LT3046B - Emulsive concentrate of synergist insecticides - Google Patents

Description

The invention relates to emulsion concentrates of synergistic insecticides containing pyrethroid or pyrethroids and creolin as active ingredient and stable aqueous emulsion compositions derived from these concentrates. ''

'. Domestic animals? attacking 'various ectoparasites, causing diseases of various clinical manifestations and causing huge economic losses. These losses can be / measured in millions / dollars per country (Nolan and Robertson, .197 8) .- / - //

Damage caused by ectoparasites occurs. in various forms / forms. 7 Some 7 blood pumping / 15 - .parasites spread a variety of viral, bacterial and protozoan diseases (protozoan disease, 1982), posing an increased risk to large groups of animals. Also, do you need to take into account that they can cause disease? also to man. For perturbacinio parasites living animal blood or 5 'horn epithelium impact of deteriorating productivity, ie ^- declining milk production, reduced body weight gain (Cambell et al, 1977) and increases the specific feed consumption.

.In addition, itching causes loss of coat and wool 7, sometimes resulting in rapid deterioration of livestock. Ectoparasites can be a cause / cause of overall decrease in resistance, thereby increasing the chance and severity of infectious diseases.

7 //// 1 /.- 7 //^-.//-/-/ 7 - // ^^ 5 //// 5-5-5 / 7 / 5Backing to the above.above , it is clear that protection against ectoparasites is of great economic importance for livestock production.

357 / The plant Chri zanthenum cinerariefoiium is known to contain different insecticides. Of these materials

Synthetic analogues of Pyrethrum-I are called pyrethroids. About 30 types of pyrethroid active substances are now commercially available, partly for plant protection and partly for sanitary and veterinary purposes. When used in veterinary medicine, besides the known advantages (low mammalian toxicity, survival time), the problem arises that the active substances usually used for washing do not adhere to animals.hair and skin, and the efficacy is often short and inadequate.

Another composition of the present invention is creolin, which has antiseptic, antiruritic, antihypertensive, and antimicrobial activity. It is used as a base substance in ointments for severe sheep fluff and. for the treatment of bovine calf diseases, in addition to its 10% emulsion is. used to kill larvae and caterpillars in their breeding grounds. Creolein is mixed with gamma - HCl to protect against oesterosis caused by blind larvae. HCH (gamma-isomer content: 9-13%), Lindane (gamma-isomer content: 96-100%) and activated creoleine jgama-isomer content are used to treat sheep scabies :). This use is recommended by the Veterinary Code of the Soviet Union.

When washing animals,. a - HCH solution dissolved in creoline from 15 ° C to - 25 ^Q C is used and the washing is continued for 30-60 seconds. However, because of its toxicity, sheep with lambs (less than 4 months old) or lambs less than 3 months old are not allowed to be laundered with this solution, and this prohibition is specifically intended for livestock. respiratory diseases, or animals in poor health.

The animals are washed with 2.5% creolin emulsion twice with an interval of 7-10 days. The last date for animal washing 'animals intended for slaughter, there are ^{two':? 3} months prior to slaughter, and in the case of annual animals and ovine animals for insemination, this period is 10 to 15 days before insemination. In addition to the increased toxicity of HCH and its isomers, their slow degradation · associated biosphere contamination is an additional disadvantage. When it comes to long-term environmental impacts, not only

- in soil, water and air (persistence); accumulates but _also: the nutrient chain (biakumuliacija) to the detriment of all living organisms.

- '107 ++ // +. + / +++ -''/;; + / +': ;;. + '' + // '/ 7'^:;;////.+/+/'^////.+'-++/.++/-//+/

The next is a problem for anthelmintics; / parasites is a fact k'ad in recent years + harmful populations have developed increased resistance to HCH .; ir; other chlorinated. hydrocarbons. In this way, even many times the increased dose of the active ingredient does not adequately protect, though due to

+ This increases consumer prices and raises serious toxicological problems. ;. + + <.//;·

The problems mentioned above require the development of binder-efficient, less toxic materials / compositions with an optimum range of action that could readily replace HCH and / or its isomers or mixtures of isomers in widely used and well-established creole compositions.

In developing the compositions of this invention, we have pursued three goals:

- Reduce the concentration of the biologically active substance (s), which is economically beneficial as well as + / + topical; :

- increase the efficiency of the compositions by using appropriate components; and

- increase the lifetime of the compositions, extend the lifetime by incorporating the active agent into the integrant, which eliminates the need for additional processing.

'' '

Comprehensive experiments have been conducted with combinations of creolin 'and various pyrethroids to solve the above problems'.

Based on the above, the present invention is directed to synergistic insecticides. . emulsion concentrates, characterized in that one liter of solution contains, as active ingredient, one or more of the following pyrethroids in an amount of 5-50 g / l: 3,4,5,6-tetrahydro-15 phthalimido-methyl (IRS) -cis-trans-chrysanthemate, * or ( s) -? - cyano-3-phenoxybenzyl (IR) - ee -3- (2,2-dibromovinyl) - 2,2-dimethyl-cyclopropanecarboxylate, or (RS) -? - cyano-3-phenoxybenzyl 2,2,3, 3. -tetramethyl-cyclopropanecarboxylate, or (RS) - α-cyano-3-phenoxybenzyl- (RS) -2- (4-chlorophenyl) -3-methylbutyrate, or 3-phenoxybenzyl -3- (2,2-dichlorovinyl) - 2. 2-dimethyl-cyclopropanecarboxylate, or (RS) -α-cyano-3-phenoxybenzyl (IRS) -cis-trans -3- (2,2-dichlorovinyl) -2,2-dimethyl-25-cyclopropanecarboxylate, or (RS) - a '-cyano-3R phenoxybenzyl (IRS) -cis-trans -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate lRcisS IScisR or a mixture of enantiomers of IRtransS IStransR, without creolin in an amount of 5-500 g / l, wherein the pyrethroid; the ratio of active substance to creole is 1:10 to 1: 100, and the surfactant is 0-100 g / l. and the amount of organic aromatic solvent normally added is such that the total volume is 1 liter.

λ '/,; ,, - ..' '· /' / '7. :

In the compositions of the present invention, the surfactant is usually citric acid and / or tartaric acid; · Λ 5 :.

acid mono- and / or dilauryl ethoxylates. How? the solvent contains mixtures of / ortho-, meta- and paroxylol or mixtures of other aromatic solvents such as Shellsol A, Shellsol / RA, Scholvess 150 or Han.

.Emulsive concentrates. aqueous working solutions diluted 100-10000 times also exhibit high emulsion stability.

Creoline contains -20-40% Coal Resin · Oil, 10-15% Extracted Pine Resin and / or Extracted Refined Resin, 3-5% Sodium Hydroxide and · Sodium Icthiol.

As set forth in the following detailed description, the compositions of the present invention not only retain the useful properties of their ingredients, but also exhibit several additional properties. - ^20th

Such an added advantage; among others, there is an increase in efficiency based on mixed component interactions (synergism) .. When tested on scabies mites (Psoroptes cuniculi) and flies (Musca domestica), an increased effect on the resistance was demonstrated. flies and prolonged effective dose retention of pyrethroid on the integrus.

Toxicity tests have shown that the doses of the compositions of the present invention which are more tolerable to sheep are significantly higher than the toxic doses of working solutions used for washing. In this way, the quotient of the two, the so-called therapy index, varies between 40 and 4000, depending on the job. dilution of the solution. The 24-day chronic studies in white mice demonstrated no accumulation of the composition and no significant abnormalities in the weight gain of treated and control animals during the study period.

The composition does not affect the antitoxic function of the liver, does not exert an anaphylactogenic effect and the treated animals have the same haemological and biochemical characteristics as the untreated sheep rates and k-creative characteristics of healthy animals: pH. size 5.8-6.1, peroxidase reaction positive, reaction. with copper sulphate negative and volatile amounts of fatty acids 3.1-3.3.

Explanation \ Explains: Far from being given by non-limiting examples of the invention.

example

'.-77 /// 77.J · /.</'/'</ 7 /. '' </ - // <

Obtaining the concentrate

Transfer 500 ml of xylene to a 2000 ml beaker. / and 70 g Euracol is added with stirring. B / M (ethoxylated lauryl citrate made by Ro'll)., • Stirring is continued / until complete dissolution of this material. The solution is heated to 50 ° C and (bound to 100% active ingredient) 250 g of Chinmix at 50 ° C (Hungarian patent no.198,612) is added with constant stirring.

Stirring is continued until completely dissolved. Cool to 20 ° C and transfer to a 1000 ml volumetric flask.

- ml; '' '- ~'

Examples 2,3,4 and 5

Receiving composition (s) *

Such compositions are prepared from the concentrate of Example 1 and phenol-free creole.

Example 2 Example 1 concentrate 10 ml Creole 50 ml Example 3 10ml ' 90 ml Example 4 Y 10 ml 100 ml Example 5 Y 10 ml Y 500 ml

⁵ -7 '.. Y 7' - Y 7.

Examples 6-13

Preparation of different working solutions (emulsions) containing various concentrates in standard hard water

A 100 mL volumetric measuring cylinder used to determine emulsion stability (CIPAC Handbook, 36.; 1) measures the volume of the formulations according to Examples 2-5 to Table 1, and adds 100 mL of standard hard water. The emulsions are shaken 15 times and after 2 hours at 30 ° C the samples are taken. The emulsion stability is measured by checking the light transmittance of the samples in a 1mm layer cell spectrometer using 845 mm wavelength light. The sediment in the measuring cylinder shall be inspected visually.

8 · Table

Working. 100 ml standard solid - Light Sediment solutions water ^ opposition by overpowered Figure 2 '. Figure 3 Figure 4 Figure 5 dumas ml. Example 6 0.6 - 1.0 there is no Example 7 0.3 0.0 there is no Example 8 - 1.0 1.0 there is no Example 9 - 0.5 1.0 there is no Example 10 - —- '1.1 2.0 there is no Example 11 - 0.55 1.0 there is no Example 12 ~; - 6.0 1.0 insignificant Example 13 - - - 3.0 1.0 insignificant

example

Compositions according to 3 under investigation. using as an example acaricidal activity on scabies mites (Psoreptes cuniculi) taken from the outer ear of scabies. . The studies were · carried out according to 10 Methodological Guidelines approved in 1982. Soviet Union -Government Veterinary Administration (Validation and Comparative Study of New .caricidal Products against Sarcoptoid Ticks) The ticks were selected on the day of the study. Groups of 10 15 fully developed ticks were placed on black wipes pre-moistened with 1 ml of different concentrations of the working solution in Example 3. The ticks were then placed in a thermostat at 30 ° C and 90% relative humidity. . .

The condition of the ticks was assessed after 24 hours. Two parallel tests were performed, which were repeated three times. The results obtained are shown in Table 2.

table

Concentration Concentrate Creole Composition (example 1) /,.,.-/ '-Τ'? //. V (example 3 z). Mortality ()

0.05 0.U25 0.0125 / <30yy /./// // .. '60 / • 0 /''\/' // '//y'.-/'45'-/y//'. yy, 'Oh.'^; y: - //. / ;; ///; / y. ± 0 '-' ////. '/' / / 100 100 / 100 Tables 2 results  clearly shows that mixture, made of creolinoir concentrate according to; L example, acaricidal effect exceeds the total components

efficiency per se.

example '///.,/'<///' ;;: <- <//

The insecticidal activity of the formulations according to Examples 3, 4 and 5 was tested under standard laboratory conditions for the susceptible strain of flea (Musca domestica) (WHO / SRS). Properly reconstituted formulations and concentrates were applied to the back of flies weighing 20 (± 1.5) mg for 4 to 5 days with 0.5 μl drops of microsyringe. The flies were previously lightly anesthetized with carbonic acid. Acetone was used as the solvent.

Each of the flies was / treated with all doses, repeated twice. Treated animals were placed in plastic beakers for 24 'at 22 ° C (± 2 ° C). After that, dead animals were counted and mortality was determined. LD ₅₀ ~ values were determined by probabilistic analysis. The results are shown in Table 3.

Table 3 Compositions or concentrates LD (± s) {ng / muse f-Zi '/ -yv'y ( Example 1 4.3 (0.41) creolin 2000 Example 2 / - /// (/ 'Z / (/ ^ / 1 / - 2., .. 1 //' {(y / '/ (/ (0.35) Example 3 · y (y: (/./ '2,2'-' ^x // y. / g / Z / yi / (0.31) y Example 4 - ^v / ^: ^ ' ² · ³ / Z / y .Z / y /// · - ·. (0.39) Data from Tables 3 are unambiguous proves compositions • Efficiency exceeds them add ii

that example

The effectiveness of the compositions of the present invention was tested on resistant flies collected under the conditions of the pig complex described in Example 15.

4 'in Table. ......-. /////. /: ///.1/--: /.15. : -.-... Table 4- '

I; Compositions or

concentrates LD (± s) (ng / museum) sensitive resistant Example 1 creolin 4.3 (0.41) 2000 85.1 2000 5 (5.98) gamma-HCH /// '/' '47.2 (6.31) 1641 (ch 19.6) Example 2 2.1 (0.35) 17) 5 (3.1) Example 3 '2.0 (0.31) 16.2 1 (2/0) Example 4 2.3 (0.39) 18.2 ! (2.7) Tables 4 data show, kac L. cheese nktos flies populations the resistance is significantly larger .s before gamma HCH than against Chinmix which was concentrate.

The use of creolin further improved the performance of the exemplary concentrate. These facts suggest that the compositions of the present invention may be useful in combating resistant populations.

Example 'The amount of Chinmix in wool from sheep washed with working solutions obtained from the composition of Example 3 was determined by gas-liquid chromatography on day 15 and day 30 after treatment. Test conditions: column temperature: 250 ° C, detector temperature: 260 ° C, -. carrier gas velocity: 40 ml / s, - solvent: hexane, residence time: 4 min. The test results are shown in Table 5.

table

Example of composition or concentrate.

example

Concentration of Chinmix in current solution (%)

0.05

0.05

Ghinmik Time (days)

4923

11594 mg / kg post-treatment

2216

3750

The data in the table show that the addition of creolin not only improves the adhesion of Chinmix active substance, but also ensures that it is retained on treated sheep wool. In the case of slaughtered animals, it was found that there was no detectable amount in the organic tissues after 15 25 'days

Chinmix active substances. Similarly, no detectable amount of active substance was found in treated mammalian sheep's milk.

Claims (3)

DEFINITION OF INVENTION Synergistic insecticidal emulsion concentrate, characterized in that, in 1 liter of solution, in an amount of 5 to 10 g / liter. as an active substance is one or more pyrethroids: 3,4,5,6-Tetrahydro-phthalimidomethyl (1RSHcis-trans-chrysanthemate, or (S) -? Or (RS) -? - cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropanecarboxylate, or (RS) -? 15 '(RS) -? -Cyano-3-phenoxybenzyl (RS) -2- (4-; chlorophenyl) 3-methylbutrate, or 3-Phenoxybenzyl-3- (2,2-dichloro-vinyl) -2,2-dimethyl-20 cyclopropanecarboxylate, or (RS) -? - cyano-3-phenoxybenzyl (IRS) -cis-trans-3 (2,2- dichlorvinyl) -2,2-dimethyl-cyclopropanecarboxylate, or IRScisS IScisR + and + Irtransa lStransR enantijomero pairs of (RS) -cyano-3-phenoxybenzyl (LRS) -cis-trans-3 (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-carboxylate, or mixtures thereof, in addition to ³⁰ ? '/;/' creolein in an amount of from 5'to 500 g / liter, wherein the ratio of pyrethroic acid to creolein is 1:10 to 1: 100 and the surfactant is present in an amount of 0100 g / liter and simply added the following organic 35 aromatic solvent to give a total volume of 1 liter. Emulsion concentrate according to claim 1, characterized in that the surfactant is mono and / or dilauryl ethoxylates of citric acid or tartaric acid. 3. aqueous emulsion composition of insecticides, characterized in that it contains ΙΟ, 0001% by volume of a solution containing 500 ml of xylene, 70 g of ethoxylated lauryl citrate and 250 Chinmix of Example 1 and water up to 100% by volume.