CZ296162B6 - Pesticidal 1-aryl-3-iminopyrazoles, process of their preparation and compositions in which they are comprised - Google Patents

Abstract

In the present invention, there are disclosed 1-aryl-3-iminopyrazoles of the general formula I, which are useful as pesticides or as intermediates to other pesticides. Compositions comprising the compounds of the general formula I and methods for their use, particularly in agriculture or for animal protection, as pesticides, especially for controlling arthropods, are described, too.

Description

Technical field

The present invention relates to novel 1-arylpyrazoles derivatives having some 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 WO 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. As far as pyrazoles are concerned, the contents of these patents do not differ substantially from the international patent application WO 87/03781 or the 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 and WO 97/28126.

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, for example anti-aphid activity, miticidal activity, hazel pest activity, soil pest activity, systemic activity, feed pest activity or pesticide activity. 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 296162 B6

The present invention relates to compounds of formula I

(I) / where

R ₃ i may be:

a hydrogen atom; cyano; nitro; NO group; SH; (C 1 -C 6) alkylthio; amino; P (O) (OR ₈ ) (OR ₉ ) or R ₃₈ ; or monoalkylamino having 1 to 6 carbon atoms; a dialkylamino group containing 1 to 6 carbon atoms in each alkyl moiety; a formyl group; C 1 -C 20 alkyl; (C 3 -C 6) cycloalkyl; or a (C 4 -C 8) cycloalkylalkyl group; each alkyl or cycloalkyl group is optionally substituted with one or more R ₃₅ groups; or a naphthyl or phenyl group, each of which is optionally substituted with one or more R ₃₆ or R ₃₇ groups; or NH-CO-NH-N = CR ₈ R _9; NH-CS-NH-N = CR _with R ₉ ; NH-CO-NR ₈ R _9; NH-CS-NR ₈ R _{9; NH-CO-OR8; NH-CS-OR8;} or NHCO-NH-NH _2;

R ₃₂ is C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkyl, wherein each alkyl group may be substituted with one or more R ₃₅ groups; phenyl optionally substituted with one or more R ₃₆ or R ₃₇ ; or R ₃₈ ;

R ₃₃ is a free electron pair or an oxygen or sulfur atom (when R ₃₃ is an oxygen or sulfur atom, it may be attached to the nitrogen atom by a covalent bond or by a bond that may be partially covalent and partially ionic) or an alkyl group containing 1 to 6 carbon atoms, the nitrogen atom to which R ₃₃ is attached is then in the form of an N ⁺ cation (if R ₃₃ is an alkyl group, the bond between the nitrogen atom and R ₃₃ is a single bond; and the compound of formula I is then an iminium salt) ; or R _3I and R ₃₃ together are alkylene having 2 to 6 carbon atoms, wherein one or two carbons are optionally replaced by a heteroatom selected from the group consisting of oxygen, sulfur or nitrogen atom (the specificity of N and the bond between N and the group R ₃₃ is then the same as indicated when R ₃₃ is alkyl);

-2GB 296162 B6

R ₃₅ is halogen, amino, (C 1 -C 6) alkylamino, (C 1 -C 6) dialkylamino, nitro, cyano, (C 1 -C 6) alkoxy, (C 1 -C 6) alkoxycarbonyl carbon, hydroxycarbonyl, alkylcarbonyl of 1-6 carbon atoms, methylene, methylidine, C1-6 alkynyl, C1-6 alkylalkynyl and 1-6 alkynyl carbon atoms; or R ₃₅ may be a phenyl group optionally substituted with one or more R ₃₆ groups; or R ₃₅ may be a heterocyclic ring containing a total of 3 to 7 ring atoms of which from 1 to 4 are heteroatoms, said heteroatoms are the same or different and are selected from the group consisting of oxygen, sulfur and nitrogen, said heterocyclic ring is saturated or unsaturated and is optionally substituted with one or more R ₃₆ groups; or R ₃₅ can be hydroxyl, SH, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfonyl, aminocarbonyl, C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 dialkylaminocarbonyl 1 to 6 carbon atoms, an alkoxycarbonyl group containing 1 to 6 carbon atoms in each alkoxy moiety, or P (O) (OR ₈ ) - (OR ₉ );

R ₃₆ can be SF ₅ , halogen, C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, nitro, cyano, amino, C 1 -C 6 alkylamino, C 1 -C 1 dialkylamino up to 6 carbon atoms, dialkylaminocarbonylamino having 1 to 6 carbon atoms in each alkyl moiety, alkylaminocarbonylamino having 1 to 6 carbon atoms in the alkyl moiety, aminocarbonylamino, alkylcarbonyl having 1 to 6 carbon atoms in the alkyl moiety, and alkoxycarbonyl having 1 to 6 alkoxy moieties 6 carbon atoms, alkylcarbonylamino group having 1 to 6 carbon atoms in the alkyl moiety, alkoxycarbonylamino group having 1 to 6 carbon atoms in the alkoxy moiety, aminocarbonyl, dialkylaminocarbonyl having 1 in each alkyl moiety (C 1 -C 6) alkylaminocarbonyl, (C 1 -C 6) alkylaminocarbonyl, hydroxycarbonyl, aminocarbonyloxy, (C 1 -C 6) alkylaminocarbonyloxy, (C 1 -C 6) dialkylaminocarbonyloxy, hydroxy (C 1 -C 6) alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, haloalkylthio (C 1 -C 6), (C 1 -C 6) haloalkylsulfinyl, P (O) (OR ₈ ) (OR ₉ ), (C 1 -C 6) alkyl (alkylcarbonyl) amino, or phenylaminoalkyl C 1 -C 6 alkyl;

R ₃₇ may be R ₃₆ or phenyl optionally substituted with one or more R _36, phenoxy optionally substituted with one or more R ₃₆ or a benzyl group optionally substituted by one or more R _36,

R ₃₈ may be a heterocyclic radical derived from a single heterocyclic ring or from two ring fused heterocyclic systems of which at least one ring is heterocyclic, each ring containing 3 to 7 ring members, each heterocyclic ring containing 1 to 4 ring heteroatoms, said heteroatoms may be the same or various and are selected from the group consisting of oxygen, sulfur and nitrogen, each ring being saturated or unsaturated; such a heterocyclic residue may be, for example, a residue derived from the following compounds: pyridine, pyrimidine, oxazole, oxadiazole, oxatriazole, isoxazole, thiazole, isothiazole, imidazole, pyran, pyrone, pyrazole, pyrrole, tetrazole, furoxan, tetrahydrofuranyl, furan, pyrazine, pyridazine, benzimidazole, quinoline, iso

Quinoline, triazine, thiophene, furopyran, furopyron, thiatriazine, thiadiazole. All these heterocyclic radicals may be attached to the nitrogen atom of the group R ₃₂ -C = NR _3] at any possible position of the heterocyclic ring and all rings may be optionally substituted with one or more R ₃₆ groups or a phenyl group optionally substituted with one or more R ₃₆ groups,

_R and R ₉ are independently selected from the group consisting of hydrogen and alkyl of 1-6 carbon atoms optionally containing one or more substituents selected from the group consisting of halogen, nitro, cyano, CHO, OH , (C 1 -C 6) alkoxy, (C 1 -C 6) alkylthio, (C 1 -C 6) alkylsulfinyl, (C 1 -C 6) alkylsulfonyl, (C 1 -C 6) alkoxycarbonyl, hydroxycarbonyl and a carbamoyl group;

R ₄ is R 11 or S (O) _n R 11;

R _n is an alkyl group containing 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or a cycloalkylalkyl group containing from 4 to 8 carbon atoms, each of which is optionally substituted by one or more halogen atoms;

n is 0, 1 or 2;

R ₅ is hydrogen, halogen, cyano, S (O) _n R ₈ , OR ₈ , NR ₈ R ₉ , N (R ₈ ) CON (R ₉ ) (R ₈ ), azido or - N = C (R ₁₀ ) (OR ₉ );

Rio may have the same meaning as _R and may be also benzyl or phenyl optionally substituted with one or more R _36;

Z is nitrogen or C-R _6; and

R 12 to R ₁₆ may be hydrogen, halogen, R ₈ , OR ₈ , SF ₅ , S (O) _n R ₈ , cyano, nitro, CHO, C (O) R ₈ or COOR ₈ ;

and their pesticidally acceptable salts.

The present invention includes all stereoisomers, geometric isomers (E and Z forms of imines), optical isomers and diastereoisomers of Formula I, as well as tautomers thereof, if appropriate, and mixtures thereof.

Also included in the present invention are salts of the compounds as defined above, in particular sodium, potassium or ammonium or iminium salts. The alkali metal or alkaline earth metal salts are generally derived from compounds of formula I wherein R ₃₃ is an electron pair and R ₃ is a hydrogen atom. Iminium salts are generally derived from compounds of formula I wherein R ₃₃ is an electron pair and R ₃₁ is as defined above for Formula I.

Unless otherwise indicated, the alkyl group or alkyl portion of another group of the invention contains 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms and may be straight or branched. Similarly, unless otherwise noted, the alkoxy groups and alkoxy moieties of other groups contain 1 to 6 carbon atoms and may be straight or branched.

The alkyl portions of the dialkylamino and other dialkylamino moieties may be the same or different, for example, N, N-dimethylamino, Ν, Ν-diethylamino and (N-ethyl-Nmethyl) amino.

-4GB 296162 B6

The term "halogen atom" as used herein before a group name means that the group is substituted with one or more halogen atoms, which may be the same or different. Thus, the term "haloalkyl" means an alkyl group bearing as substituents one or more halogen atoms that are the same or different and may thus include monohaloalkyl groups and polyhaloalkyl groups (i.e. containing more than one halo substituent), wherein the polyhaloalkyl groups include perhaloalkyl groups (i.e., groups completely substituted by halogen atoms). The term "haloalkoxy" likewise includes monohaloalkoxy and polyhaloalkoxy, wherein the latter term includes perhaloalkoxy.

The term "halogen atom" includes fluorine atom, chlorine atom, bromine atom and iodine atom. If more than one halogen atom is present as a substituent, such as on the phenyl ring, the substituents may be the same or different.

The present invention further relates to compositions of said compounds and methods of using said compounds for controlling arthropods, nematodes, parasitic worms, and protozoal pests. In particular, it relates to the use of the compounds or compositions of the present invention in agricultural uses, in particular as pesticides.

According to the present invention, the term imines is used to denote compounds containing the group C = NR.

One aspect of the present invention provides compounds for use in the control of arthropods, nematodes, parasitic worms and protozoal pests having the general formula I. In another aspect, the present invention provides pesticidal compositions (ie, anti-arthropod, nematode, parasitic worm or anti-worm) protozoa) comprising a pesticidally effective amount (ie, an effective amount against arthropods, a nematocidally effective amount, an effective amount against parasitic worms, or an antiprotozoally effective amount) of a compound of Formula I and agriculturally acceptable carriers. The term "compound of formula I" as used in the specification includes a variety of different stereoisomeric forms of the compounds of formula I.

Another aspect of the present invention provides a method of controlling arthropods, nematodes, parasitic worms or protozoal pests in an area comprising administering a pesticidally effective amount (ie, an effective amount against arthropods, a nematocidally effective amount, an effective amount against parasitic worms or an antiprotozoally effective amount). Or a pesticidal composition as defined above.

Preferred compounds of the present invention have one or more of the following properties:

Z is CR ₁₆ ;

R 12 is chlorine or bromine;

R ₁₃ and R 11 ₅ are hydrogen;

R 14 is perhaloalkyl, perhaloalkoxy or SF ₅ , preferably CF ₃ , OCF ₃ or SF ₅ ;

R ₆ is a chlorine atom or a bromine atom;

R ₃₁ is amino; an alkyl group optionally substituted with one or more R ₃₅ groups; phenyl optionally substituted with R ₃₆ or R ₃₇ ; R ₃₈ ; NH-CONH-N = CR ₈ R _9; NH-CS-NH-N = CR ₈ R _9; NH-CO-NR ₈ R _9; NH-CSNR ₈ R ₉ ; _NH-CO-OR8; or NH-CS-OR ₈ ;

-5 CZ 296162 B6

R ₃₂ is C 1 -C 6 alkyl, preferably methyl;

R ₃₃ is a free electron pair or oxygen atom, preferably a free electron pair;

R 4 is S (O) _n R 11;

R]! is methyl or ethyl;

n is 0 or 1, preferably 1; or

R ₅ is NR ₈ R ₉ ; preferably amino or NHR _9th

Preferred compounds of the present invention have one or more features listed in connection with the following classes of preferred compounds:

A first class of preferred compounds are those wherein:

R ₃₂ is C 1 -C 6 alkyl; Z is CR ₁₆ ; R4 is S (O) _n R _n;

R ₁₃ and R 15 are hydrogen; and R ₄ is perhaloalkyl, perhaloalkoxy or SF group _5th

A second preferred class includes compounds wherein:

R ₃₂ is methyl; R 4 is S (O) _n R 11; and _n R is methyl or ethyl.

A third preferred class includes compounds wherein

R ₄ is CF ₃ , OCF ₃ or SF ₅ ; and R ₁₂ and R ₁₆ are chlorine or bromine.

A fourth preferred group includes compounds wherein:

R ₅ is amino or alkylamino, wherein the alkyl is optionally substituted with cyano, CO-NH ₂ , alkoxycarbonyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl.

A fifth preferred class of the present invention are compounds wherein:

R ₃₃ is a free electron pair or oxygen atom;

R _3] is amino; an alkyl group optionally substituted with one or more R ₃₅ groups; phenyl optionally substituted with R ₃₆ or R ₃₇ ; R ₃₈ ; NH-CONH-N = CR ₈ R _9; NH-CS-NH-N = CR ₈ R _9; NH-CO-NR ₈ R _9; NH-CSNR ₈ R ₉ ; _NH-CO-OR8; or NH-CS-OR ₈ ;

Particularly preferred compounds of the present invention are those wherein R ₁₂ = R ₁₆ = chloro; _{R] 3} = R _I5 = hydrogen; R ₁₄ = trifluoromethyl; R ₅ = amino; R ₃₂ = methyl; R ₃₃ = free electron pair and R ₄ and R ₃₁ are given in the following table:

-6GB 296162 B6

D SOCHi CHj SOCHj Et SOCHj CHiCHjCHj SOCH, CH, CH, CH _; CHj SOCH, CH, CH-CH _; SOCHj CH ₂ CH, Ph SOCH, CH.CHjCN SOCH3 CH, CH; C (O) NH, SOCHj CH, C (O) CH3 SOCHj CHjC (O) OCH ₃ SOCHj CHjCHjCOOCHj SOCH, CH.CHjCOOH SOCHj CH, C (O) OC ₂ H _s SOCHj CH ₂ OCH

SOCHj CHjCHjSOCHj SOCHj CH.CHjSCHj SOCHj CH, CH, S (O), CH 3 SOCHj CH, CH _; NHj statues ₃ CHjCHjNOj SOCHj CHjCH.COOCjHj SOCHj CH (CH3) CH3COOH SOCHj CH, COOH SCHj CH, COOH S (O) Et CH, COOH S (O) ₂ Et CH3COOH SEt CH ₂ COOH SOCHj CH _(CH3) COOCHj SOCHj CH (COOCHj) CH ₂ CONH ₂ SOCHj CH (COOCHj) CH ₂ COOH SOCHj CH (COOCH3) CH, SCH3 SOCHj CH (COOH) CH ₂ CH ₂ CH ₂ COOCH

SOCH; CH (COOH) CH ₂ CH ₂ CH ₂ CONH ₂ SOCH; CH ₂ CH ₂ -4-imidazolyl SOCH; CH (COOCH3) -4-imidazole SOCH; CH 2 COOC 3 H 2 CHCCH 3 JCH 3 -C 1 H 2 statues ₃ CH (COOC ₂ H _$ ) CH ₂ CH (CH ₃ ), SOCHj (CH ₂ ) ₄ CH (NH ₂ ) COOH SOCH; CH (COOH) CH ₂ CH ₂ SCHj SOCH; CH (COOH) (CH ₂ ); SOCH; CH (C00CH;) CH ₂ CH ₂ CH; S (O) ₂ CH; CH (COOCH 3) CH ₂ CH ₂ CH; SOCH; CH ₂ (CH ₂ ) ₄ CH (NH ₂ ) COOCH 3 SOCH; CH ₂ (CH ₂ ) ₃ CH (NH ₃ ) (C00CH ₃ ) SOCH; C (COOCH2) (SH) CH (CH2) ₂ SOCH; CH ('COOH) CH ₂ C ₆ H $ SOCH; CH (COOCH,) CH ₂ OH SOCH; CH (COOCH2) (OH) CHCH; SOCH; CH (COOC ₂ H _{I) 2} CH C ₆ H ₄ (4-OH)

-9EN 296162 B6

SOCHj CH (COOCH2) CH (CH3) ₂ SOCH; (CH ₂ ) ₄ COOH SOCH; (CH ₂ ) _with COOH SOCH; N (CH ₂ ) ₂ SOCH; P (O) (OCH2) ₂ SOCH; CH, CH _; S (O), CH; SOCH; NOj SOCH; NHCH, C ₆ H; SOCH; NHCH; CH = CH; SOCH; N’HCH, C = CH SOCH; CH; CH _; CH _; CH; SOCH; cyclohexylamine SOCH; CH _: CH (OH) CH; SOCH; 2-pyridyl SCH; 2-pyridyl S (O) Et 2-pyridyl S (O), Et 2-pyridyl

- 10GB 296162 B6

SEt 2-pyridyl SOCH ₃ 3-pyridyl SOCHj 4-pyridyl SO ₂ CH ₃ 2-pyridyl statues ₃ N - = \ --OF SOjCHj N - = \ --- L N SOCH ₃ zzr * N · —— 6 / - - OCH ^ statues ₃ N-s = \ - # - C (O) NH ?. SOCH3 - / - —C (O) NH? 7 /

-11 CZ 296162 B6

SOCHj 1 H-C (O) NH 2 statues ₃ --- (ζ N (CH 3) C (O) CH 3 SOCH, CHnOH X) SOCHj SOCHj N — N A> SOCH ₃ N- = sr \ AJ SOCHj ^CH 2 SCHj

- 12GB 296162 B6

S (O) Et ^ch ₂ -hQ S (O) ₂ Et SEt ^CH2 - 4 / X - f statues ₃ ^ch ₂ _hQ SOCH ₃ ^ch hQ SOCH, CH ·? ................. \ V-CH.OH IN# SOCHj --— OH SOCHj --- S (O) CH3

- 13 GB 296162 B6

SOCHj S (O 2 CH ₃ SCHj —0 γΊ] ^ Cl cr ηρ .N. X N 1LU CH3S COCI-b

If certain symbols are not specifically defined in the following description, they are understood to have the meaning As defined above.

Compounds of formula I are prepared by reaction of a compound of formula II

where

R ₃₄ is an oxygen atom with a suitable amine of formula III: R ₃₁ -NH ₂ . Compound 10 of formula I is obtained, wherein R ₃₃ is a free electron pair.

This reaction is essentially dehydration, which is preferably carried out in the presence of a solvent. The reaction temperature is between -78 to 200 ° C, preferably between -20 to 120 ° C. Dehydrating agents are suitable as catalysts. Suitable dehydrating agents include bases or acids, or molecular sieves.

The reaction can be carried out in many solvents, including organic aromatic solvents such as benzene, toluene, xylene; alcohols such as methanol, ethanol, isopropanol, ethyl

-14EN 296162 B6 lenglycol, propylene glycol; ethers such as tetrahydrofuran, ethyl ether, dimethoxyethane, diglyl, dioxane, crownethers; halogenated hydrocarbons such as methylene chloride, chloroform; amides such as dimethylformamide; ketones such as acetone, but the invention is not limited to these examples. The reaction may also be carried out in a solvent mixture. If possible, azeotropic water removal is also suitable.

Examples of catalysts for use in the above reaction are alkali metal hydroxides and trialkylamines, as well as inorganic and organic acids. Examples of the latter catalysts are hydrochloric acid and paratoluenesulfonic acid.

Compounds of formula II wherein R ₃₄ is an oxygen atom may be prepared from a compound of formula IV

(IV) by reaction with a Grignard reagent, including organomagnesium compounds of formula R ₃₁ -Mg-X, wherein X is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom. Most preferred is a chlorine atom. The reaction is carried out in a liquid solvent (such as an ether, a haloalkane, an aromatic solvent, an amide, or a mixture thereof) at a temperature between -70 to 150 ° C depending on the particular reactors and solvent.

The reactants of formula IV can be prepared according to the methods described in the prior art mentioned above.

Compounds of formula I wherein R ₃₃ is an oxygen or sulfur atom may be prepared from a compound of formula II by reaction with an amine of formula R ₃ i-NHOH or R ₃₁ -NHSH to give directly the corresponding compound of formula I wherein R ₃₃ is an oxygen atom or a sulfur atom. The reaction may be carried out in a liquid organic solvent at a temperature between -30 to 150 ° C.

Compounds of formula R ₃ -NHOH or R ₃₁ -NHSH are known or can be prepared by methods known to those skilled in the art.

The formation of iminium salts when R ₃₃ is an alkyl group or R ₃₃ and R ₃ together form a bivalent group can be achieved by reacting the ketone or thioketone with a secondary amine under conditions similar to those described above for the general procedure.

In many of the reactions described above, it is apparent that the selected substituents may sometimes interfere with the reactions. This undesirable phenomenon can be prevented by the use of suitable protecting groups, thereby preventing unwanted side reactions. It is also possible to use reagents which do not act on groups other than those on which the reactions are carried out. Selection of suitable protecting groups and reagents will be readily apparent to those skilled in the art.

-15GB 296162 B6

Using Chemical Abstracts and all available or computerized databases and the knowledge of those skilled in the art, it is possible to select a suitable method for carrying out the various processes described according to the present invention.

To further illustrate the present invention and its advantages, the following specific examples are set forth. It is to be noted that these examples are given for illustration only and in no way limit the scope of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Preparation of N-phenyl-5-amino-1- [2,6-dichloro-4-trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazol-3-yl) ethanimine [Compound No. 6]

A stirred mixture of 3-acetyl-5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] N-methylsulfinyl-1H-pyrazole (1.0 g, 2.5 mmol) / 2-toluenesulfonic acid of acid (47.5 mg, 0.25 mmol), aniline (232.5 mg, 2.5 mmol) and benzene (20 mL) was heated to reflux for 15 hours while removing water. The mixture was evaporated, chromatographed to give 360 mg of compound 6 (mp 179 ° C).

Example 2

Preparation of N- (2,4-dichlorophenyl) - [5-amino-1- (2,6-dichloro-N-trifluoromethyl) phenyl-4-methylsulfinyl-1H-pyrazol-3-yl] ethanimine (Compound No. 41)

A mixture of 3-acetyl-5-amino-1- [2,6-dichloro-N- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole (100 mg, 0.25 mmol), titanium tetrachloride (0.25 mL) , 0.25 mmol), 2,4-dichloroaniline (202 mg, 1.25 mmol), triethylamine (0.104 mL, 0.75 mmol) and methylene chloride (2 mL) were stirred at 20 ° C for 12 h. The mixture was purified by chromatography to give 80 mg, compound 41 (m.p. 83 ° C).

Example 3

Preparation of N- (methoxycarbonylamino) - [5-amino-1- (2,6-dichloro-4-trifluoromethyl) phenyl-4-methylsulfinyl-1H-pyrazol-3-yl] ethanimine (Compound No. 2)

A mixture of 3-acetyl-5-amino-1- [2,6-dichloro-N- (trifluoromethyl) phenyl] -4-methylsulfonyl-1H-pyrazole (1 g, 2.5 mmol), methoxycarbonylhydrazine (0.236) g (2.625 mmol) and methanol (10 mL) was stirred at 20 ° C for 2 days. The mixture was evaporated and then purified by chromatography to give 536 mg of Compound # 2 as a white powder (mp 121 ° C).

Example 4

Preparation of N-oxide of N-methyl- [5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazol-3-yl] ethanimine (Compound No. 4)

A mixture of 2.0 g (0.005 mol) of 3-acetyl-5-amino-1- [2,6-dichloro-N- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole, 0.83 g, (0, N-methylhydroxylamine hydrochloride (1 mol), pyridine (1.21 ml, 0.015 mol) and methanol (150 ml) were stirred at 20 ° C for 68 hours. The mixture is gradually evaporated,

Washed with dichloromethane and water, filtered, washed with hot acetonitrile, acetone, hot methanol and dried to give 0.79 g of compound of formula 4 (mp 228 ° C).

Example 5

Preparation of N - [[[1 - [[5-amino-1- [2,6-dichloro-N- (trifluoromethyl) phenyl] -4- (methylthio) -1H-pyrazol-3-yl]] ethylidene]] -4- (methylthio) -3- [1-phenylamino) ethyl] -1H-pyrazol-5-amine (Compound No. 22)

A stirred mixture of the product of Example 1 (2.5 g, 5.5 mmol) in methanol (25 mL) was treated with sodium borohydride (0.41 g, 11 mmol) at room temperature. The methanol was removed under reduced pressure and the residue was partitioned between dichloromethane and water. The organic layer was dried over sodium sulfate, filtered, evaporated and purified by column chromatography to give 77 mg of compound 22 (melting point 189 ° C).

The compounds listed in Table I below can usually be prepared using the modified methods described in the foregoing examples and modifications that will be apparent to those skilled in the art. If no melting point is given, the compound is characterized by mass spectroscopy.

- 17GB 296162 B6

Table I

The compounds listed in Table I have the general formula (E is a free electron pair)

Merge. R ₃ ; n Rn R.4 m.p. 1 NHj E 1 H CF; 212 2 NHC (O) OCH ₃ E 1 H cf ₃ 121 3 H E 1 H CF ₃ ί 180 4 CH, 0 1 H Cr ₃ | 228 5 NHC (O) NH, E 1 H CF ₃ 114 6 phenyl E 1 H CF, 179 7 CH.CHjOH E 1 H cf ₃ 93 8 CF_ AND Χλ CHjA COCHj E 0 H cf ₃ oil

-18GB 296162 B6

9 1 CH, 0 0 H CF, 196 10 CH, 0 2 H CF, 240 11 CH, 0 1 CH, CF, 155 12 4- (OCH3) C ₆ H ₄ E 1 H CF, olei 13 CH, 0 l H SF, oil 14 NHC (O) NHN = C (CH3) i E l H CF, 209 15 Dec NHC (O) NHNH ₂ E AND H CF, 197 16 3- (O) C _s H ₄ 1 ^E 1 H CF, 95 17 4-Cl ₆ H ₄ E 1 H CF, 165 18 3-BrC ₆ H ₄ E 1 H CF, 176 19 Dec 3-NO 3 C ₆ H ₄ E 1 H CF, 170 20 May 3-OH-4-OCH, -C ₄ H, | e l H CF, 120 21 NHC (S) NHN = C (CH, J, E AND | H CF, 200 22nd H ₃ c = CH, s _x E 0 H Cr, 189 X / 1 CFj 23 (3-OCH3) (5-OCH3) C _with H, E l H CF, 70 24 4-NO, C ₅ H ₄ E 1 H CF, oil 25 3-CNC _» H < E l H CF, 95 26 4-CNCjH, E l H CF, 13! 27 Mar: 3-SCH, C _and H ₄ E 1 H CF, 107 28 1 3,4-ClAH, X 1 H CF, 172 29 3,5-CLC _and Hj E 1 H CF, 172 30 4-FC ₄ H ₄ E AND H CF, 191

- 19GB 296162 B6

31 CHXOOCHj E l H CFj OIL 32 3-ClC ₄ H ₄ E 1 H cf ₃ 162 33 2-FC _& H < E AND H CFj 163 34 4-CF ₃ C ₄ H ₄ E l H CFj 156 35 CHjPh E 1 H CFj 188 36 3-FC ₆ H ₄ E 1 H CFj 175 37 4-CH 3 C _with H? E 1 H CFj 85 41 (2,4-CL) C ₆ H ₃ E 1 H CFj 183 42 (3-CH 2) C ₆ H ₄ E 1 H CFj 166 43 (2,4-F ₂ ) C ₆ H ₃ E 1 H CFj 179 44 (3.4-F,) C ₆ H ₃ E 1 H CF ₃ 186 45 (2-CH ₃ -4-F) C ₆ H ₃ E 1 H CFj ! oiej 46 CH ₃ - (2-tstrahydrofuran) E AND H CFj 90 47 CH ₃ - (2-furan) E 1 H CFj 88 48 CFLCH = CH E 1 and H CFj 134 49 (2-CH ₃ ) C ₆ H ₄ E 1 H CFj 72 50 C ₆ H ₅ E 2 H CFj 186 51 (2-Cl-4-S _(O) CH 3) C H _{3 e} E 2 H CFj 52 (2-Cl-4-Br) C ₆ H ₃ Έ 1 H CFj 175 53 (2-F-4-Br) C ₄ H ₃ E 1 H CFj 174 54 (2-Br-4-F) C ₆ H ₃ E 1 H CFj 187 55 (2-Cl-5-CF ₃₎ C ₆ Hj E AND H CFj 182 56 (2-F-4-C 1) C ₆ Hj E 1 H CFj I 183 57 (2-Cl-4-F) C ₆ H ₃ E 1 H CFj 184 58 (2-CFj-4-.Cl) C _e Hj E l H CFj 193 59 (2,4,6-F ₃ ) C ₄ H ₂ E 1 H CFj 186 60 (4-CF ₃ ) C ₆ H ₄ E 1 H CFj 75 61 (2,4-F, 6-Br), C _s H, E 1 H CFj 164 62 (3,5-F,) C ₆ H ₃ E AND H CFj 198

-20GB 296162 B6

63 1 (2,3-Dig _R 4-Cl) C ₆ H E 1 H CFj 178 65 _(3-CF-R 5 OCH _{3) 3} C ₄ H E 1 H CF ₃ I 96 66 _{(3-F-4-OCH3),} C _s Hj E 1 H CF ₃ 98 67 (2-Br-4-Cl) C ₅ H ₃ E 1 H cf ₃ 174 68 (3-Cl-4-Br) _C6 Hj E 1 H cf ₃ 132 69 (2,6-Cl-4-Br) C ₄ H ₂ E 1 | H CF ₃ 213 70 (3,5-C) ₂ -4-Br), C ₄ H ₂ E 1 H cf ₃ 137 71 CH ₂ - (4-Cl-C ₄ H ₄ ) E 1 H CFj 73 jCH ₃ (2.4-Cl-C ₄ H ₃ ) E 1 H cf ₃ 74 CH ₃ - (2-OC _; H ₅ -C ₄ H ₄ ) E AND H Cr, 75 CH 2 - (2-FC ₄ H ₄ ) E 1 H CF ₃ 76 | CH ₂ - (3-FC ₄ H ₄ ) E 1 H cf ₃ 77 1 CH ₂ (4-FC ₆ H ₄ ) E 1 H cf ₃ 78 CHj- _{(4-O-R e} C H <) E AND H cf ₃ 79 CH (CH ₃ ) -C ₄ H _S E 1 H CF, 80 CH ₂ - (2-CH ₃ -C ₆ H ₄ ) E 1 H CF; 81 CH _; - (3-CH ₃ -C ₄ H ₄ ) E 1 H CF. 82 CH, - (4-CH ₃ -C ₄ H ₄ ) E 1 H CF _} 83 CH ₂ - (2-CF ₃ -C ₄ H ₄ ) E 1 H cf ₃ 84 CH ₂ - (4-CF ₃ -C ₆ H ₄ ) E 1 H CFj 85 CH ₂ - (3-CF ₃ -C ₄ H ₄ ) E 1 H CFj 86 (4-Br) H c _{T 4} E 1 H CF3 87 (2,4-dínicro-6-Br) C _{t H:} E 1 CFj 1 88 (4-NHC (O) CH ₃ ) C ₆ H ₄ E 1 H CFj 89 (2-C 1-4 -S (O) ₂ CH ₃ ) C ₆ Hj E 1 H CFj 155 90 (2-NO ₂ -4-OCH ₃ ) C ₆ H ₃ E l H CFj 131 91 (3-CH ₃ -4-Cl) C ₄ Hj E 1 H CFj 189 92 cyclopropyl E 1 H CFj 207 93 (2.5-Cl) C ₄ H ₃ E 1 H CFj 172

-21 GB 296162 B6

94 (2,4-CH ₃ -6-NO ₃ ) C _with H ₃ E l H cf ₃ 185 95 (3-Cl-4-CN) C ₆ H ₃ E 1 H cf ₃ 96 (4-OCH ₃ ) C ₆ H ₄ E 2 H cf ₃ 80 97 (3-OH-4-OCH ₃ ) C ₆ H ₃ E 2 H cf ₃ 102 98 (2-SCH ₃ ) C ₄ H ₄ E 1 H cf ₃ 191 99 (3-NO 3) C _with H ₄ E 2 H cf ₃ 195 100 ALIGN! (2-Br-4-CF ₃ -6-NO ₃ ) C ₆ H E and H cf ₃ 115 101 (2-NO, -4-CH ₃ ) C ₆ H ₃ E 1 and H cf ₃ 145 102 (4-Cl) C ₄ H ₄ E H cf ₃ 191 103 (3-CF ₃ -5-OCH ₃ ) C ₆ H ₃ E 1 H cf ₃ 104 (3,4-CyCl 3 H 3) ,E 2 H cf ₃ 188 105 - E AND H cf ₃ 106 ~ 0 E 1 H CF; 107 E 1 H cf ₃ 108 N-ssr \ E 1 H cf ₃

-22 GB 296162 B6

109 E 1 H CFj 110 E 1 H cf ₃ 111 Cl E 1 H cf ₃ 112 NC H $ hr H E 1 H cf ₃ 113 __ ^ CN \ _CN E 1 H CFj 115 / = \ AF E 1 H cf ₅

-23GB 296162 B6

ΓΪΪΤ XD Γ and 1 H cf ₃ 117 3-OCH 3 -5-CF ₃ -C ₆ H ₃ E 1 H CF ₃ 118 3-C1-5-C1-C _with H ₃ ' E 1 H cf ₃ 188 119 4-C ₆ H ₅ OC _with H ₅ E 2 H cf ₃ 196 120 4-C ₆ H ₄ NHC · H ₄ E 2 H cf ₃ 85 121 3-C (O) NH ₂ -C ₆ H 4 E 1 H CFj 122 OCH3 E 1 H cf ₃ 123 / ^ • N E 1 H cf ₃ 124 s ^{J /} E 1 H cf ₃ 125 O E 1 H cf ₃ ΓΪ26 i ΐ and 1 - / Λ \ = ζΖ E 1 H cf ₃ j 127 CH ₂ CH ₂ C (O) OCH ₃ E 1 H cf ₃ 69 CH ₂ C = CH E 1 H cf ₃ 127 129 cTch ₂ ) ₅ ch ₃ E 1 H cf ₃ 114 130 No (CH ₂ ) ₄ CH ₃ E 1 H cf ₃ 132 131 θ'Tch ₂ ) ₃ ch ₃ '' E 1 H cf ₃ 131 132 CH _{(CH3) 2} E 1 H cf ₃ 194 133 ch ₂ ch ₂ ch ₃ E 1 H cf ₃ 129 AND 134 (cW) 7h ₃ E 1 H cf ₃ 108 135 (CH ₂ ) ₇ CH ₃ E 1 H cf ₃ 124 136 ~ (CH ₂ ) ₈ CH ₃ E 1 H cf ₃ 125 137 (CH ₂ ) ₉ CH ₃ E 1 H cf ₃ 83 138 (CH ₂ h _and CH ₃ E 1 H cf ₃

-24GB 296162 B6

139 (CH ₂ ) 17 CH ₃ E 1 H cf ₃ 64 140 ε and H cf ₃ 141 (ch ₂ ) ₁₃ ch ₃ E 1 H cf ₃ 142 (CH _{2) 3 0} CH E 1 H cf ₃ 143 CH ₂ CH (CH ₃ ) 2 E 1 H cf ₃ 144 ch ₂ ch ₂ ch CchTG E 1 H cf ₃ 138 145 CH ₂ CH (CH ₃ ) CH ₂ CH ₃ E 1 H cf ₃ 150 146 CH _(CH3) -O-CH _{(CH3) 2} ~~ E 1 H cf ₃ 178 147 (CH ₂ ) ₁₂ CH ₃ E 1 H cf ₃ 14 8 (CHJ15CH3 E 2 1 H cf ₃ 56

The following non-limiting examples illustrate the use of the compounds of the present invention for pest control.

The following species were tested:

Genus, species______________

Aphis gossypii

Musea domestica

Diabrotica virgifera Periplaneta americana Schodaphis graminum Ctenocephalides felis Rhipicephalus sanguineus

Common name aphid cotton fly domestic american cockroach

Soil watering 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 after 5 days under treatment. The number of aphids on the treated plants was compared with the number of aphids on the untreated plants. The systemic activity of the compounds of the present invention (active ingredient transfer) is evident from this assay.

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 the 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.

-25GB 296162 B6

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 kept 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 no activity.

Compound number Systemic activity on the scoops Systemic activity on Schizaphis graminům Activity on house flies on contact Activity on aphids on leaves 1 + X X X 2 - - X - 3 X X NT NT 4 X X X X 5 - - X X 6 X X NT X 7 + X X X 8 - X - 9 T X X - 10 - X X - 11 - X X 12 X X X X 13 X X - 14 - X X - 15 Dec - X + - 16 X X X +

-26GB 296-62 B6

Compound ČÍ31O Systemic activity on the scoops Systemic activity on Schizaphis graminum Activity on house fly flies on contact Activity on aphids on leaves 17 X X X X 18 + X X X 19 Dec X X X - 20 May X X X X 21 -r 4- X - 22nd - - + X 23 X X X X 24 X X NT NT 25 X X X X 26 4- X X X 27 Mar: • ř X X X 28 4- X X - 29 X X - 30 Τ ' X X - 31 Ř X X X 32 X X X -

-27GB 296162 B6

Compound Number Systemic activity on aphids Systemic activity on Schizaphis graminům [Activity on house flies on contact Activity on aphids on leaves 33 -r X X X 34 X X X 35 X X X X 36 X X X - 37 •F X X X 41 - - X + 42 X X X 43 -r X X - 44 X X X - 45 -r X X Ť · 46 X X X X 47 X X X X 48 X X X X 49 X X X X 50 + X X X 51 X X X -

-28GB 296162 B6

Compound number System aphid activity 1 Systemic activity on Schizaphis graminum Activity on house flies on contact Activity on aphids on leaves I 52 + X X X 53 -L X X X 54 4 · X X - 55 - X X - 56 + X X X 57 - X X X 58 - X X - 59 -r X X - 60 X X X X 61 - X X - 62 - X X X 63 X X - X 65 X X X X 66 X X X X 67 l · X X 68 X X X X

-29GB 296162 B6

Compound number Systemic activity on aphids Systemic activity on Schizaphis graminum Activity on house flies on contact Activity on aphids on press those 69 - X - - 70 X X X X · 71 -r X X X 74 -r X X X 75 X X X X 76 + X X X 77 X X X X 78 X X X X 79 X X X X 80 X X X X 81 X X X X 82 -r X X X 83 + X X X 84 X X X X 85 X X X X 86 - - X

-30GB 296162 B6

Compound number Systemic activity on aphids Systemic activity on Schizaphis gramínum Activity on house flies on contact Activity on aphids on sheets AND F 87 NT NT - - 88 NT NT X X 89 NT NT X + 90 -r • 4 * X - 91 -4- X X - 92 + · X X X 93 NT NT * - 94 NT NT X - 95 - X NT NT 96 Γ X X NT 97 * r X X NT 98 • t * X X - 99 -r -r X 100 ALIGN! NT NT X - 101 - 4 " X - 102 X X X

-31 GB 296162 B6

Compound number Systemic activity on the scoops Systemic activity on Schizaphis gramines Activity on house flies on contact 'Ativxtá on aphids on sheets 103 NT NT - X 104 X X X NT 105 X X X - 106 NT NT X X 107 NT NT X - 108 NT NT X X 109 NT NT X NT 110 X X X lil - + - 112 NT NT X 113 - X - - 115 -r X X X 116 - X X X 117 - - 118 X X X 119 X X X X 120 4- X X - 121 X X X + 122 X X X

-32GB 296162 B6

Compound number Systemic activity on aphids Systemic activity on Schizaphis graminum Activity on house flies on contact Activity on aphids on leaves 123 X X X - 124 X X - 125 X X X 126 X X X - 127 X 128 X X X - 129 X X - 130 X X - 131 X X - 132 X X 133 X X - 134 - X X - 135 X - X - 136 X X X 137 X X X Ϊ38 X X X - 139 + X X - 140 X X X - 141 X X X 142 X X - 143 X X - 144 X X - - 145 X X X 4- 146 4 ™ X X X 147 X X I -

-33 GB 296162 B6

Compound number Systemic activity on aphids Sys activity of Schlzaphis graain® Activity on house flies on contact Activity on aphids on leaves 148 X X 4- -

The present invention provides a method for controlling pests in an area comprising administering to the area a pesticidally effective amount of a compound of Formula I, or a pesticidally acceptable salt thereof, or a composition comprising it as an active ingredient. The method is particularly suitable for the systematic control of arthropods in the area, in particular some insect or aphid species which feed on above-ground plant parts. The control of these leaf pests can be carried out either by direct application to the leaves or by application, for example, by soil spraying or application of granules to plant roots or plant seeds, followed by systemic transfer to above-ground plant parts. 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 (drilling-absorbent), the order of the Hemiptera (drilling-absorbing), and the order of 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 cattle operations 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.

Accordingly, the present invention provides a method for controlling pests in an area comprising treating the area (for example by deposition 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.

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

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

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

-34EN 296162 B6 • In the protection of stock products, such as cereals, including grain or flies, peanuts, 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, dressing or mite piers, for example, Ephestia species, Anthrenus species, Carpet beetles, Flour beetles, Sitophilus species, or Acarus species.

• 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 Heliohis zea. Against adult and larvae of Coleptera (beetles) of, for example, Anthonomus, for example grands, Leptinotarsa decemlineata, Diabrotica species. Against Heteroptera (Hemiptera and Homoptera), for example Psylla species, Bemisia species, Trá / eMrodes.druh 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 such as Gryllus and Acheta species such as Blatta orientalis, Periplaneta americana, Blatella germanica, Locusta Migratoria migratorioides and Schistocerca gregaria. Against Collembola, for example, the species Periplaneta and the species Blattela. Against Isoptera, for example, the species Coptermes (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 the field of veterinary medicine or in the operation of livestock or in maintaining public health, against arthropods, worms or protozoa which 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, such as Acarina, including ticks (e.g., Ixodes, Boophilus, e.g., Boophilus microplus, Rhipicephalus, e.g., Rhipicephalus appendiculatus, Ornithodorus, e.g., Rhipicephalus appendiculatus, Ornithodorus, e.g., Ornithodorus moubata, and Rozto , for example, Aedes, Anopheles, Musea, Hypoderma), Hemiptera, Distioptera (for example, Periplaneta, Blatella), Hymenoptera, for example, gastrointestinal infections caused by helminthic parasites, n in the control and treatment of protozoal diseases caused, for example, by Eineria 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 method, 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 controlled pest, can provide answers

Giving less 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 in 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 kg of active ingredient / ha, preferably 25 to 200 mg of active ingredient / ha. Application can be carried out, if 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 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 using drag 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 pest control method therewith are particularly valuable in the protection of field crops, forage, plantation fruits, greenhouses, orchards or vineyards, ornamental trees 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 fruit or citrus), ornamental plants, flowers or vegetables, or shrubs in greenhouses or in gardens or parks or forest trees (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 species such as hides, fur, wool or feathers in natural or processed form (such as carpets or textiles) against attack by moths or beetles, as well as stored meat, fish or grains against attack by beetles, moths or flies.

Furthermore, the compounds of the present invention and methods of their use are particularly suitable for controlling arthropods, nematodes or protozoa which are harmful or spread or act as carriers of a diseased domestic animal, such as those listed above, and are particularly useful in 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 who live in or on the skin or suck blood to animals and can be administered orally, parenterally, through the skin or topically for this purpose.

Furthermore, the compounds of the present invention are useful against coccidiosis, a disease caused by infection of Eimeria-like anti-parasites. This infection can cause significant economic losses in domestic animals and birds, especially those that are kept 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 reduces the risk of coccidiosis. The compounds are effective against both the cecal form and the intestinal form. Furthermore, the compounds of the present invention can also inhibit 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 the passage of blood

-36GB 296162 B6 for excrement, weakness and indigestion. 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 seed, 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; single bait, licking salt, dietary supplements, irrigation, spraying, bathing, soaking, 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;

• administering pet food to control fly larvae in their feces.

In practice, the compounds of the present invention most often form part of the compositions. 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 against the 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 can be prepared by any method known in the art, form part of the present invention.

These compositions may also contain other kinds of additives such as colloidal preservatives, adhesives, thickeners, thixotropic substances, penetration enhancers, spray oils (especially for acaricidal use), stabilizers, preservatives (especially against mold), sequestering agents and the like, and the like; 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, in particular depending on the nature of the pest to be eliminated or the degree of attack, for example, by the harvest of these pests. In general, the compositions of the present invention will generally contain from 0.05 to 95% by weight of one or more of the active compounds of Formula I or pesticides thereof

3796162 B6 acceptable salts, 1 to 95% of one or more solid or liquid carriers, and optionally 0.1 to 50% of one or more other compatible ingredients 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).

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 Frenchized 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 acetone, 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, especially trichloroethane, or methylene chloride; aromatic chlorinated hydrocarbons, in particular chlorobenzenes; water-soluble and strongly polar solvents such as dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone; liquefied 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 may be used to control arthropods, plant nematodes, worms or protozoal pests, may also contain synergists (e.g., piperonyl butoxide or sesamex), stabilizers, other

-38EN 296162 B6 insecticides, acaricides, plant nematocides, antihelmicides or anticoccidial agents, fungicides (agricultural or veterinary as appropriate, such as benomyl and iprodione), bactericides, arthropodal or vertebral attractants or repellents or phenomones, deodorants, flavoring agents, coloring agents, colorants , such as trace elements. These substances may increase efficacy, stability, safety, if appropriate absorption, spectrum of controlled pests, or impart to the compositions other suitable functions in the same animals or in the treated area.

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

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

Solid forms of compositions which can be used are powders for dusting (containing up to 80% of a compound of formula I or a pesticidally acceptable salt thereof), wettable powders or granules (including water-dispersible granules), in particular obtained by extrusion, compression impregnation granule carrier or powder granulation (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 the dropwise dosing or occasional dosing of the water-dispersible concentrates described in the present invention.

Liquid compositions, for example, include aqueous and non-aqueous solutions or suspensions (such as emulsifiable concentrates, emulsions, flowables, dispersions, or solutions) or aerosols. Liquid formulations also include, in particular, emulsifiable concentrates, dispersions, emulsions, flowable formulations, aerosols, wettable powders (or sprayable powders), dry flowable formulations or pastes as formulations for formulations that are liquid or intended for the preparation of liquid formulations 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 can be in the form of water in oil or oil in water and can have a thick consistency.

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

-39GB 296162 B6

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. The irrigation may be sprinkler irrigation, or it may be ground irrigation or underground irrigation for earth and systemic pests.

Concentrated suspensions, which can be applied by spraying, are prepared to form a stable liquid product which does not settle (finely divided) and usually contains 10 to 75% by weight of active ingredient, 0.5 to 30% of surfactant, 1 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, dyes 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 a wet process (by mixing the finely divided active ingredient with an inert filler and a small amount of water, e.g. 1 to 20% by weight, or with an aqueous solution 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 a pesticidally acceptable salt thereof together with other parasitic 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. Feed containing

The therapeutic agent typically comprises from about 0.001% to about 3% by weight of one or more compounds of Formula (I) 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.

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 from 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 vertebrate 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, helminths or protozoal pests. 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:

Trade name Chemical description

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

CZ 296162 B6

Example 2A

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

Active ingredient Ethylan BCP N-methylpyrrolidone 7% 10% 83%

To the solution of ethylene BCP 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.

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 Arylan 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%

CZ 296162 B6

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 Solvesso 150 30.0% 10.0% 0.5% 59.5%

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

Example 2F

Water dispersible granules are prepared from the following ingredients:

Active ingredient Darvan No. 2 Arylan S Celite PF 30% 15% 8% 47%

The ingredients are mixed, micronized in a fluid mill and then granulated in a rotary granule preparation machine by spraying with 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 Very fine talc powder 1 to 10% 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, in landfills, for stored products, or for household consumer goods, or for animals infested or endangered by arthropod infections 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 prepared as appropriate for the edible bait. The edible bait may be distributed to an area, for example, a home or industrial enterprise, such as a kitchen, a hospital or a warehouse, or an arthropod infested area such as ants, grasshoppers, cockroaches or flies, to achieve oral control.

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 administered via a skin drip to an arthropod-infected pet or, after sterilization by filtration through a polytetrafluoroethylene membrane (0.22 µm pore size), as a parenteral injection, in an amount of 1.2-12 ml of solution per 100 kg animal weight.

Example 2J

A wettable powder is prepared from the following ingredients:

Active ingredient 50% Ethylene 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 0.01% to 2% by weight of the active compound and applied to the arthropod infested area, double-winged larvae or plant nematodes, by spraying, or domestic animals infested 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:

-44GB 296162 B6

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 can 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, nematodes 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

Water dispersible granules having the following composition:

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

The ingredients are mixed as a 45% suspension 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 (10)

PATENT CLAIMS 1-Aryl-3-iminopyrazole of general formula I (I): wherein R31 is: a hydrogen atom; cyano; nitro; NO group; SH; (C 1 -C 6) alkylthio; amino; P (O) (OR 3 / OR 8) or R ₃₈ ; or monoalkylamino having 1 to 6 carbon atoms; a dialkylamino group containing 1 to 6 carbon atoms in each alkyl moiety; a formyl group; C 1 -C 20 alkyl; (C 3 -C 6) cycloalkyl; or a (C 4 -C 8) cycloalkylalkyl group; each alkyl or cycloalkyl group is optionally substituted with one or more R ₃₅ groups; or a naphthyl or phenyl group, each of which is optionally substituted with one or more R ₃₆ or R ₃₇ groups; or NH-CO-NH-N = CR ₈ R _9; NH-CS-NH-N = CR ₈ R _9; NH-CO-NR ₈ R _9; NH-CS-NR ₈ R _9; NH-CO-OR _S ; _NH-CS-OR8; or NHCO-NH-NH _2; R ₃₂ is C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkyl, wherein each alkyl group may be substituted with one or more R ₃₅ groups; phenyl optionally substituted with one or more R ₃₆ or R ₃₇ ; or R ₃₈ ; R ₃₃ is a free electron pair or an oxygen atom or a sulfur atom, when R ₃₃ is an oxygen atom or a sulfur atom, it can be attached to the nitrogen atom by a covalent bond or a bond which can be partially covalent and partially ionic or carbon atoms, the nitrogen atom to which R ₃₃ is attached is then in the form of an N ⁺ cation; when R ₃₃ is therefore an alkyl group, the bond between the nitrogen atom and R ₃₃ is a single bond; and the compound of Formula I is then an iminium salt; or R ₃ and R ₃₃ together form an alkylene group having 2 to 6 carbon atoms, wherein one or two carbon atoms are optionally replaced by a heteroatom selected from the group consisting of oxygen, sulfur or atom Nitrogen, the specificity of N, and the bond between N and R ₃₃ is then as described when R ₃₃ is an alkyl group; R ₃₅ is halogen, amino, (C 1 -C 6) alkylamino, (C 1 -C 6) dialkylamino, nitro, cyano, (C 1 -C 6) alkoxy, (C 1 -C 6) alkoxycarbonyl carbon, hydroxycarbonyl, alkylcarbonyl of 1-6 carbon atoms, methylene, methylidine, C1-6 alkynyl, C1-6 alkylalkynyl and 1-6 alkynyl carbon atoms; or R ₃₅ may be a phenyl group optionally substituted with one or more R ₃₆ groups; or R ₃ 5 may be a heterocyclic ring having a total of 3-7 ring atoms, of which from 1 to 4 heteroatoms latter heteroatoms being identical or different and are selected from the group consisting of oxygen, sulfur and nitrogen, said heterocyclic ring is saturated or unsaturated and is optionally substituted with one or more R ₃₆ groups; or R ₃₅ can be hydroxyl, SH, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfonyl, aminocarbonyl, C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 dialkylaminocarbonyl 1 to 6 carbon atoms, an alkoxycarbonyl group containing 1 to 6 carbon atoms in each alkoxy moiety, or P (O) (OR ₈ ) (OR ₉ ); R ₃₆ can be SF ₅ , halogen, C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, nitro, cyano, amino, C 1 -C 6 alkylamino, C 1 -C 1 dialkylamino up to 6 carbon atoms, dialkylaminocarbonylamino having 1 to 6 carbon atoms in each alkyl moiety, alkylaminocarbonylamino having 1 to 6 carbon atoms in the alkyl moiety, aminocarbonylamino, alkylcarbonyl having 1 to 6 carbon atoms in the alkyl moiety, and alkoxycarbonyl having 1 to 6 alkoxy moieties 6 carbon atoms, alkylcarbonylamino group having 1 to 6 carbon atoms in the alkyl moiety, alkoxycarbonylamino group having 1 to 6 carbon atoms in the alkoxy moiety, aminocarbonyl, dialkylaminocarbonyl having 1 in each alkyl moiety (C 1 -C 6) alkylaminocarbonyl, (C 1 -C 6) alkylaminocarbonyl, hydroxycarbonyl, (C 1 -C 6) alkylaminocarbonyloxy, (C 1 -C 6) alkylaminocarbonyloxy, hydroxy group, (C 1 -C 6) alkoxy, (C 1 -C 6) haloalkyl, (C 1 -C 6) haloalkoxy, (C 1 -C 6) alkylthio, (C 1 -C 6) alkylsulfinyl, (C 1 -C 6) alkylsulfonyl , halogenoalkylthio having 1 to 6 carbon atoms, a haloalkylsulfinyl group having 1 to 6 carbon atoms, P (O) (oR ₈₎ (oR _9), alkyl (alkylcarbonyl) amino in which each alkyl part of 1-6 carbon atoms or fenylaminoalkyl C 1 -C 6 alkyl; ₃ R 7 may be R ₃₆ or phenyl optionally substituted with one or more R _36, phenoxy optionally substituted with one or more R ₃₆ or a benzyl group optionally substituted by one or more R _36, R ₃₈ may be a heterocyclic radical derived from a single heterocyclic ring or from a two-ring fused heterocyclic system whose at least one ring is heterocyclic, each ring containing 3 to 7 ring members, each heterocyclic ring containing 1 to 4 ring heteroatoms, said heteroatoms may be the same or are different and are selected from the group consisting of oxygen, sulfur and nitrogen, each ring being saturated or unsaturated; such a heterocyclic radical may, for example, be a residue of the following compounds: pyridine, pyrimidine, oxazole, oxadiazole, oxatriazole, isoxazole, thiazole, isothiazole, imidazole, pyran, pyrone, pyrazole, pyrrole, tetrazole, furoxane, tetrahydrofuranyl, furan , pyrazine, pyridazine, benzimidazole, quinoline, isoquinoline, triazine, thiophene, furopyran, furopyrone, thiatriazm, thiadiazole wherein all these heterocyclic radicals can be attached to the nitrogen atom of the group R ₃₂ -C = NR ₃ even at any possible position of the heterocyclic ring and all the rings may be optionally substituted with one or more R ₃₆ groups or a phenyl group optionally substituted with one or more R ₃₆ groups, R ₈ and R 8 are independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl optionally containing one or more substituents selected from the group consisting of halogen, nitro, cyano, CHO, hydroxyl, (C 1 -C 6) alkoxy, (C 1 -C 6) alkylthio, (C 1 -C 6) alkylsulfinyl, (C 1 -C 6) alkylsulfonyl, (C 1 -C 6) alkoxycarbonyl, acarbamoyl hydroxycarbonyl group; R ₄ is R 11 or S (O) _n R 11; R 11 is C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 4 -C 8 cycloalkylalkyl, each of which is optionally substituted with one or more halogen atoms; n is 0, 1 or 2; R ₅ is hydrogen, halogen, cyano, S (O) _n R ₈ , OR ₈ , NR ₈ R ₉ , N (R ₈ ) CON (R ₉ ) (R ₈ ), azido or - N = C (R ₁₀ ) (OR ₉ ); R _lo may have the same meaning as _R8 and may be also benzyl or phenyl optionally substituted with one or more R _36; Z is nitrogen or C-R _6; and R12 to _R16 may be hydrogen, halogen, R _8, a group _{OR8, SF5,} S (O) _n R _8, cyano, nitro, CHO, C (O) _R or COOR ₈ ; and pesticidally acceptable salts thereof. 1-Aryl-3-iminopyrazole according to claim 1 of the general formula I, which has one or more of the following properties: Z is CR ₁₆ ; R 12 is chlorine or bromine; R 11 and R 15 are hydrogen; R ₁₄ is perhaloalkyl, perhaloalkoxy or SF ₅ , preferably CF ₃ , OCF ₃ or SF ₅ ; R ₁₆ is chlorine or bromine; And R ₃ is amino; an alkyl group optionally substituted with one or more R ₃₅ groups; phenyl optionally substituted with R ₃₆ or R ₃₇ ; R ₃₈ ; NH-48 group 296162 B6 CO-NH-N = CR ₈ R _9; NH-CS-NH-N = CR ₈ R _9; NH-CO-NR ₈ R _9; NH-CS-NR ₈ R _{9; NH-CO-OR8;} or NH-CS-OR ₈ ; R ₃₂ is C 1 -C 6 alkyl, preferably methyl; R ₃₃ is a free electron pair or oxygen atom, preferably a free electron pair; R 4 is S (O) _n R 11; R 11 is methyl or ethyl; n is 0 or 1, preferably 1; or R ₅ is _{NR, with} R _9; preferably amino or NHR _9th 1-Aryl-3-iminopyrazole according to any one of claims 1 or 2, of the general formula I, wherein R ₃₂ is C 1 -C 6 alkyl; Z is C-R _6; R 4 is S (O) _n R 11; R 13 and R 15 are hydrogen; and R _I4 is perhaloalkyl, perhaloalkoxy or SF group _5th The 1-aryl-3-iminopyrazole of any one of claims 1 to 3, wherein: R ₃₂ is methyl; R4 is S (O) _n R _n; and R 11 is methyl or ethyl. 5. A compound according to any one of claims 1 to 4, wherein: R 14 is CF ₃ , OCF ₃ or SF ₅ ; and R ₁₂ and R ₁₆ are chlorine or bromine. A pesticidal composition comprising 1-aryl-3-iminopyrazole of the formula I according to any one of claims 1 to 5 or a pesticidally acceptable salt thereof and a pesticidally acceptable carrier. 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 a pesticidally effective amount of 1-aryl-3-iminopyrazole of formula I, or a pesticidally acceptable salt thereof, as defined in any one of claims 1 to 5, or the composition of claim 6. The method of claim 7, wherein the area is an area that is or will be used for growing crops. -49GB 296162 B6 A process for the preparation of 1-aryl-3-iminopyrazole of general formula I according to claim 1, wherein R ₃₃ is a free electron pair, characterized in that the compound of general formula II (II) / wherein R ₃₄ is an oxygen atom and other structural variables in the formula as defined in claim 1, react with an amine of formula III R ₃ ] -NH ₂ (III), wherein R ₃ is as defined in claim 1. A process for the preparation of 1-aryl-3-iminopyrazole of general formula I according to claim 1, wherein R ₃₃ is an oxygen atom or a sulfur atom, characterized in that the compound of general formula II (II) / wherein R ₃₄ is an oxygen atom and the other structural variables in the formula are as defined in claim 1, reacted with an amine of formula R ₃₁ -NHOH or R ₃ i-NHSH, wherein R ₃ i is as defined in claim 1.