HRP980249A2 - Pesticide compounds, compositions and process for the preparation thereof - Google Patents

Description

The invention relates to (+) optically active isomers of active ingredients of formula (I), isomeric mixtures rich in (+) optically active isomer, pesticide preparations containing (+) optically active isomer of the active ingredient of formula (I), pesticide preparations containing (+ ) optically active isomer of the active ingredient of the formula (I) in addition to known pesticide synergists, synergistic pesticide preparations containing the (+) isomer of the pesticide synergist of the formula (I) in addition to the known pesticidally active ingredients, further to preparations containing the (+) isomer of the pesticide synergist of the formula (I ) with the known pesticidally active ingredient and synergist, and to the procedures for their preparation.

A racemic compound of formula (I) (MB-599) is described in WO 97/19040.

The compound of formula (I) has one center of asymmetry, and therefore has two optical isomers. These two isomers can be distinguished - among other things - most simply by their direction of optical rotation. The above-mentioned (+) optical isomer is a compound that rotates the plane of linearly polarized light in the (+) direction in an acetone solution, i.e. to the right. Two optical isomers are mirror pairs, their general physical properties (boiling point, refraction of light, solidification temperature) are the same, but in optically active systems, and therefore in biological environments, they behave differently. Consequently, their synergistic efficacies may also differ.

Compounds that are non-toxic by themselves, or only slightly toxic, but mixed with a pesticide, most often with an arthropod agent, significantly increase the power of the pesticide, are called synergists. The synergistic strength is characterized by the so-called synergistic ratio SR, which in the case of insecticides is represented by the following expression:

LD50 insecticide

SR50 = ——————————

LD50 insecticide + synergist

The more the SR50 value differs from 1, the greater the synergistic strength.

The use of synergists in arthropodicidal preparations is very attractive, since they enable the preparation of new preparations with practically all representatives of the field. These new preparations, compared to the previous ones, are less expensive, less toxic, more selective, cause less danger to the environment, suppress the development of resistance, and are active even for species that have already developed resistance.

So far, the number of registered synergists is less than 10, but only 2-3 molecules are listed as products in the Pesticide Manual, and only two materials (PBO, MKG264) are actually on the market. The reason for this: it is difficult to find a chemical agent that can be applied selectively and safely, and whose price/performance ratio is competitive with that of the active ingredient. In order for the synergist to be economically usable, it must be very strong, and must work in small doses (around the value of the original dose of the active ingredient).

Both selectivity and specific efficiency can be increased by using pure material containing only one isomer. PBO does not contain, but MKG264 has several centers of asymmetry. Therefore, for this compound, there is a possibility of taking advantage of the preparation in an optically pure form. Despite this, the material was not used in that form. This can be explained by two non-opposite reasons: there are only small differences between the activities of the isomers, and the cost of preparing optically pure material is not covered by the savings achieved due to higher activity.

In the case of some compounds described in WO 97/19040 having a center of asymmetry - such as an α-methyl substituted benzyl derivative - the R(+) derivatives were found to be more potent than the S(-) enantiomer. As described in the publications, the difference between the isomer strengths increases with increasing activity of the racemic compound, but never exceeds a threefold value. This means that the more powerful isomer is at most 1.5 times more powerful than the racemic compound. This increase in power does not cover the special costs of preparing an optically pure connection.

The racemic compound of formula (I), known as MB-599, is an excellent pesticide synergist, and its optical isomers have not been previously prepared. According to our invention, we managed to prepare both the (+) isomer (MB-755) and the (-) isomer (MB-754), and we subjected the compounds to a wide range of biological research. As expected, here too the (+) optical isomer was more biologically active. However, the difference between the activities of the isomers, achieved for the resistant species, was much higher than we expected, and showed values higher by one order of magnitude (results are shown in Table 1).

Table 1.

[image] RR: resistance factor (resistance);

SR: synergistic factor

A similar trend of differences was found with decreasing synergist-active ingredient ratio.

Table 2.

[image] RR: resistance factor (resistance);

SR: synergistic index; synergist / active ingredient ratio

For the use of synergists in practice, the main criterion is that the amount of synergists must be comparable to that of the active ingredient, while the total amount of synergists and active ingredients must be as small as possible. The meaning of our invention is precisely that. It not only enables savings, which can cover the additional costs of preparing optical isomers, but is also very important from the point of view of environmental biology. The material can be applied in much smaller quantities, it is more selective and safer. A large difference in the activities of the isomers was observed for different types of active ingredients. The following known arthropodicidal active ingredients can be advantageously synergized with the compound according to our invention:

acetamide derivatives: eg oxamyl; acetamidine derivatives: eg acetamiprid; benzoylurein compounds: eg flucycloxuron, hexaflumuron, teflubenzuron, triflumuron, novaluron, lufenuron, chlorofluazuron; bicycloheptadiene compounds: eg heptenophos; bridged diphenyl compounds: eg etofenprox, bromopropylate, methoxycolor, temephos, tetradifon; carbamates: eg aminocarb, aldicarb, aldoxycarb, asulam, bendiocarb, benfuracarb, carbaryl, carbetamide, carbofuran, carbosulfan, dietofencarb, dioxacarb, etiofencarb, fenobucarb, fenoxycarb, furatiocarb, isoprocarb, methomyl, oxamyl, pirimicarb (pirimor), propoxur, thiodicarb , thiophanox, xylylcarb; carbamoyloxime derivatives: eg alanicarb, butocarboxime; cyclodienes: eg aldrin, chlordane, endosulfan, heptachlor; diazoles: eg fipronil; diphenyl ethers: eg diphenol; hydrazides: RH 5992, RH 5849, CGA 215'944; non-reistoxin analogues: eg bensultap, kartap; chlornicotinyl analogues: eg imidacloprid; nitroethylene and nitromethylene analogues: eg nitenpyram; organophosphorus compounds: eg quinalphos, diazinon, phosalon, dimethoate, azinphos-methyl; organotin compounds: eg azocyclotin, cyhexatin, fenbutatin oxide; oxadiazine carboxylates: eg DPX-MP062, DPX-JW062; phenoxy compounds: eg diafenthiuron, diphenolan; pyrazoles: eg pyrazophos; pyrethroids: eg allethrin, bioallethrin (esbiol), acrinathrin, deltamethrin, halfenprox, flumethrin, fenvalerate, empenthrin, pralethrin, resmethrin, MTI-800, flufenprox, permethrin, tetramethrin, ZX-8901, cypermethrin, and their isomers and isomeric combinations, such as β-cypermethrin, theta-cypermethrin; pyridazinones: eg pyridaben, NC-196; pyridine derivatives: eg chlorpyrifos; pyrimidine derivatives: eg pirimiphos-ethyl, pirimiphos-methyl; pyrroles: eg AC 303, 630 (chlorfenapyr); quinazolines: eg phenazaquine; terpenoid derivatives: eg methoprene; tetrazines: eg clofentezine, SzI-121 (fluphenzine); thiadizins: eg buprofezin; thiazolidine: eg hexithiazox, etoxazole; triazoles: eg isazophos, RH 7988; chlorinated hydrocarbons: eg lindane; macrocyclic lactones: eg ivermecrin/avermectin, doramectin, nocidectin, emamectin, milbemycin; tebufenpyrade; pheniproximate; triazamate; insecticides of plant origin: eg azadirachtin, naphthoquinones, pyrethroids and their derivatives, plant extracts.

(the above known active ingredients are described in Pesticide Manual, 8th and 10th ed., A.G.Chem.New Compound Review, Vol 11(1993); ACS Symposium Series 504 p. 272; or European Patent Application No. 0635499 (SZI-121 ).

We demonstrated the effect on different arthropod species. The compounds according to our invention have been shown to be effective against insects, aphids and scabies (acari). An important advantage of the compound of formula (I) is that it shows practically the same activity on species that have already shown resistance and on susceptible species.

Compounds of formula (I) can be prepared by stereoselective substitution, reaction of compounds of general formulas (II) and (III), where X and Y represent groups suitable for ether formation. First of all, alkali or alkaline earth metal salts of resolved benzyl alcohol of the general formula (II) can be reacted, under SN2 conditions, with a 2-butynyl derivative of the general formula (II) containing a suitable releasing group.

The compound according to the present invention is not known from the literature. In the identification of the compound, after purity testing by GC and TLC, the structure was unequivocally supported by IR, 1H and 13C NMR studies. Optical purity characterized by optical rotation values and optical purity of the starting material, determined by NMR measurements.

The compound of formula (I) can be formulated as an independent preparation or in a mixture with other known pesticides, primarily arthropodicidally effective ingredients, and according to the application goal, known carriers and other auxiliary substances can be used. Emulsion concentrates, microemulsions, ULV, microsuspensions, suspensions, dusters, aerosols, evaporating agents and smoke agents can thus be prepared by methods known per se. [Rhone Poulenc-Geronazzo: Surfactant and Specialties for Plant Protection, Application Manual (1994); ICI: Surfactants, Application Manual (1992)].

In the course of application, preparations containing the compound according to the present invention and preparations containing known active ingredients can be used consecutively, or their mixture can be previously prepared in a container.

We present the following examples, by means of which the object of the present invention is shown, whereby the object of the invention is not limited to the examples mentioned.

EXAMPLES OF PREPARATION

Example 1

(+)-4-(but-2-ynyloxyethyl)-1,2-dimethoxybenzene, MB-755, (+)VERBUTIN

Add 8 ml of abs. THF and 0.44 g (0.0165 mol, approx. 90 %) of NaH is suspended in it. A solution prepared from 5 ml abs. is added to this suspension slowly, drop by drop, at room temperature. THF and 1.0 g (0.0055 mol) of (+)-α-methylveratryl alcohol (rotational values: [α]20D = +33.1°, c = 1 methanol and [α]20D = +35.5°, c = 1 acetone; m.p. : 43.2-44.9 °C), and the mixture is heated with reverse cooling for 1 hour. The mixture is then cooled to room temperature, 0.77 g (0.082 mol) of 1-bromo-2-butyne is added and heating is continued with reflux. The reaction was monitored by TLC (eluent: hexane-Etac 7:3). Expected reaction time: 3-4 hours.

50 ml of water and 50 ml of ethyl acetate are added to the cooled thick suspension, the mixture is filtered through celite, the filtrate is washed with distilled water, dried over magnesium sulfate and evaporated. The residue is purified by column chromatography (eluent: hexane-Etac 7:3, Rf = 0.536).

Yield: 0.926 g (3.95 mmol), 72.34 %.

Purity was tested by GC analysis: (CP 9000, CP-SIL-5CB, 60 m x 0.53 μm, 5 ml/min N2, FID, 250 °C) tR = 3.87 min, >97.4 %.

It turned out that the material is homogeneous and well defined. Based on its behavior in TLC, GC and NMR studies, it is identical to the racemic compound MB-599.

Illumination of the structure:

1H-NMR (200 MHz, CDCl3) δ: 1.45 (3H, d, J = 6.47 Hz, ArCH-CH3), 1.85 (3H, t, J = 2.35 Hz, ≡C-CH3), 3.87 and 3.89 (6H, s, aryl-OCH3), 3.79 and 3.98 (2H, ABX3, JAB = 14.97 Hz, JAX = JBX = 2.3 Hz, ≡C-CH2O), 4.54 (2H, q, J = 5.83 Hz, Ar-CHO), 6.83 -6.89 (3H, m, aromatic).

13C-NMR (50 MHz, CDCl3) δ:3.66 (≡C-CH3), 23.86 (ArCH-CH3), 55.88 (OCH3), 56.02 (≡C-CH2O), 75.38 (≡C-CH2), 81.97 (≡ C-CH3) 109.08 (C-3), 110.87 (C-6), 118.98 (C-5), 135.33 (C-4), 148.55 (C-1), 149.22 (C-2).

Optical rotation:

A solution of (+)-verbutin was prepared using an accurate weighing (54.7 mg / 5 ml of acetone in a 5 ml volumetric flask, c = 1.094 g/l), and then the optical rotation was determined at different wavelengths in a cuvette of length 1 dm and volume 1 cm3.

[image]

Optical purity:

The optical purity of the starting material was determined by H-NMR measurements, with the use of an optically active reagent to determine the shift. This method showed a content of 3% enantiomeric impurity. According to the accuracy of the method, the material MB-755 contains the (+) isomer in the amount of 94%.

Example 2

(-)-4-(but-2-ynyloxyethyl)-1,2-dimethoxybenzene, MB-754, (-)VERBUTIN

Add 8 ml of abs. THF and 0.44 g (0.0165 mol, approx. 90 %) of NaH is suspended in it. A solution prepared from 5 ml abs. is added to this suspension slowly, drop by drop, at room temperature. THF and 1.0 g (0.0055 mol) of (-)-α-methylveratryl alcohol (rotational values: [α]20D = -31.7°, c = 1 methanol and [α]20D = -34.3°, c = 1 acetone; m.p. : 44 °C), and the mixture is heated with reverse cooling for 1 hour. The mixture is then cooled to room temperature, 0.77 g (0.082 mol) of 1-bromo-2-butyne is added and heating is continued with reflux. The reaction was monitored by TLC (eluent: hexane-Etac 7:3). Expected reaction time: 3-4 hours.

50 ml of water and 50 ml of ethyl acetate are added to the cooled thick suspension, the mixture is filtered through celite, the filtrate is washed with distilled water, dried over magnesium sulfate and evaporated. The residue is purified by column chromatography (eluent: hexane-Etac 7:3, Rf = 0.536).

Yield: 0.79 g (3.37 mmol), 61.7 %.

Purity was tested by GC analysis: (CP 9000, CP-SIL-5CB, 60 m x 0.53 μm, 5 ml/min N2, FID, 250 °C) tR = 3.87 min, >93.5 %.

It turned out that the material is homogeneous and well defined. Based on its behavior in TLC, GC and NMR studies, it is identical to the racemic compound MB-599.

Illumination of the structure:

1H-NMR (200 MHz, CDCl3) δ: 1.46 (3H, d, J = 6.47 Hz, ArCH-CH3), 1.85 (3H, t, J = 2.33 Hz, ≡C-CH3), 3.90 and 3.88 (6H, s, aryl-OCH3), 3.82 and 4.01 (2H, ABX3, JAB = 14.98 Hz, JAX = JBX = 2.37 Hz, ≡C-CH2O), 4.54 (2H, q, J = 6.47 Hz, Ar-CHO), 6.83 -6.89 (3H, m, aromatic).

13C-NMR (50 MHz, CDCl3) δ:3.66 (≡C-CH3), 23.80 (ArCH-CH3), 55.88 (OCH3), 56.02 (≡C-CH2O), 75.38 (≡C-CH2), 81.97 (≡ C-CH3) 109.08 (C-3), 110.87 (C-6), 118.98 (C-5), 135.33 (C-4), 148.55 (C-1), 149.22 (C-2).

Optical rotation:

A solution of (-)-verbutin was prepared using an accurate weighing (52.8 mg / 5 ml of acetone in a volumetric flask of 5 ml, c = 1.056 g/l), and then the optical rotation was determined at different wavelengths in a cuvette of length 1 dm and volume 1 cm3.

[image]

Optical purity:

The optical purity of the starting material was determined by H-NMR measurements, with the use of an optically active reagent to determine the shift. This method showed a content of 4% enantiomeric impurity. According to the accuracy of the method, the material MB-754 contains the (-) isomer in the amount of 92%.

RESULTS OF ACTIVITIES

Example 3

Test of synergistic activity on a population of resistant housefly (Musca domestica)

In two parallel experiments, 10 female, 2-3 day old houseflies were treated from the ventral side of their thorax with 0.2 μl of the test solution using a Hamilton MicroLab P microdispenser. In addition to the fixed synergistic dose of 1000 ng/fly, the animals were treated with carbofuran at a dose of 20 ng/fly. Celosolv was used as a solvent. The selection and counting of flies was done under the influence of CO2. After processing, the flies were kept in plastic cups covered with tulle. Mortality after 24 hours is expressed in %. LD50 values (ng/fly) were calculated from the dose-mortality relationship.

For the CHXEL, CARBSEL and IX tests, insecticide-resistant species of flies were used. Resistance factors (RR) are expressed as quotients of LD50 values obtained for carbofuran-resistant and susceptible species (WHO/SRS).

The results are shown in the table below:

Table 3.

[image] * PBO: piperonyl butoxide;* MGK 264: N-(2-ethylhexyl)-8,9,10-trinorborn-5-ene-2,3-dicarboxamide

(ENT-8184)

Example 4

Examination of the synergistic spectrum on the housefly (Musca domestica) and the cotton bollworm (Helicoverpa armigera).

The synergistic activities of the compound MB-755 according to the present invention and the reference compound MB-599 were determined for different active ingredients on the housefly (Musca domestica) and on the L2 stage of the larva of the cotton bollworm (Helicoverpa armigera) using the processing method described in biological Example 3. For active ingredients are listed by common ISO names (see: Pesticide Manual 1994). The obtained synergistic ratios are shown in the table below:

Table 4

[image]

Example 5

Influence of the active ingredient / synergist ratio on synergistic activity

The treatment was carried out as described in Example 3, using a Hamilton MicroLab P microdispenser. In two parallel experiments, 10 female 2-3 day old flies were treated from the ventral side of the thorax with 0.2 μl of the test solution. In addition to 1000-400-200-80 ng/fly fixed dose of synergist, they were also treated with constant 20 ng/fly carbofuran. The selection and counting of flies was done under the influence of CO2. After processing, the flies were kept in plastic cups covered with tulle. After 24 hours, % mortality was recorded. Depending on the results, the experiments were repeated in the same way 2 to 4 times. The results are shown in the table below.

Table 5

[image]

FORMULATION EXAMPLES

(The names of marketed auxiliary materials are indicated by supposed signs, along with the manufacturer's name.)

Example 6

Preparation of powders

A) 158 g of fine-grained perlite, 20 g of carbofuran and 20 g of compound 755 were mixed in a homogenizer, 2 g of fatty alcohol polyglycol ether ("G-3920" ICI) was added to this mixture, and the mixture was homogenized. The powder mixture was pulverized in an exclusion mill, and 5 g of octylphenolpolyglycone ether (EO=20) ("Triton X-165" Rohm & Haas) and 2 g of alkyl sulfosuccinate ("Aerosol-13" Cyanamid) were added to it. The resulting product is a wettable powder (WP) compound.

B) 10 g of compound 755 and 10 g of carbofuran were diluted with 2 g of ethanol. The solution was mixed in a powder homogenizer with 5 g of calcium lignin sulfonate ("Borrespeseca" Borregard), 5 g of nonylphenol-polyglycol ether (EO=20) ("Arkopal N-200" Hoechst) and 70 g of calcium carbonate. The resulting product was pulverized in a type 100 high mill. The average particle size was 1-2 μm. This preparation can be used for the preparation of microsuspensions.

C) A mixture of 3 g of diazinon, 3 g of compound 755 and 0.3 g of fatty alcohol polyglycol ether ("G-3920" ICI) was taken in a homogenizer into a mixture of 1.0 g of synthetic silicic acid (Aerosil 200) and 191 g of talc (dmax = 15- 30 μm), and the pH of this second mixture was previously adjusted to pH 7 using potassium and sodium phosphate buffer. With further mixing, 1 g of dioctyl sulfosuccinate ("Aerosol OTB" Cyanamid) and 1 g of fatty alcohol polyglycol ether sulfonate ("Genapol LRD" Hoechst) were added, and finally the mixture was crushed to an average particle size of 20 μm. The resulting product is an easily flowing powder preparation.

Example 7

Preparation of emulsion concentrates

A) A mixture of 5 g of pirimicarb and 5 g of compound 755 was dissolved in a mixture of 20 g of xylene and 40 g of propanol. A mixture of 4 g of ethoxylated alkylphenol + linear calcium alkylarylsulfonate salt ("Geronol FF/U" Geronazzo) and 6 g of ethoxylated amine + fatty acid + linear alkylarylsulfonate alkali metal salt ("Geronol MS" Geronazzo) was added to that solution. After complete dissolution, 20 g of water was added. A transparent solution was obtained, which, when diluted with water, forms an emulsion with a drop diameter of 0.8-1.5 μm.

B) A mixture of 5 g of quinalphos and 10 g of compound 755 and a mixture of 7 g of ethoxylated-(EO=13)-propoxylated(PO=21)-nonylphenol, 2 g of the calcium salt of linear dodecylbenzenesulfonic acid and 12 g of POE-(20)-sorbitan- monooleate, was dissolved in a mixture of 28.6-28.6 ml of propylene glycol and boric fatty acid and 23.8 ml of sunflower oil, 9.5 ml of ethanol and 95 ml of aliphatic hydrocarbon with 45% naphthene content. The material thus obtained can primarily be used for the preparation of microemulsions.

C) A mixture of 0.02-0.02 mass parts of the active ingredient and synergist was dissolved in 10 mass parts of propanol, 99.96 mass parts of odorless kerosene were added to the resulting solution and the mixture was mixed until a homogeneous solution was formed. The resulting oil dispersion composition can be directly used in ULV applications.

Example 8

Preparation of granules

In a mechanical granulator, 300 g of carbofuran, 300 g of compound 755, 1500 g of polycarboxylate alkali salt ("Sorphol" Toho), 500 g of sodium salt of dodecylbenzenesulfonic acid ("Marlon TP 370" Hüls), 500 g of beet sugar and 7200 g of kaolinite. The thus obtained powdery mixture was mixed with 8300 ml of water using a mixer with high rotational power (v = 10 m/s). The mixture was finally spray-dried. The product particle size distribution is 0.1-0.4 mm.

Example 9

Aerosol preparation

In a 100 l apparatus equipped with a mixer, 1 kg of bioalethrin, 0.5 kg of compound 755, 0.1 kg of aerosil-air 972, 0.1 kg of ethylene glycol monosalicylate, 15 kg of odorless kerosene and 50 kg of propanol were mixed. After melting, it was filled into cylinders with 33.3 kg of liquid propane-butane gas (25-75).

Example 10

It prepares the means that it evaporates

5 g of S-bioalethrin, 5 g of compound 755 and 1 g of lemon flavor were dissolved in 60 ml of ethanol. The solution was applied in evaporators at a temperature of 50 °C.

Claims (7)

1. 1.(+) Optical isomer, isomeric mixture rich in (+) optical isomer, indicated by the fact that it is an alkynyl component of the compound of formula (I). 2. The procedure for the preparation of the (+) optical isomer or isomeric mixture rich in the (+) optical isomer of the compound of formula (I), characterized by the fact that it is carried out by the reaction of the (+) optical isomer or isomeric mixture rich in the (+) optical isomer of the compound of formula (II) with a compound of the general formula (III), where X and Y represent groups suitable for the formation of an ether bond. 3. Pesticidal preparations, characterized by the fact that as an active ingredient they contain 0.0001-99.9 wt.% (+) optical isomer or isomeric mixture rich in the (+) optical isomer of the compound of formula (I), and optionally another known pesticidally active ingredient, except for the carrier and auxiliary materials. 4. Arthropodicidal ingredient, characterized by the fact that as an active ingredient it contains 0.0001-99.9 wt.% (+) optical isomer or isomeric mixture rich in (+) optical isomer of the compound of formula (I), and optionally another arthropodicidally active ingredient, except for the carrier and auxiliary materials. 5. The preparation according to claims 3 and 4, characterized in that it contains one or more of the following active ingredients as the second active ingredient: acetamide derivatives: eg oxamyl; acetamidine derivatives: eg acetamiprid; benzoylurein compounds: eg flucycloxuron, hexaflumuron, teflubenzuron, triflumuron, novaluron, lufenuron, chlorofluazuron; bicycloheptadiene compounds: eg heptenophos; bridged diphenyl compounds: eg etofenprox, bromopropylate, methoxycolor, temephos, tetradifon; carbamates: eg aminocarb, aldicarb, aldoxycarb, asulam, bendiocarb, benfuracarb, carbaryl, carbetamide, carbofuran, carbosulfan, dietofencarb, dioxacarb, etiofencarb, fenobucarb, fenoxycarb, furatiocarb, isoprocarb, methomyl, oxamyl, pirimicarb (pirimor), propoxur, thiodicarb , thiophanox, xylylcarb; carbamoyloxime derivatives: eg alanicarb, butocarboxime; cyclodienes: eg aldrin, chlordane, endosulfan, heptachlor; diazoles: eg fipronil; diphenyl ethers: eg diphenol; hydrazides: RH 5992, RH 5849, CGA 215'944; non-reistoxin analogues: eg bensultap, kartap; chlornicotinyl analogues: eg imidacloprid; nitroethylene and nitromethylene analogues: eg nitenpyram; organophosphorus compounds: eg quinalphos, diazinon, phosalon, dimethoate, azinphos-methyl; organotin compounds: eg azocyclotin, cyhexatin, fenbutatin oxide; oxadiazine carboxylates: eg DPX-MP062, DPX-JW062; phenoxy compounds: eg diafenthiuron, diphenolan; pyrazoles: eg pyrazophos; pyrethroids: eg allethrin, bioallethrin (esbiol), acrinathrin, deltamethrin, halfenprox, flumethrin, fenvalerate, empenthrin, pralethrin, resmethrin, MTI-800, flufenprox, permethrin, tetramethrin, ZX-8901, cypermethrin, and their isomers and isomeric combinations, such as β-cypermethrin, theta-cypermethrin; pyridazinones: eg pyridaben, NC-196; pyridine derivatives: eg chlorpyrifos; pyrimidine derivatives: eg pirimiphos-ethyl, pirimiphos-methyl; pyrroles: eg AC 303, 630 (chlorfenapyr); quinazolines: eg phenazaquine; terpenoid derivatives: eg methoprene; tetrazines: eg clofentezine, SzI-121 (fluphenzine); thiadiazines: eg buprofezin; thiazolidine: eg hexithiazox, etoxazole; triazoles: eg isazophos, RH 7988; chlorinated hydrocarbons: eg lindane; macrocyclic lactones: eg ivermecrin/avermectin, doramectin, nocidectin, emamectin, milbemycin; tebufenpyrade; pheniproximate; triazamate; insecticides of plant origin: eg azadirachtin, naphthoquinones, pyrethroids and their derivatives, plant extracts. 6. Preparation according to claims 4-5, characterized by the fact that as an active ingredient it contains 0.0001-99.9 wt.% (+) optical isomer or isomeric mixture rich in (+) optical isomer of the compound of formula (I) and some arthropodicidal carbamate, pyrethroid, pyrethrin , chlornicotinyl analogue, diazole, macrocyclic lactone, especially carbofuran, carbosulfan, pirimicarb, alanicarb, fipronil, imidacloprid and ivermectin/avermectin. 7. A method of destroying pests, primarily arthropods, indicated by the fact that it contains the treatment of insects, primarily arthropods, with a suitable amount of the preparation according to claims 5 or 6, as desired in such a way that the preparations containing the (+) optical isomer or an isomeric mixture rich in (+ ) by an optical isomer of the compound of formula (I), and a preparation or preparations containing a known active ingredient or ingredients, applied either in a container mixture or consecutively.