SK284351B6 - 1-Arylpyrazoles and their salts, pesticide agents including these compounds as active agents, a method of their preparation and a method of the regulation of pests - Google Patents

Abstract

1-Arylpyrazole-3-thiocarboxamide derivatives of general formula (I), pesticide agents including these compounds, a method of their preparation and a method of their use as the insecticides.

Description

Technical field

The present invention relates to novel 3-thiocarboxamide derivatives of 1-arylpyrazoles and derivatives thereof. The invention further relates to compositions of these compounds and methods of using these compounds for controlling arthropod pests, in particular the application of these compounds or compositions in agricultural uses, in particular as pesticides for controlling arthrododes, particularly insects, by systemic action.

BACKGROUND OF THE INVENTION

The control of insects, nematodes or nematodes using 1-arylpyrazoles is already described in International Patent Publication Nos. WO 93/06089 (and equivalent US Patent No. 5,451,598) WO 94/21606 and WO 87/03781, as well as European Patent Publication Nos. 295 117,659 745, 679 650, 201 852 and 412 849, in German patent no. DE 19511269 and U.S. Pat. 5,232,940.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides novel pesticidal compounds of class 1-arylpyrazoles and processes for their preparation.

The invention further provides pesticidal compositions and methods of using these pesticidal pyrazoles against arthropods, especially insects, particularly in agricultural or horticultural crops, in forestry, veterinary medicine or in livestock, or in health and public hygiene.

Further, the present invention provides highly potent compounds with a broad spectrum of pesticidal activity, as well as compounds with selective activity, for example against aphids, mites, leaf insects, soil insects, systemic activity, antifungal or pesticidal activity in seed treatment.

The invention furthermore relates to compounds with substantially increased and faster activity, especially against insects and in particular against larval insects.

Further, the invention relates to compounds with greatly improved (faster and greater) penetration into insect species upon topical application and thus with increased penetration of the compounds into the sites of action of the pests.

This is apparent from the following description of the present invention, both in its entirety and in part.

The present invention provides insecticidal 1-arylpyrazoles of formula (I)

where

R ¹ is a hydrogen atom or a halogen atom, each R ² and R ⁴ which are the same or different, are a hydrogen atom, a halogen atom or an alkyl group,

R ³ is halogen, haloalkyl, haloalkoxy or R ¹⁰ S (O) _m , preferably R ³ is halogen, haloalkyl, haloalkoxy,

R ⁵ is an alkyl, haloalkyl, alkenyl, and alkynyl or cycloalkyl ring of 3 to 5 carbon atoms, preferably R ^{5 is an} alkyl group,

Z is hydrogen, halogen, alkyl, formyl, -C (O) -alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylidenamino, 1H-pyrrol-1-yl or 1H- pyrazol-1-yl, or preferably Z is amino, R ⁶ NH- or R ⁷ R ⁸ N-, each R ⁶ , R ⁷ and R ⁸ , which are the same or different, are alkyl-S (O) _p -, formyl, C 3 -C 6 alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl, or alkyl, C 3 -C 6 alkenyl, or -C (O) alkyl, wherein alkyl and alkenyl the moieties are optionally substituted with one or more R ⁹ , or R ⁷ and R ⁸ are joined to form a divalent radical having 4 to 6 carbon atoms in the chain, the divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably form a morpholine, pyrrolidine, piperidine or piperazine ring, R ⁹ is cyano, nitro, alkoxy, haloalkoxy, R ¹⁰ S (O) _q -, -C (O) alkyl, alkoxycarbonyl, alkylaminocarbonyl, aminocarbinocarbonyl , dialkylaminocarbonyl, COOH, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl,

R ¹⁰ is lower alkyl or lower haloalkyl, m, n, p and p are 0, 1 or 2,

M is C-halogen, C-CH ₃ , C-CH ₂ F, C-CH ₂ Cl, C-NO ₂ or N, and their pesticidally active salts.

By "pesticidally active salts" are meant salts with anions and cations that are known and acceptable in the art for preparing pesticidally acceptable salts. Preferably, these salts are water-soluble. Suitable salts with acids formed from compounds of formula (I) that contain an amine group are salts with inorganic acids, for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids, for example acetates. Suitable salts with bases formed from compounds of formula (I) which contain a carboxyl group are alkali metal salts (e.g., sodium or potassium salts), ammonium salts and salts with organic amines (e.g., diethanolamine or morpholine).

Unless otherwise indicated, alkyl, alkoxy and alkylthio groups have from 1 to 6 (preferably up to 4) carbon atoms. Alkenyl and alkynyl groups have from 2 to 6 (preferably 2 to 4) carbon atoms. The description uses certain words with a specific meaning:

The term "aminocarbonyl" means a carbamoyl radical, a tallow group of the formula -C (O) NH ₂ . Similarly, the term "alkylaminocarbonyl" means an alkylcarbamoyl radical, i.e. a radical of formula -C (O) -NH-alkyl and the term "dialkylaminocarbonyl" means a dialkylcarbamoyl radical, a radical of formula -C (O) -N (alkyl) ₂ , wherein the alkyl moieties they may be the same or different. The term "aminosulfonyl" means a sulfamoyl radical, i.e. a group of the formula -SO ₂ NH ₂ . Similarly, the term "alkylaminosulfonyl" means an alkylsulfamoyl radical which is a group of the formula -SO ₂ -NH-alkyl, while the term "dialkylaminosulfonyl" means a dialkylsulfamoyl radical having the formula -SO ₂ N (alkyl) ₂ , wherein the alkyl moieties may be the same or different.

The term "halogen" before the residue name means that the residue is partially or fully halogenated, that is, it is substituted with fluorine, chlorine, bromine or iodine in any combination, preferably fluorine or chlorine. The term "halogen" refers to fluorine, chlorine, bromine or iodine. Where the name of any substituent is repeated, it has the same meaning unless otherwise indicated. The term "aroyl" means a carbonyl aromatic moiety, i.e. aryl-C (O) -, which is preferably benzoyl, optionally substituted with one or more alkyl groups or halogen atoms.

Particularly preferred are compounds of formula (I) wherein:

R ¹ is fluoro, chloro, bromo or hydrogen,

R ² and R ⁴ are hydrogen,

R ³ is -CF ₃ , -OCF ₃ , -CHF ₂ , -S (O) _m CF ₃ , -CFC ₁₂ , -CF ₂ Cl, -OCF ₂ Cl, -OCFC ₁₂ , chloro, bromo or fluoro,

R ⁵ is methyl or ethyl,

Z is hydrogen, halogen (fluoro, chloro, bromo), (C 1 -C 3) alkyl, (C 1 -C 3) haloalkyl, (C 2 -C 3) alkenyl or amino, -NHR ⁶ or NR ⁷ R ⁸ , wherein each R ⁶ , R ⁷ and R ⁸ , which may be the same or different, is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 3 carbon atoms, or a -C (O) alkyl group wherein alkyl and alkenyl moieties are unsubstituted or substituted by cyano, alkoxy, alkyl-S (O) _p , nitro, alkoxycarbonyl, -C (O) alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -COOH, hydroxy or an atom halogen (fluorine, chlorine, bromine); and

M is CCl, CF, CBr or N.

Another particularly preferred group of compounds are those wherein:

R ¹ is chlorine or bromine,

R ² and R ⁴ are hydrogen,

R ³ is -CF ₃ , -OCF _3, or chloro,

R ⁵ is methyl or ethyl,

Z is hydrogen, halogen (fluoro, chloro, bromo), (C 1 -C 3) alkyl, (C 1 -C 3) haloalkyl, (C 2 -C 3) alkenyl or amino, -NHR ⁶ or NR ⁷ R ⁸ , wherein each of R ⁶ , R ⁷ and R ⁸ , which are the same or different, is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 3 carbon atoms or a -C (O) alkyl group wherein the alkyl groups and alkenyl moieties are unsubstituted or substituted by cyano, alkoxy, alkyl-S (O) _p , nitro, alkoxycarbonyl, -C (O) alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -COOH, hydroxy or halogen (fluorine, chlorine, bromine) and

M is CCl, CBr or N.

Another particularly preferred group of compounds are those wherein:

R ¹ is chlorine or bromine,

R ² and R ⁴ are hydrogen,

R ³ is -CF ₃ , -OCF _3, or chloro,

R ⁵ is optionally halogenated methyl or ethyl,

Z is hydrogen or amino; and

M is CCl, CBr or N.

Another particularly preferred group of compounds are those wherein:

R ¹ is chlorine or bromine, R ² and R ⁴ are hydrogen atoms, R ³ is -CF 3, -OCF 3 or chlorine, R ⁵ is methyl or ethyl, Z is hydrogen or amino, and M is CC 1, CBr or N.

For the preferred compounds mentioned, combinations of substituents are optimal.

Preferred phenyl or pyridyl groups containing R ¹ -R ⁴ and M in formula (I) are: 2,6-dichloro-4-trifluoromethylphenyl,

2,6-dichloro-4-trifluoromethoxyphenyl, 2-bromo-6-chloro-4-trifluoromethylphenyl, 2-bromo-6-chloro-4-trifluoromethoxyphenyl,

2,6-Difluoro-4-trifluoromethylphenyl, 2-chloro-4-trifluoromethylphenyl, 2,6-dichloro-3-methyl-4-trifluoromethylphenyl, 3-chloro-5-trifluoromethyl-2-pyridinyl, 3-chloro-5-trifluoromethoxy- 2-pyridinyl, 3,5-dichloro-2-pyridinyl, 2,6-dichloro-4-bromophenyl,

2,4.6-trichlorophenyl, 2-bromo-6-fluoro-4-difluoromethylphenyl, 2-chloro-6-fluoro-4-trifluoromethylphenyl, 2,6-dibromo-4-trifluoromethylphenyl, 2,6-dibromo-4-trifluoromethoxyphenyl, and 2-Bromo-4-trifluoromethylphenyl.

Other preferred Z substituents in Formula (I) are: acetylamino, amino, 2-n-butoxypropionylamino, methyl, hydroxyacetylamino, ethyl, 3-ethylsulfinylpropyllamino, bromo, formylamino, chloro, methylamino, methoxy, ethylamino, 2-n-amino, 2-n-butylamino; methylsulfonylamino, 2-etylsulfonyletylaminoskupina, 4-methoxybenzoylamino, 2-cyanoethylamino, 2-metyltioetylaminoskupina, 2-aminokarbonyletylaminoskupina (2-carbamoylethylamino), 2-metylsulfinyletylaminoskupina, 3-metoxykarbonylpropylaminoskupina, 2-etylsulflnyletylaminoskupina, 2-methylsulfonylethylamino, cyanomethylamino, 2-etyltioetylaminoskupina, aminokarbonylmetylaminoskupina (carbamoylmethylamino), dimethylamino, 2-nitroethylamino, 2-acetylethylamino, methylcarbonylmethylamino (acetylmethylamino), methoxycarbonyl and ethoxycarbonyl.

Other preferred -S (O) R ⁵ substituents in formula (I) are: methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfonyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfonyl, isopropylsulfonyl, isopropylsulfonyl, isopropylsulfonyl, isopropylsulfonyl, isopropylsulfonyl, and isopropylsulfonyl.

Particularly preferred pyrazole derivatives, which are designated by numbers 1 to 11, are now incorporated herein by reference and for identification purposes.

5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthiopyrazole-3-thiocarboxamide

5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylthiopyrazole-3-thiocarboxamide

4-Dichlorofluoromethylsulfonyl-1- (2,4,6-trichlorophenyl) pyrazole-3-thiocarboxamide

5-Amino-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -4-methylsulfinyl-pyrazole-3-thiocarboxamide

5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfonylpyrazole-3-thiocarboxamide

5-Amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide

5-Amino-1- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide

5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide

5-amino-l- (2-chloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide

5-Amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide

5-amino-l- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-ctylsulfmylpyrazol-3-thiocarboxamide

Compounds of formula (I) may be prepared by application or adaptation of known methods (i.e., methods hitherto used or described in the chemical literature, including Chemical Abstracts) using known 3-cyano-1-phenylpyrazoles or 3-cyano-1- (2-pyridinyl) pyrazoles as intermediates or obtainable by methods similar to those described in EP 0 295 117, EP 0 234 119, WO 87/03781, EP 0 500 209 and EP 780 378.

According to the invention, compounds of formula (1) may be prepared by reacting a compound of formula (II)

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , M and Z are as defined herein, with an alkali metal or alkaline earth metal hydrosulfide salt such as lithium, potassium, calcium or preferably sodium hydrosulfide in an inert a solvent, for example in N, N-dimethylformamide, pyridine, dioxane, tetrahydrofuran, sulfolane, dimethylsulfoxide, methanol or ethanol, at a temperature from -35 ° C to 50 ° C, preferably from 0 ° C to 30 ° C. Alternatively, the hydrosulfide can be released in situ by reaction with H ₂ S in the presence of an organic base such as a metal alkoxide or a trialkylamine, or an inorganic base such as an alkali metal or alkaline earth metal hydroxide, or an alkali metal or alkaline earth metal carbonate sodium, potassium or ammonium. By using a complexing agent with metals such as crown ether, acceleration of the reaction can be achieved. The reaction of the hydrosulfide salt with 3-cyanopyrazole can also be carried out in a two-phase water / solvent system using a phase transfer catalyst such as crown ether and a tetraalkylammonium salt such as tetra-n-butylammonium bromide or benzyltrimethylammonium chloride. Organic solvents suitable for use in a two-phase water system are benzene, toluene, dichloromethane, 1-chlorobutane and methyl tert-butyl ether.

Compounds of formula (I) may also be prepared from compounds of formula (II) by reaction with a reagent of formula Ph ₂ PS ₂ as described in Tetrahedron Lett., 24 (20), 2059 (1983).

According to another embodiment of the invention, compounds of formula (I) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , M and Z are as defined above and wherein n is 1 or 2 may be prepared by oxidation of the corresponding compounds of formula (I) ), where n is 0 or 1. The reaction should be carried out with a mild oxidizing agent (to avoid destruction of the thioamide functionality) such as sodium periodate in an inert solvent such as dichloromethane at a temperature of from -40 ° C to boiling point. solvent.

According to another embodiment of the invention, compounds of formula (I) wherein Z is hydrogen, halogen, alkyl, haloalkyl, amino, R ⁶ NH- or R ⁷ R ⁸ N-, wherein R ⁶ , R ⁷ and / or R ⁸ are an alkyl group, a haloalkyl, -C (O) alkyl, alkoxycarbonyl, formyl, and -S (O) _p alkyl, or R ⁶ and R ⁷ are joined to form a divalent radical having 4 to 6 atoms in the chain, prepared according to the procedures described in one or more of International Publication Nos. WO 94/21606, WO 93/06089 and WO 87/03781; 0 295 117 and EP 511 845, Hatton et al. U.S. Pat. 5,232,940 and in German patent publication DE 19511269.

According to another embodiment of the invention, the compounds of formula (I) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and M are as defined above and wherein Z is R ⁶ NH-, where R ⁶ is ethyl substituted in the position 2 is R ⁹ , wherein R ⁹ is cyano, nitro, -S (O) _q R ¹⁰ , -C (O) alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl, prepared by reaction a corresponding compound of formula (I) wherein Z is an amino group with a compound of formula (III)

R ⁹ -CH = CH ₂ (III), wherein R ⁹ is as defined above. The reaction may conveniently be carried out in the presence of a base such as sodium hydride, an alkali metal hydroxide such as potassium hydroxide or tetraalkylammonium hydroxide, such as N-benzyltrimethylammonium hydroxide, in a solvent such as N, N-dimethylformamide, tetrahydrofuran, toluene, ethanol or water; at -20 ° C to boiling point.

According to another embodiment of the invention, compounds of formula (I) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and M are as defined above and wherein Z is R ⁶ NH- or R ⁷ R ⁵ N-, wherein: R ⁷ and R ⁸ are an alkyl or haloalkyl group, optionally substituted with one or more R ⁹ groups, prepared by reaction of the corresponding compound of formula (I) wherein Z is an amino group with a compound of formula (IV)

RY (IV) wherein R ¹¹ is alkyl or haloalkyl optionally substituted by one or more R ⁹ and Y is a leaving group, preferably halogen (e.g., chloro). The reaction may be carried out in the presence of a base such as potassium hydroxide, potassium methoxide, sodium hydride or triethylamine, in an inert solvent such as Ν, Ν-dimethylformamide, tetrahydrofuran, toluene or ether and at a temperature from -20 ° C to boiling point.

According to another embodiment of the invention, compounds of formula (I) wherein Z is alkoxycarbonyl can be prepared by reaction of a corresponding compound of formula (I) wherein Z is carboxy with an alcohol of formula (V)

R ¹² -OH (V), wherein R ¹² is an alkyl group. The reaction is preferably carried out in the presence of an acid catalyst such as sulfuric acid, generally in the presence of an excess of alcohol or optionally in a solvent, at a temperature of from 0 ° C to the boiling point. Alternatively, the reaction may be carried out using a coupling reagent such as dicyclohexylcarbodiimide (DCC) in an inert solvent.

According to another embodiment of the invention, compounds of formula (I) wherein Z is alkylthiocarbonyl may be prepared by reacting a corresponding compound of formula (I) wherein Z is carboxy with a thiol of formula (VI)

R ¹² - SH (VI) wherein R ¹² is an alkyl group. The reaction may be carried out using a coupling reagent such as dicyclohexylcarbodiimide (DCC) in an inert solvent.

In another embodiment of the invention, compounds of formula (I) wherein Z is R ^I3 CH (C1) _CH2 -, wherein R ¹³ is alkyl may be prepared by diazotisation of the corresponding compound of formula (I) wherein Z represents amino followed by reaction of with a compound of formula (VII)

R ¹³ CH = CH ₂ (VII).

The reaction is generally carried out using an alkylnitrile such as tert-butylnitrile in the presence of a copper salt such as copper (I) chloride in a solvent such as acetonitrile at a temperature of from -10 ° C to 50 ° C.

According to another embodiment of the invention, compounds of formula (I) wherein Z is -C (O) alkyl may be prepared by oxidation of the corresponding compound of formula (VIII),

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and M are as defined above and R ¹⁴ is an alkyl group. The reaction may be carried out using, for example, chromic acid and sulfuric acid in a solvent such as water and acetone, at a temperature of from 0 ° C to 60 ° C. The compounds of formula (VIII) are novel and thus form a further aspect of the present invention.

In another embodiment of the invention, compounds of formula (I) wherein Z is R ¹³ CH = CH may be prepared by the dehydrochlorination of the corresponding compound of formula (I), wherein Z is CH R ^I3 (C1) _CH2 -. The reaction is generally carried out using a base such as sodium hydroxide or triethylamine in an inert solvent such as dichloromethane or tetrahydrofuran at a temperature from -70 ° C to the boiling point.

According to another embodiment of the invention, compounds of formula (I) wherein Z is hydrazino, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl can be prepared according to the procedure described in EP 0 352 944.

Intermediates of formula (I) wherein Z is carboxy may be prepared by oxidation of the corresponding compound of formula (1), wherein Z is formyl. The reaction is usually carried out using potassium permanganate or chromic acid in a solvent such as water at a temperature of from 0 ° C to the boiling point.

Intermediates of formula (VIII) may be prepared by reacting the corresponding compound of formula (I) wherein Z is a formyl group with an organometallic reagent of formula R ¹⁴ Q, wherein Q is preferably an alkali metal or alkaline earth metal such as lithium or magnesium halide ( Grignard reagent). The reaction may be carried out in an inert solvent such as ether or tetrahydrofuran and at a temperature from -78 ° C to the boiling point of the solvent.

Intermediates of formula (I) wherein Z is formyl may be prepared by oxidation of the corresponding compound of formula (I) wherein Z is R ¹³ CH = CH-. The reaction is usually carried out using a reagent such as ozone or sodium metaperiodate in an inert solvent, for example dichloromethane, at a temperature of from -100 ° C to 100 ° C.

Certain compounds of formula (II) are novel and form a further aspect of the present invention.

The intermediates of formula (III) and (IV) are known or can be prepared by known methods.

Table 1 illustrates specific compounds of Formula (I). In this table, the term c-Pr represents cyclopropyl and CH ₂ CH ₂ H represents a propargyl group.

Table 1

zl. no. R ⁵ S (O) _n FROM R ¹ R ² R ³ R ⁴ M 1 SCH ₃ NH ₂ Cl H cf ₃ H CC1 2 SCF ₃ nh ₂ Cl H cf ₃ H CC1 3 SO ₂ CFC1 ₂ H Cl H Cl H CC1 4 SOCH ₃ nh ₂ Cl H cf ₃ H CC1 5 SO ₂ CH ₃ nh ₂ Cl H cf ₃ H CC1 6 statues ₃ nh ₂ br H cf ₃ H CC1 7 statues ₃ nh ₂ Cl H ocf ₃ H CC1 8 soc ₃ h ₃ nh ₂ Cl H cf ₃ H CC1 9 SOCH ₃ nh ₂ H H cf ₃ H CC1 10 SOC ₂ H ₅ nh ₂ br H cf ₃ H CC1 11 soc ₃ h ₅ nh ₂ Cl H ocf ₃ H CC1 12 SC ₂ H, nh ₂ Cl H cf ₃ H CC1 13 sch ₂ ch = ch ₂ nh ₂ br H cf ₃ H CC1 14 soc ₃ h ₅ nhcoch ₃ Cl H cf ₃ H CF 15 Sat ₂ ch ₃ nh ₂ Cl H cf ₃ o H CC1 16 SOCHj nhc ₃ h ₅ Cl H cf ₃ H CC1 17 SOCjHs nhch ₃ F H CF, CH, CC1 18 SO-c-Pr nhch ₂ and ₃ br H CF ₃ H CC1

19 Statues, NHCH ₂ CONH ₂ Cl H cf ₃ H N 20 S-i-C, H, nh ₂ Cl H cf ₃ o H CC1 21 Sat ₂ c ₂ h ₅ NHCHO Cl CH cf ₃ p H CBr 22 sch ₃ nh ₂ Cl H cf, ch ₃ CF 23 SOCH ₃ nhso ₂ c ₂ h ₅ Cl H CHFj H CC1 24 SO-c-Pr br F H ccif ₂ H CF 25 sch ₂ c ₂ h H Cl H cf. H CBr 26 soc ₃ h ₅ ch ₃ Cl H cf ₃ o H CC1 27 sch ₂ ch = ch ₂ NHNHj br ch ₃ cf ₃ H CC1 28 statues ₃ nh ₂ Cl H cf. H cch ₃ 29 sch ₃ NHSCjHj Cl H cf, H CC1 30 statues ₃ nhch ₂ ch ₂ cn Cl H cf, H CC1 31 Sat ₂ ch ₃ nhch ₂ ch ₂ and ₃ Cl H cf, CH, CC1 32 SO-C ₃ H ₇ nh ₂ Cl H CF, H N 33 soc ₃ h ₅ COCH, br H CF 0 H CC1 34 Statues, nhch ₃ Cl H CF, H CC1 35 Statues, nh ₂ br H cf. H N 36 SOClH ₅ NH (CH ₂ ) ₂ CONH ₂ Cl H CF, H CC1 37 Statues, ch = ch ₂ F CH, CF, H CF 38 SO ₂ CH ₃ nh ₂ Cl H CF, H cno ₂ 39 SO-c-Pr nhco ₂ ch ₃ Cl H CF ₂ C1 H cci 40 sch ₃ NHSCCIj Cl H cfci ₂ H CC1 41 sch ₂ c ₂ h nhch ₂ ch ₂ sch ₃ F H CF, H CCI 42 SOCjHj nhch ₂ ch ₂ soc ₂ h ₅ Cl H CF, H CCI 43 SOC ₂ H ₅ ch ₃ H H cf ₃ H CCI 44 soc ₃ h ₅ N _{(CH3) 2} H H CF, H CCI 45 Statues, N _{(CH3) 2} Cl H CF, H CBr

The present invention is illustrated by the following examples, which are not intended to limit the invention in any way but merely to facilitate its use.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

5-Amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthio-3-thiocarboxamide

To a stirred solution of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4-methylthiopyrazole (4.7 g) and drops of 15-crown-5 in degassed N, N-dimethylformamide was added during a solution of sodium hydrosulfide hydrate (0.79 g) in degassed water was added over a few minutes. The mixture was stirred at 20 ° C for 18 hours and the residue was purified by flash chromatography on silica gel eluting with hexane / acetone 2: 1 to give 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4 methyl thiopyrazole-3-thiocarboxamide (0.38 g), m.p. 161 ° C. Compound 1.

In a similar manner, compounds 2 to 11 of the general formula (I) shown in Table 2 are also obtained.

Table 2

zl. no. R ' R ² R ³ R ⁴ M R ' S (O) _n from t. t. ° C 2 Cl H CF, H CCI SCF nh ₂ 182 3 Cl H Cl H CCI SO ₂ CFC1 ₂ H 180.5 4 Cl H CF, H CCI Statues, nh ₂ 192 5 Cl H cf ₃ H CCI SO ₂ CH, N H 231 6 br H CF, H CCI Statues, nh ₂ 188.5 7 Cl H OCF. H CCI Statues, nh ₂ 137 8 Cl H cf ₃ H CCI SOC ₂ H ₅ nh ₂ 167 9 H H cf ₃ H CCI Statues, nh ₂ 153.5 10 br H cf ₃ H CCI SOC ₂ H ₅ nh ₂ 113.5 11 Cl H OCF. H CCI SOC ₂ H ₅ nh ₂ 102

Comparative Example 1

5-Amino-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole

To concentrated sulfuric acid (106 mL) was slowly added sodium nitrite (27.6 g) and the mixture was allowed to cool to 30 ° C. Acetic acid (216 ml) was added to the stirred mixture over 30 minutes, cooled to 20 ° C, and a solution of 2,4,6-trichloroaniline (70.7 g) in acetic acid was added over 30 minutes while maintaining the temperature. to 20-25 ° C.

The mixture was heated at 52 ° C for 30 min, then added over 20 min to a solution of ethyl 2,3-dicyanopropionate (52.0 g) in 36% aqueous acetic acid (774 mL) while cooling to 10-50 ° C. Low: 14 ° C. The reaction mixture was allowed to warm to 20 ° C, diluted (water) and extracted (dichloromethane). The organic layer was then washed with dilute ammonium hydroxide solution and stirred with 29% ammonium hydroxide solution for 17 hours. The organic phase was washed with water, then with hydrochloric acid (1 N), dried _(MgSO4) and evaporated. Crystallization from toluene gave 5-amino-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (32.82 g). 1 H NMR (CDCl 3): NH ₂ (2H, broad s, 3.84) ppm), 4-H (1H, s, 5.97 ppm), aroma. (1H, s, 7.53 ppm).

Comparative Example 2

-Amino-4-dichlorofluoromethylthio-1- (2,4,6-trifluorophenyl) -3-cyanopyrazole

To a stirred solution of 5-amino-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (8.0 g, 0.028 mol) in acetic acid (70 mL) was added dichlorofluoromethylsulfenyl chloride (4.4 mL) over 5 minutes. . The mixture was allowed to stir at 20 ° C for 65 hours, then poured into water and extracted (dichloromethane). The organic layer was then washed with cold sodium bicarbonate solution, then with water, dried (MgSO ₄ ) and evaporated. Silica gel column chromatography eluting with dichloromethane / hexane 3: 1 to give 5-amino-4-dichlorofluoromethylthio-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (6.06 g), m.p. 189 mp 191 ° C.

Comparative Example 3 4-Dichlorofluoromethylthio-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole

A solution of 5-amino-4-dichlorofluoromethylthio-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (2.19 g) and tert-butylnitrile (90%, 4.1 mL) in tetrahydrofuran was heated to reflux. for 3.5 hours and then evaporated. The residue was purified by flash chromatography on silica gel and eluted with dichloromethane to give 4-dichlorofluoromethylthio-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (1.56 g), m.p. 106-108 ° C.

Comparative Example 4 4-Dichlorofluoromethylsulfonyl-3-cyano-1- (2,4,6-trichlorophenyl) pyrazole

A solution of 4-dichlorofluoromethylthio-3-cyano-1- (2,4,6-trichlorophenyl) pyrazole (0.80 g) and 3-chloroperbenzoic acid (80%, 0.86 g) in chloroform was heated to reflux. for 2 hours, cooled, diluted (ethyl acetate) and washed sequentially with 10% sodium bisulfite, 2N NaOH, water and brine. The dried (MgSO ₄ ) solution was evaporated and purified by flash chromatography on silica gel, eluting with dichloromethane to give 4-dichlorofluoromethylsulfonyl-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (0.41 g), temperature mp 143.5-145 ° C.

Comparative Example 5

-Amino-1- (2-chloro-4-trifluoromethyl) -3-cyano-4-methylsulphinylpyrazole

Stage 1

To a stirred solution of sodium thiocyanate (1.7 g) in anhydrous methanol was added bromine (0.5 mL) at -65 ° C for 10 min. A solution of 5-amino-1- (2-chloro-4-trifluoromethyl) -3-cyanopyrazole (1.5 g) in anhydrous methanol was added over 10 minutes and the stirred mixture was allowed to warm to 20 ° C over 16 hours. After pouring water, the precipitate was filtered off and dried to give 5-amino-1- (2-chloro-4-trifluoromethyl) -3-cyano-4-thiocyanatanopyrazole (1.64 g). According to HPLC (C18 column, eluting with CH ₃ CN and H ₂ O 3: 1 at 1.0ml / min), the compound had a peak area of 86.6% at 5.11 minutes.

Stage 2

To a stirred suspension of 5-amino-1- (2-chloro-4-trifluoromethyl) -3-cyano-4-thiocyanatanopyrazole (1.64 g) in methanol was injected iodomethane (0.7 mL) at 4 ° C. Aqueous sodium hydroxide (2.8 mL) was added and the reaction mixture was stirred at 4 ° C for 1 h, poured into water and extracted with dichloromethane and ethyl acetate. The dried (Na ₂ SO ₄ ) combined organic phase was evaporated and purified by flash chromatography on silica gel, eluting with hexane / ethyl acetate 4: 1 to give 5-amino-1- (2-chloro-4-trifluoromethyl) after trituration with hexane / dichloromethane. -3-Cyano-4-methylthiopyrazole (0.4 g), m.p. 129-132 ° C.

Stage 3

To a stirred solution of 5-amino-1- (2-chloro-4-trifluoromethyl) -3-cyano-4-methylthiopyrazole (3.0 g) in trifluoroacetic acid (20 mL) was added 30% hydrogen peroxide (0.5 mL). ) while cooling to 4 ° C. The mixture is warmed to 20 ° C for 2 hours, then poured onto ice and the solid, washed with water is dried. Flash chromatography on silica gel gave 5-amino-1- (2-chloro-4-trifluoromethyl) -3-cyano-4-methylsulphinylpyrazole (0.69 g), m.p. 146-147 ° C.

Comparative Example 6

In a similar manner to Comparative Example 5, steps 1 and 2, the following compounds were also prepared: 5-amino-1- (2,6-dichloro-4-trifluoromethoxyphenyl) -3-cyano-4-methylthiopyrazole, m.p. 147-148 C and 5-amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -3-cyano-4-methylthiopyrazole, m.p. 178-180 ° C.

Comparative Example 7

In a similar manner to Comparative Example 5, Step 3, the following compounds were also prepared: 5-amino-1- (2,6-dichloro-4-trifluoromethoxyphenyl) -3-cyano-4-methylsulfinylpyrazole, m.p. 137-138 ° C and 5-amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -3-cyano-4-methylsulfinylpyrazole, m.p. 150-151 ° C.

Biological efficacy

The following methods were used to administer the compounds of the invention and the results obtained were observed: leaf spray / contact in mammalian insects (aphids) or insect bites (Lepidoptera).

The following species were tested:

kind of

Aphis gossypii (Schizapis graminum)

Musca domestica Common name aphid cotton bug fly house abbreviation

APHIGO

TOXOGR

MUSCDO

Soil irrigation test (systemic efficiency)

Cotton and sorghum plants are placed in flower pots. One day before treatment, each pot is infested with 25 aphids of the mixed population. Cotton plants are infested with aphids and sorghum plants are infested with bugs (Schizapis graminum). Selected compounds of formula (I) are applied to the soil surface at a dilution that delivers an equivalent of 10.0 ppm by weight concentration in the soil. The number of aphids is obtained 5 days after treatment. The number of aphids on the treated plants is compared with the number of aphids on the untreated control plants.

Bait / contact fly test (Musca domestica)

About 25 four to six days old adult house flies are anesthetized and placed in a cage containing a bait of a sugar water solution containing the test compound. The concentration of the selected compound of formula (I) in the bait solution is 100 ppm. After 24 hours, flies that show no movement for stimulation are considered dead.

Test sheet / contact for Aphis gossypii

The aphid-infected cotton plants are placed on a rotating rotary table and sprayed with 100 ppm of the preparation of the selected compound of formula (I). The treated aphid-infected plants are maintained for three days after treatment and then the dead aphids are counted.

Compounds 1 to 11 according to the invention have an activity of 10 ppm on Aphis gossypii and Schizapis graminum in the systemic test, a bait / contact concentration of 100 ppm on Musca domestica and 100 ppm on Aphis gossypii in said test / exposure test. .

The present invention relates to a method of systemically killing arthropods at their habitat, in particular certain insects or mites, which feed on said above-ground parts of plants. The destruction of these leaf pests may be effected by direct application to the leaves or, for example, by spraying the soil or by applying granules to the roots of plants or plant seeds, followed by systematic translocation to the above-ground parts of the plants. This systemic efficacy involves the control of insects that remain not only at the application site, but also in distant parts of the plants, for example by translocating from one side of the leaf to the other or from treated leaves to untreated leaves. Examples of insect pest classes that can be systemically destroyed by the compounds of the invention include the Homoptera (stinging-sucking) family, the Hemipier (stinging-sucking) family, and the Thysanoptera family. The invention is particularly suitable for aphids and chips.

As is evident from prior art use, the present invention provides active compounds and methods of using these compounds for controlling many insect species, such as arthropods, particularly insects or mites, plant nematodes, or nematodes and protozoa. Thus, the compounds of formula (I) or their pesticidally acceptable salts are preferably used in practice, for example, for agricultural or horticultural crops, in forestry, veterinary medicine or in livestock farming, or in health care and public hygiene. In this regard, whenever the term "compounds of formula (I)" is used, it is also meant to include their pesticidally acceptable salts. The term "compound of formula (I)" includes a compound of formula (I) and a pesticidally acceptable salt thereof.

Accordingly, the present invention relates to a method for controlling pests at their locus by treating the locus (e.g., by administering or administering) an effective amount of a compound of formula (I) or a pesticidally acceptable salt thereof, importance. For example, a locus refers to the pest itself or the place (plant, animal, field, organism, buildings, forest, orchard, waterway, soil, plant or animal product or the like) where the insect resides or feeds.

The compounds of the invention may also be used for controlling soil insects such as corn rootworms, termites (especially for building protection), root manure, wireworms, root weevils, stalk drills, reticulate, root aphids or pandravas. They may also have efficacy on plant pathogenic nematodes such as roots, cysts, cracks, lesions or nematodes on strains or tubers, or on mites. For the control of soil pests, for example wireworms on corn roots, the compounds are preferably applied in an effective amount to the soil where the crops are to be or to be grown, or incorporated into the seeds or to the roots of growing plants.

In the field of health and public hygiene, the compounds are used in particular for controlling many insect species, in particular flies or other Diptera pests such as house flies, stall flies, gates, cattle, deer, horse flies, midges, flies or mosquitoes.

The compounds of the invention can be used in the following applications and against the following pests, including arthropods, in particular insects or mites, nematodes or nematodes or protozoa:

In the protection of stored products such as cereals, including grain or flour, groundnuts, animal food, wood or household goods such as carpets and textiles, the compounds of the invention are used to protect against arthropods, in particular beetles, including mole, mites such as Ephestia spp., Arthrenus spp. (carpet beetles), Tribolium spp. (flour beetles), Sitophillus spp. (grain beetles) or Acarus spp. (Aphids).

For the destruction of cockroaches, ants or termites, or similar arthropod pests in infested domestic or industrial buildings or for the destruction of mosquito larvae in waterways, wells or other running or stagnant waters.

For the treatment of foundations, buildings or soil to prevent the attack of buildings by termites, for example Reticulitermes spp. Heterotermes spp., Coplotermes spp ..

In agriculture against adults, larvae and eggs of Lepidoptera (butterflies and seas), for example, Heliothis spp., Such as Heliotis virescens, Heliothis armigera and Heliothis zea. Against adults and larvae of Coleoptera (beetles), for example Anthonomus spp., For example grandis, Leptinotarsa decemlineata, Diabrotica spp. (corn pest). Against Heteroptera (Hemiptera and Homoptera), for example Psylla spp., Bemisia spp., Trialeurodes spp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp., Nephotettix spp., Nilaparvata spp.

Against Diptera, for example Musca spp., Against Thysanoptera, such as Thrips tabaci, against Orthoptera, such as Locusta and Schistocerca spp. (grasshoppers and crickets), for example Gryllus spp. and Acheta spp., for example, Blatta orientalis, Periplaneta americana, Blatella germanica, Locusta migratoria migratorioides, and Schistocerca gregaria. Against Collembola, for example Periplaneta spp. and Blatella spp. Against Isoptera, for example Coplotermes spp. (Termites).

Against agriculturally important arthropods such as Acarina (mites), for example Tetranychus spp. and Panonynchus spp ..

Against nematodes that attack plants or trees of importance to agriculture, forestry or horticulture, or directly, or by the spread of bacterial, viral, mycoplasma or fungal plant diseases. For example, these nematodes are Meloidogyne spp. (e.g. M. ineognita).

In the field of veterinary medicine or animal husbandry, or in health and public hygiene against arthropods, nematodes or protozoa which parasitize internally or externally vertebrate animals, in particular 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 spp., Boophilus spp. e.g. Boophilis microplus, Rhipicephalus spp. e.g. Rhipicephalus appendiculatus Omithodorus spp. (e.g. Ornithoporus moubata) and mites (e.g. Damalinia spp.) Diptetra (e.g. Aedes spp., Anopheles spp., Musca spp., Hypoderma spp.), Hemiptera, Dictyoptera (e.g. Periplaneta spp., Blatella spp.), Hymenoptera, e.g. for controlling and treating diseases caused by elements such as Ei such as Trypanosoms cruzi, Leishaminia spp., Plasmodium spp., Babesis spp., Trichomonadidae spp., Toxoplasma spp., and Theileria spp.

In practical use for controlling arthropods, in particular insects and mites or nematode pests on plants, the method consists in applying an effective amount of a compound of the invention to the plants or environment where the pests are growing. In this method, the active compound is generally applied to a site infested with arthropods or nematodes to be controlled in an effective amount ranging from about 5 g to about 1 kg of active compound per hectare of site to be treated. Under ideal conditions and depending on the pest being controlled, a smaller amount may provide adequate protection. On the other hand, adverse weather conditions, pest resistance and other factors may require the use of the active ingredient in higher amounts. The optimum dose usually depends on many factors, for example the type of pest being controlled, the type or growth stage of the infested plant, the row spacing and also the method of application. More preferably, the effective amount of the active compound is in the range of about 50 g / ha to about 400 g / ha.

If the insects are insects living in the soil, the active compound is usually formulated into a composition that is distributed evenly over the surface to be treated (e.g., scattering or stripping) by any suitable method, with an amount of from about 5 to about 1 kg / ha, preferably from about 50 to about 250 g of active ingredient. When applied as an infusion to the roots of plants or as a drip irrigation on plants, the liquid solution or suspension contains from about 0.075 to about 1000 mg / l, preferably from about 25 to 200 mg / l of active ingredient. The application can be carried out, if necessary, in a field or crop growing area or in close proximity to the seed or plant to be protected from attack. The active ingredient may be flushed into the soil by spraying water over the surface or may be flushed out by the natural action of rain. During or after application, the compound may optionally be crushed mechanically into the soil, for example by means of a plow, a plate plow or the use of trailing chains. Application can be carried out before planting, during planting, after planting or before germination, or even after germination.

The compounds of the invention and methods of controlling pests are particularly important in the protection of fields, fodder plants, seedlings, greenhouses, orchards or vineyards, or ornamental flowers, or planting, or forest trees such as cereals (such as wheat or rice), cotton, vegetables (such is paprika), field crops (such as sugar beet, soybeans or oilseed rape), pastures or fodder plants (such as corn or sorghum), orchards or groves (such as stone fruit or citrus trees), ornamental plants, flowers or vegetables, or shrubs in greenhouses (both deciduous and still green), in forests, plantations or nurseries.

The compounds of the invention are also suitable for protecting wood (standing, felled, treated, stored or construction) against attack by, for example, sawdust or beetles or termites.

They can also be applied to protect stored products such as grain, fruit, nuts, spices or tobacco, either whole, ground or processed into products, from seas, beetles, mites or beetles attacking the grain. It is also possible to protect stored animal products such as hides, hair, wool or fur in natural or processed form (for example, carpets or textiles) against attack by seas or beetles, as well as stored meat, fish or grain from beetles, mites or flies.

In addition, the compounds according to the invention and the methods according to the invention can be used in particular for the destruction of arthropods, nematodes or protozoa which harm or spread diseases in domestic animals, for example as mentioned above, and in particular for the control of ticks, mites, lice, flies, of mammalian annoying flies. In particular, the compounds of the invention are useful for destroying arthropods, helminths or protozoa which are present in or live on their skin or in the skin of their host animals or suck the blood of the animals, which are administered orally, parenterally, percutaneously or topical.

Furthermore, the compounds of the invention can be used for coccidiosis, an infection caused by infestation with protozoan parasites of the genus Eimeria. This represents an important potential reason for economic loss in domestic animals and birds, especially those that are kept under intensive conditions. For example, cattle, sheep, pigs or rabbits may be infected, but in particular the disease is important in poultry, especially chickens. Administration of a small amount of a compound of the invention, preferably in combination with feed, is effective to prevent or greatly reduce the incidence of coccidiosis. The compounds are effective against both cecal and intestinal form. Furthermore, the compounds of the invention may have an inhibitory effect on oocytes by greatly reducing their number and sporulating. This poultry disease is generally spread by birds that collect infectious organisms in droppings or in contaminated rubbish, ground, food or drinking water. The disease is manifested by bleeding, appendicitis, passage of blood to the faeces, weakness and digestive disorders. The disease often results in the death of the animal, but poultry that survive a strong infection has a significantly reduced cost to the market as a result of infection.

The disclosed compositions for application to growing crops or to crop-growing sites, or as seed coatings can generally be used alternatively for topical application to animals or to protect stored products, household goods, property or areas of the environment. Suitable methods of administering the compounds of the invention are carried out:

on growing crops as spraying of leaves, dusts, granules, mists or foams, or also as suspensions of finely crushed or encapsulated formulations such as soil or root treatment with liquid irrigation, dust, granules, smoke or foam, in crop seeds by application as seed coatings with liquid suspensions or by dusting, in animals infected or exposed to infection by arthropods, helminths or elements by parenteral, oral or topical application of the compositions in which the active ingredient has immediate and / or prolonged action over a period of time on arthropods, helminths or protozoa, for example pharmaceutical preparations, edible baits, salt licks, dietary supplements, infusions, sprays, baths, dives, showers, fluid flow, dusting, brushing, shampooing, creams, wax disinfection or a system that animals or operate in the environment in general or in specific locations where the pests are hidden, including stored products, wood, household goods or domestic or industrial objects such as sprays, mists, dusts, fumes, wax disinfectants, lacquers, granules or baits, or in slow inlets to waterways, wells, reservoirs or other running or standing waters, in domestic feeding animals by controlling larvae feeding on their feces.

In practice, the compounds of the invention are most often part of the compositions. These compositions can be used to kill: arthropods, especially insects or mites, nematodes or nematodes, or protozoa. These compositions may be of known types suitable for application to the desired pests in any building or interior or exterior surface or for internal or external administration to vertebrate animals. These compositions comprise at least one compound of formula (I) or a pesticidally acceptable salt thereof as described, as an active ingredient in combination or in conjunction with one or more compatible ingredients, such as solid or liquid carriers or diluents, excipients, surfactants substances or substances appropriate for the intended use and which are agriculturally or medically acceptable. These compositions, which can be prepared by known methods, also form part of the invention.

These compositions may also contain other kinds of ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, spray oils (especially for acaricidal use), stabilizers, preservatives (especially antifungals), masking agents or the like, as well as other known active ingredients with pesticidal properties (in particular insecticidal, acaricidal, nematicidal or fungicidal agents) or with plant growth-regulating properties. Usually, the compounds of the invention are used in combination with all solid or liquid additives corresponding to conventional formulation techniques.

Compositions suitable for application in agriculture, horticulture or the like are those suitable for use as sprays, granules, mists, foams, emulsions or the like.

The effective dosages of the compounds of the invention used may vary within wide limits, particularly depending on the nature of the pest to be controlled or the degree of infestation, for example, by the crops of such pests. In general, the compositions of the invention will generally comprise from about 0.05 to about 95% by weight of one or more active ingredients of the invention, from about 1 to 95% of one or more solid or liquid carriers, and optionally from about 0.1 to about 50% of one or more. a plurality of other compatible ingredients, such as surfactants or the like.

The term "carrier" means an organic or inorganic component of natural or synthetic origin which, in conjunction with the active substance, facilitates its application, for example to a plant, seed or soil. These carriers are therefore generally inert and must be acceptable (for example, agriculturally acceptable, especially for the treatment of plants).

The carrier may be solid, for example clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers (for example, ammonium salts), ground natural materials such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, bentonite, or diatomaceous earth, or ground synthetic minerals such as silica, alumina or silicates, in particular aluminum or magnesium. Suitable solid carriers for granules are: crushed or fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic or organic flour, granules of organic materials such as sawdust, coconut shells, corn cobs, corn husks or tobacco stems, diatomaceous earth, calcium phosphate, cork powder or absorbent carbon black, water-soluble polymers, resins, waxes or solid fertilizers. These solid compositions may optionally contain one or more compatible wetting, dispersing, emulsifying or coloring agents which, if solid, may also serve as a diluent.

The carrier may also be liquid, for example, water, alcohols, especially butanol or glycol, as well as their ethers or esters, especially methyl glycol acetate, ketones, especially acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone, petroleum fractions such as paraffinic or aromatic hydrocarbons. xylenes or alkylnaphthalenes, mineral or vegetable oils, aliphatic chlorinated hydrocarbons, in particular trichloroethane or methylene chloride, aromatic chlorinated hydrocarbons, especially chlorobenzenes, water-soluble or strongly polar solvents such as dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone or N-methylpyrrolidone mixture.

The surfactants may be emulsifying agents, dispersing agents or wetting agents of the ionic or non-ionic type or a mixture of these surfactants. For example, polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or fatty acids, or fatty esters, or fatty amines, substituted phenols (especially alkylphenols or arylphenols), ester salts , taurine derivatives (especially alkyl taurates), phosphoric alcohol esters or polycondensates of ethylene oxide with phenols, fatty acid esters of polyols or sulfates, sulfonates or phosphates of functional derivatives of said compounds. Generally, the presence of at least one surfactant is suitable if the active ingredient and / or the inert carrier are only slightly soluble in water or are not water soluble and the carrier material for application is to be water.

The compositions of the invention may further comprise other additives such as binders and colorants. In the compositions, carboxymethylcellulose or natural or synthetic polymers in the form of powders, granules or latexes such as acacia, polyvinyl alcohol or polyvinyl acetate, natural phospholipids such as cephalins and lecithins, or synthetic phospholipids can be used as binders. Inorganic pigments such as iron oxides, titanium oxides or Berlin blue, organic dyes such as alizarin dyes, azo dyes or metal phthalocyanines or trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum or zinc salts can be used as colorants .

Compositions containing compounds of formula (I) or pesticidally acceptable salts thereof which can be used to kill arthropods, plant nematodes, nematodes or protozoa may also contain synergists (e.g. piperonyl butoxide or sesamex), stabilizers, other insecticides, acaricides, plant nematides, anthelmintics or anti-coccidiosis agents, fungicides (agricultural or veterinary, for example benomyl and iprodione), bactericides, arthropod or vertebrate attractants, or repellents, or pheromones, deodorants, flavorings, coloring or auxiliary therapeutic agents, for example trace elements. These are intended to improve the effectiveness, persistence, safety, absorption, spectrum of insect control or allow the composition to perform other useful functions on a flat animal or on the treated area.

Examples of pesticidally active compounds that may be included in the compositions of the invention or used in conjunction with the compositions of the invention include: acephate, chlorpyrifos, demetone-S-methyl, disulfotone, ethoprophos, fenitrothion, fenamiphos, phonophos, isazophos, isofenphos, malathion, monocrotophos, parathion, phorate, phosalone, pirimiphos-methyl, terbufos, triazophos, cyfluthrin, cypermethrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, tefluthrin, aldicarbyl, carbosimethol, methomine, methomine endosulfan, lindane, benzoximate, cartap, cyhexatin, tetradifon, avermectins, ivermectins, milbemycins, thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole.

For agricultural application, the compounds of formula (I) or pesticidally acceptable salts thereof are generally in the form of compositions which are in various solid or liquid forms.

Solid form preparations which can be used are dusting powders (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, by impregnation of the granular carrier or by powder-based granulation (the content of the compound of formula (I) or a pesticidally acceptable salt thereof is between about 0.5 to 80%). Solid homogeneous or heterogeneous formulations containing one or more compounds of formula (I) or a pesticidally acceptable salt thereof, for example granules, pellets, briquettes or capsules, may be used to treat standing or running water for a period of time. A similar effect can be achieved by using a thin or intermittent supply of water to the dispersible concentrate described above.

Liquid formulations are, for example, aqueous or non-aqueous solutions or suspensions (such as emulsifiable concentrates, emulsions, flowable preparations, dispersions or solutions) or aerosols. Liquid formulations are also in particular emulsifiable concentrates, dispersions, emulsions, flowable formulations, aerosols, wettable powders (or sprayable powders), dry flowable formulations or pastes as formulations which are liquid or are intended to be liquid for application, for example as aqueous sprays (including small and ultra-small volumes) or as mist or aerosols.

Liquid formulations, for example in the form of emulsifiable or soluble concentrates, most commonly contain about 5 to about 80% by weight of the active ingredient, while ready-to-use emulsions or solutions contain about 0.01 to about 20% of the active ingredient. In addition to the solvent, the emulsifiable or soluble concentrates may contain, if desired, about 2 to about 50% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or binders. Emulsions of any desired concentration, which are particularly suitable for application to, for example, plants, can be obtained from these concentrates by dilution with water. These compositions are also within the scope of the present invention. The emulsions may be in the form of a water-in-oil or oil-in-water type and may have dense coexistence.

The liquid compositions of the invention may be used, for example, in addition to normal agricultural applications, for the treatment of substrates or sites infested or susceptible to arthropod infestation (or other pest-destroyed compounds of the invention), including buildings, exterior or interior storage areas or work areas, containers or equipment; standing or running water.

All of these aqueous dispersions or emulsions or spray mixtures can be applied, for example, to crops by any suitable method, in particular by spraying in amounts which are usually of the order of about 100 to about 1200 liters of spray mixture per hectare but can be higher or lower (e.g. ultra-low volume), depending on need or application technique. The compounds or compositions of the invention are suitably applied to vegetation and in particular to roots or leaves at which pests are to be eliminated. Another method of applying the compounds or compositions of the invention is by chemization, i.e., by adding a formulation containing the active ingredient to irrigation water. This irrigation may be effected by spraying on leaf pesticides or by spraying the ground, or by underground spraying on soil or systemic pesticides.

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 from about 10 to about 75% by weight of the active ingredient, from about 0.5 to about 30% of surfactants from about 0.1 to about 10% of thixotropic agents, from about 0 to about 30% of suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetration agents, binders, and as a carrier water or organic liquid in which it is effective low soluble or insoluble component. Certain organic solids or inorganic salts may be dissolved in the carrier to prevent settling or to serve as an antifreeze agent for water.

Wettable powders (or spray powders) are usually formulated to contain from about 10 to about 80% by weight of the active ingredient, from about 20 to about 90% solid carrier, from about 0 to about 5% wetting agent, from about 3 to about 5%. about 10% of a dispersing agent and, if desired, from about 0 to about 80% of one or more stabilizers and / or other additives such as penetrating agents, binders, anti-caking agents, coloring agents or the like. To produce these wettable powders, the active ingredient (s) is carefully mixed in a suitable mixer with other substances which may be impregnated on the porous filler and ground in a mill or other suitable crusher. This results in wettable powders whose wettability and suspensibility are preferred. They can be suspended in water to any desired concentration, and these suspensions can be used very advantageously, especially when applied to plant leaves.

"Water-dispersible granules (WG)" (granules that are readily dispersible in water) have a composition substantially similar to that of wettable powders. They can be prepared by granulating the compositions described for wettable powders, either by wetting (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 an aqueous dispersant or binder solution and then drying and sieving. ) or by a dry process (pressing and then grinding and sieving).

The amount and concentration of the formulations prepared may vary according to the method of application or the nature of the formulations or their use. Generally, the compositions for application to destroy arthropods, plant nematodes of nematodes or protozoa usually comprise from about 0.00001% to about 95%, in particular from about 0.0005% to about 50% by weight of one or more compounds of formula (I) or a pesticide thereof. an acceptable salt, or all active ingredients (ie, a compound of formula (I) or a pesticidally acceptable salt thereof together with other substances that are toxic to arthropods or plant nematodes, anthelmintics, anticoccidally acting agents, synergists, trace elements or stabilizers). The actual compositions to be used and the amount thereof to be applied are selected by the farmer, the livestock farmer, the medical or veterinary practitioner, the pest control worker or other skilled person, depending on the desired effect.

Solid or liquid compositions for topical application to animals, wood, stored products or household goods typically contain from about 0.00005% to about 90%, in particular from about 0.001% to about 10% by weight of one or more compounds of formula (I), or their pesticidally acceptable salts. For administration to animals orally or parenterally, including percutaneously, the solid or liquid compositions comprise from about 0.1% to about 90% by weight of one or more compounds of Formula (I) or pesticidally acceptable salts thereof. Concentrates or supplements for mixing with feed normally contain from about 5% to about 90%, preferably from about 5% to about 50% by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof. Mineral salt licks usually contain from about 0.1% to about 10% by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof.

Dusts or liquid compositions for application to livestock, goods, buildings or exterior surfaces may contain from about 0.0001% to about 15%, in particular from about 0.005% to about 2% by weight of one or more compounds of formula (1) or a compound thereof pesticidally acceptable salts. Suitable concentrations in the applied waters are between about 0.0001 ppm and about 20 ppm, especially about 0.001 ppm to about 5.0 ppm of one or more compounds of formula (I) or pesticidally acceptable salts thereof, and can be used therapeutically in fish farming with appropriate time of impact. Edible baits may contain from about 0.01% to about 5%, in particular from about 0.01% to about 1.0% by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof.

When administered to a vertebrate parenterally, orally or percutaneously, or otherwise, the doses of the compounds of formula (I) or their pesticidally acceptable salts depend on the vertebrate species, age or health and the nature and degree of its actual or potential infestation by arthropods, helminths or elements. For sustained medication by oral or parenteral administration, a dose of about 0.1 to about 100 mg, preferably about 2.0 to about 20.0 mg per kg of animal body weight, or a dose of about 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg per kg animal body weight per day. By using sustained-release preparations or devices, the required daily doses may be combined and administered to the animals at one time over months.

The following examples of compositions designated 2A to 2M illustrate compositions for use against arthropods, in particular mites or insects, plant nematodes or nematodes, or protozoa, which compositions contain as an active ingredient a compound of formula (I) or a pesticidally acceptable salt thereof such as are described in the preparation examples. The compositions described in Examples 2A-2M can be diluted to give sprayable compositions at concentrations suitable for field use. The generic chemical names of the ingredients (for which the following weight percentages are always given) used in Examples 2A to 2M are as follows:

business name chemical nature Ethylan BCP nonylphenolethylene oxide condensate Soprophor BSU tristyrylphenolethylene oxide condensate Arylan CA 70% w / w calcium dodecylbenzenesulfonate solution Solvesso 150 light C 10 aromatic solvent Arylan S sodium dodecylbenzenesulfonate Darvan č. 2 sodium lignosulfonate Celite PF synthetic carrier of magnesium silicate Sopropon T36 sodium salts of polycarboxylic acids Rhodigel 23 polysaccharide xanthan gum Bentone 38 an organic derivative of montmorillonite magnesium Aerosil very fine silica Example 2A To be prepared in a water-soluble concentrate with the following- composition: active ingredient 7% Ethylan BCP 10% N-methylpyrrolidone 83% To the solution of Ethylan BCP dissolved in a portion of N-methylpyrrolidone is added the active ingredient with heating and stirring until dissolved. The resulting solution was adjusted to a final volume with the remaining solvent. Example 2B An emulsifiable concentrate (EC) is prepared, followed by the following: Composition: active ingredient 25% (max) Soprophor BSU 10% Arylan CA 5% N-methylpyrrolidone 50% Solvesso 150 10%

The first three components were dissolved in N-methylpyrrolidone and Solvesso 150 was added to the final volume.

Example 2C

A wettable powder (WP) is prepared with the following

composition: active ingredient 40% Arylan S 2% Darvan č.2 5% Celite PF 53% The ingredients are mixed and ground in a hammer mill powder with a particle size less than 50 µm. Example 2D Ready an aqueous flowing preparation with the following composition getting married: active ingredient 40,05% Ethylan BCP 1.00% Sopropon T360 0.20% ethylene glycol 5,00% Rhodigel 230 0.15% Water 53,69% The ingredients are mixed thoroughly and ground in a bead mill until a mean particle size of less than 3 µm is obtained. Example 2E Ready an emulsifiable concentrate with the following composition: active ingredient 30.0% Ethylan BCP 10.0% bentone 38 0.5% Solvesso 150 59.5%

The ingredients are mixed intimately and milled in a bead mill until a median particle size of less than 3 µm is obtained.

Example 2F

Water dispersible granules are prepared, followed by the following:

composition: active ingredient 30% Darvan č.2 15% Arylan S 8% Celite PF 47%

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

Example 2G

A dusting powder is prepared having the following composition: active ingredient 1 to 10% very fine talc powder 99 to 90%

The ingredients are mixed thoroughly and optionally re-milled to a fine powder. The powder is applied to sites infested with arthropods, for example, landfills, stored products or household goods, or to animals infested or susceptible to infestation by arthropods, thereby destroying pests by oral use of the powder. Suitable devices for distributing the dusting powder to the atropod infestation sites are blowers, hand shakers or equipment operated by the livestock itself.

Example 2H

An edible bait having the following composition is prepared: active ingredient 0.1 to 10% wheat flour 80% molasses 19.9 to 19%

The ingredients are mixed thoroughly to form the desired bait form. This edible bait is distributed to sites infested with arthropods, such as ants, locusts, cockroaches or flies, such as residential and industrial buildings such as kitchens, hospitals or warehouses, or exterior areas, thereby destroying arthropods by oral bait ingestion.

Example 21

A preparation is prepared in the form of a solution having the following composition: active ingredient 15% dimethylsulfoxide 85%

The active ingredient is dissolved in dimethylsulfoxide by stirring or optionally by heating. This solution is administered percutaneously as an infusion to pets infested with arthropods or after sterilization by filtration through a polytetrafluoroethylene membrane (0.22 µm pore size), by parenteral injection, in an amount of from 1.2 to 12 ml solution per 100 kg animal weight.

Example 2J

A wettable powder is prepared with the following composition:

him: active ingredient 50% Ethylan BCP 5% Aerosil 5% Celite PF 40%

Ethylan BCP is absorbed into Aerosil, then mixed with the other ingredients and ground in a hammer mill to give a wettable powder which is diluted with water to a concentration of from 0.001% to 2% by weight of the active compound and applied to a site infested with arthropods. Diptera larvae or plant nematodes, spray or pets contaminated or susceptible to infestation by arthropods, helminths or elements by spraying or immersion, or by oral administration in drinking water to destroy arthropods, helminths or protozoa.

Example 2K

A slow-release large pellet is prepared from granules containing the following ingredients in varying percentages (similar to those described for the prior art), depending on need: the active ingredient thickener slow release agent binder.

The thoroughly blended ingredients are formed into granules which are compressed into large tablets with a specific density of 2 or more. These can be administered orally to domestic ruminants for retention in the rumen and cap, whereby the active compound continuously releases a prolonged period of time and thus is destroyed in domestic ruminants by arthropods, helminths or protozoa.

Example 2L

A slow release composition is prepared in the form of granules, pellets, briquettes or the like having the following composition:

active ingredient 0.5 to 25% polyvinyl chloride 75 to 99.05% dioctyl phthalate (plasticizer)

The components are mixed and then formed into suitable shapes by melt extrusion or compression molding. These compositions can be used, for example, to be added to standing water or to produce collars or ear tags for attachment to domestic animals in order to control pests by slow release.

Example 2M

Dispersible granules were prepared with the following

composition: active ingredient 85% polyvinylpyrrolidone 5% attapulgite clay 6% sodium lauryl sulfate 2% glycerin 2%

(Max)

The ingredients are mixed as a 45% slurry in water and wet milled to a particle size of 4 gm and then spray dried to remove water.

While the invention is described in various preferred embodiments, it will be apparent to those skilled in the art that various modifications, substitutions, deletions, and changes can be made without departing from the spirit of the invention. Accordingly, the intended scope of the invention is limited only by the following claims, including equivalents thereof.

Claims (25)

PATENT CLAIMS A 1-arylpyrazole of general formula (I) ⁿ (I) wherein R ¹ is hydrogen or halogen; each R ² and R ⁴ , which are the same or different, is a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; R ³ is halogen, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy or R ¹⁰ S (O) _m ; R ⁵ is a lower alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms and an alkynyl group having 2 to 6 carbon atoms or a cycloalkyl ring having 3 to 6 carbon atoms 5 carbon atoms; Z is a hydrogen atom, a halogen atom, an alkyl group having from 1 to 2 carbon atoms; 6 carbon atoms, formyl, -C (O) alkyl of 1-6 carbon atoms in the alkyl moiety, haloalkyl of 1-6 carbon atoms, alkenyl of 2-6 carbon atoms, hydrazino, alkoxycarbonyl of 1-6 carbon atoms carbon atoms in the alkoxy moiety, alkylthiocarbonyl having 1 to 6 carbon atoms in the alkyl moiety, alkoxyalkylidenamino having 1 to 6 carbon atoms in the alkyl moiety and the alkoxy moiety, 1H-pyrrol-1-yl or ΙΗ-pyrazol-1-yl, amino R ⁶ NH- or R ⁷ R ⁸ N-; each R ⁶ , R ⁷ and R ⁸ , which are the same or different, is C 1 -C 6 alkyl-S (O) _p -, formyl, C 3 -C 6 alkynyl, C 1 -C 6 alkoxycarbonyl C 1 -C 6 alkoxy, C 1 -C 6 alkylthiocarbonyl or aroyl, or C 1 -C 6 alkyl, C 3 -C 6 alkenyl or -C (O) alkyl of 1 to 6 carbon atoms in the alkyl moiety, wherein the alkyl and alkenyl moieties are optionally substituted with one or more R ⁹ groups; or R ⁷ and R ⁸ are joined to form a divalent radical having 4 to 6 atoms in the chain, the divalent radical being an alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene group, preferably forming a morpholine, pyrrolidine, piperidine or piperazine ring; R ⁹ is cyano, nitro, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, R ¹⁰ S (O) _q -, -C (O) C 1 -C 6 alkyl, alkoxycarbonyl C 1 -C 6 alkoxy, aminocarbonyl, C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 dialkylaminocarbonyl, COOH, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl (C 1 -C 6) or (C 1 -C 6) dialkylaminosulfonyl; R ¹⁰ is lower alkyl of 1 to 6 carbon atoms or lower haloalkyl of 1 to 6 carbon atoms; m, n, p and q are 0, 1 or 2; M is C-halogen, C-CH ₃ , C-CH ₂ F, C-CH ₂ Cl, C-NO ₂ or N; or a pesticidally acceptable salt thereof; excluding the 1-arylpyrazoles of formula (I) wherein R ⁵ is haloalkyl of 1 to 6 carbon atoms; and Z is H, 1 H-pyrrol-1-yl, amino or NH-R ^6, wherein R ⁶ is a formyl group, an alkynyl group having 3 to 6 carbon atoms, alkoxycarbonyl having 1 to 6 carbon atoms in the alkoxy a moiety, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, or a -C (O) alkyl group having 1 to 6 carbon atoms in the alkyl moiety, wherein the alkyl moiety is optionally substituted with one or more R ⁹ substituents, wherein R ⁹ is halogen; and the other symbols are as previously defined. A compound according to claim 1, wherein R ³ is halogen, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy. A compound according to claim 1 or 2, wherein R ⁵ is an alkyl group having 1 to 6 carbon atoms. A compound according to claim 1, 2 or 3 wherein Z is amino, R ⁶ NH- or R ⁷ R ⁸ N-. The compound of claim 1, wherein: R ¹ is a fluorine, chlorine, bromine or hydrogen atom; R ² and R ⁴ are hydrogen atoms; R ³ is -CF ₃ , -OCF ₃ , -CHF ₂ , -S (O) _m CF ₃ , -CFC ₁₂ , -CF ₂ Cl, -OCF ₂ Cl, -OCFC ₁₂ , a chlorine, bromine or fluorine atom; R ⁵ is methyl or ethyl; Z is hydrogen, halogen (fluoro, chloro, bromo), (C 1 -C 3) alkyl, (C 1 -C 3) haloalkyl, (C 2 -C 3) alkenyl or amino, -NHR ⁶ or - NR ^{7 R,} wherein each R ^6, R ⁷ and R ^8, which may be the same or different, is alkyl of 1 to 3 carbon atoms, alkenyl of 3 carbon atoms or -C (O) alkyl wherein the the alkyl or alkenyl moieties are unsubstituted or substituted by cyano, C 1 -C 6 alkoxy, C 1 -C 6 alkyl-S (O) _p , nitro, C 1 -C 6 alkoxycarbonyl, -C (O) alkyl of 1 to 6 carbon atoms in the alkyl moiety, aminocarbonyl, alkylaminocarbonyl of 1 to 6 carbon atoms in the alkyl moiety, dialkylaminocarbonyl of 1 to 6 carbon atoms in the alkyl moiety, another -COOH, hydroxy or halogen (fluorine, chlorine, bromine) and M is CCl, CF, CBr or N. The compound of claim 1, wherein: R ¹ is a chlorine or bromine atom; R ² and R ⁴ are hydrogen atoms; R ³ is -CF ₃ , -OCF _3, or a chlorine atom; R ⁵ is methyl or ethyl, Z is hydrogen, halogen (fluoro, chloro, bromo), (C 1 -C 3) alkyl, (C 1 -C 3) haloalkyl, (C 2 -C 3) alkenyl or amino, -NHR ⁶ or - NR ⁷ R ⁸ , wherein each R ⁶ , R ⁷ and R ⁸ , which are the same or different, is a C 1 -C 3 alkyl group, a C 3 alkenyl group or a C (O) alkyl group having from 1 to 3 carbon atoms; 6 carbon atoms wherein the alkyl and alkenyl moieties are unsubstituted or substituted by cyano, C1-C6 alkoxy, C1-C6 alkyl-S (O) _p , nitro, C1-C6 alkoxycarbonyl moieties, -C (O) alkyl of 1 to 6 carbon atoms in the alkyl moiety, aminocarbonyl, alkylaminocarbonyl of 1 to 6 carbon atoms in the alkyl moiety, dialkylaminocarbonyl of 1 to 6 carbon atoms in the alkyl moieties a COOH group, a hydroxy group or a halogen atom (fluorine, chlorine, bromine) and M is CCI, CBr or N. The compound of claim 1, wherein: R ¹ is chlorine or bromine; R ² and R ⁴ are hydrogen atoms; R ³ is -CF ₃ , -OCF _3, or a chlorine atom; R ⁵ is methyl or ethyl; Z is hydrogen or amino and M is CCI, CBr or N. The compound of claim 1, wherein: R ¹ is chlorine or bromine; R ² and R ⁴ are hydrogen atoms; R ³ is -CF ₃ , -OCF _3, or a chlorine atom; R ⁵ is methyl or ethyl; Z is hydrogen or amino and M is CCI, CBr or N. The compound of claim 1, wherein the 1-aryl group is: 2,6-dichloro-4-trifluoromethylphenyl, 2,6-dichloro-4-trifluoromethoxyphenyl, 2-bromo-6-chloro-4-trifluoromethylphenyl, 2-bromo- 6-chloro-4-trifluoromethoxyphenyl, 2,6-difluoro-4-trifluoromethylphenyl, 2-chloro-4-trifluoromethylphenyl, 2,6-dichloro-3-methyl-4-trifluoromethylphenyl, 3-chloro-5-trifluoromethyl-2- pyridinyl, 3-chloro-5-trifluoromethoxy-2-pyridinyl, 3,5-dichloro-2-pyridinyl, 2,6-dichloro-4-bromophenyl, 2,4,6-trichlorophenyl, 2-bromo-6-fluoro- 4-difluoromethylphenyl, 2-chloro-6-fluoro-4-trifluoromethylphenyl, 2,6-dibromo-4-trifluoromethylphenyl, 2,6-dibromo-4-trifluoromethoxyphenyl, or 2-bromo-4-trifluoromethylphenyl. A compound according to claim 1, wherein Z is acetylamino, amino, 2-n-butoxypropionylamino, methyl, hydroxyacetylamino, ethyl, 3-ethylsulfinylpropylamino, bromo, formylamino, chloro, methylamino, ethylamino, 2-hydroxyethylamino, 2-hydroxyethylamino, 2-hydroxyethylamino, 2-hydroxyethylamino, 2-etylsulfonyletylaminoskupina, 4-methoxybenzoylamino, 2-cyanoethylamino, 4-methoxybenzylamino, 2-metyltioetylaminoskupina, 2-aminokarbonyletylaminoskupina, 2-metylsulflnyletylaminoskupina, 3-metoxykarbonylpropylaminoskupina, 2-etylsulfinyletylaminoskupina, 2-methylsulfonylethylamino, cyanomethylamino, 2-etyltioetylaminoskupina, aminokarbonylmetylaminoskupina, dimethylamino, 2-nitroethylamino, 2-acetylethylamino, methylcarbonylmethylamino, methoxycarbonylamino or ethoxycarbonylamino. A compound according to claim 1, wherein the -S (O) _n R ^{5 group} is methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfonyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl or isopropylthio. A compound of formula (I) according to claim 1 which is: 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthiopyrazole-3-thiocarboxamide, 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide, 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfonylpyrazole-3-thiocarboxamide, 5-amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide, 5-amino-1- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide, 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-ethylsulphinylpyrazole-3-thiocarboxamide, 5-amino-1- (2-chloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide, 5-amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide, or 5-amino-1- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide. A pesticidal composition comprising a pesticidally effective amount of 1-arylpyrazole of formula (I) according to any one of claims 1 to 12 or a pesticidally acceptable salt of 1-arylpyrazole of formula (I) as defined in claim 1 together with an agriculturally acceptable inert carrier. Pesticidal composition according to claim 13, characterized in that it contains from 0.05 to 95% by weight of the compound of the formula (I). Pesticidal composition according to claim 13, characterized in that it contains from 0.00005 to 90% by weight of the compound of the formula (I). A method for controlling pests at a locus thereof, comprising applying to said locus a pesticidally effective amount of 1-arylpyrazole of formula (I) according to any one of claims 1 to 12 or a pesticidally acceptable salt of 1-arylpyrazole of formula (I) as defined in claim 1 or the composition of claims 13, 14 or 15. 17. The method of claim 16, wherein the pest is an insect. 18. The method of claim 17, wherein the insect is a mammalian insect. 19. The method of claim 16, wherein the site is a crop area. The method of claim 16, wherein the compound is applied to the locus in an amount of from 5 g to 1 kg / ha. 21. The method of claim 16, wherein the site is an animal. 22. The method of claim 21, wherein the compound is applied to the locus in an amount of from 0.1 to 20 mg per kg of animal body weight per day. A method for controlling vertebrate pests comprising administering 1-arylpyrazole of formula (I) according to claim 1 or a pesticidally acceptable salt thereof in a single dose of 0.1 to 100 mg per kg body weight of the animal or in doses of 0 0.01 to 20 mg per kg animal body weight per day. A process for the preparation of a compound of formula (I) according to claim 1 or 12, characterized in that: (a) reacting a compound of formula (II) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , M, and Z are as defined in claim 1 with an alkali metal or alkaline earth metal hydrosulfide; wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , M and Z are as defined in claim 1 and is 1 or 2, the corresponding compound of formula (I) is oxidized, wherein n is 0 or 1, ( c) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and M are as defined in claim 1 and Z is R ⁶ NH-, wherein R ⁶ is an ethyl group substituted at the 2-position with R ⁹ , wherein R is ⁹ is cyano, nitro, -S (O) _q R ¹⁰ , -C (O) alkyl of 1 to 6 carbon atoms in the alkyl moiety, alkoxycarbonyl of 1 to 6 carbon atoms in the alkoxy moiety, alkylaminocarbonyl of 1 to 6 carbon atoms in the alkyl moiety, dialkylaminocarbonyl having 1 to 6 carbon atoms in the alkyl moiety, aminosulfonyl group, alkylaminosulfonyl having 1 to 6 carbon atoms, or dia C 1-6 alkylaminosulfonyl, alkylates the corresponding compound of formula (1) wherein Z is amino, a compound of formula (ΠΙ) R ⁹ - CH = CH ₂ (III) wherein R ⁹ is as defined in claim 1, (d) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and M are as defined in claim 1 and wherein Z R ^{6 is} NH- or -NR ⁷ R ⁸ , wherein R ⁶ , R ⁷ and R ⁸ are C 1 -C 6 alkyl or C 1 -C 6 haloalkyl optionally substituted by one or more R ⁹ groups, alkylates the corresponding compound of formula (I) wherein Z is amino, a compound of formula (IV) RY (IV) wherein R ¹¹ is an alkyl group having 1 to 6 carbon atoms or haloalkyl having 1 to 6 carbon atoms, optionally substituted by one or more R ⁹ and Y is a leaving group, (e) wherein Z is an alkoxycarbonyl group 1 to 6 carbon atoms, the corresponding compound of formula (I) wherein Z is carboxy is esterified with an alcohol of formula (V) R ¹² -OH (V) wherein R ¹² is C 1 -C 6 alkyl, (f) where Z is C 1 -C 6 alkylthiocarbonyl, esterifies the corresponding compound of formula (I) wherein Z is carboxy , a thiol of formula (VI) R ¹² - H (VI) wherein R ¹² is alkyl of 1 to 6 carbon atoms, (g) wherein Z is R ^I3 CH (C1) _CH2 -, wherein R ¹³ is an alkyl group having 1 to 6 carbon atoms , diazotizing the corresponding compound of formula (I) wherein Z is amino and then reacted with a compound of formula (VII) R ^{, 3} CH = CH ₂ (VII) in the presence of a copper salt, (h) wherein Z is -C (O) alkyl of 1 to 6 carbon atoms in the alkyl moiety, the corresponding compound of formula (VIII) is oxidized wherein R ¹ , R ^2, R ^3, R ^4, R ^5, the M are as defined in claim 1 and R ¹⁴ is alkyl of 1 to 6 carbon atoms, (i) wherein Z is R ^I3 = CH-, and R ¹³ is alkyl of 1 to 6 carbon atoms, the dehydrochlorinated corresponding compound of formula (I) wherein Z is R ³ CH (C1) _CH2 -, and optionally converting the resulting compound of formula (I) into a pesticidally acceptable salt. A process for preparing a pesticidally acceptable salt of 1-arylpyrazole of formula (I) as defined in claim 1, comprising converting such a 1-arylpyrazole of formula (I) to a pesticidally acceptable salt thereof.