CZ296158B6 - 1-Arylpyrazoles, process of their preparation and pesticidal composition in which the 1-arylpyrazoles are comprised - Google Patents

Abstract

In the present invention, there are disclosed 1-arylpyrazoles of the general formula I that are useful as pesticides or as intermediates to other pesticides, further process of their preparation and compositions comprising these compounds and methods for their use, particularly in agriculture and for animal protection, as pesticides, especially for controlling arthropods.

Description

1-Arylpyrazoles, process for their preparation and pesticidal compositions containing them

Technical field

The present invention relates to novel 1-arylpyrazoles derivatives having valuable properties either as pesticides or as intermediates for the preparation of other pesticides. The invention further relates to compositions comprising these compounds and methods using said compounds as intermediates for the preparation of other pesticides or for control of arthropod pests, in particular the use of said compounds or compositions in agricultural uses for animal protection, in particular as pesticides for control of arthropods.

BACKGROUND OF THE INVENTION

International patent application 87/03781 and European patent applications EP 0 295 117, EP 0 154 115, EP 0 201 852 disclose insecticidal 1- (substituted phenyl) pyrazoles. Other prior art publications are also found in the specification of this patent application or in the patents cited herein.

International patent applications WO 93/06089 and WO 94/21606 also disclose insecticidal 1- (SF ₅ substituted phenyl) heterocycles, which may be pyrroles, as well as imidazoles or pyrazoles. WO 87/03781 or European Patent Application EP 0 295 117.

Various pesticidal pyrazoles are described in various patents or patent applications; EPO 418,016, EP 0,403,309, EP 0 352 944; US 5,104,994, US 5,079,370, US 5,047,550, US 5,232,940, US 4,810,720, US 4,804,675, US 5,306,694, US 4,614,533, US 5,187,185, US 5,223,525; WO 93/06089; WO 94/21606.

Since there are many pests and crops and pest infestation conditions, there is a need for additional new pesticidal compounds.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide novel pesticidal compounds of the 1-arylpyrazole family, as well as a process for their preparation.

A second object of the present invention is to provide pesticidal compositions and pesticidal methods of using pesticidal pyrazole compounds against arthropods, in particular against harmful insects, in particular on agricultural or horticultural crops, in forestry, veterinary medicine or in livestock or public health.

A third object of the present invention is to provide very active compounds with a broad spectrum of pesticidal activity as well as compounds with selective specific activity, e.g. pesticide activity through seed treatment.

These and other objects of the present invention that have been wholly or partially achieved will become clearer from the description of the present invention that follows.

The present invention encompasses novel chemical compounds having insecticidal, miticidal, nematicidal or anti-nematode activity.

-1 CZ 296158 B6

The present invention relates to compounds of formula I:

where

R-31 and R ₃₂ are independently OR ₂₀ , S (O) _n R ₂₀ , or N (R ₂₀ ) (R ₂₎ ); or R ₃₁ and R ₃₂ may also combine to form O [C (R ₂₂ ) (R ₂₃ )] _m O, S (O) _n [C (R ₂₂ ) (R 23)] _m S (O), _and , groups O (CH ₂ ) _m S (O) _n , groups O [C (R ₂₂ ) (R ₂₃ )] _m (NR ₂₀ ), groups S (O) _n [C (R ₂₂ ) (R ₂₃ )] _m (NR ₂₀ ), NR ₂ i [C (R ₂₂ ) (R ₂₃ )] _m NR ₂₀ , NR ₂₁ [C (O) (CH ₂ ) _m ] NR ₂₀ ;

when m is greater than 1, the groups [C (R ₂₂ ) (R ₂₃ ) J may be the same or different

R ₂₀ , R ₂₁ may independently be hydrogen, alkyl, aryl, benzyl, allyl, propargyl;

R ₂₂ , R ₂₃ independently of one another may be hydrogen; a halogen atom; a hydroxyl group; amino; COOR ₂₀ ; C (O) NH _2; C (O) N (R ₂₀ ) (R ₂₁ ); C (S) NH _2; OC (O) N (R ₂₀ ) (R ₂₁ ), cyano; nitro; C (S) N (R ₂₀ ) (R ₂₁ ); alkyl optionally substituted by hydroxyl, amino, halogen, cyano, nitro, COOR ₂₀ , C (O) NH ₂ , C (S) NH ₂ ; S (O) balkyl; alkoxy; S (O) _c R ₂₀ ;

R 4 is R ₂₆ ; S (O) _d R ₂₆ ; S - (= R ₂₇ ) (= NR ₂₈ ) R ₂₆ ;

R ₂₆ is an alkyl group optionally substituted with one or more halogen atoms, which may be the same or different;

R ₅ is amino, alkylamino, wherein the alkyl may be substituted with nitro, halogen, cyano, alkoxycarbonyl, hydroxyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, or carbamoyl; or R ₅ is a group of the formula:

-2CZ 296158 B6 wherein R4, _R12, R13, Ri4, Ris, _R33 and Z are the same as R 4, _{R] 2,} R _{J3, R] 4,} R _IS, Z and R ₃₃ in formula I above;

R ₂₇ is NR ₂₈ , an oxygen atom, or a free electron pair;

R ₂₈ is selected from the group consisting of hydrogen; (C 1 -C 6) alkyl; haloalkyl having 1 to 6 carbon atoms; COR ₂₄ ; S (O) _e R ₂₄ , COOR ₂₄ ; C (O) N (R ₂₀ ) (R ₂₁ ); C (O) -SR ₂₄ ; C (S) OR _24; SO ₂ NR ₂₀ R ₂₁ ; P (O) _q (R ₂₀ ) (R ₂₁ ); P (O) _q (OR ₂₀ ) (OR ₂₁ ); C (= NR ₂ O) n R _{2 O 2];} group C (= NR ₂₀ ) (OR ₂₁ ); C (S) N (R ₂₀₎ (R _21); C (O) C (O) R _20; C (O) C (O) OR _20; C (O) C (O) NR ₂₀ R ₂₁ ; and C (O) NR ₂ iR _21;

q is 0 or 1;

R ₂₄ is alkyl optionally substituted by nitro, cyano, halogen, alkoxy, amino, alkoxycarbonyl or hydroxyl;

Z is N or CR ₁₆ ;

R ₁₂ , R ₁₃ , R 14, R ₁₅ and R ₁₆ are independently hydrogen; a halogen atom; SF ₅ ; cyano; nitro; R ₂₅ ; S (O) _f R ₂₅ ; a hydroxyl group; OR ₂₅ ; N (R ₃₆ ) (R ₃₇ ); CON (R ₂₅₎ (R _37); N ₃ (azido);

R ₃₆ and R ₃₇ are independently hydrogen, alkyl;

R ₂₅ is an alkyl group optionally substituted with one or more halogen atoms, which may be the same or different;

R ₃₃ is C 1 -C 3 alkyl optionally substituted by one or more halogen atoms, nitro, alkoxy, cyano, carboxyl, COO-alkyl, C (O) NH ₂ ;

n, a, b, c, d, e and f are independently 0, 1 or 2; and m is an integer from 1 to 5;

or a pesticidally acceptable salt thereof.

The present invention also includes stereoisomers, for example, diastereoisomers and optical isomers of Formula I.

According to the present invention, the term "alkyl", unless otherwise specified, means a straight or branched alkyl chain containing one to six carbon atoms. The term "aryl group" means an aryl group having 6 to 10 carbon atoms, for example a phenyl group or a naphthyl group, optionally carrying one or more substituents selected from the group consisting of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 C 1 -C 6 alkoxy, cyano, nitro, haloalkyl of 1 to 6 carbon atoms and haloalkoxy of 1 to 6 carbon atoms. The definitions apply even if these groups form part of other groups.

Preferred compounds of formula I are those wherein R ₃ and R ₅ are hydrogen or halogen; R ₁₂ is halogen; R ₁₆ is hydrogen or halogen; and / or R ₁₄ is halogen; SF ₅ ; R ₂₅ ; S (O) _f R ₂₅ ; or OR ₂₅ . Compounds wherein R ₁₂ is chloro; R _I3 and _{R] 5} are particularly preferred.

-3GB 296158 B6

Compounds of formula I wherein R ₄ is S (O) _n R ₂₆ and Z is C-R ₁₆ are also preferred.

Preferably m is 2, 3 or 4, more preferably 2 or 3, most preferably 2.

Other preferred compounds of formula I are those wherein:

R ₂ 6 is methyl or ethyl; Z is CR ₁₆ ; R ₃ and R ₁₅ are hydrogen; R ₂ is halogen; R ₁₆ is hydrogen or halogen; R ₁₄ is CF ₃ , OCF ₃ is SF ₅ ; and / or R ₃₃ is a methyl group.

The most preferred compounds of formula I are those wherein:

R _{3 and} R ₃₂ are independently OCH ₃ ; OC ₂ H ₅ ; SCH ₃ ; group SC ₂ H _5; R _{3 and} R ₃₂ may also be combined to form an OCH ₂ CH ₂ O group; O (CH ₂ ) ₃ O; S (CH ₂ ) ₂ S; S (O) (CH _{2) 2} S; S (O) (CH ₂ ) ₃ O; S (CH ₂ ) ₂ S; S (O) (CH _{2) 2} S; S (O) (CH ₂ ) ₂ S (O); S (O) ₂ (CH ₂ ) ₂ S (O); S (O) ₂ (CH ₂ ) ₂ O; S (O) (CH ₂ ) ₂ O; S (O) ₂ (CH ₂ ) ₂ O; O (CH ₂ ) [CH (CH ₂ OH)] O; O (CH ₂ ) [C (CH ₂ OH) (CH ₂ OH)] O; OCH (COOCH ₃ ) CH (COOCH ₃ ) O groups; OCH (COOC ₂ H ₅ ) CH (COOC ₂ H ₅ ) (COOC ₂ H ₅ ) CH ₂ O groups; OCH ₂ CH (CH ₃₎ O; SCH ₂ CH ₂ NH; OCH ₂ CH (CH ₂ CH ₂ OH) O; or OCH ₂ C (CH ₂ ) ₂ CH ₂ O; O (CH ₂ ) CH (CH ₂ SCH ₃ ) O groups; O (CH ₂ ) CH (CH ₂ SOCH ₃ ) O; especially if:

R4 is S (O) _{n 2} R 6; R 26 is methyl or ethyl; Z is CR ₁₆ ; R ₁₃ and R 18 are hydrogen; R ₁₂ is halogen; R ₆ is hydrogen or halogen; R ₁₄ is CF ₃ , OCF ₃ , SF ₅ ; and R ₃₃ is methyl.

Preferably, the compounds of formula I have one or more of the following features:

R ₁₂ is halogen; X is C-Cl;

R ₁₃ and R 15 are hydrogen;

R ₁₄ is CF ₃ or SF ₅ ;

R ₅ is amino, CH ₃ NH or CH ₃ CH ₂ NH;

R 4 is CH ₃ S (O) CH ₃ S (O) ₂ or CH ₃ S;

R 31 and R ₃₂ are OMe or together form OCH ₂ CH ₂ O; OCH ₂ CH (CH ₃₎ O; S _{(CH2) 2} = _S; S (O) (CH ₂ ) ₂ S; S (O) (CH _{2) 2} S (O); S (O) ₂ S (O) ₂ ; O (CH ₂ ) [CH (CH ₂ OH)] O; SCH ₂ CH ₂ NH; O (CH ₂ ) CH (CH ₂ ) SCH ₃ ) O; O (CH ₂ ) CH (CH ₂ SOCH ₃ ).

Compounds of formula I may be prepared by reaction of compounds of formula II:

(II) j

-4GB 296158 B6 where

R _4, R _5j R _{i2, R] 3,} R _14, R _15, Z and R ₃₃ are as defined above and R ₃₄ is an oxygen atom or a sulfur atom, with a compound of general formula III containing at least one reactive functional group selected from the group consisting of an alcohol group, a thiol group, a primary amino group, and a secondary amino group; i.e. with an alcohol R ₂₀ OH;

a thiol of the formula R ₂₀ SH;

an amine of formula NH (R ₂₀₎ (R ₂ i) or a compound of formula

HO [C (R ₂₂ ) (R ₂₃ )] _m OH, HS [C (R ₂₂ ) (R ₂₃ )] _m SH, HO [C (R ₂₂ ) (R ₂₃ )] _m SH, HO [C (R ₂₂ )] (R ₂₃ ) _m N (R ₂₀ ) H, HS [C (R ₂ Z), (R ₂₃ )] _m H or NHR ₂ o [C (R ₂ 2) (R 23)] mNHR ₂₁ where R ₂₂ and R ₂₃ may be the same or different and R ₂₀ and R ₂₁ may be the same or different.

The reaction of the compound of formula II with the compound of formula III is carried out directly by reacting the compound of formula II with the compound of formula III in a liquid medium at a temperature in the range of -35 to 250 ° C, preferably -10 to 150 ° C. Water removal is preferred. The liquid medium is prepared using reactants or solvent. Suitable solvents for this reaction include organic solvents including alcohols such as methanol, ethanol, isopropanol; ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane; nitriles such as acetonitrile; aromatic solvents such as toluene, benzene, chlorobenzene; haloalkanes such as chloroform, methylene chloride; amides such as dimethylamide; ketones such as acetone, methyl isobutyl ketone; esters such as ethyl acetate. The amount of the reactants is usually between 50 and 200% of the amount required by the reaction (except when the reactant is used as a solvent, the amount of the reactants is higher). The reaction may be carried out in the presence or absence of an acid catalyst. The acid catalyst may be an inorganic acid such as hydrochloric acid, sulfuric acid; an organic acid such as acetic acid, formic acid, / toluenesulfonic acid; Lewis acids such as ferric chloride, ammonium chloride, boron trifluoride, aluminum chloride, zinc iodide, zinc chloride; acidic ion-exchange resins; clays such as Montmorillonite.

In the method mentioned in the above paragraph, when in the starting compound of formula II R ₅ amino and R ₃₄ is oxygen, may occur in addition to the compounds of formula I wherein R ₅ is amino, by reaction with another molecule of the starting material of formula II, the compound of formula I, wherein R ₅ is a group of formula Ia as defined above. Both products are active as pesticides.

The sulfoxide and sulfone compounds of formula I, i.e. compounds wherein n, a, b, c, d, e, or f, are 1 or 2, can also be prepared by oxidation of the corresponding sulfide using a suitable oxidizing agent such as peroxide , such as hydrogen peroxide, t-butyl peroxide; peracids such as metachloroperbenzoic acid; acyl nitrates such as acetyl nitrate and other non-peroxide agents such as sodium periodate, sodium perborate, manganese dioxide, potassium permanganate, N-bifomsuccinimide, preferably hydrogen peroxide and sodium periodate, but are not limited to these examples.

In cases such as oxyketalsulfides, where mild conditions are required, sodium sulfite is the preferred sulfoxidizing agent.

The invention will be further illustrated by the following non-limiting examples.

-5GB 296158 B6

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Preparation of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3 - [(1,1-dimethoxy) ethyl] -4-methylthio-1H-pyrazole

A mixture of 2.0 g (0.0052 mol) of 3-acetyl-5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-1H-pyrazole, 1.7 ml ( Trimethyl orthoformate (0.0156 mol), peratoluenesulfonic acid monohydrate (0.060 g, 0.03 mol) and methanol (10 ml) were heated at 40 ° C for 8 hours, then left at 20 ° C for 64 hours. To the mixture was added saturated sodium bicarbonate solution, extracted with dichloromethane and then dried, filtered, evaporated and chromatographed on silica gel. 0.59 g of the title compound of melting point about 149 ° C is obtained.

Example 2

Preparation of 5-amino-1 - [(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-dioxolan-2-yl) 4-methylthio-1H-pyrazole

A mixture of 10.0 g (26.03 mmol) of [2,6-dichloro-4- (trifluoromethyl) phenyl] -3-acetyl-4-methylthio-1H-pyrazole, 1.94 g (31.23 mmol) of 1,2- of ethanediol, 0.49 g (2.6 mmol) of p-toluenesulfonic acid and 500 ml of benzene are heated at reflux for 10 hours while removing water. An aqueous solution of sodium bicarbonate was added to the mixture. The organic layer was washed with a saturated aqueous solution of potassium chloride and then dried, evaporated and purified by chromatography. 2.33 g of the title compound are obtained (m.p. about 143 ° C).

Example 3 Preparation of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-dioxolan-2-yl) -4-methylsulfinyl-1H-pyrazole

To a solution of 244 μΐ of a 0.5 M solution of sodium periodate in 2.5 ml of methanol at 0 ° C was added 500 mg of Compound # 2. The mixture was stirred at 0 ° C for 20 minutes and then allowed to stir at 20 ° C for 10 hours. The mixture was then extracted with dichloromethane and water, partitioned, dried, evaporated to give the title compound; the mass spectrum of the compound is M + H = 444 (molar mass = 443).

Example 4

Preparation of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-dithiolan-2-yl) 4-methylthio-1H-pyrazole

A mixture of 1 g (2.60 mmol) of 5-amino-1- [2,6-dichloro-N- (trifluoromethyl) phenyl] -3-acetyl-4-methylthio-1H-pyrazole, 0.26 ml (3, 10 mmol) of 1,2-ethanedithiol, 0.084 g (0.5 mmol) of ferric chloride and 25 ml of methylene chloride are stirred under an inert atmosphere at 20 ° C for 6 days. The mixture was then evaporated and purified by chromatography to give 100 mg of the title compound as a yellow oil. According to the mass spectrum, the molar mass is 460.

-6GB 296158 B6

Example 5

Preparation of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methylthiazolidin-2-yl) -4-methylsulfinyl-1H-pyrazole

A mixture of 1 g (2.5 mmol) of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3-acetyl-4-methylsulfinyl-1H-pyrazole, 0.284 g (2.5 mmol) of 2-aminoethanethiol hydrochloride, 348 μΐ (2.50 mmol) of triethylamine, 50 mg μ-toluenesulfonic acid and 30 ml of benzene are heated to remove water through the nose. The mixture was then cooled, filtered, evaporated and chromatographed to give 20 mg of the title compound as a white solid, mp 85 ° C.

Example 6

Preparation of 5-amino-1 - [(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-oxathiolan-2-yl) -4-methylsulfonyl-1H-pyrazole

To a stirred solution of 54.34 g (0.131 mol) of 3-acetyl-5-amino-1 - [(2,6-dichloro-4-trifluoromethyl) phenyl] -4-methylsulfonyl-1H-pyrazole in 500 ml of dioxane was added in cooling to 0 ° C in an ice bath gradually add 36.7 ml (0.522 mol) of mercaptoethanol, 71.1 g (0.522 mol) of anhydrous zinc chloride and 62.1 g (0.522 mol) of anhydrous sodium sulfate. The mixture was then stirred for about 17 hours while allowing to warm to room temperature. The salt was removed by filtration and the filtrate was evaporated under reduced pressure and diluted with 40 ml of acetonitrile and the product was filtered off at 35 ° C. The filtrate was then diluted with acetonitrile to give an additional crop of product. Combined portions of 5-amino-1 - [(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-oxathiolan-2-yl) -4-methylsulfonyl-1H-pyrazole afforded 30.53 g, m.p. 201 DEG C. This compound is then designated compound 23.

Example 7

Preparation of 5-amino-1 - [(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,1,3,3-tetraoxo-1,3-thiolan-2-yl) -4 —Methylsulfonyl-1H-pyrazole

To an ice cold solution of 0.49 g (0.00096 mol) of 5-amino-1 - [(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1-oxo-1,3) -dithiolan-2-yl) -4-methylsulfonyl-1H-pyrazole in 4 mL of trifluoroacetic acid was added dropwise with 0.4 mL (0.004 mol) of 30% hydrogen peroxide and the mixture was stirred while warming to room temperature for about 17 hours. between ethyl acetate and water and the organic layer was separated, washed with saturated sodium bicarbonate solution, then brine and dried over sodium sulfate. The solution was filtered, evaporated under reduced pressure and chromatographed on silica gel to give 0.14 g of 5-amino. -1 - [(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,1,3,3-tetraoxo-1,3-dithiolan-2-yl) -4-methylsulfonyl-1H -pyrazole as a cream powder, m.p. 231 DEG C. This compound is designated compound 25.

Example 8

Preparation of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-3- (4-hydroxymethyl-2-methyl-1,3-dioxolan-2-yl) -5-N1 - [[[2 6-dichloro-4 (trifluoromethyl) phenyl] -4-methylthio-1H-pyrazol-3-yl] ethylidene] amino-1H-pyrazole

In the synthesis of compound 6, Table 1, by condensation of 3-acetyl-5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl) -4-methylthio-1H-pyrazole with glycerol, using the procedure described in Example 2 and after working up the reaction mixture, 1- [2,6-dichloro-4] is obtained as a by-product

-7EN 296158 B6 (Trifluoromethyl) phenyl] -4-methylthio-3- (4-hydroxymethyl-2-methyl-1,3-dioxolan-2-yl) -5-N1 - [[[2,6-dichloro-4] (trifluoromethyl) phenyl] -4-methylthio-1H-pyrazol-3-yl] ethylidene] amino-1H-pyrazole, m.p. This compound is hereinafter referred to as Compound No. 9.

The following compounds were prepared according to one of the methods described in Examples 1 to 5:

Compound R31 r ₃₂ n Temp. thaw 1 och ₃ och ₃ 0 149 2 och ₃ och ₃ 1 153

cf ₃

Compound R310 R ₃ 20 Rn n Temp. thaw 3 0 0 H 0 143 4 0 0 ch ₃ 0 126 5 0 0 H 2 194 6 0 0 CH ₂ OH 0 71 7 0 0 ch ₂ oh 2 183 8 0 0 ch ₃ 2 202 10 0 0 H 1 68 11 0 0 ch ₃ 1 90 15 Dec with NH H 1 85 16 with WITH H 0 (M + H) < + & gt ^; = 460 17 with WITH H 2 207 18 with WITH H 1 127 19 Dec Sat WITH H 0 179.5 20 May Sat with H 1 182

-8GB 296158 B6 continued

Compound R310 R320 r _I7 n Temp. thaw 21 Sat with H 2 195 22nd Sat Sat H 2 175 23 with 0 H 2 201 24 with 0 H 0 (M + H) < + & gt ^; = 144 25 Sat ₂ Sat ₂ H 2 231 26 0 0 CH ₂ OH 1 153 27 Mar: 0 0 ch ₂ sch ₃ 0 43 28 0 0 ch ₂ statues ₃ 0 68 29 0 0 ch ₂ statues ₃ 1 82 30 0 0 ch ₂ sch ₃ 2 68 31 0 0 ch ₂ statues ₃ 2 110

Cr ₃

Compound Rs n Temp. thaw 34 EtNH 2 119 35 MeNH 2 188 36 EtNH 0 (M + H) < + & gt ^; = 456 37 EtNH 1 (M + H) < + & gt ^; = 472 38 MeNH 0 (M + H) < + & gt ^; = 442 39 MeNH 1 (M + H) < + & gt ^; = 458

-9EN 296158 B6

Compound 9

merge R-310 R-320 R.7 R18 n M.p. 12 0 0 H H 0 143 13 0 0 H H 2 223 14 0 O CH ₂ OH CH ₂ OH 0 85

The present invention further provides a method for controlling pests in an area which comprises treating the area (e.g., by application or administration) with an effective amount of a compound of Formula I or a pesticidally acceptable salt thereof, wherein the substituents are as defined above. The area is, for example, the pest itself or the site (plant, animal, field, construction, land, forest, orchard, canal, soil, plant or animal product or the like) where pests settle or feed.

In particular, the present invention provides a method of systemic control of arthropods in the field, in particular of certain insect or aphid species that feed on aboveground plant parts. Control of these leaf pests can be carried out either by spraying the soil or by applying granules to plant roots or plant seeds, followed by systemic transfer to above-ground parts of the plants. This systemic activity involves not only the control of pests that are present at the application site, but also in the distant part of the plant, for example by transfer from one side of the leaf to another side or from the treated leaf to the untreated leaf. Examples of insect pest classes that can be systemically controlled by the compounds of the present invention are the order of the Homoptera, the order of the Hemiptera, and the order of the Thysanoptera. The compounds of the present invention are particularly useful against aphids and thrips.

As is apparent from prior pesticidal use, the present invention provides pesticidally active compounds and methods of using said compounds for controlling many pest species including: arthropods, especially insects and aphids; plant nematodes; or worms or protozoal pests. The compounds of the formula I or their pesticidally acceptable salts can thus be used practically on agricultural or horticultural crops, in forestry, veterinary medicine or in livestock farming or in public health. Thus, when the term "compound of formula I" is used, it includes the compounds of formula I and their pesticidally acceptable salts. The term "compound of formula I" includes a compound of formula I and pesticidally acceptable salts thereof.

The compounds of the present invention can further be used to control soil pests such as Diabrotica, termites (especially for building protection), flowering plants, wireworms, weevils, animals drilling stems, seedlings, aphids or caterpillars. They can also be used as agents active against plant pathogenic nematodes such as root-knot nematodes, cyst nematodes, lesions or nematodes in pest stalks, for example Diabrotica, the compounds are preferably applied to the soil in an effective amount or admixed with the soil in which are or will be planted with crops or added to the seeds or roots of growing plants.

-10GB 296158 B6

In the field of general health, the compounds are particularly useful in the control of many pests, particularly flies or other double-winged pests such as housefly, thistle, thistle, phylloxera, hornet, horsefly, horsefly, mosquito, aphids or mosquitoes.

The compounds of the present invention may be used in the following applications and on the following pests including arthropods, in particular insects and mites, nematodes or worms or protozoal pests:

• In the protection of stored products such as cereals, including grain or flour, groundnuts, animal feed, wood or household consumer goods such as carpets, textiles, the compounds of the present invention are suitable for attacking arthropods, especially beetles, including cereal piers, piers clothes or mites, for example, Ephestia (flour beetles), Andhrenus (carpet beetles), Tribolium (flour beetles), Sitophilus (corn moths) or Acarus (mites).

• When inspecting cockroaches, ants or termites or similar arthropod pests in attacked homes or industrial sites or when controlling mosquito larvae in waterways, springs, reservoirs or other running or stagnant waters.

• In the treatment of foundations, buildings or soil to prevent the attack of buildings by termites, such as Reticulitermes, Heterotermes, Coptotermes.

• In agriculture against Lepidoptera (butterflies and moths), adults, larvae and eggs, such as Heliothis species such as Heliothis virescens, Heliothis armigera and Heliothis zea. Against adults and larvae of Coleptera (beetles) of, for example, Anthonomus, for example, grandis, Leptinotersa decemlineata, of Diabrotica. Against Heteroptera (Hemiptera and Homoptera), for example, Psylla species, Bemisia species, Trialeurodes species, Aphis species, Myzus species, Megoura viciae, Phylloxera species, Nephotettix species, Nilaparvata species.

• Against double-winged species such as Museum. Against Thysanoptera such as Thrips tabaci. Against Orthoptera such as Locusta and Schistocerca species for example Gryllus and Acheta species for example Blatta orientalis, Periplanata americana, Blatella germanica, Locusta migratorie migratorioides and Schistocerca gregaria. Against Collembola, for example, the species Periplaneta and species Blattela. Against Soptera, for example, the species Coptotermes (termites).

Against arthropods of agricultural importance such as Acari (mites) such as Tetranychus and Panonychus.

• Against nematodes that attack plants or trees that are important for agriculture, forestry or horticulture, either directly or by the spread of bacteria, viruses, mycoplasma or fungal diseases of plants. For example, Meloidogyne worms (for example M. ineognita).

• In veterinary medicine or livestock farming or in maintaining public health, against arthropods, worms or protozoa that parasitize internally or externally on vertebrate animals, particularly warm-blooded vertebrates, such as domestic animals such as cattle, sheep, goats, horses, pigs, poultry, dogs or cats, for example Boophilus, for example Boophilus microplus, Rhipicephalus, for example Rhipicephalus appendiculatus, Rnithodorus, for example Ornithodorus moubata, and mites, for example Damalinia ', double-winged (for example, Aedes, Anopheles, Museum, Hypoderma) , Hemiptera; Dictioptera (for example Periplaneta species, Blatella species), Hmymenoptera, for example against gastrointestinal infections caused by helminthic parasites, for example members of the Trichostrongylidea family; in the control and treatment of protozoal diseases caused, for example, by Eimeria such as Trypanosoms cruzi, Leishaminia, Plasmodium, Babesis, Trichomonadidae, Toxoplasma and Theileria.

In practical use for controlling arthropods, particularly insects and mites or nematode pests on plants, the method, for example, comprises applying an effective amount of a compound of the present invention to the plant or medium in which the plant is grown. For this way you

The active compound is usually applied to the area in which infested arthropods or helminths are to be controlled, in an effective amount ranging from 5 g to 1 kg of active compound per hectare of treatment area. Under ideal conditions, depending on the pest being controlled, smaller amounts may provide adequate protection. Conversely, under adverse weather conditions, pest resistance or other factors may make it necessary to use more active compound. The optimum amount usually depends on many factors, for example the type of pest to be controlled, the type or stage of growth of the infected plant, the spacing or also the mode of application. More preferably, the effective amount of active compound is between 50g / ha and 400g / ha.

When the pest hatches in the ground, the active compound, usually formulated into the composition, is distributed evenly over the area to be treated in any known manner and applied in an amount of 5 to 1 kg of active ingredient per ha, preferably 50 to 250 g of active ingredient per ha. When applied as a seed solution or plant dressing, the liquid solution or suspension contains 0.075 to 1000 mg of active ingredient / ha, preferably 25 to 200 mg of active ingredient / ha. Application may be carried out, where appropriate, in a field or area where the plant is grown or in close proximity to the seeds or plants to be protected from attack. The active ingredient may enter the soil prior to attack. The active ingredient can enter the soil by spraying the surface with water or let natural rain. During or after application, the composition containing the compound may, if appropriate, be distributed to the soil mechanically, for example by plowing, disking or by using trailing chains. The application can be performed before betting, during betting, after betting but before germination or after germination.

The compounds of the present invention and the method of controlling pests therewith are particularly valuable in the protection of field crops, forage, plantation fruits, greenhouses, orchards or vineyards, ornamental machines or forest trees such as cereals (such as wheat or rice), cotton, vegetables ( such as peppers), field crops (such as sugar beets, soybeans or oilseed rape), greenhouse crops or feed (such as corn or sorghum), orchards or forests (such as stone fruits or citrus), ornamental plants, flowers or vegetables, or shrubs in greenhouses or in gardens by steam or forest machines (both deciduous and coniferous) in forests, orchards or nurseries.

They are also suitable for protecting wood (standing, felled, processed, stored or construction) against attack by, for example, saw blades or beetles or termites.

The compositions of the invention may be used to protect stored products such as cereals, fruits, nuts, spices or tobacco that are wholly or milled prior to attack by moths, beetles, mites, or cereal moths. It is also possible to protect stored animal products such as leather, fur, wool or feathers in natural or processed form (for example as carpets or textiles) against attack by moths or beetles, as well as stored meat, fish or grains against beetles, moths or flies.

Furthermore, the compounds of the present invention and methods of their use are particularly suitable for controlling arthropods, helminths or protozoa which are harmful or spread or act as a vector disease carrier, for example those listed above, and are particularly useful for controlling ticks, mites, lice, fleas, mosquitoes. or biting or difficult insects or flies. The compounds of the present invention are particularly useful in controlling arthropods, helminths or protozoa that are present in domestic host animals or that live in or on the skin or suck blood to animals and can be administered orally, parenterally, before the skin or topically for this purpose.

Furthermore, the compounds of the present invention are useful against coccidiosis, a disease caused by infection of protozoal parasites of the genus Eimeria. This infection can cause significant economic losses in domestic animals and birds, especially those under intensive conditions. For example, cattle, sheep, pigs or rabbits can be attacked, but the disease is particularly dangerous in poultry, especially chickens. Administration of a small amount of a compound of the present invention, preferably in combination with a feed, is preventive or reduced

-12EN 296158 B6 risk of coccidiosis. The compounds are effective against both the cecal form and the intestinal form. Furthermore, the compounds of the present invention may also inhibit or oocytes by greatly reducing the number and sporulation of these individuals. Poultry disease is usually spread by birds ingesting infected organisms in water in contaminated bedding, ground, food or drinking water. The disease is manifested by bleeding, congestion of the blood in the appendix and passage of blood to the faeces, weaknesses and digestive disorders. The disease usually results in the death of the animal, but poultry that survive a serious infection has a reduced price on the market as a result of the infection.

The compositions below for use on growing crops or as a seed dressing may alternatively be used for topical application to animals or to protect stored products, domestic consumer goods, property or areas in the wild. Suitable methods of using the compounds of the present invention include:

• application to growing crops such as spraying on leaves, powders, granules, aerosols or foams or also suspensions of finely ground or encapsulated soil or root treatment with liquid dressing, powders, granules, smoke or foam; to the seeds of the crops, wherein the application is carried out by embedding the seeds with liquid suspensions or powders;

• administration to animals infected or threatened by arthropods, helminths or protozoa, by parenteral, oral or topical application of compositions in which the active ingredient acts in the medium and / or long term against arthropods, helminths or protozoa, for example by addition to feed or appropriate oral pharmaceutical compositions; edible baits, licking salts, food supplements, irrigation products, sprays, baths, soaking preparations, powders, ointments, shampoos, creams, wax lubricants or other cattle treatment systems;

• application to the environment in general or to a specific area where pests may occur, including stored products, wood, household consumer goods or households or industrial buildings in the form of spray, aerosol, smoke, wax paints, varnishes, granules or baits water channels, pits, reservoirs or other running or standing waters;

• feeding to pet animals to control fly larvae in their feces.

The following examples illustrate the use of the compounds of the present invention for pest control, but do not limit the scope of the invention in any way.

The following species were tested:

Genus _________________________ Common name ________

Aphis gossypii cotton aphid

Musea domestica house flies

Diabrotica virgifera

Periplaneta americana american cockroach

Spodoptera eridania

Schizaphis graminum - Ctenocephalides felis

Rhipicephalus sanguineus

Soil water test (systemic effect)

The sorghum and cotton plants were planted in pots. One day before treatment, 25 aphids from different populations were placed in each pot. Cotton plants were infested with aphids and sorghum plants infested with Schizaphis graminum. The selected compound of formula I was applied to the soil surface at a dilution equivalent to 10.0 ppm by weight of the soil concentration. Aphids were counted 5 days after treatment. The number of aphids on the treated plants was compared with the number of aphids

-13EN 296158 B6 on untreated plants. From this test, the systemic activity of the compounds of the present invention (active ingredient transfer) is apparent.

Bait for flies / contact test

About 25 four to six days old adult flies are anesthetized and placed in a cell with an aqueous bait solution containing a compound of the invention. The concentration of the selected compound of formula I in the bait solution is 50 ppm. After 24 hours, flies that do not show stimulation are considered dead.

Application to leaves (contact test) with aphids

The aphid-infected cotton plants are placed on a turntable and sprayed with 100 ppm of the composition of the selected compound of the formula so that the liquid flows down. Treated plants infected with A. gossypii are left for three days and then dead aphids are counted.

The following results were obtained. In the table that follows, "X" means a highly active compound; the symbol "+" of a moderately active compound; and the symbol indicates low activity. The “NT” symbol means not tested.

Compound number Systemic activity against aphids Systemic activity against Schizaphis graminum Activity against house fly on contact Activity against aphids when applied to leaves 1 X X X + 2 + X X X 3 X X X X 4 X X X X 5 X X X X 6 + X - - 7 X X + X 8 X X X X 9 - - X - 10 X X X X 11 X X X X 12 X X X X 13 X X X 14 - - - 15 Dec X X X - 16 - X X + 17 X X X + 18 - + X X 19 Dec - + X X 20 May - - X - 21 - - X - 22nd X + - - 23 X - 24 X X 25 - - 26 - + X - 27 Mar: X + X - 28 X - X X 29 X - X X 30 X -

-14GB 296158 B6 continued

Compound number Systemic activity against aphids Systemic activity against Schizaphis graminum Activity against house fly on contact Activity against aphids when applied to leaves 31 X + + 32 X X X X 33 - - - - 34 X X X X 35 X X X X 36 X X + 37 X X X 38 X X X 39 + X -

In practice, the compounds of the present invention most often form part of the compositions. The present invention therefore also relates to a pesticidal composition comprising a compound of formula I or a pesticidally acceptable salt thereof and a pesticidally acceptable carrier. These compositions may be used to control arthropods, particularly insects or mites; nematodes; or parasitic worms or protozoal pests. The compositions may be formulated in any manner known for administration to a desired pest in any environment, whether internal or external, or for internal or external administration to vertebrates. These compositions comprise at least one compound of formula I or a pesticidally acceptable salt thereof, as mentioned above, as an active ingredient in combination or in conjunction with one or more compatible ingredients such as solid or liquid carriers or diluents, adjuvants, surfactants or the like which are suitable for the particular use and which are agronomically or medically acceptable. These compositions, which may be prepared by any means in this field, form part of the present invention.

These compositions may also contain other kinds of additives such as colloidal preservatives, adhesives, thickeners, toxitropic substances, penetration enhancers, spray oils (especially for acaricidal use), stabilizers, preservatives (especially against mold), sequestering agents and the like and also other known active ingredients having pesticidal properties (in particular insecticides, miticides, nematicides or fungicides) or plant growth-regulating properties. More generally, the compounds of the present invention may be combined with all solid or liquid additives according to conventional formulation techniques.

Compositions suitable for use in agriculture, horticulture or the like include those suitable, for example, as sprays, powders, granules, aerosols, foams, emulsions and the like.

Effective dosages of the compounds of the present invention may vary according to a number of criteria, particularly depending on the nature of the pest to be eliminated or the degree of attack by, for example, the crop of these pests. In general, the compositions of the present invention will usually contain 0.05 to 95% by weight of one or more active compounds of formula I or pesticidally acceptable salts thereof, 1 to 95% of one or more solid or liquid carriers and optionally 0.1 to 50% of one or more other compatible additives such as surfactants or the like.

According to the present invention, the term "carrier" means an organic or inorganic ingredient, natural or synthetic in nature, with which the active ingredient is combined to facilitate its application, for example to plants, seeds or soil. This carrier is therefore generally inert and must be acceptable (e.g. agronomically acceptable, especially for the treated plants).

-15 CZ 296158 B6

The carrier may be solid, for example clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers (for example, ammonium salts), natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceous earth or synthetic minerals such as silica, alumina or silicates, in particular aluminum and magnesium silicates. Suitable solid carriers for use in granules are the following: crushed or fractionated stones such as calcite, marble, pumice, sepiolite and dolomite; synthetic granules of inorganic or organic fertilizers; granules of organic substances such as sawdust, coconut shells, corn cobs, corn husks or tobacco stalks; diatomaceous earth, calcium phosphate, powdered cork or adsorbent carbon black; water-soluble polymers, resins, waxes; or solid fertilizers. These solid compositions may, if appropriate, contain one or more wetting, dispersing, emulsifying or coloring agents which, when solid, may also serve as diluents.

The carrier can also be liquid, for example: water, alcohols, especially butanol or glycol, as well as ethers or esters, especially methyl glycol acetate; ketones, in particular cetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone; petroleum fractions such as paraffinic or aromatic hydrocarbons, in particular xylenes or alkylnaphthalenes; mineral or vegetable oils; aliphatic chlorinated hydrocarbons, in particular trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons, in particular chlorobenzenes; water-soluble and strongly polar solvents such as dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone; liquefaction by gases; and the like or mixtures thereof.

The surfactants may be emulsifying agents, dispersing agents or wetting agents of the ionic or non-ionic type, or mixtures of such surfactants. These include, for example, polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic acid or naphthalenesulfonic acid salts, polycondensation products of ethylene oxide with fatty alcohols or fatty acids or fatty acid esters or fatty amines, substituted phenols (especially alkylphenols or arylphenols), sulfosuccinic acid ester salts , taurine derivatives (especially alkyltaurates), phosphoric acid esters of alcohols or polycondensates of ethylene oxide with phenols, fatty acid esters of polyols, or sulfate, sulfonate or phosphate functional derivatives of the above compounds. The presence of at least one surfactant is usually necessary if the active ingredient and / or the inert carrier are only slightly soluble in water or not soluble in water and the carrier of the composition is water.

The compositions of the present invention may further comprise other additives such as adhesives or dyes. Carboxymethylcellulose or natural or synthetic polymers in the form of powders, granules or lattices such as acacia, polyvinyl alcohol or polyvinyl acetate, natural phospholipids such as cephalins or lecithins or synthetic phospholipids can be used as adhesives in the compositions. Dyes such as inorganic pigments may be used, for example: iron oxides, titanium oxides or Berlin blue; organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes; or trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

Compositions containing compounds of Formula I, or pesticidally acceptable salts thereof, which can be used to control arthropods, plant nematodes, worms or protozoal pests, may also contain synergists (e.g., piperonyl butoxide or sesamex), stabilizers, other insecticides, acaricides, plant nematocides, antihelmicides or anticoccidial agents, fungicides (agricultural or veterinary as appropriate, such as benomyl and iprodione), bactericides, anthropodal or vertebral attractants or repellents or pheromones, deodorants, flavors, colorants or suitable therapeutic agents, for example trace elements. These substances may increase efficacy, stability, safety, if appropriate by adsorption, the spectrum of controlled pests, or impart to the compositions other suitable functions in the same animals or in the treated area.

-16GB 296158 B6

Examples of other pesticidally active compounds that can be added or used together with the compositions of the present invention are: acetate, chlorpyrifos, demetone-S-methyl, disulfotone, ethoprophos, fenitrophion, fenamiphos, phonophos, isophos, malathios monocrotophos, parathion, phorate, phosalone, pirimiphos-methyl, terbufos, triazophos, cyfluthhrin, cypermethrin, deltamethrin, fenproparthrin, fenvalerate, permethrin, tefluthrin, aldicarb, carbosulfan, methomyl, oxamyl, pirimicarb, bendiocarb, dendanofosine, teflubenzuronate, teflubenzuron, carton, tetradifon, avermectins, invesmectins, milbemycins, thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole.

For agricultural use as compounds of formula I or their pesticidally acceptable salts, usually in the form of compositions which are in various solid or liquid forms.

Solid form preparations which can be used are powders for dusting (containing a compound of formula I or a pesticidally acceptable salt thereof in the range of 80%), wettable powders or granules (including water-dispersible granules), in particular obtained by extrusion, compression, by impregnating the granular carrier or powder granules (the content of the compound of formula I or a pesticidally acceptable salt thereof in these wettable powders or granules ranges from 0.5 to 80%). Solid homogeneous or heterogeneous compositions comprising one or more compounds of formula I or pesticidally acceptable salts thereof, for example granules, pellets, briquettes or capsules, may be used for the treatment of standing or running water. A similar effect can be achieved using dropwise dosing or intermittent dosing of water-dispersed concentrates as described herein.

Liquid compositions, for example, include aqueous and non-aqueous solutions or suspensions (such as emulsifiable concentrates, emulsions, flowables, dispersions, or solutions) or aerosols. Liquid compositions also include, in particular, emulsifiable concentrates, dispersions, emulsions, flowable compositions, aerosols, wettable powders (or sprayable powders), dry flowable compositions or pastes as forms or compositions which are liquid or intended for the preparation of liquid compositions when applied, for example, as aqueous sprays (including low and ultra-low volume) or as mists or aerosols.

Liquid formulations, for example in the form of emulsifiable or soluble concentrates, most often contain about 5% to 80% by weight of the active ingredient, while emulsions or solutions, when ready for application, contain 0.01 to 20% of the active ingredient. In addition to the solvent, the emulsifiable or soluble concentrates may contain, if appropriate, 2 to 50% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives. Emulsions of any desired concentration that are particularly suitable for application, for example to plants, can be prepared from these concentrates by dilution with water. These compositions form part of the compositions that can be used in accordance with the present invention. The emulsions may be in the form of water-in-oil or oil-in-water and may have a thick consistency.

The liquid compositions of the present invention may furthermore be used in addition to conventional agricultural applications, for example, for treating substrates or sites attacked or threatened by arthropod infestations (or other pest-controlled arylpyrazoles or the present invention) including buildings, exterior or interior warehouses or processing areas. containers or equipment or standing or running water.

All of these aqueous dispersions or emulsions or spray mixtures can be applied, for example, to the crops by any suitable method, in particular by spraying, in amounts usually between 100 and 1200 liters of spray mixture per hectare, but can be higher or lower (e.g. low or ultra-low volumes) depending on the need or method of application. The compounds or compositions of the present invention are usually applied to vegetation and in particular to roots or leaves containing pests to be removed. Another way of administering the compounds or compositions of the present invention is by chemigation, i.e., adding a composition containing the active ingredient to water for irrigation. This irrigation can be

- 17GB 296158 B6 sprinkler irrigation, or it may be ground irrigation or underground irrigation for land and systemic pests.

Concentrated suspensions which can be applied by spraying are prepared to form a stable liquid product which does not settle (finely ground) and usually contains 10 to 75% by weight of active ingredient, 0.5 to 30% of surfactant, 0.1 up to 10% of thixotropic agents, 0 to 30% of suitable additives such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrating agents, adhesives and, as a carrier, water or an organic liquid in which the active ingredient is poorly soluble or insoluble. Certain organic salts or inorganic salts may be dissolved in the carrier to prevent sedimentation or to prevent water freezing.

Wettable powders (or powders for spraying) are usually prepared containing 10 to 80% by weight of active ingredient, 20 to 90% by weight of solid carrier, 0 to 5% of wetting agent, 3 to 10% of dispersing agent and, if appropriate, 0 up to 80% of one or more stabilizers and / or other additives such as penetrating agents, adhesives, anti-caking agents, coloring agents and the like. To prepare these wettable powders, the active ingredients are well mixed in a suitable mixer with other substances which may be impregnated on the porous filler and ground using a mill or other suitable friction device. This results in wettable powders having advantageous wettability and suspendability. They can be suspended in water to obtain any desired concentration, and this suspension can be used very advantageously especially for application to plant leaves.

"Water-dispersible granules (WG)" (granules that are readily dispersible in water) have a composition that is very similar to that of wettable powders. They may be prepared by granulating the compositions described for wettable powders, either by wet means (by mixing the finely divided active ingredient with an inert filler and a small amount of water, for example 1 to 20% by weight or with aqueous solutions of a dispersing agent or binder then drying and stitching) or dry. way (by pressing and then grinding and stitching).

The ratios and concentrations of the formulated compositions may vary according to the mode of application or the nature of the compositions or their use. In general, compositions for administration to control arthropods, plant nematodes, worms and protozoal pests generally comprise from 0.00001 to 95%, more preferably from 0.0005 to 50% by weight of one or more compounds of Formula I, or pesticidally acceptable salts thereof, or all active components (i.e., compounds of formula (I) or pesticidally acceptable salts thereof together with other substances toxic to arthropods or plant nematodes, antiparasitic worms, anticoccidial agents, synergists, trace elements or stabilizers). The particular means and ratios in which they are used will be selected by the farmer, livestock farmer, physician or veterinarian, pest control person or other expert in the field to achieve the desired effect.

Solid or liquid formulations for topical application to animals, wood, stored products or household consumer goods usually contain 0.00005% to 90%, more preferably 0.001 to 10% by weight of one or more compounds of formula I or pesticidally acceptable salts thereof. Compositions for oral or parenteral administration to animals, including solid or liquid skin compositions, typically contain from 0.1% to 90% by weight of one or more compounds of Formula I, or pesticidally acceptable salts thereof. The drug-containing feeds typically contain 0.001 to 3% by weight of one or more compounds of formula (1) or pesticidally acceptable salts thereof. Concentrates or additives for admixture with feed will normally contain 5 to 90%, preferably 5 to 50% by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof. Mineral licking salts typically contain from about 0.1% to about 10% by weight of one or more compounds of Formula (I) or pesticidally acceptable salts thereof.

-18GB 296158 B6

Powders and liquid compositions for use in cattle, goods, buildings or outdoor areas may contain from 0.0001% to 15%, in particular from 0.005% to 2.0% by weight of one or more compounds or pharmaceutically acceptable salts thereof. Suitable concentrations in the treated water are between 0.0001 ppm to 20 ppm, more preferably 0.001 ppm to 5.0 ppm, of one or more compounds of formula (I) or pesticidally acceptable salts thereof, and can be used therapeutically in fish farms at appropriate exposure times. The edible baits may contain from 0.01% to 5%, preferably 0.01% to 1.0% by weight, of one or more compounds of Formula I or pesticidally acceptable salts thereof.

When the compounds of formula I or their pesticidally acceptable salts are administered to vertebrates parenterally, orally, or through the skin, or otherwise, their dose will depend on the species, age or medical condition and the nature and degree of actual or potential infestation by arthropods, helminth or protozoal pest. A single dose is between 0.1 to 100 mg, preferably 2.0 to 20.0 mg, per kg body weight of an animal or a dose of 0.01 to 20.0 mg, preferably 0.1 to 5.0 mg per Oral or parenteral administration is usually appropriate in supportive therapy. Using slow release formulations or devices, the daily doses required for a period of months may be combined and administered to animals on individual occasions.

The following compositions of Examples 2A to 2M illustrate compositions for use against arthropods, in particular mites and insects, plant nematodes or worms or protozoan pests, which contain the active ingredient, a compound of formula I or a pesticidally acceptable salt thereof, as described in the preparation examples. . The compositions described in Examples 2A to 2M can be diluted to provide a spray composition having a concentration suitable for field use. The generic chemical names of the ingredients (for which all the following percentages are by weight) used in the compositions of Examples 2A to 2M below are as follows:

Business name Chemical description Ethylan BCP Soprophor BSU condensate of nonylphenol and ethylene oxide condensate of tristyrylphenol and ethylene oxide Arylan CA 70% w / v calcium dodecylbenzenesulfonate solution Solvesso 150 light aromatic solvent containing 10 carbon atoms Arylan S Darvan No 1 sodium dodecylbenzene sulfonate sodium lignosulfonate Celite PF synthetic magnesium silicate carrier Sopropon T36 Rhodigel 23 sodium polycarboxylic acid polysaccharide xanthan gum Bentone 38 organic derivative of montmorillonite magnesium salt Aerosil microfine silica

Example 2A

The water-soluble concentrate is prepared from the following compositions:

Active ingredient 7%

Ethylene BCP 10%

N-methylpyrrolidone 83%

To the ethylene BCP solution dissolved in a portion of N-methylpyrrolidone, the active ingredient is added with heating and stirring until dissolution. The resulting solution is made up to the desired volume with the remaining solvent.

CZ 296158 B6

Example 2B

An emulsifiable concentrate (EC) is prepared from the following components:

Active ingredient Soprophor BSU Arylan CA N-methylpyrrolidone Solvesso 150 25% (max) 10% 5% 50% 10%

The first three components are dissolved in N-methylpyrrolidone and Solvesso 150 is added to this solution to give a final volume.

Example 2C

Wettable powder (WP) is prepared from the following ingredients:

Active ingredient Aryl S Darvan No. 2 Celite PF 40% 2% 5% 53%

The ingredients are mixed and ground in a hammer mill to a particle size of less than 50 µm.

Example 2D

The aqueous liquid composition is prepared from the following ingredients:

Active ingredient Ethylan BCP Sopropon T360 Ethylene glycol Rhodigel 230 Water 40,05% 1.00% 0.20% 5,00% 0.15% 53,67%

The ingredients are mixed well and ground in a screw mill to a mean particle size of less than 3 µm.

Example 2E

A concentrated emulsifiable suspension is prepared from the following components:

Active ingredient Ethylan BCP Bentone 38 Sovesso 150 30.0% 10.0% 0.5% 59.5%

The ingredients are mixed well and ground in a screw mill to a median particle size of less than 3 µm.

Example 2F

Water dispersible granules are prepared from the following ingredients:

Active ingredient

30%

Darvan No. 2

15%

Arylan S 8%

Celite PF 47%

The ingredients are mixed, micronized in a fluid mill and then granulated in a rotary granulator by spraying water (up to 10%). The resulting granules are dried in a fluid bed dryer to remove excess water.

Example 2G

Powdered powder is prepared from the following ingredients:

Active ingredient 1 to 10%

Very fine talc powder 99 to 90%

The ingredients are mixed well and then rubbed until a fine powder is formed. The powder may be applied to an arthropod infested area, for example, landfills, stored products or household consumer goods, or to animals infested or endangered by arthropod infestations to achieve arthropod control by oral administration. Suitable methods of distributing the powder to the area affected by arthropods include mechanical blowers, manual devices or cattle treatment devices.

Example 2H

The edible bait is prepared from the following means:

Active ingredient

Wheat flour

Molasses

0.1 to 1.0%

80%

19.9 to 19%

The ingredients are mixed well and adjusted as appropriate for a single bait. This edible bait or industrial enterprises, such as kitchens, hospitals or warehouses, or outdoor areas 40 infested by arthropods such as ants, grasshoppers, cockroaches or flies to achieve control by oral administration.

Example 21

The composition solution is prepared from the following components:

Active ingredient 15%

Dimethylsulfoxide 85%

The active ingredient is dissolved in dimethylsulfoxide, if necessary, with stirring and / or heating. This solution can be applied over the skin as a run-off to pets infected with arthropods or, after sterilization by filtration through a polytetrafluoroethylene membrane (pore size 0.22 μηι), as a parenteral injection, in an amount of 1.2 to 12 ml of solution per 100 kg weight 55 animal.

-21 GB 296158 B6

Example 2J

A wettable powder is prepared from the following ingredients:

Active ingredient 50%

Ethylan BCP 5%

Aerosil 5%

Celite PF 40%

Ethylan BCP is adsorbed onto Aerosil, which is then mixed with the other ingredients and spread in a hammer mill to give a wettable powder which can be diluted with water to a concentration of 0.001% to 2% by weight of the active compound and applied to the arthropod infested area. or plant nematodes, by spraying, or by domestic animals attacked or endangered by arthropods, worms or protozoa, by spraying or immersion, or by oral administration in drinking water, to control arthropods, worms or protozoa.

Example 2K

Slow release tablets are prepared from granules containing the following ingredients in varying percentages (similar to those described in the previous compositions), depending on the need:

Active ingredient

Thickener

Slow release agent

Binder

The well-blended ingredients are granulated and the granules are compressed into tablets having a specific gravity of 2 or more. They may be administered to ruminant domestic animals where the active ingredient is retained in the rumen and the active compound is released slowly over a longer period of time to control infestation of domestic ruminant animals by arthropods, helminths or protozoa.

Example 2L

Slow release formulations in the form of granules, pellets, cubes or the like are prepared from the following ingredients:

Active ingredient 0,5 to 25%

Polyvinyl chloride 75 to 99.5%

Dioctyl phthalate (plasticizer)

The components are mixed and then formed into suitable shapes by extrusion or compression. These compositions are suitable, for example, for adding to standing water or for processing into collars or ear tags for pets, whereby the pests are controlled by slow release.

Example 2M

The water-dispersible granules have the following composition:

-22EN 296158 B6

Active Ingredient Polyvinylpyrrolidone Attapulgite clay Sodium lauryl sulphate Glycerin 85% (max) 5% 6% 2% 2%

The ingredients are mixed as a 45% slurry with water and wet milled to a particle size of 4 µm, then spray dried and water is removed.

Although the invention is described in various preferred embodiments, it will be apparent to those skilled in the art that various modifications, substitutions, omissions and changes may be made without departing from the spirit of the invention. Thus, the scope of the present invention is limited only by the scope of the following claims, including equivalents thereof.

Claims (9)

PATENT CLAIMS A 1-arylpyrazole of the general formula I wherein R _{3 and} R ₃₂ are independently OR ₂₀ , S (O) _n R ₂₀ , or N (R ₂₀ ) (R ₂₁ ); or R _{3 and} R ₃₂ may also together form O [C (R ₂₂ ) (R ₂₃ )] _m O, S (O) _n [C (R ₂₂ ) (R ₂₃ )] _m S (O) _and , O (CH ₂ ) _m S (O) _n , O [C (R ₂₂ ) (R ₂₃ )] _m (NR ₂₀ ), S (O) _n [C (R ₂₂ ) (R ₂₃ )] _m (NR ₂₀ ), NR ₂₁ [C (R ₂₂ ) (R ₂₃ )] _m NR ₂₀ , NR ₂₁ [C (O) (CH ₂ ) _m ] NR ₂₀ ; when m is an integer greater than 1, the groups [C (R ₂₂ ) (R ₂₃ ) J may be the same or different; R ₂₀ , R ₂ may independently be hydrogen, C 6 -C 10 alkyl, C 6 -C 10 aryl, benzyl, allyl, propargyl; R ₂₂ , R ₂₃ independently of one another may be hydrogen; a halogen atom; a hydroxyl group; amino; COOR ₂₀ ; C (O) NH _2; C (O) N (R ₂₀ ) (R ₂₁ ); C (S) NH _2; OC (O) N (R ₂₀₎ (R _21), cyano; nitro; C (S) N (R ₂₀ ) (R ₂₁ ); (C 1 -C 6) alkyl optionally substituted by hydroxyl, amino, halogen, cyano, nitro, COOR ₂₀ , -23EN 296158 B6 C (O) NH ₂ , C (S) NH ₂ ; S (O) _b alkyl having 1 to 6 carbon atoms; (C 1 -C 6) alkoxy; S (O) _c R ₂₀ ; R 4 is R ₂₆ ; S (O) _d R ₂₆ ; S - (= R ₂₇ ) (= NR ₂₈ ) R ₂₆ ; R ₂₆ is an alkyl group having 1 to 6 carbon atoms, optionally substituted with one or more halogen atoms, which may be the same or different; R ₅ is amino, alkylamino wherein the alkyl group contains 1 to 6 carbon atoms and may be substituted by nitro, halogen, cyano, alkoxycarbonyl of 1 to 6 carbon atoms in the alkoxy moiety, hydroxyl, alkoxy of 1 to 6 carbon atoms, alkylthio containing (C 1 -C 6) alkyl, (C 1 -C 6) alkylsulfinyl, (C 1 -C 6) alkylsulfonyl, or carbamoyl; or R ₅ is a group of the formula: wherein R 4, R _I2, R _13, R 14, R 15, R ₃₃ In the same as R 4, R _i2, R _3, R _14, R ₅ to R ₃₃ in formula I above; R ₂₇ is NR ₂₈ , an oxygen atom, or a free electron pair; R ₂₈ is selected from the group consisting of hydrogen; (C 1 -C 6) alkyl; haloalkyl having 1 to 6 carbon atoms; COR ₂₄ ; S (O) _e R ₂₄ , COOR ₂₄ ; C (O) N (R ₂₀ ) (R ₂₁ ); C (O) -SR ₂₄ ; C (S) OR _24; SO ₂ NR ₂₀ R ₂₁ ; P (O) _q (R ₂₀ ) (R ₂₁ ); P (O) _q (OR ₂₀ ) (OR ₂₁ ); group C (= NR ₂₀ ) NR ₂₀ R ₂₁ ; C (= NR ₂₀₎ (OR ₂ i); C (S) N (R ₂₀ ) (R ₂₁ ); C (O) C (O) R _20; C (O) C (O) OR _20; C (0) C (0) NR ₂ oR2i; and C (O) NR ₂₁ R ₂ and; q is 0 or 1; R ₂₄ is C 1 -C 6 alkyl optionally substituted by nitro, cyano, halogen, C 1 -C 6 alkoxy, amino, C 1 -C 6 alkoxycarbonyl, or hydroxyl; Z is N or CR ₁₆ ; R ₁₂ , R ₁₃ , R ₁₄ , R 15 and R ₁₆ are independently hydrogen; a halogen atom; SF ₅ ; cyano; nitro; R ₂₅ ; S (O) f R ₂₅ ; a hydroxyl group; OR ₂₅ ; N (R ₃₆ ) (R ₃₇ ); CON (R ₂₅₎ (R _37); N ₃ ; R ₃₆ and R ₃₇ are each independently hydrogen, C 1 -C 6 alkyl; -24GB 296158 B6 R 5 ₂ is an alkyl group containing 1 to 6 carbon atoms optionally substituted by one or more halogen atoms, which may be the same or different; R ₃₃ is C 1 -C 3 alkyl optionally substituted by one or more halogen atoms, nitro, C 1 -C 6 alkoxy, cyano, carboxyl, C 1 -C 6 alkyl in the alkyl moiety, C (O) NH _2; n, a, b, c, d, e and f are independently 0, 1 or 2; and m is an integer from 1 to 5; or a pesticidally acceptable salt thereof. A compound according to claim 1, wherein: R 13 and R 15 are hydrogen or halogen; R ₁₂ is halogen; R ₁₆ is hydrogen or halogen; and / or R ₁₄ is a halogen atom; SF ₅ ; R ₂₅ ; S (O) _f R ₂₅ ; or OR ₂ s; and the other symbols are as defined in claim 1. A compound according to claim 1 or claim 2, wherein: m is preferably 2, 3 or 4, more preferably 2 or 3, most preferably 2; and the other symbols have the meanings given in claim 1 or 2. A compound according to any one of claims 1 to 3, wherein: R 31 and R ₃₂ are independently OCH ₃ ; OC ₂ H ₅ ; SCH ₃ ; group SC ₂ H _5; R 31 and R ₃₂ may also be combined to form the OCH ₂ CH ₂ O group; O (CH ₂ ) ₃ O; S (CH ₂ ) ₂ S; S (O) (CH _{2) 2} S; S (O) (CH ₂ ) ₂ S (O); S (CH ₂ ) ₂ S (O); S (O) (CH ₂ ) ₂ S (O) ₂ ; S (CH ₂ ) ₂ O; S (O) ₂ (CH ₂ ) ₂ O; S (O) ₂ (CH ₂ ) ₂ O; O (CH ₂ ) [CH (CH ₂ OH)] O; O (CH ₂ ) [C (CH ₂ OH) (CH ₂ OH)] O; OCH (COOCH ₃ ) CH (COOCH ₃ ) O groups; OCH (COOC ₂ H ₅ ) CH (COOC ₂ H ₅ ) groups; OCH ₂ C (COOCH ₃ ) (COOCH ₃ ) CH ₂ O groups; OCH ₂ C (COOC ₂ H ₅ ) (COOC ₂ H ₅ ) CH ₂ O groups; OCH ₂ CH (CH ₃₎ O; SCH ₂ CH ₂ NH; OCH ₂ CH (CH ₂ CH ₂ OH) O; or OCH ₂ C (CH ₂ OH) ₂ CH ₂ O; O (CH ₂ ) CH (CH ₂ SCH ₃ ) O; O (CH ₂ ) CH (CH ₂ SOCH ₃ ) O; R ₄ is S (O) _n R ₂₆ ; R ₂₆ is methyl or ethyl; Z is CR ₁₆ ; R ₁₃ and R 15 are hydrogen; R ₁₂ is halogen; R ₁₆ is hydrogen or halogen; R ₁₄ is CF ₃ , OCF ₃ , SF ₅ ; and R ₃₃ is methyl; and the other symbols have the meanings given in claims 1 to 3. 5. A pesticidal composition comprising 1-arylpyrazole of formula (I) or a pesticidally acceptable salt thereof according to claim 1 and a pesticidally acceptable carrier. Pesticidal composition according to claim 5, characterized in that it contains from 0.05 to 95% by weight of 1-arylpyrazole of the general formula (I). A method for controlling pests in a region, with the exception of therapeutic and diagnostic methods carried out on a human or animal body, comprising administering to the region 1-arylpyrazole of formula I or a pesticidally acceptable salt thereof according to claim 1 or a composition according to claim 5. 8. The method according to claim 7, wherein the pest is an insect. -25GB 296158 B6 9. A process for the preparation of a compound of formula (I) according to claim 1 wherein the compound of formula (II) is reacted with a compound of formula (III) containing at least one reactive functional group selected from the group consisting of alcohol, thiol, primary amino. and a secondary amino group, wherein the compound of formula III is selected from the group consisting of an alcohol of formula R ₂₀ OH; A thiol of the formula R ₂₀ SH; amine of formula HN (R ₂₀ ) (R 21) and • a compound of formula HO [C (R ₂₀ ) (R ₂₃ )] _m OH, HS [C (R ₂₂ ) (R 23)] _m SH, HO [C (R 23)] ₂₂ ) (R ₂₃ ) _m N (R ₂₀ ) H, HO [C (R ₂₂ ) (R ₂₃ )] _m SH and HS [C (R ₂₂ ) (R ₂₃ )] _m N (R ₂₀ ) H where R34 is oxygen or sulfur, and the other symbols are as defined in claim 1.