerosol, the prepared mixture is filled into an aerosol can and the aerosol is prepared with a suitable propellant during use. Preferably, the evaporator sheet is prepared by mixing the active ingredient, the required polymer and other suitable components and solidifying the mixture in a form.

An advantage of the composition according to the invention is that a smaller amount of 2,2-dichloro-vinyl-dimethyl-phosphate achieves the same or greater insecticidal activity than the known composition. It is also possible to produce a pesticide having a broad spectrum insecticidal activity against which virtually no resistance develops.

One of the above advantages of the composition of the present invention will be demonstrated by the following test.

We prepared 5-5 liters of ULV with the following composition:

Quantity,% by weight, of

Component 1. 2.

sample

2,2-dichlorovinyl dimethyl phosphate 9.4 30.0 2-chloro-vinyl dimethyl phosphate 0.6 0.2 n-octyl alcohol 20.0 20.0 epichlorohydrin 1.0 1.0 paraffin 69.0 49.0

The resulting compositions were used to control mosquito control on 10-10 hectares using a Tifa ULV generator. To determine the efficacy of mosquito control, mosquito density measurements were performed just before and 24 hours after treatment in approximately the middle of the experimental areas. The mosquito density values measured before and after mosquito control and the percentage reduction are shown below;

Sample number Szúnyogsűrűség, tweak / hour / person Decontamination efficiency,% First before extermination after slaughter 24 92 Second before extermination after slaughter 36 86

The results of experimental mosquito control show that while sample 2 contained 3-fold concentration of 2,2-dichloro-vinyl dimethyl phosphate than sample 1 (in which the optimum amount of synergist was present), the effectiveness of its control was still not achieved. behind the efficacy of eradication with the composition of the invention.

The exact physical or chemical basis of the synergistic effect of 2-chloro-vinyl-dimethyl-phosphate on 2,2-dichloro-vinyl-dimethyl-phosphate is not known. However, it can be assumed that 2-chloro-vinyldimethylphosphate competitively inhibits the action of the enzyme that breaks down 2,2-dichloro-vinyl-dimethyl-phosphate in the insect, presumably by reacting 2,2-dichloro-vinyl-dimethyl- it is bound to the active sites of the enzyme by its chemical structure similar to phosphate. The resulting slower decomposition of 2,2-dichloro-vinyl-dimethyl-phosphate is capable of inhibiting higher amounts of the enzyme acetylcholinesterase, which explains the increased insecticidal activity.

The compositions of the present invention are illustrated in detail by the following examples.

Example 1

a) 20 g of 2-chloro-vinyl-dimethyl-phosphate, 950 g of 2,2-dichloro-vinyl-dimethyl-phosphate and 30 g of 1-chloro-2,3-epoxypropane are mixed. The resulting liquid can be used directly to control flying insects, especially flies, by spraying the insecticide formulation into the air space of rooms, greenhouses, stables, in an amount of 8 to 12 mg per cubic meter. The treatments are preferably conducted weekly from May to October.

Hereinafter, as described in (a) above

We do 190,843, but we mix the following ingredients:

b) 15 g of 2-chloro-vinyl-dimethyl-phosphate 715 g of 2,2-dichloro-vinyl-dimethyl-phosphate

250 g of S-6-chloro-2,3-dihydro-2-oxooxazolo [4,5b] pyridin-3-ylmethyl-0,0-dimethyl phosphorothioate 20 g of 1-chloro-2,3- epoxypropane

c) 19 g of 2-chloro-vinyl-dimethyl-phosphate 951 g of 2,2-dichloro-vinyl-dimethyl-phosphate g (S) -alpha-cyano-3-phenoxybenzyl- (1R, 3R) -3 (2) , 2-dibromo-vinyl) -2,2-dimethyl-cyclopropanecarboxylate g 1-chloro-2,3-epoxy-propane

d) 10 g of 2-chloro-vinyl-dimethyl-phosphate 470 g of 2,2-dichloro-vinyl-dimethyl-phosphate

250 g of (E) -0-2- (isopropoxycarbonyl) -1- (methylvinyl) -0-methylethylphosphoramidothioate

250 g of 3,4,5,6-tetrahydrophthalimidomethyl- (1RS) cis, trans-chrysanthemate g of 1-chloro-2,3-epoxypropane. formulation at a given dose after 2-3 years of application leads to the development of resistance, lb., le. and see. however, they can be used for 4-6 years without developing resistance.

Example 2

1.5 g of 2-chloro-vinyl dimethyl phosphate, 3.5 g of 2,2-dichloro-vinyl dimethyl phosphate, 3.5 g of (RS) -alpha-cyano-3-phenoxybenzyl (1 RS) -cis, trans-3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylate, 0.5 g of epichlorohydrin and 96.5 g of 1-naphthylmethylcarbamate are dissolved in 49.5 g of isopropanol and In 0 g dichloromethane. The resulting mixture was filled into a 200 g aerosol can with mechanical metering valve. The preparation is used primarily for the control of hidden insects by surface treatment. The preparation

It can be used for 6 to 8 years at constant dose without development of detectable resistance.

Example 3

Synergized 2,2-dichloro-vinyl-dimethyl-phosphate is prepared as follows.

In a stainless steel reactor equipped with glass atomizers and jacket cooling, trimethyl phosphite is sprayed at a rate of 27 kg / h and a 93: 7 mixture of trichloroacetaldehyde and dichloroacetaldehyde at a rate of 31 kg / h. Meanwhile, the pressure is maintained at 0.3 bar and the temperature is maintained at 140 ° C. The reaction product, which forms a film on the reactor wall, is collected in collecting containers through a barometric system. That's it. The resulting product, consisting of about 7% by weight of 2-chloro-vinyl-dimethyl-phosphate and about 93% by weight of 2,2-dichloro-vinyl-dimethyl-phosphate, is used in the preparation of various compositions of the invention.

2.5 kg of synergized 2,2-dichlorovinyldimethyl phosphate, 0.5 kg of epichlorohydrin and 0.5 kg of lavender oil prepared above are dissolved in a mixture of 20.0 kg of odorless petroleum and 176.5 kg of isopropanol.

40 g to 40 g of the resulting mixture are filled into a 150 g aerosol can and 60 g to 60 g propellant (Freon 11 and Freon 12 1: 1 by volume) are charged.

The aerosol produced in this way is capable of controlling the flying insects by treating the air space.

Example 4 A kg of synergized 2,2-dichloro-vinyl-dimethylphosphate prepared in Example 3 and 10 kg of epichlorohydrin was dissolved in a mixture of 200 kg of n-octyl alcohol and 717 kg of paraffin oil. The resulting U L V15 concentrate can be used for aircraft mosquito control.

Example 5

15 kg of 2-chloro-vinyl dimethyl phosphate, 35 kg of 2,2-dichloro-vinyl dimethyl phosphate, 2 kg of 1-chloro-2,3-epoxypropane and 15 kg of xylene are mixed. Then, 15 kg of Atlox 1086 (polyethylene glycol sorbitol hexaoleate) and 15 kg of Brij 35 (polyethylene glycol lauryl ether) emulsifiers were dissolved in the mixture, and the mixture was made up to 100 liters with xylene.

The resulting emulsifiable concentrate diluted with water is suitable for LV treatments and spraying against insect pests in agricultural crops.

Example 6

Dissolve in 938.4 kg isopropyl alcohol 10 kg a

Synergized 2,2-dichloro-vinyl-dimethyl-phosphate, 1.5 kg, 3,4,5,6-tetrahydro-phthalimidomethyl (1RS) -cis, trans-chrysanthemate, 0.1 kg of lavender oil, prepared in Example 3, and so on. The resulting mixture is filled with 150-150 g into 200 g aerosol bottles, and then 5-5 g of carbon dioxide is added per bottle. The aerosol formulation thus prepared can be used to control flying insects (fly, mosquito).

Example 7

20 g of synergized 2,2-dichloro-vinyl-dimethyl-phosphate, 60 gPolicon RI polyester resin containing 30% by weight of styrene (manufactured by NIKE), 20 g of dioctyl phthalate and 1 g are weighed into an enameled vessel. 10% dimethylamine solution and the mixture was stirred until homogeneous. To the viscous liquid was added 0.8 g of 50% benzoyl peroxide and the mixture was immediately poured into 0.6 x 5 x 60 cm molds. Once solidified, the evaporator slab slowly releases its active ingredient content when suspended in rooms, thus ensuring a constant insecticide concentration in the air, resulting in the death of flying insects.

Claims (1)

A patent claim 1, Synergistic insecticide combinations, preferably ready-to-use insecticide5 190,843 fractions, aerosols, evaporators, ULV, LV or emulsifiable concentrates, characterized in that the active ingredient is 0.5-95% by weight of 2,2-dichloro-vinyldimethylphosphate, the synergist being 2-30% by weight of the active ingredient. 2-chloro-vinyldimethylphosphate containing stabilizer, preferably 1-chloro-2,3-epoxypropane, optionally liquid carriers, preferably odorless petroleum and isopropanol or octanol and paraffin oil or xylene, propellants preferably carbon dioxide or trichloro fluoromethane and dichlorodifluoromethane, emulsifiers, preferably polyethylene glycol sorbitol hexaoleate and polyethylene glycol lauryl ether, a solid support, preferably a polyester resin, and a total of 0-50% by weight of organic phosphoric ester and / or pyrethroid, preferably S-6-chloro-2,3-dihydro-2-oxooxazolo [4,5-b] pyridin-3-ylmethyl-0,0-dimethyl phosphorothioate and / or (E) -O-2 (isopropoxycarbonyl) -1-methylvinyl-0-methylethylphosphorus amidothioate and / or (S) -alpha-cyano-3- (phenoxybenzyl) - (1R, 3R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate and / or 3,4, 5,6-tetrahydrophthalimido-methyl (1RS) -cis, trans-chrysanthemate and / or RS-alpha-cyano-3-phenoxybenzyl- (1 RS) -cis, trans-3- (2,2-dichloro) vinyl) -2,2-dimethylcyclopropanecarboxylate.