HU183539B - Process for producing emulsifiable insecticide and acaricide compositions of heat-improved activity from piretroides containing phenoxy-benzyl groups - Google Patents

Abstract

Field of the Invention The present invention relates to a method for the preparation of a combined effect of insecticidal and acaricidal compositions with heat treatment. According to the process of the present invention, a pyrethroid containing from 0.5 to 50% by weight of phenoxybenzyl, preferably permethrin, and / or deltamethrin, and / or cypermethrin and / or fenvalerate, and / or AC-222,705 (Cyanamid), 5- 30% by weight of nonionic and / or anionic emulsifiers, 1-90% by weight of C3-5 alcohol. , preferably ϊ-propanol, and optionally up to 93.5% by weight of other excipient, preferably liquid carrier and / or stabilizer and / or antioxidant mixture, heated at 50-60 ° C for 0.5 to 2 hours. The use of the compositions of the present invention is particularly advantageous in the field of animal health, since these preparations are emulsified in water at a ratio of 1: (25 to 400) and then to farm animals, e.g. by spraying on the wall of cattle or pigs on stables, killing flies, ticks, and blood-sucking lice disturbing the calmness of the animals. At the same time, they are emulsified in water at a ratio of 1: (100 to 200) and used for the bathing or spraying of farm animals for the safe eradication of various infestations. -1-

Description

FIELD OF THE INVENTION The present invention relates to a process for the preparation of combined insecticidal and insecticidal compositions having increased activity by heat treatment. According to the process of the invention, the pyrethroid (s) containing from 0.5 to 50% by weight of phenoxybenzyl group, from 5 to 30% by weight of nonionic and / or anionic emulsifier (s), from 1 to 90% by weight of aliphatic alcohols ) and in any given case at most

93.5% by weight of a mixture of known excipients; Heat at 50-60 ° C for 0.5-2 hours. The emulsifiable compositions of the present invention can be used as sprayers as insecticides and for the treatment of mammals in both spray and bathing baths to kill mites.

A major disadvantage of the pesticides used so far is that different compositions must be used against different pests, even though their active ingredients are often the same. Purchasing and stocking a variety of formulations increases the risk of confusion and significant damage is also caused by the disintegration of unpackaged but unused pesticides over time.

Thus, emulsion concentrates for aerosolization cannot be used as a bath for treating mumps in livestock, even though they are suitable for this purpose on account of their active ingredient content, since such detergents and mineral oils used in yen also have a skin irritating and toxic effect.

Conversely, concentrates used for making animal bathing baths do not produce aerosol spray spray on the hair of the scents because of the high degree of dispersion of the active ingredient and its absorption into the first coat of hair, where it is lost for residual effect.

The present invention provides a process for sustained, well-preserved spray application of animal hair to insecticide, spray application in spray baths or spray application, as a result of the increased activity of the active compounds and the proper physico-chemical properties of the emulsion when diluted in water. and pesticidal compositions suitable for this purpose are prepared.

The present invention is based on the discovery that when treated with aliphatic alcohols and emulsifiers and processed into conventional emulsion concentrates, the pyrethroids are effective in both spray and bath applications, and have significantly higher insecticidal activity and insecticidal activity. insecticidal activity of the composition of the invention.

It has been found that this beneficial effect does not occur with all pyrethroids, but only with those employing a phenoxybenzyl group. In addition, the aliphatic alcohols used are not neutral in terms of their intended effect, since methyl and ethyl alcohols reduce the activity of the active compounds, while alcohols having more than 5 carbon atoms render the formulation toxic, skin irritant. Of the required emulsifiers, only anionic and nonionic emulsifiers are suitable for this purpose.

The present invention thus provides a process for the preparation of emulsifiable insecticidal and insecticidal compositions having a combined activity of meg2. Pyrethroid (s) containing from 0.5% to 50% by weight of phenoxybenzyl group based on the total weight of the preparation:

1. Deltarnetrin of formula (I), S-alpha-cyano-S-phenoxybenzyl-77? -C (5z- [3- (2,2-dibromovinyl)] - 2,2-dimethylcyclopropane- carboxylate,

2. permethrin of formula II, 3-phenoxybenzyl-77? S-cis,?,? - 3- (2,2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylate,

3. Fenvalerate of Formula III, A'S-alpha-cyano-3-phenoxybenzyl-7S-2- (4-chlorophenyl) -3-methylbutyrate;

4. cypermethrin of formula (IV), 7S-alpha-cyano-3-phenoxybenzyl-77S-cis, 7H, 2S-3- (2,2-dichloro-vinyl) -2,2-dimethyl cyclopropanecarboxylate,

5. pyrethroid AC-222,705 of Formula V, manufactured by Cyanamid, 7? -Alpha-cyano-3-phenoxybenzyl-S-2- (4-difluoromethoxyphenyl) -3-methyl- butyrate, and from 5 to 30% by weight of anionic and / or nonionic emulsifier (s), from 1.0 to 90% by weight of aliphatic alcohol (s) of 3 to 5 carbon atoms and optionally other excipients known per se. Typically, the mixture of pyrethroids, alcohols and emulsifiers, optionally together with other excipients, is heated at 50-60 ° C, preferably 55 ° C, with constant stirring for 0.5-2 hours.

The pyrethroids (named by ILJPAC) containing the phenoxybenzyl group have the structural formula shown in the attached figure.

Of the alcohols having 3 to 5 carbon atoms, isopropanol has been found to be most preferred. Suitable emulsifiers are e.g. Emulsogen EL and Emulsogen 1TN manufactured by Hoechst AG (Germany).

The formulations of the present invention containing the above components may be used as emulsifiable concentrates without further addition. However, it is more preferred that the compositions are supplemented with known auxiliaries known for such formulations. Thus, special stabilizers, e.g. epichlorohydrin (1-chloro-2,3-epoxypropane), antioxidants e.g. butylhydroxytoluene (2,6-di-tert-butyl / p-cresol), synergists, e.g. piperonyl butoxide (3,4-methylenedioxy-6-propylbenzyl diethylene glycol ether) and optionally liquid carriers, e.g. The use of p-xylene has been found to be advantageous. The listed excipients may be mixed before or after heat treatment.

The compositions thus obtained may be diluted with water to form ready-to-use emulsions, depending on the concentration of the active ingredient and the activity of the active ingredient. Depending on the degree of dilution, the resulting form of application, i.e., ready-to-use juice for spraying on the hair of the animals or on the walls of the stables, or for spraying the animals, can be used to eliminate mumps.

However, the compositions of the present invention also have the additional advantage that they can be used to treat wort not only by spraying, but also by spraying technology by selecting only the dilution of the formulations and the technological parameters of spraying (spray rate, appropriate nozzles, pressure, etc.). need. Currently worldwide

The advantages of spraying (fastness, economy, material saving) are extremely significant compared to the use of the 2133539 Sweeper.

The compositions of the present invention - in water 1: (25-400) vol. emulsified and then sprayed on livestock (eg cattle, pigs) and possibly sprayed on stables - suitable for blood suction (eg Haematobia atripalpis, Stomoxys calcitrans) and disturbing the calm of animals (eg Musca domestica, Musca autumnalis) Ixodes ricinus, Haemophysalis punctata), and blood-sucking lice such as Haematopinus suis. However, these formulations in water are 1: (100-2000) vol. proportion emulsified and used for bathing or spraying livestock (cattle, sheep, pigs, rabbits) to produce various mites (e.g. Sarcoptes scabiei var. bubulus, scvar.suis, Psoroptes equi var. ovis, Pevar.cuniculi, Chorioptes b) infection can certainly be eradicated.

The following examples further illustrate the process of the invention.

Example 1

S-alpha-cyano-3-phenoxybenzyl-77R-cu [3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate. 0.5 grams

Emulsogen EL (Hoechst) 5.0 grams / propanol, 90.0 grams of p-xylene 4.5 grams were heated with 200 ml round bottom flask with a reflux condenser, water bath at 50 ⁰ C for 2 hours, then cooled to room temperature.

Dilution for spraying flies, ticks against lice: 1: (25-100).

Dilution for spraying and spraying against scab: 1: (250-1000).

Example 2

3-Phenoxybenzyl-77S-cis, trans 2Z-3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylate 10.0 grams

Emulsogen ITN (Hoechst) 15.0 grams

Emulsogen EL (Hoechst) 15.0 grams 1-chloro-2,3-epoxypropane 2.7 grams

2,6-di (tert-butyl) -p-cresol 0.3 grams

3,4-methylenedioxy-6-propyl-benzyl ether of diethylene glycol, 30.0 grams "27.0 grams of butanol was heated with a 200-ml round bottom flask with a reflux condenser on a water bath of 60 ⁰ C for 30 minutes. The mixture was then cooled to room temperature.

Dilution for spraying against flies, ticks, lice: 1: (50-200).

Dilution for spraying and spraying against scab: 1: (50-2000).

Example 3

7β-alpha-cyano-3-phenoxybenzyl-7β-2- (4-chlorophenyl) -3-methylbutyrate 25.0 grams

7β-alpha-cyano-3-phenoxybenzyl-7β-cis, trans-3- (2,2-methylvinyl) -2,2-dimethylcyclopropanecarboxylate 25.0 grams

Emulsogen F, L (Hoechst) 10.0 grams

Emulsogen ITN (Hoechst) 10.0 grams 1-chloro-2,3-epoxypropane 2.0 grams

2,6-di (tert-butyl) -p-cresol 1.0 grams

3,4-methylenedioxy-6-propyl-benzyl ether dieíilénglikol 26.0 grams / tert-amyl alcohol, 1.0 grams was heated on a steam bath with 200 ml round bottom flask with a reflux condenser, 55 ⁰ C for 1 h . The mixture was then cooled to room temperature.

Dilution spray for flies, ticks, lice: 1: (100-400).

Dilution for spraying and spraying against scab: 1: (500-2000).

Example 4

100 kg of emulsifiable concentrate are prepared as follows:

a) S-alpha-cyano-3-phenoxybenzyl-77? -cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate 2.0 kg / - propanol 48.7 kg

Emulsogen EL (Hoechst) 18.0 kg

Emulsogen ITN (Hoechst) 2.2 kg

b) 2,6-di (tert-butyl) -p-cresol 0.1 kg

3,4-Methylenedioxy-6-propylbenzyl diethylene glycol ether 29.0 kg of the substances listed in the sub-paragraph are heated in a 150-liter condenser duplicator for 30 minutes with constant stirring at 57 ° C and then the composition is brought to 26 ° C. brought back. The resulting mixture is added) -point materials listed ab, the mixture was warmed to 45 ⁰ C and stirred at this temperature for 10 minutes. The product is then cooled to 18 ° C.

Dilution for spraying against flies, ticks, lice: 1: (100-400).

Dilution for spraying and spraying against scab: 1: (500-2000).

Example 5 An emulsifiable concentrate was prepared with the following composition:

3-Phenoxybenzyl-77S-cis, trans -ZZ-3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylate 40.0 kg / propanol 95.4 kg

Emulsogen EL (Hoechst) 40.0 kg 1-chloro-2,3-epoxypropane 4.4 kg

2,6-di (tert-butyl) -p-cresol 0.2 kg

3,4-Methylenedioxy-6-propylbenzyl diethylene glycol ether 20.0 kg of the above materials were fed into a 50 L condenser duplicator and heated at 58 ° C for 30 minutes with constant stirring. The product is then cooled to 25 ° C with continuous stirring.

Dilution spray for flies, ticks, lice: 1: (100-400).

Dilution for spraying and spraying against scab: 1: (500-2000).

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Example 6 An emulsifiable machine concentrate was prepared with the following composition:

a) 3-Phenoxybenzyl-7S-dsi, w -zy-3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylate 10.0 kg

S-alpha-cyano-3-phenoxybenzyl-77? -Cis (3- (2,2-dibromovinyl)) - 2,2-dimethylcyclopropanecarboxylate 1.0 kg

Emulsogen EL (Hoechst) 18.0 kg

Emulsogen ITN (Hoechst) 2.0 kg i-propanol 48.7 kg

b) 2.2 kg of 1-chloro-2,3-epoxypropane

2,6-di (tert-butyl) -? - cresol 0.1 kg

3,4-Methylenedioxy-6-propylbenzyl diethylene glycol ether 18.0 kg of the preparation were prepared as described in Example 4. Dilution for spraying against flies, lice, lice: 1: (100-400).

Dilution for spraying and spraying against scab: 1: (500-2000).

Example 7

7β-alpha-cyano-3-phenoxybenzyl-S-2- (4-difluoromethoxyphenyl) -3-butylbutyrate 15.0 kg

7β-alpha-cyano-3-phenoxybenzyl RS-2- (4-chlorophenyl) -3-methylbutyrate 15.0 kg

Emulsogen EL (Hoechst) 35.0 kg

Emulsogen ITN (Hoechst) 5.0 kg z'-propanol 95.4 kg

3,4-methylenedioxy-6-propylbenzyl diethylene glycol ether 30.0 kg

2,6-di (/ -? - butyl) -? - cresol 0.2 kg of 1-chloro-2,3-epoxypropane 4.4 kg of the components were homogenized cold for 15 minutes in a 300-liter condenser and then heat treated as described in Example 5. The product is then cooled to 20 ° C with continuous stirring.

Dilution spray for flies, ticks, lice: 1: (100-400).

Dilution for spraying and spraying against scab: 1: (500-2000).

Example 8

7β-alpha-cyano-3-phenoxybenzyl-S-2- (4-difluoromethoxyphenyl) -3-methylbutyrate 20 grams z'-propanol 60 grams

Atlox 4861 B (Adas Chem. Div.) 10 grams

Atlox 1285 (Atlas Chem. Div.) 10 g of the mixture was refluxed in a 200 ml round bottom flask for 1 hour at 55 ° C.

Dilution spray for flies, ticks, lice: 1: (50-200).

Dilution for spraying and spraying against scab: 1: (100-400).

The insecticidal and acaricidal activity of the products of the present invention was tested in large-scale livestock farming experiments.

Experiment A The preparation of Example 4 was diluted 1: 200 in volume with water and sprayed onto watering calves. One animal has approx. 100 ml spray was used. Flies on the animals were counted before and 7 and 12 days after treatment.

Before treatment: 150-200 fly / animal, day after day: 0 fly / animal, day after day: 15-40 fly / animal.

From the data it can be seen that the air density decreased significantly and permanently as a result of the treatment.

Experiment B The composition of Example 5 was diluted 1: 200 and then sprayed on cattle using 0.5 L of aqueous emulsion per animal. Evaluating the treatment of 200 cattle yielded the following data:

Before treatment: 80-120 fly / animal, day after day: 8-10 fly / animal, day after day: 50-80 fly / animal.

C trial

From the formulations prepared in Examples 4 and 5! dilutions of different proportions were made and the rabbits heavily infected with the resulting solutions were sprayed 3 consecutive times every 3 days. The following results were obtained:

the ratio of dilution of product and treatments is treatment 1 treatment 2 treatment 3 treatment

Example 4 preparation 1: 200 ± ± + 1: 400 ± + + 1: 1500 X ± + Example 5 1: 200 + + 1: 400 + + + 1: 1500 ± ±

± = healing + - fully healed

It can be seen from the table that the compositions of the present invention, even when diluted 1: 1500, were suitable (by spray technology) for the treatment of rabbit hoarseness. Thus, the same formulations can be used effectively for both insecticide and eradication of scabies.

Experiment D To demonstrate that, without the heat treatment of the present invention, merely by simply mixing the components, the desired composition would not be obtained, the following experiment was performed:

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The composition of Example 2 was prepared by mixing the components on one hand and by heat treatment according to the invention on the other hand. Different dilutions of the two formulations were prepared with water and used to rabbit rumen depletion as described in Experiment C.

The following results were obtained:

dilution ratio of product and treatments treatment 1 treatment 2 treatment 3 treatment

the composition of Example 2 without heat treatment 1: 200 ± ± + 1: 400 ± ± + 1: 1500 ± ± ± 1: 3000, - ± ± the composition of Example 2 by the heat treatment of the invention 1: 200 ± ± + 1: 400 ± ± + 1: 1500 ± ± + 1: 3000 ± ± +

- - no change ± - partially healed + - fully healed.

Comparison of the data in the two tables shows that while a simple mixing of the components, a 1: 400-fold dilution of the exterminator was able to eliminate cartilage, the same composition, but using the composition of the invention, resulted in a total recovery of 1: 1500-fold. after three treatments with dilution. Thus, it can be seen from the data in the table that the composition of the invention is much more effective in the treatment of scabies than the product obtained by simply mixing the components.

The described advantages of the composition of the present invention are believed to be based on the fact that the emulsifiers, the pyrethroids containing the phenoxybenzyl group and the higher alcohols, undergo a heat treatment, but only for a defined amount of time, to form a complex condensation crosslinked form. As a result, on the one hand, the activity and stability of the active compounds in the products so prepared is enhanced, as confirmed by the laboratory measurements described below, and on the other, emulsification of the composition results in an emulsion of physico-chemical structure (degree of dispersion, wettability, etc.). flies settling on hairs and parasites parasitic on the upper epidermis of the skin, as opposed to products which have not been heat-treated or dissolved only at room temperature or have been homogenized.

The enhanced insecticidal activity and stability of the compositions of the present invention can also be well demonstrated by biological titration. This was done by impregnating glass slides with 0.5% aqueous emulsions from various samples, and then eluting the same volume of freshly prepared plates incubated for 5 days at 50 ° C under illumination in a thermostat. The LC50 values for each eluate were then determined (method: WHO Techn. Rep. Ser. No. 443, pp. 114-118 and PJ Finney, Probit Analysis 3th Ed. Cambridge, 1971), i.e. the concentration required. to kill 50% of the bison fly (Stomoxis calcitrans) used in our measurements. To characterize the accuracy of our measurements, we also calculated the confidence interval of the LC 50 values at the 95% significance level. (hereinafter referred to as "conf. limit"). Obviously, the lower the LC50 value, the greater the insecticidal activity of the sample, so the activity is proportional to the 1 / LC50 value. Therefore, to characterize the stability of the samples, the difference between the 1 / LC50 value of freshly prepared samples and the 1 / LC50 value of incubated samples (hereinafter referred to as "% decrease in activity") was given.

Experiment 1 In our embodiment 1, we modified the following

a) sample: p-xylene instead of Emulsogen EL,

(b) sample: p-xylene instead of / -propanol,

c) sample: no heat treatment was applied, the components were simply mixed,

Sample d: Preparation of Example 1.

Data for freshly prepared and incubated samples are given in Appendix I. are summarized in Table.

The data in the table illustrates that the presence of alcohol and detergent in the presence of pyrethroid by heat treatment results in a significant increase in activity and stability, whereas the absence of any of the listed factors causes this effect to be absent.

Experiment 2:

In Example 2, we have modified the following

(e) sample: methanol instead of n-butanol,

(f) sample: ethanol instead of z-butanol,

(g) sample: no change,

(h) sample: n-amyl alcohol instead of n-butanol,

(i) sample: hexyl alcohol instead of n-butanol

Sample j: It contained n-octyl alcohol instead of n-butanol.

The details of the samples thus prepared are given in Annex II. s. Table summarizes. From the data in this table it can be concluded that, taking into account the sample made with N-propanol in Experiment 1, an increase in activity and an increase in stability occurs only when the compositions contain at least 3 carbon atoms. However, the use of alcohols with more than 5 carbon atoms - and aromatic alcohols - cannot be considered for toxicological reasons, so it would not make sense to extend the scope of our protection.

Experiment 3: Exemplary embodiment 3 was modified so that

(k) sample: cypermethrin instead of fenvalerate,

(l) sample: fenvalerate instead of cypermethrin,

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(m) sample: bioresmethrin (5-benzyl-3-furylmethyl-JR-trans-trans-chrysanthemate) in place of cypermethrin and fenvalerate,

(n) sample: bioallethrin (7S-3-allyl-2-methyl-4-oxo-cyclopent-2-enyl-7H-trans-5z-chrysanthemate) in place of cypermethrin and fenvalerate,

o) sample: cadetrin (5-benzyl-3-furylmethyl - <- e / 5j; - 1R, 3S, E-2,2-dimethyl-3- (2-oxo, 2,2) instead of cypermethrin and fenvalerate) , 4,5-Telhydro-thiophenylidene-methyl) -cyclopropanecarboxylate), Example r): Same as in Example 3.

Details of the above samples are given in Appendix III. s. food included.

Claims (5)

Process for the preparation of emulsifiable acaricidal and insecticidal compositions having increased activity by heat treatment, comprising a pyrethroid containing from 0.5 to 50% by weight of a phenoxybenzyl group, preferably - S-alpha-cyano-3-phenoxybenzyl-1R-cis - / 3- ( 2,2-dibromo-vinyl) / - 2,2-dimethyl-cyclopropane carboxylate; and / or - Formula II 3-phenoxybenzyl lRS-: bis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-carboxylate; and / or - RS-alpha-cyano-3-phenoxybenzyl-RS-2- ( 4-chlorophenyl) -3-methylbutyrate; and / or an increase in RS-alpha-cyano-3-phenoxybenzyl-RS5 (IV) can be recorded only for cypermethrin and fenvalerate, and combinations thereof, but not for the other three pyrethroids tested. Because cypermethrin and fenvalerate share a common feature In combination with deltamethrin and permethrin used in Experiments 1 and 2, and having phenoxybenzyl groups as opposed to the other pyrethroids tested, it is clear that the compositions of the present invention exhibit activity enhancement and stability enhancement only when the active ingredient is phenoxybenzyl. pyrethroids containing a group. This finding is confirmed by the results of our investigations with other pyrethroids. -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-carboxylate; and or 45 - RS-alpha-cyano-3-phenoxybenzyl-S-2- (4-difluoromethoxyphenyl) -3-methylbutyrate of formula (V), 5 to 30% by weight of nonionic and / or anionic emulsifiers, 1.0 to 90.0% by weight of C3 -C5 alcohols, preferably propanes, and optionally Containing up to 93.5% by weight of other excipients, preferably liquid carriers and / or stabilizers and / or antioxidants, characterized in that the active ingredient (s), alcohol (s) and emulsifier (s) are mixed with the other components. mixing Prior to 55, the entire composition is heated at 50-60 ° C, preferably 55 ° C, with constant stirring for 0.5-2, preferably 1 hour.