HU198612B - Arthropodicide comprising determined stereo isomers of pyrethroid as active ingredient and process for producing the active ingredients - Google Patents

Abstract

The procceding of obtaining the isomer mixture of synthetic pyrotroizi (piretroizi)The use: in agriculture, because it manifests insecticide activity. The summary: the method of obtaining the new isomer mixture of synthetic pyrotroizi with the general formula:X2C =CH - COOCH(CN) - C6H4OC6H5where X1 chlorine, bromine that contains at least 95% mass of the enantiomeric pairs IR cis S, IS cis R (a), IR trans S and IS trans R (b) into a mass report from 55:45 till 25:75.The efficiency constitues 70-80% of the product.The melting temperature of the product, the mass report of the isomer 1a:1b is 55:45, 50:50, 40:60, 30:70, 25:75, is equal with 61,5 - 64, 60,5-62, 63,5-65, 65-68, 67-71,5°C. In the melted mass or in the saturated solution of mixter of the enantiomeric pairs IR cis S, IS cis R (1a) and IR trans S, IS trans R (ab) and IR cis R, IS cis S (1c), IR trans R, IS trans S (1b) in primary alcohol or a mixture of haloid hydrocarbon saturated and primary and with primary alkylek ether so as oil-bearing ether or hexane. For initiation crystals are added and the crystallization is made at the temperature from (+) 30 till (-) 10°C with the further separation at the indicated temperature of the pair enantiomerik crystals that contain 1a and 1b.

Description

The present invention relates to arthropodicidal compositions consisting of or containing a mixture of defined stereoisomers of pyrethroids and to a process for the preparation of the active compounds.

As used herein, the positions of the substituents relative to the chiral carbon of of are represented by S and R, respectively. The "cis" or "trans" designates the position of the substituents on the carbon atom of the cyclopropane ring relative to the spatial orientation of the carbon atom substituent. The absolute position of the carbon atom substituent - IR or IS - is given as a prefix.

The following abbreviations are used to designate the various enantiomers or pairs of enantiomers as used herein:

la Mixture of iris and lyscisR Fastac) (Alphametrin, ib A mixture of IRtransS and IStransR (Transinix) ic A mixture of iris and lyscis Id A mixture of IRtransR and IStransS If ÍReiszS lg IRtransS ih lSciszR ii IStranszR la + Ib Asymmetry (Chinmix)

More particularly, the present invention relates to:

Multi-active arthropodicidal composition containing from 0.001% to 95% by weight of the pyrethroid of formula (I) as active ingredient and at least 95% of the 8 isomers which are theoretically possible in the form of Ia trans and ItransS and ItransR (Ib) enantiomeric pairs. : Ib = (55: 451 - (25:75) by weight), optionally an activator and, to the extent necessary, 100% by weight of a formulation aid such as antioxidant, stabilizer, wetting, emulsifying, dispersing, antifoaming, diluent, with carrier and / or filler.

The present invention is based on the discovery that the mixture of la + Ib isomers has beneficial biological properties. These properties are surprising, despite extensive research in the field of pyrethroids of formula (I).

It is known that pyrethroid of formula (I), known as cypermethrin under the free name, can be used as insecticide (Hungarian Patent No. 170,866). For its preparation, m-phenoxybenzaldehyde cyanohydrin was first reacted with cycloproponecarboxylic acid chloride in the presence of a base [Pestic. Sci. (1975) 6377-.]. The product obtained is a mixture of 8 stereoisomers, i.e. 4 pairs of enantiomers, which, when used in a 60:40 trans: cis: cycloproponecarboxylic acid chloride, have 18-19% by weight of la, 21-22% by weight of Ic, 26-27%. contains 1% by weight of Ib and 33-34% of ld enantiomeric pair.

It is known in the literature that the stereoisomers of each cypermethrin have a different biological activity. Molecules containing cis-cyclopropane / carboxylic acids have been reported to have higher potency than their corresponding trans isomers (Pest. Sci. 1976. 7, p. 273).

In a comparative biological study of various pyrethroids (Pest. Sci. 1978 9 112-116), cis and trans stereoisomer pairs were evaluated together, including cypermethrin stereoisomer pairs.

Comparative studies were performed with Musca domestica L. and Phaedon cochleariae Fab. strains. For chlorine derivatives, data are provided on the trans isomers IRtransS (Ig) and IRtransR. These confirm that while the activity of IRtransR is strong, the activity of IRtransR is significantly lower [1400 and 81 in Musca domestica and 2200 and 110 in Phaedon cochleariae, respectively, as compared to bioreserethrin activity (100). It was also reported that the mixture of the two test L isomers did not give the calculated value, but less; thus, the reported isomers did not exhibit the expected additive interaction but antagonism with a factor of 1.42 for the house fly and 1.46 for the mustard beetle.

As a result of the above studies and publications, the trans isomers and their mixtures are at the edge of biological interest and further development towards active cis derivatives or mixtures thereof has led to the development of a mixture of the iris and lScisR (la) isomers known as alphamethrin. chlorine derivatives and decamethrin containing the only iris (If) isomer of bromine derivatives.

Therefore, several processes are known for preparing cystermethrin isomeric mixtures which are cis-isomeric.

Crystallization from solutions containing other isomers is believed to make it possible to form mixtures more rich in cis-isomers. (Chem. Abstr. Japanese Patent Publication No. 57755/81, 951981). The preparation of a substantially 1: 1 mixture of the iris and lScisR isomers by solvent separation has been described from the other mixture containing the other cis isomers (British Patent No. 2,064,528). The resulting mixture of la isomers is considered to be very active. In order to achieve a specific cis ratio greater than a certain (about 50) percent, a special so-called "cis-cyclopropane / carboxylic acid" intermediate is prepared. .high cis'-syntheses have been developed which are quite expensive. (Angew. Chem. I.E. 1981, p. 20,703)

On the one hand, the present invention is based on the discovery that the most potent Ig isomer of the trans isomers of the compounds of formula (I), together with the other 7 isomers which are considered to be minor, does not antagonize the previously published isomer pairs, salt has a synergistic activity beyond the additive effect for pure trans isomers

HU 198612 In comparison. This has allowed for novel selection of isomers of synthetic pyrethroids and development of a new type of active ingredient, which has many advantages over previously known isomeric selections: less toxic for warm-blooded humans, thus more economically produced, more beneficial to insect -parasites, entomophages and bees, does not cause allergies. 10

The present invention is also based on the further realization that the previously observed bioactivity series for each isomer and the regularities observed for previously identified isomer pairs are not necessarily valid for other isomer pairs.

Thus, we have attempted to compare or co-investigate the lRtransS and IStransR (lb) enantiomeric pairs we have found to be effective with other isomers. Comparison showed that the synergism between the members of the lb enantiomeric pair (lg and li) does not occur between the members of the corresponding cis series of the la enantiomeric pairs (If and Ih).

Further, the present invention is based on the observation that, while most of the IrIsIS (If) and lRtransS (Ig) isomers are more active, the biological efficiency between the I enantiomeric pair and the lb enantiomeric pair is, however, limited in certain species. 30 turns.

Using the foregoing, it has been surprisingly discovered in our experiments that the combination of the la and lb enantiomeric pairs results in a synergistic interaction of more than 35 additive effects.

It has been found that the synergistic biological activity of la + lb mixtures is not limited to mixtures of substances in which the effect of lb is inherently superior to that of la. Thus, for example, measured on Leptinotarsa decemlineata (potato beetle), there is significant synergism when the two enantiomeric pairs are used together. All of these results are illustrated in the Examples.

The above observations therefore warranted a new selection from previously known isomeric mixtures which led to the novel composition of the present invention.

In addition to the synergistic effect, the composition of the present invention has several other benefits and is therefore excellent. It is important that the compounds have reduced mammalian toxicity compared to formulations previously in the 55 active range. This rat po. (280 and 355 mg / kg) and the topical (0.54 and 0.48 mg / kg) LD50 values, respectively, of the house fly, the selectivity index (517 and 747) clearly demonstrates. (The same selectivity index for la is 50: 0.45 = 111). Synergistic interactions can also be observed with mites, so the compositions can be used as acaricides. In addition to their low uterine toxicity, the formulations also protect useful entomophages and parasites. (See Examples ΙΙΙ / 15 and ΙΙΙ / 16) These properties are due at the same time to their repellant activity, favorable persistence and appropriate inherent activity.

Because of their properties above, the present invention is contemplated, mixtures of forming enantiomeric pairs may be suitable for use in Integrated Pest Management Technologies (JPM).

Economic benefits are even more important than biological benefits. Because the preparation of the pure cis-enantiomeric pair of la requires highly expensive synthetic procedures, or involves the loss of the trans component in the reaction mixture, the present invention permits the use of virtually all of the components la and lb from the most economical syntheses. depending on the isomer ratio of Ia: Ib and by which synthesis).

According to the present invention, the active ingredient containing the Ia + lb isomeric pair can be formulated with known additives for direct use. Thus, for agricultural use, the compositions can be used in the form of ULV formulations, sprays, dispersible granules, wettable powders, stable emulsions, etc. for spraying vegetables, soles in orchards and other large-scale agricultural crops, cereal fields. Due to their lower mammalian toxicity, they are well suited for use against flying insects and insectivorous insects around the house, on barn walls, in pasture management and in mosquito control.

The agents of the invention are applied in conventional manner, for example by dipping, sprinkling, spraying, spraying, smoking, dusting, spraying, impregnating the packaging material, etc. The amount to be used depends on the intended use and is usually 2-25 g / ha or 0.10-2 g active compound per 100 kg seed / propagating material. The isomeric mixture of the present invention may be used in combination with known gonicides, herbicides, equine herbicides, growth regulators or fertilizers, disinfectants, for broader application and protection.

Preferably, an activator or additional synergist such as piperonyl butoxide may be added to the mixture of isomers. This enhances the efficacy of the active ingredient without increasing warm-blood toxicity.

Conventional formulations of the present invention include mocha, emulsion concentrates, powders, sprays, pastes, granules, isomer mixtures such as solutions, suspensions, dusts, aerosols, dressing agents and the like. can be processed. The effect-35

Mixtures of the substances are dissolved, dispersed or co-ground or otherwise formulated in admixture with conventional diluents, such as liquid diluents, pressurized liquefied gases, and / or solid carriers, optionally in the presence of a surfactant. Liquid solvents include medium and high boiling petroleum oils such as kerosene or gas oil, vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, alkylated naphthalene, cyclohexane, paraffin, or derivatives thereof such as low-carbon, , esters, ketones and halogenated hydrocarbons such as butanol, ethylene glycol, methyl ethyl ketone, cyclohexanone, chloroform, chlorobenzene or a polar solvent such as dimethylformamide, diraethyl sulfoxide or N-methylpyrrolidone. Liquefied gases under pressure may be conventional aerosol propellants such as halogenated hydrocarbons such as freon, butane, propane, nitrogen or carbon dioxide.

Solid mineral carriers include natural mineral flour, rock flour such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, diatomaceous earth and artificial mineral flour such as highly dispersed silica, alumina and silica. Suitable carrier materials for granules are synthetic granules of crushed natural minerals such as calcite, marble, limestone, dolomite, inorganic or organic ground, and granules made of organic material such as sawdust, corn shavings and torso, ash stalks, poppy waste, furfural bran.

Suitable surfactants include emulsifiers and / or dispersants and / or antifoams, such as alkali metal, alkaline earth metal and ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid; alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates; alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid; lauryl ether sulfate, fatty alcohol sulfates; alkali and alkaline earth metal salts of fatty acids; salts of sulfated hexadecanols, heptadecanols and octadecanols; sulphated fatty alcohol glycol ether salts; condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde; polyoxyethylene octylphenyl ether;

ethoxylated isooctylphenol, octylphenol and nonylphenol; alkylphenyl polyglycol ether, tributylphenyl polyglycol ether; . condensates of alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol and ethylene oxide; ethoxylated castor oil; poly (oxyethylene) alkyl ether; ethoxylated polyoxypropylene; lauryl alcohol polyglycol ether acetal; sorbitol ester, sulphite impurity, methylcellulose.

The present invention provides various wettable powders and dispersible granule formulations containing from 1 to 95% by weight of the active ingredient. As an excipient, 0.1 to 10% by weight of anionic and / or nonionic surfactant is preferred. Such materials include, for example, alkali metal salts of alkyl, arylsulfonic acids; alkali metal salts of formaldehyde condensate of alkylarylsulfonic acids; alkylaryl polyglycol ethers; sulfated high carbon alcohols; poly (ethylene oxide) s; sulfated fatty alcohols; fatty acid polyglycol esters 6b are other commercially available surfactants. Other excipients: 0.5-10% by weight of anti-caking agent, 1-2% by weight of adhesive, 10-60% by weight of filler or carrier.

According to the present invention, emulsion concentrates may also be prepared. This composition preferably contains from 5% to 50% by weight of the active ingredient, with 50% to 95% by weight of an additive providing a stable emulsion when the emulsion concentrate is emulsified in water or in the presence of water.

As excipients, 0.1 to 2% by weight of surfactant, 0.1% to 5% by weight of stabilizer and organic solvent are added, which makes up to 100% by weight. Anion as a surfactant. and a mixture of nonionic surfactants ... should be used. For example, the following anionic surfactants may be used:

calcium salts of alkylarylsulfonic acids, e.g. Ca (Na) salt of dodecylbenzenesulfonic acid; (K-salt) as

SULFARIL-50 (United Chemicals)

MARLON AFR (Hüls)

mono- and di-esters of phosphoric acid, e.g. orthophosphoric acid mono / di- (oxyethylaryl) ester, Gafac RM 520 '(GAF) orthophosphoric acid mono / di- (oxyethyl) alkyl ester. SURFACTANT QS-5' (ROHM and HAAS).

Preferred nonionic surfactants include:

- polyethylene glycol ether of nonyl and tributyl phenol: ANTAROX, IGEPAL (GAF)

ARKOPAL, EMULSOGEN (HOECHST)

AVOLAN, EMULSIFIER (BAYER)

DOWTAX (DOW)

CATAREX (SHELL)

RENEX (ATLAS)

- fatty alcohol ethylene oxide adducts, eg:

BRIJ (ATLAS)

DISPERSOL A (ICI)

GENAPOL S-XO (HOECHST)

ethoxylated amines, e.g.

G - 3525 (Ethoxylated Alkylamine) (ATLAS)

G - 3684 (Ethoxylated Alkylamine) (ATLAS) GENAMIN S: (Ethoxylated Petearyl Arain) (HOECHST)

NEOVADINE AL: (ethoxylated alkylamine) (CIBA GEIGY)

polyethylene glycol esters of fatty acids, e.g.

MYRJ 49 (ATLAS)

MYRJ 51 (ATLAS)

MYRJ 52 (ATLAS)

MYRJ 53 (ATLAS)

-4HU 198612 A • 7

FROM AF to AF (ICI)

NINISOL 110 (CIBA GEIGY)

Ready-to-use mixtures of surfactants may also be used, e.g. Geronol (Rhone Poulenc) preparations, e.g. an isobutanol mixture of FF / 4 ethoxylated alkyl phenols and calcium dodecylbenzene sulfonate; M S, which is a calcium salt of dodecylbenzenesulfonic acid, a mixture of ethoxylated amines and ethoxylated fatty acids in isobutanol, etc.

Suitable solvents for this purpose are: aromatic solvent mixtures, xylene, cyclohexanol, butanol, methyl ethyl ketone, isopropanol and the like.

The active compound mixture of the present invention may be used in the form of an aerosol spray. Propellants may be various liquefied gas mixtures of freon or propane-butane.

As the solvent, the following can be used, in particular, in an amount which makes up to 100% by weight of the mixture:

aromatic solvents: xylene, toluene;

aliphatic alcohols: butanol, isopropanol, cyclohexanol;

aliphatic ketones: acetone, methyl ethyl ketone, diethyl ketone;

vegetable, animal or mineral oils: olive oil, sunflower oil, rapeseed oil, kerosene, creole; and aliphatic hydrocarbon mixtures e.g. kerosene;

and water.

The present invention preferably provides a suspension concentrate containing from 0.1 to 30% by weight of an active ingredient in the concentration of 99.9 to 40% by weight of an additive as 1-10% by weight of a surfactant, 5 to 10% by weight of antifreeze. 50-90% by weight of diluent or carrier, 0.2-0.3% by weight of viscosity enhancer, 0.1-0.3% by weight of defoamer.

The granules may contain as active ingredient from 1 to 20% by weight of a mixture of (Ia + Ib) isomers and optionally from 2 to 30% by weight of piperonyl butoxy, 80 to 99% by weight of excipients such as 5 to 15% by weight of diluent, 70 to 80% by weight. next to.

The composition of the present invention is 0.01 to 1% by weight of the active ingredient 2,6-di (t-butyl) -4-methylphenol, 2,2-dimethyl-4- (azulfonylmethyl) -1,2- dihydroquinoline, hydroquinone, hydroquinone monomethyl ether, benzophenone, 2,2,4-trimethyl-1,2-dihydroquinoline and / or phenylsalicylate derivative.

The present invention also relates to processes for the preparation of a mixture of the 8 possible isomers of the compounds of formula (I) essentially comprising only the enantiomeric pairs of (Ib) and (Ia) by

a.) a solution of a mixture of la + Ib isomeric pairs with other possible isomers and / or at a ratio other than the desired ratio is prepared by saturating a protic or apolar aprotic inert organic solvent and inoculating the crystals of the la and Ib enantiomeric pairs 55:45 - 25 : Inoculants containing 75% by weight Effective crystals are isolated, then at a temperature of 30 - (- 30) ° C, or

b. ) melting the melt of a mixture of Ia + Ib isomeric pairs with other possible isomers in a ratio of ⁴ and / or at a different ratio from the desired ratio at a temperature of 10 to 60 ° C with a seed crystal containing 55:45 - 25:75 wt. Crystallize at (-10) ° C, whereupon the resulting mixture is slurried at -10 to -20 ° C in a protic or apolar aprotic inert organic solvent, and isolate the excellent crystals, or

c. ) Enantiomeric pairs of la and Ib in a mixture other than the desired ratio and / or other isomers, or in an organic solvent solution or melt thereof, are added in an amount of la or Ib enantiomeric pairs such that the mixture or solution contains 55:45 to 25:75 isomers and then optionally crystallizing by one of the process variants a) or b), or

d. ) mixing the Ia and Ib pairs of enantiomers, optionally in the presence of a protic or apolar aprotic inert organic solvent, in the desired ratio, homogenizing or optionally crystallizing after inoculation according to process variant a).

The organic solvents used in process (a) according to the invention are preferably C 1 -C 12 hydrocarbons, C 1 -C 6 chlorinated hydrocarbons, C 2 -C 6 dialkyl ether or C 1 -C 10 alkanol, where the solvents may be straight or branched or cyclic alicyclic.

Inoculation with the seed crystal is preferably carried out in the presence of an antioxidant. The antioxidants used are 2,6-di (t-butyl) -4-methylphenol or 2,2,4-trimethyl-1,2-dihydroquinoline.

Preferably the solvent is ethanol, isopropanol, petroleum ether or hexane.

Slow cooling is preferred for crystallization.

In a preferred embodiment of the process, 60% by weight of trans and 40% by weight of cis-cypermethrin enantiomeric pairs (la 18.2% by weight, Ib

Of cypermethrin (26.8%, Ic 21.8% and Id 33.2%) (hereinafter le) using isopropanol in the presence of 0.01% antioxidant after inoculation with crystals of mixture la and lb absolute yields a crystalline material, m.p.

EN 198612 The ratio is essentially 40/60 and 5% by weight of the impurity pair Ic and Id. The products thus obtained can be recrystallized in the same manner as above to give a mixture of substances Ia and Ib with a purity greater than 99%.

There are good results obtained when crystallizing other cis / trans mixtures. The starting cypermethrins may be prepared by esterification of the appropriate cis / trans ratio cyclopropanecarbonBavak. The following table shows the melting points of the various weight ratio Ia: Ib mixtures.

Ia / Ib 25:75 30:70

M.p. 67-71.5 65-68

40:60 50:50 55:45

63.5-65 60.5-62 61.5-64

The feasibility of crystallization in the proper direction strongly depends on the purity of the starting cypermethrin mixture. With a purity of less than 95%, the yield is reduced. Tar-like impurities can also prevent crystallization from occurring.

The crystallization of the mixture of Ia and Ib pairs of enantiomeric pairs of this invention can be accomplished without solvent by inoculating the oily 8-isomeric cypermethrin with the crystals of la and Ib. In a refrigerator, a mixture of la and Ib precipitates within 1 week. The crystals were isolated by adding ethanol cooled to -20 ° C and, after suspension, the precipitated crystals were filtered off.

The Ia: Ib enantiomeric pair mixtures falling within the scope of the present invention can also be prepared by mixing and / or crystallizing the amounts of Ia and Ib or different mixtures thereof and by mixing and / or crystallizing the calculated amounts of Ia and Ib and Ib.

The biological effects of the materials of the present invention were tested on several insect species. By methods known as comparative standards in the description of studies - cf. The effects of the stereoisomers obtained by chromatographic separation or by chromatographic separation of cypermethrins from chiral acids are also shown.

Further details of our process are given in the following examples.

I. Production of active substances

1/1. example

100 g of cypermethrin (18.2% by weight, 21.8% by Ic by gas chromatography,

26.8% by weight of Ib, 33.2% by weight of Id isomers), 2000 ml of isopropanol, 0.2 g of potassium hydroxide and 0.2 g of 2,6-di-tert-butyl-4-methylphenol it was dissolved at 45.0 ° C with constant stirring, then cooled slowly to 30 ° C, clarified with charcoal and then filtered at 30 ° C. The colorless solution is seeded with crystalline material containing 60% by weight Ib and 40% by weight of isomer and

Stir at -10 ° C for 24 hours. The precipitate was filtered off, washed with isopropanol and dried in vacuo. 36.02 g of an off-white crystalline solid are obtained. M.p. 62-65 ° C (uncorrected). Gas chromatography and TLC analysis showed the product to contain 37% by weight and 58% by weight of Ib isomer. Yield 76% based on la + Ib isomers of cypermethrin. la isomer Re 0.25 and Ib isomer Re 0.20. Recrystallized from isopropanol, the first generation of thermos consisted of 32 g, mp 63.5-65.0 ° C, 39.5% la and 59.5% Ib isomer pairs.

IR (KBr) [nu] C-O: 1730, 1735 cm <^-1>. NMR (CDCl3) (ppm): 1.05-2.45 m (8H); 5.6, 30 d, J = 8 Hz (= CH trans, 0.6 H); 6.14, d,

J = 8 Hz (= CH cis 0.4); 6.35, d, (1H); 6.85-7.60 m, (9H).

1/2. example

100 g of colorless clear clear oily cypermethrin (la 18.2%, Ic 21.8%, Ib 26.8%, Id 33.2%) were inoculated with 60% Ib and 40% la 40 isomers crystals, then crystallized at 7 ° C for one week, suspended in 100 ml 1: 1 'isopropanol-diisopropyl ether and filtered at -15 ° C. The crystals were washed with isopropanol 45 and dried in vacuo. 40.1 g of an off-white crystalline material are obtained, containing 37.5% and 59% Ib. Mp: 62.5-65 ° C. Avoids, uplift 86%. Recrystallization from isopropanol gave a first generation of 36 g of a needle-white crystalline solid, m.p. 63.5-65 ° C, containing 40% by weight of la and 60% by weight of Ib (GC) IR and NMR signals. are the same as in example.

1/3. example

100 g of cypermethrin (18.2 wt% la, 21.8 wt% Ic, 26.8 wt% Ib, 33.2 wt% Id) in 100 ml diisopropyl 50 ether and 0.05 g 2,6-di (tertiary) butyl) -4-methylphenol was clarified with 2 g of charcoal under constant stirring at 0 ° C. After filtration, the solution was seeded with crystals containing 60% Ib and 40% Ia at -15 ° C. Crystallize for 72 hours, filter, with diisopropyl ether

-611

Wash with dry isopropanol and isopropanol. 38 g of a white crystalline substance are obtained. Mp: 62-65 ° C. Contains 37.5 tX la, 58 tX Ib. Yield: 80.6X. Recrystallization from isopropanol gave the first generation 35 g of a snow-white crystalline material. M.p. 63.5-65 ° C. Ia: Ib weight ratio 40:60. Physical data of 1/1. are the same as those described in Example 3a.

1/4. example

10 to 10 grams of the substance containing the isomers Ia and Ib in a ratio of 4: 1 are mixed with 4.60 g, 6 g, 10 g, 16.67 g, 22.0 g of pure Ib crystal each, and the resulting α is mixed with ten times the amount of isopropanol. recrystallized. The composition and melting point of the products obtained gave the following values.

Ia: Ib Melting point (° C) 55:45 61.5 to 64 5: 5 60.5 to 62 4: 6 63.5 to 65 3: 7 65-68 25:75 67 to 71.5

1/5. example

10 to 10 g of the pure crystalline pair of isomers Ia are mixed with 8.20 g, 10.00 g and 15.00 g of the pure crystalline pair of isomers Ib, respectively, and the mixture is homogenized. The resulting crystalline mixture contains la + Ib in a weight ratio of 55:45, 50:50 and 40:60, m.p. 61.5-64 ° C, 60.5-62 ° C, 63.5-65 ° C.

1/6. example

10-10 g of pure crystalline pair of isomers Ia are dissolved in 10 times of isopropanol and 23.34 g and 30.0 g of pure crystalline isomer Ib are added to each sample. The resulting solution was crystallized. It is white crystalline product (m.p. 65-68 ° C, 67-71.5 ° C), containing Ia: Ib products in a weight ratio of 30:70 and 25:75 and used as an arthropodicidal active ingredient.

1/7. example

100 g of cypermethrin was weighed into a magnetic stirring apparatus, which according to gas chromatography analysis was 18.2% by weight, respectively; 26.8 tX Ib;

It consists of a mixture of 33.2 LX Id, 21.8 tX Ic isomers, a mixture of 1900 ml isopropanol and 100 ml carbon tetrachloride, 0.2 g potassium hydroxide and 0.2 g 2,6-di-tert-butyl - 4-methylphenol.

With constant stirring, dissolve at 45.0 ° C and slowly cool to 30 ° C. The slightly opalescent solution is clarified with 2 to 5 g of charcoal and filtered rapidly to maintain a temperature of 30 ° C. The resulting colorless, clear solution was seeded with crystalline material containing 60 tX lb and 40 tX 1a isomers and then gradually cooled to -15 ° C. After crystallization began, the mixture was stirred for 6 hours and then allowed to warm to room temperature. After stirring at this temperature for 2 hours, it was gradually cooled to -12 ° C and crystallized for an additional 4 hours. The precipitated material was rapidly filtered, washed twice with 50 ml of cold isopropanol and dried in vacuo at room temperature. 36.0 g of an off-white crystalline solid are obtained. M.p. 62-65.5 ° C (uncorrected). Gas chromatography analysis of the product contained 38t.X in Ia and 57.5tX in Ib. The yield of the active ingredient calculated for the corresponding isomer of cypermethrin is 76.4X. The crude product (36 g) was recrystallized from 360 ml of isopropanol. In the first generation, 31.5 g of a snow-white crystalline solid, m.p. 63.5-65.0 ° C, is obtained, which according to GC analysis consists of isomers Ia at 39.5 tX and 59.5 LX. The product was identified by IR and NMR as shown in Fig. is identical to the product of example.

1/8. example

Weigh 100 g of cypermethrin into a magnetic stirrer which, according to gas chromatography analysis, is la 18.2 tX, Ic

It consists of a mixture of 21.8 tX, Ib 26.8 I.X, Id 33.2 tX isomers. The colorless, clear translucent oily material was crystallized at + 11 ° C for two weeks. The resulting viscous suspension was cooled to -15 ° C, suspended in 100 ml of isopropanol-diisopropyl ether mixture cooled to -15 ° C and filtered rapidly. The resulting crystals were washed twice with 50 ml of isopropanol and dried in vacuo. 38 g of an off-white crystalline solid are obtained, m.p. 62-65.5 ° C. The product was found by gas chromatography to contain the la isomer at 38 tX and the Ib isomer at 59 tX. The yield of the product is 81.5X calculated for the corresponding isomers of cypermethrin. The crude product (38 g) was prepared as described in Fig. 1/1. Recrystallize from isopropanol (380 mL). First generation 32 g

Snow white crystals, m.p. 63.5-65 ° C. According to GC, the substance contains the isomer la at 40 tX and the Ib at 60 tX. The IR and NMR signals of the final product are as given in Example 1/1.

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HU 198612 A

1/9. example

Weigh 40 kg of cis-cypermethrin into a 250-L mixing duplicator containing 96% by weight of the isomeric pair la and the isomeric pair Ic

Contains 3.5% w / w and 60 kg trans cypermethrin, containing 98% w / w Ib and 1.5% w / w Id. The material was dissolved in 100 L of isopropanol at 50 ° C and then crystallized. After crystallization of the material, the mixture was cooled to -5 ° C and filtered. Wash with 10 L of cold isopropanol and dry at room temperature. 92 kg of a white crystalline material are obtained. Mp: 62-64 ° C. Active ingredient content: la 38.2%, Ib 60.0%, Ic 0.8%, Id 0.5%.

II. products

The exact formulation of the commercially available excipients used is indicated by quotation marks, followed by the name of the manufacturer.

II / l. Production of powders aj

To 166.2 g of perlithium (dnax = 120 µm), 0.8 g of synthetic silica (Aerosil 300) is mixed in a fluidized bed mixer. While stirring, 20 g of a mixture of Ia: Ib = 40:60 (w / w) cypermethrin enantiomeric pair and 2 g of Z6 alcohol alcohol polyglycol ether (.G-3920 'ICI) are added so that the mixture is homogenized uniformly. The powder mixture was milled in a mechanical then air-jet mill and then 5 g of octylphenol polyglycol ether (EO = 20) (.Triton X-165 Rohm and H.) and 2 g of alkylsulfosuccinate (.Aerosol 13, 'Cyanamide) were added in a rapid mixer. added. The resulting wettable powder mixture (WP) was subjected to a suspension stability test with a wetting time of 23 seconds and a buoyancy of 89% (standard WHO method).

b.) g Ia: Ib = 3: 7 by weight mixture of cypermethrin enantiomeric pair and 0.3 g of fatty alcohol polyglycol ether (.G-3920 'ICI) in a homogenizer 0.8 g of synthetic silica (Aerosil 200) and 193 g. , With 9 g of potassium and sodium phosphate buffered talc (dnax = 15 μι ») adjusted to pH 6.5. With further stirring, 1 g of dioctyl sulfosuccinate (.Aerosol OTB 'Cyanamide) and 1 g of fatty alcohol polyglycol ether sulfonate (.Genapol LRD Hoechst) are added and ground to an average particle diameter of 20 µm. The product obtained is a mercury stream powder.

II / I / c).

A solution of 1.5 g Ia: Ib = 25:75 in weight ratio of cypermethrin and 1.5 g fatty alcohol polyglycol ether in a powder homogenizer with 30 g synthetic silica (WessalonS), 60 g talc, pH 7.1, 5 g beet sugar and 3 g, Homogenize with 35 g of dodecylbenzenesulfonic acid (.Marion T-370 'Hüls). The product obtained is a mercury flowing powder.

ΙΙ / 1 / d) g Ta: Tb = 35:65 cypermethrin mixture was diluted with 2 g ethanol. The solution was mixed with 5 g of calcium lignin sulfonate (.Borrespeseca 'Borregard), 5 g of rionyl phenol polyglycolol ether (EO = 20, (.Arkopal N-200' Hoechst), 70 g of calcium carbonate in a powder hogenogenizer. The product was ground in an Alpine 100 mill, according to CIPAC, a buoyancy of 81% and a wetting time of 18 sec.

ΙΙ / 1 / e.) Dusting agent

0.1 parts by weight of a mixture of cypermethrin isomer Ia: Ib = 50:50 by weight is mixed with 99.8 parts by weight of natural rock flour and the mixture is ground to a porphinoin. The resulting composition is always sprayed in the required amount onto the infected site.

I / l / f) kg of cypermethrin (Ia: Ib = 55:45) is mixed with 1 part by weight of dibutyl naphthalene sulphonate, 4 kg of lignin sulphonate), 8 kg of highly dispersed silica and 67 kg of natural middlour and the mixture is ground to a powder. Before use, the wettable powder is mixed with water so that the resulting mixture contains the active ingredient in the desired concentration.

You can make as follows:

U / l / g) 10% w / w powder

Ia: Ib = 55:45 Cypermethrin 10.0% Montmorillonite 30.0% Hydroquinone 0.05% Hydroquinone Monomelyl Ether 0.05% Talc 59.9%

ΙΙ / 1 / h.) 25% solid concentrate

Ia: Ib = 50:50 by weight

cypermethrin 25.0 t% Sodium ligninsulfonate 1.5 t% sodium ril sulfonate 1.5 t% montmorillonite 72.0 t%

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ΙΙ / 1 / i.) 90 tX wettable powder

Ia: Ib = 30:70 by weight

cypermethrin 90.0 t% sodium dibutylnaphthalenesulfonate 0.5 t% Sodium ligninsulfonate 3.5 t% kaolin clay 6.0 t%

11/1 / j.)

Ia: Ib = 40:60

cypermethrin 25.0 t% calcium lignosulphonate 5.0 t% alkyl-phen phenol-ethylene n-oxide condensation product 4.8 t% ethylene glycol monosalicylate 0.2 t% silica 20.0 t% kaolin 45.0 t%

ΙΙ / 1 / k).

Ia: Ib = 40:60

cypermethrin 40.0% silica 10.0% diatomaceous earth 10.0% dextran 20.0% cyclohexanone 5.0% alkylphenol ethylene oxide condensed product 2.0 1% oxyethylated anhydrosorbite- monolaurate 1.0 L% oxyethylated anhydrosorbite- monostearate 1.0% oxyethylated anhydrosorbite- monopalmitate 1.0% polyethylene glycol 6000 9.6% phenyl salicylate 0.4 1%

II / second emulsions

ΙΙ / 2 / a.) G Ia: Ib = 55:45 by weight mixture of cypermelrine enantiomeric pair 21.25 g xylene and

Dissolve in a mixture of 42.5 g of n-propanol with slow stirring. To the solution was added 4 g of ethoxylated alkylphenol + linear alkylaryl sulfonate calcium salt (.Geromol FF / U Geronazzo) and 6 g of ethoxylated arain + fatty acid + linear alkylaryl sulfonate (.Geronol MS 'Geronazzo) total alkali metal salt mixture. until dissolved, 21.25 g of water are added. The product obtained is a clear solution which retains this property for a long time between 0 and 50 ° C. Optionally diluted with water to form 0.8-1.5 μηι droplets.

ΙΙ / 2 / b) g Ia: Ib = 25:75 by weight mixture of cypermelrine enantiomeric pair is dissolved in a mixture of 75 g xylene and 10 g aliphatic oil, then slowly stirred 7.5 g ethoxylated alkyl10

-phenol + linear alkyl aryl sulfonate calcium salt mixture (.Geronol FF / U Geronazzo) and 2.5 g ethoxylated fatty acid and linear alkylaryl sulfonate salt (.Geronol MS Geronazzo) are added. The resulting emulsion concentrate is stable after 170 hours as measured by CIPAC.

Il / 2 / c.)

By mixing the appropriate components, the following emulsion concentrates are prepared:

EC

Ia: Ib = 40:60 (w / w) 105 kg cyclohexanol 290 kg .Atlox 3386 B (ICI) 20 kg .Atlox 3400 B- (ICI) 45 kg odorless petroleum 539.5 kg

2,6-di (t-butyl) -4-: methylphenol 0.5 kg

II / 2 / d).

EC

Ia: Ib = 40:60 weight ratio 50 kg cyclohexanol 294 kg .Atlox 3386 B- (TCT) 20.5 kg .Atlox 3400 B (TCT) 45 kg odorless petroleum 590 kg

2,2-dimethyl-4- (sulfonylmethyl) -1,2-dihydroquinoline 0.5 kg

II / µ / e) 52.0 g of the active ingredient (containing 38% by weight of the isomer la, 60% by weight of the lb isomer, 0.9% of the Te isomer and 0d of the ld isomer in a 1 liter flask, 9% (w / w) dissolved in 700 g xylene at 25 ° C followed by isobutanol mixture of 45.0 g commercial ethoxylated alkyl phenol and calcium benzenesulfonate (. Geronol FF / U Geronazzo) and 55.0 g commercial calcium dodecyl. benzenesulfonate ethoxylated amine and isobutanol surfactant (.Geronal MS Geronazzo) containing ethoxylated fatty acids are added to the solution. The solution is stirred for 10 minutes, homogenized, filtered, transferred to a 1 L standard flask and made up to the mark with xylene.

ΙΙ / 2 / f).

In a 250 liter mixing enamel duplicator, 140 kg (163 liters) of industrial xylene was stirred at room temperature with 10.4 kg of the crystalline thiopermethrin active ingredient containing 40: 60 by weight of Ta: lb isomers and 98% by weight. Add to the solution:

kg of alkyl aryl sulfonate (.Atlox 4861 b 'ICI) kg of ethoxylated nonylphenol (.Renes 647' ICI) 4 kg of ethoxylated. alkylamine (.G-4962 ^- ICI) kg ethoxylated stearic acid (.MYRJ 45 'ICI) lenses.

The material was stirred at room temperature for 1 hour, homogenized and then 18 kg

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HU 198612 Industrial xylene (21 liters) is added. The solution was filtered.

ΙΙ / 2 / g) g Ia: Ib = 55:45 by weight mixture of cypermethrin enantiomeric pair and 0.01 g of 2,6-di-tert-butyl-β-cresol are dissolved in 78 g of xylene and g of piperonyl buloxide, 7.5 g of a mixture of commercial ethoxylated alkylphenol 10 and a linear alkylaryl sulfonate calcium salt (.Geronol FF / U Geronazzo), and 2.5 g of ethoxylated fatty acid and linear alkylaryl sulfonate calcium salt ( Geronol MS Geronazzo) is added. 15

The resulting emulsion concentrate mixture was filtered.

II / 3rd Gran ulas

In a mechanical granulator, a mixture of 300 g of a pair of Ia: Ib = 50:50 by weight cypermethrin enantiomeric pair 1500 g polycarboxylate alkaline salt (.Sorphol * Toho), 500 g dodecylbenzenesulfonic acid sodium salt (.Marion TP 370. Hüls), 25,500 g beet sugar. 7200 g of kaolinite are mixed and the powder mixture is mixed with 8300 ml of water with a high shear mixer (v = 10 m / s) and spray dried. The product has a particle size distribution of 95% 0.1-0.4 mm. The buoyancy is 98% according to the WHO method.

II / 4th Oily sprayable formulation

0.02 parts by weight of the active ingredient Ia: Tb = 40:60 are dissolved in 10 parts by weight of n-propanol, 99.96 parts by weight of petroleum are added to the resulting solution until a homogeneous solution is obtained. The 40 oily spray formulations thus obtained are ready-to-use, home-use insecticides.

II / 5. Preparation of aerosol formulations 45

0.12 kg of active ingredient (Ia: Ib = 50:50) are dissolved in 25 kg of methylene chloride and 15 kg of kerosene are added. The solution was filled into diffusers (59.78 kg) in diffluorodichloromethane.

II / 5b.

A 100 L mixing apparatus is charged with 1 kg of crystalline active ingredient containing the isomers Ia and Ib in a ratio 40:60 and 98%, 0.5 kg piperonyl butoxide, 0.1 kg aerosil air 972, 0.1 kg of ethylene glycol monosalicylate, 15 kg of odorless petroleum and 60 50 kg of isopropyl alcohol, and after complete dissolution, 33.3 kg of liquid propane-butane (25-75) gas are filled into bottles.

III. Biological examples

III / l. example

Table 1 shows the efficacy of the various stereoisomers of cypermethrin in domestic fly (Musca domestica).

The experimental method:

120 mg by weight of the active compounds were dissolved in 10 ml of a 1: 2 oil / acetone mixture. After the desired dilution of this stock solution with an oil-acetone mixture, the indicated doses of the active compounds were added to filter paper disks (Whatman No. 1, 9 cm diameter) placed in Petri dishes and insects were placed on the filter paper discs after evaporation of the acetone.

Three replicates per dose were used, 15 animals were placed in a Petri dish, and mortality percentages were determined after 24 hours. Corrected mortality percentages were obtained using the Abbot formula *.

Table 1 dose (mg / disk)

agent 0.04 0.11 0.33 1.00 3.00 24-hour mortality (%) If 68 93 100 100 100 la 44 84 100 100 100 lg 48 68 83 100 100 r> 32 62 95 100 100 Ia: Tb = 40:60 41 81 100 100 100

* See Busvine, J.R.: Techniques for Testing Insecticides (1971) Commonweallh Agriculture.ural Bureau, 267

The efficacy of the la + Ib mixture in this test is good for pure la.

III / second example

The study was carried out on adult small flea beetles (Tribolium confusum) at 1-2 weeks of age at ΙΠ / l. in the same way as the example,

As shown in Table 2, Table III / l. The increase in efficiency of Example 1 is due to the synergistic interaction of the trans isomers.

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Table 2

agent 0.11 dose (mg / disk) 0.33 in 24 hours 1.00 mortalití 3.00 is% lSciszR (Ih) 0 38 80 100 IRISK (If) 80 100 100 100 la 22 65 94 100 IStraris (ii) 0 0 71 90 IRtrans (lg, 70 92 100 100 lb 64 89 100 100 Ia: Ib = 40:60 61 89 100 100

LDw values and Bzinergist factors calculated from Table 2:

agent I was expecting szinerg- ism factor (FS) to LDW (Mg / - puck) lSciszR (Ih) 0.47 - IRISK (If) 0.07 - - ltransR (II) 0.81 - - IRTransmission (Tg) 0.10 - - Ih: If: Ii: Ig * 0.10 0.15 " 1.5 x "

'Ih: If: Ti: Ig = 20: 20: 30: 30 (%) 7 Ia: Ib = = 40:60' LDw Expected =

0.2 0.2 0.3 0.3 - + - + - + 0.47 0.07 0.81 0.15 0.10 FS = - = 1.5 0.10

1/3. example

In Table 3, the insecticidal efficacy of different ratios of combinations of the Ta and Tb enantiomeric pairs is shown on a small flour beetle (Tribolium confusum). The experimental methodology is ΠΙ / l. .

Table 3 dose (mg / disk)

Ia: Ib 0.02 0.06 24 hour 0.25 mortality 1.00% 10: 0 0 14 54 100 · 5: 5 0 43 100 100 4: 6 14 53 100 100 3: 7 20 81 100 100 0:10 8 46 100 100

The data show synergism between the enantiomeric pairs la and lb.

ITI / 4th example

Effect on potato beetle

Experimental method:

In 100 ml of 2-ethoxyethanol (cellosolve)

133.3 mg of various active compounds were dissolved. Doses taken from the stock solution thus obtained were diluted with cellulose at the desired dose to give 0.3 μΙ droplets on the abdomen of the infant. Treatments were performed in 2 replicates with 10-10 animals and mortality was determined after 48 hours.

Table 4 dose (ug / beetle) agent 0.05 0.10 24 hours 0.20 mortality 0.40 % la 50 55 75 80 lb 0 25 75 85 Ia: Ib = 4: 6 45 60 70 80 Ia: Ib = 3: 7 45 65 75 85 deltamethrin 45 60 75 85 cypermethrin 0 20 45 75

Thus, synergism between Ia and lb enantiomeric pairs exists despite the fact that in potato beetle mammals, la is more efficient than lb. Mixtures of Ia and lb enantiomeric pairs gave the same effect as deltamethrin.

III / 5th example

Comparative efficacy studies of Ia, lb and Ia: Ib = 40:60 on bean weevil (Acanthoscelides obtectus), small mealy bug beetle (Tribioliuni confusum), house fly (Musca domestica) and weevil (buciba sericata). Experimental method, see III / l. example.

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Table 5

species enantiomer -powder 0.02 0.07 dose (itig / disk) 0.22 0.67 mortality% 2.0 6.0 A. obleclus la 10 37 63 95 100 100 (imago) ib 32 55 87 100 100 100 Ia: Ib = 4: 6 30 55 90 100 100 100 T. confusum la 0 18 51 100 100 100 (imago) ib 14 73 100 100 100 100 Ia: Ib = 4: 6 16 80 100 100 100 100 M. domestica la 36 63 88 100 100 100 (imago) ib 0 18 67 100 100 100 Ia: Ib = 4: 6 25 45 85 100 100 100 L. sericata Ta 0 30 29 57 60 65 (imago) ib 22 55 70 75 100 100 Ia: Ib = 4: 6 18 50 60 75 100 100 Table 5 of the patent reported LDsu values and synergistic factors agent because expected FS LDsu ( mg / disc) Acunlhoscelides la 0,116 obleclus tb 0,052 - - Ia: Ib = 4: 6 0,052 0,067 1.3 Tribolium Ta 0.131 confusum lb 0.046 - - Ta: Ib = 4: 6 0,044 0.062 1.41 Musea domestica la 0,045 - ib 0.123 - - Ia: Ib = 4: 6 0.062 0.073 1.2 Lucilia sericata la 0,950 ib 0,084 - - Ta: Ib = 4: 6 0.102 0,132 1.3

ΙΙΙ / 6th example

Efficacy of zipermethrin ether stereoisomer pairs on T. confusum (small flour beetle) versus time.

In III / l. similar to the experimental example, small flour (T. confusum) images were exposed in a petri dish. We performed 3 replicates per dose and 15-15 animals per replicate. At the times indicated, the individuals on their backs were counted and the results obtained were expressed as a percentage. (J ()

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Table 6

Stereoisomers and. pair of enantiomers exposure time (minutes) 0.11 dose (mg / disk) 3.00 Night club 0.33 poisoning 1.00 ii symptoms of insectsX ih 30 0 0 0 0 60 0 0 0 8 120 0 0 0 67 180 0 0 0 88 If 30 0 0 48 64 60 0 5 84 100 120 0 40 100 100 180 39 61 100 100 la 30 0 0 0 33 60 0 0 16 88 120 0 14 66 100 180 10 49 100 100 ii 30 0 0 0 15 60 0 0 0 70 120 0 0 0 100 180 0 0 0 100 lg 30 0 0 15 68 60 18 34 98 100. 120 30 70 100 100 180 34 84 100 100 ib 30 0 0 47 61 60 0 21 82 100 120 28 100 100 100 180 56 100 100 100 Ia: Ib = 4: 6 30 0 0 50 55 60 15 85 85 100 120 30 100 100 100 180 55 100 100 100

KD50 values and synergistic factors calculated from 60 minutes of Table 6:

agent because KDso expected (Mg / kc FS irong) 50 la 1.56 ib 0.51 - - Ia: Ib = 4: 6 0.23 0.70 3.0 55 Ia: Ib = 4: 6 mixture so - running around

(KDso) - exhibits a very significant synergistic effect. 60

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Table 9

ΙΠ / 7th example

Use of piperonyl butoxide

In III / l. T. confusum (small flour beetle) was treated in the same way. The dose of synergistic piperonyl butoxide used was 0.5 mg / disk, i.e. 12 per active ingredient; 4.5; 1.5; Weights of 0.5 and 0.16 times.

Table 7 cypermethin dose (mg / disc) stereoisomer 0.4 0.2 0.1 0.05 0.025 hours mortality%

la 96 53 12 0 0 la + PBO 100 58 16 0 0 la + Ib 100 90 57 18 0 la + Ib + PBO 100 95 75 43 7

Thus, the enantiomeric mixtures of la + Ib can be more synergized than the enantiomer of la. la:: Ib = 4: 6

ΙΙΙ / 8th example

The ITI / 4. The drug solution was applied to the back of L7-Ls larvae Hyphantria cunea (American white moth caterpillars) in 0.2 μΐ droplets, and the treated caterpillars were counted in a petri dish after 24 hours and stored in a petri dish. caterpillars. The experiment was performed in 5 doses in 2 replicates with 10-10 animals.

Table 8 effective dose (pg / larva)

material 0.023 0.047 0.094 0.188 24-hour mortality 0,375 la 40 60 65 80 90 ib 10 15 30 70 80 Ia: Ib - = 4: 6 40 50 55 65 75 ciper- deltamethrin 0 10 25 50 75

agent approx LDso (ppm) la 0,056 lb .340 Ia: Ib = 4: 6 0,060 cypermethrin 0,120 deltamethrin 0.185 111/10. example .5 according to II / 2c EC 'emulsion concentrate- fresh water from roth 50x, 100x, 200x, 400x,

800x and 1600x dilution emulsions were prepared and 0.5 ml portions were sprayed onto glass slides. After drying, 10-10 L. decemlineata imago were placed on each plate and covered with a Petri dish. The studies were performed in 6 doses, in triplicate per dose. Dead beetles were counted after 48 hours. The results are shown in Table 10.

Table 10 Dilution

authorities material 1600x 800x 400x 200x mortality Loox 50x la 0 27 53 63 87 97 Ia: Ib = = 4: 6 0 33 53 73 80 93 delta- deltamethrin 7 35 53 67 83 100 ciper- deltamethrin 0 17 33 50 67 83

III / II. example

TTI / 10. Acanthoscelides obtectus (bean weed) images were tested using the same method and formulations as in Example 1. Evaluation was performed after 24 hours. The results are shown in Table 11.

111/9. example

Leaves infected with mites (Tetranychus urticae) were sprayed in Potte Tower with the active compounds prepared as in the previous example. After 24 hours, mortality was compared with control leaves (water treated). The results are shown in Table 9:

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Table 11

authorities material 1600x dilution 800x 400x 200x 100x mortality% 50x la 0 13 27 33 50 70 Ia: Ib = = 4: 6 10 17 30 37 53 70 delta- deltamethrin 7 13 20 37 57 75 ciper- deltamethrin 0 3 10 20 45 60

III / 12. example

15 to 15 bean plants were grown per pot and infested with aphids (Myzus persicae) at 6 days of age. At the age of 12 days, highly and uniformly infected plants were selected and sprayed to run-off with freshly prepared emulsions from .5 EC 'of Example II / 2c. Treatments were performed in 3 doses (2.5, 5, 10 ppm active ingredient) and 4 repetitions (each repetition was one pot). After spraying 2, 4 and

On day 8, aphids were swept from treated plants with a fine brush on white paper, and the live animals were counted. The results are shown in Table 12.

Table 12

authorities material concentration rationality (Ppm) average number of aphids per pot after treatment In the days 8 2 4 la 2.5 44 83 245 5.0 22 29 90 10.0 8 17 30 Ia.'Ib = = 4: 6 2.5 38 71 251 5.0 21 32 82 10.0 10 11 21 delta- deltamethrin 2.5 26 47 137 5.0 13 19 29 10.0 6 11 23 control 1850 2780 4120

111/13. example

0.1 g of the active ingredient was suspended in 100 ml of a 1: 1 by volume mixture of acetone + water and sprayed on tomato plants grown in pots with this stock solution and dilutions at the desired concentration of active ingredient. The treated plants were placed in isolators and infected with L.3 stage Leptinotarsa decemlineata larvae. After 6 hours, the percentage of paralyzed larvae that had fallen from the plants was determined. The results are shown in Table 13 for Ia and Ia: Ib = 2: 3.

Table 13

bulk chemicals concentration (Ppm) Ta Ia: Ib = 2: 3 paralyzed larvae percent 1000 100 100 200 100 100 40 46 75 8 18 60

111/14. example

Plots heavily infected with potato beetles were plated on 25 m ^z experimental plots. 10-10 plants were individually labeled on each experimental plot after counting the number of beetles on them (only second-generation summer mosquitoes were considered as the proportion of L1 and 1.4 larvae in the population was low at the time of the study). The treatments were carried out in triplicate on 25 m ² plots of aqueous suspensions of 10 g of active ingredient / ha of the concentrates pre-conditioned according to Example II / 2g. For evaluation, live beetles were counted on the labeled plants. The average data for the three replicates are shown in Table 14. The table shows the number of live beetles per 10 plants on the day of treatment and the 1st, following,

Day 3 and Day 9.

Table 14

drugs 0 1 3 9 days la 171 11 9 25 Ia: Ib = 213 8 4 22 deltamethrin 181 7 10 19 control 211 206 179 183

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Table 16

ΠΙ / 15th example

Contact residue experiment on adult Aphidinus matricariae specimens. For the experiments, a 1 cm high aluminum frame with a 10 x 10 cm edge length was provided with separate holes on its side to feed the parasites and provide adequate ventilation. The two wide sides of the frames were covered with 10x10 cm glass sheets. thus, the frame and the glass sheets together form a test .ketrec '(hereafter .ketrec'). The test compositions were applied to the inside of the glass panes of the cages using a Potter spray tower with a 1 mm diameter nozzle at a pressure of 1.5 bar. This yielded a spray coverage of 1 mg / cm ² . One day before the start of the studies, aphid mummies (A. matricariae) were collected from the parasite cultures in Petri dishes. The next day, freshly-raised (0-24 hours) imagoes required for experiments were placed in prepared cages.

As a control, water was repeated at least 3x. The active compounds were used in aqueous suspension at concentrations of 5 and 1 ppin. Ten female A. matricariae were placed in each cage and fed with honey. The number of surviving females was determined after 1.5 and 24 hours in independent races. The total number of survivors in each cage was determined. The result is shown in Table 15.

Table 15 Concentration 5 ppm 1 ppm h 1 h 5 h 24 h mortality i%

la 100 100 100 96 Ia: Ib = 4: 6 100 50 90 63 deltamethrin 100 20 100 85

Example III / 16

Direct contact experiment on paprika leaves on the developed larvae of A. matricariae.

We used pepper leaves with larvae of the parasites 2-3 days before emergence. The leaves were treated with an aqueous suspension of the active ingredients and water as a control on wet filter paper, and the treated leaves were stored in clean Petri dishes in a clarified chamber at 20 ° C, 70% real humidity and 16: 8 hour light: dark cycle. The surviving larvae hatched after 2-3 days. Hatched and dead larvae were counted.

The result is shown in Table 16.

agent Concentration in ppm 30 10 5 1 morality! % Ib: Ta = 3: 2 14.3 0 0 0 deltamethrin 75 33 0 0 la 77 12.5 0 0 control 0 0 0 0

Claims (13)

PATENT CLAIMS Claims 1. An arthropodicidal composition containing pyrethroid stereoisomers as active ingredient, characterized in that at least 95% of the 8 possible isomers of the synthetic pyrethroid of formula (I) are present in an amount of 0.001 to 95% by weight as the active ingredient. 1 Ia: Ib = (55:45) - (25:75) by weight of a mixture of enantiomeric pairs of RcisS and lScisR (Ia) and IRtransS and ISLransR (Ib) in an amount necessary to form 100% by weight of a formulation aid, preferably as follows or mixtures thereof together with an ionic and nonionic surfactant, preferably an alkyl arylsulfonic acid alkaline earth metal and / or an alkylaryl polyglycol ether, a solid or liquid carrier, preferably tulcumnium, kaolirite or xylene, or a propellant, preferably an antioxidant, butoxide. 2. A composition according to claim 1, characterized in that it contains as active ingredient Ia: Ib = 40:60 by weight in enantiomeric pairs. 3. A composition according to claim 1, characterized in that the Ia: Ib = 30:70 weight ratio comprises enantiomeric pairs. 4.) The composition of claim 1, wherein the Ia: Ib = 50:50 is by weight enantiomeric pairs. 5). Composition according to any one of claims 1 to 3, characterized in that it contains 0.1 to 20% by weight of the active ingredient piperonyl butoxide as an activator. 6). Composition according to any one of claims 1 to 4, characterized in that 0.01 to 1% by weight of the active ingredient, 2, 5-dimethyl-4- (sulfonyl) -2,5-dimethyl-4-methylphenol, methyl) -1,2-dihydroquinoline, hydroquinorthl, hydroquinone inonomethyl ether, benzophenone and / or phenylsalicylates, or a mixture thereof. 7). Composition according to any one of claims 1 to 3, characterized in that 0.1-50% by weight of anionic and / or nonionic surfactants, such as alkali metal or calcium salts of alkyl and arylsulfonic acids, are used as surfactant 17 -1 631 It contains monoethers of phosphoric acid, esters of nonyl and tributylphenol polyethylene glycols, fatty alcohol ethylene oxide adducts, ethoxylated aliphatic amines, polyethylene glycol esters of fatty acids or mixtures thereof. 8. A composition according to any one of claims 1 to 3, characterized in that the diluent or the diluent is selected from the group consisting of: as a solvent, 99.999-1% by weight of aromatic solvents such as xylene, toluene, aliphatic alcohols such as butanol, isopropanol, cyclohexanol, aliphatic ketones such as acetone, methyl ethyl ketone, vegetable, animal or mineral oils such as sunflower oil, containing kerosene and / or a mixture of its aliphatic carbohydrate clot as kerosene and, in particular, water at the time of use. 9). Composition according to any one of claims 1 to 3, characterized in that the carrier comprises 99-1% by weight of silica gel, talcum, kaolinite and / or zeolite. 10). Composition according to any one of claims 1 to 3, characterized in that the spray propellant comprises 10 to 90% by weight of a liquefied propane-butane gas mixture and / or 25 liquefied freon gas or a mixture thereof. 11.) An arthropodicidal composition comprising a mixture of pyrethroids of formula (I) with the restriction that at least 95 wt.% Of a mixture of iris and lScisR (la) and IRtransS and IStransR (lb) enantiomeric pairs are present. , so that la: : The weight ratio of Ib enantioiner pairs (55:45) to (25:75). 35 12.) Process for at least 95% by weight of the possible 8 isomers of the synthetic pyrethroids of the formula (I) in the ratio of the enantiomeric pairs of IrisS and lScisR (Ia) and IRtransS and IStransR (lb): Ia: Ib = 55:45 - 25:75 40 for the manufacture of a multi-component insecticidal active ingredient, characterized in that: a.) preparing a solution saturated with a protic or apolar aprotic inert organic solvent from a mixture of the Ia + lb isomeric pairs with other possible isomers and / or at different ratios, then inoculating the crystals of the la and lb enantiomeric pairs 55: : 45 to 25:75 by weight of seed crystals, followed by isolation of excellent crystals at 30 to -30 ° C, or b. ) the melt of the mixture of the Ia + lb isomeric pairs with other possible isomers and / or at a temperature ranging from 10 to 60 ° C with a seed crystal containing 55:45 to 25:75 by weight crystals of the Ia and Tb enantiomeric pairs . The resulting mixture is crystallized at 30 to -10 ° C and suspended at -10 to -20 ° C in a protic or apolar aprotic inert organic solvent and the crystals which are precipitated are isolated, or c. ) to mixtures of the enantiomeric pairs of la and lb in a ratio other than the desired ratio and / or other isomers, or to an organic solvent solution thereof, is added an enantiomeric pair of la or lb so that the mixture or solution 55: : 45 to 25:75 by weight, and then optionally crystallizing by either a) or b), or d. ) mixing the pairs of enantiomers 1a and 1b, optionally in the presence of a protic or apolar aprotic inert organic solvent, homogenizing and optionally crystallizing, optionally after inoculation according to process a), optionally in the presence of an antioxidant. 13.) Process a) according to claim 12, characterized in that the organic solvent is C1-C6 chlorinated hydrocarbon, C2-C6 dialkyl ether or C1-C10 alkanol.