SK85699A3 - 1-arylpyrazoles and their salts, pesticidal agents containing such compounds as the active substances, process for the preparation of 1-arylpyrazoles and method for killing pests - Google Patents

Abstract

The invention relates to 1-arylpyrazole-3-thiocarboxamide derivatives of formula (I), wherein R1, R2, R3, R4, R5, M, Z and n are as defined in the description, and to their use as 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

The present invention provides novel pesticidal compounds of the class 1-arylpyrazoles and a process 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

(I) where

R ¹ is a hydrogen atom or a halogen atom, each of R ² and R ^{4 '*} , which are the same or different, is 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 ΙΗ-pyrazole -l-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 the alkyl and alkenyl moieties are optionally substituted with one or more R ⁹ , or R ⁷ and R ⁸ are joined to form a bivalent radical having 4 to 6 carbon atoms in the chain, the bivalent radical being alkylene, alkyleneoxyalkylene or an alkyleneaminoalkylene group, preferably forms a morpholine, pyrrolidine, piperidine or piperazine ring,

R ⁹ is cyano, nitro, alkoxy, haloalkoxy, R ¹⁰ S (O) _q -, -C (O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, COOH, halogen, hydroxy, amino , alkylaminosulfonyl or dialkylaminosulfonyl,

R ¹⁰ is lower alkyl or lower haloalkyl, 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, and their pesticidally active salts.

By pesticidally effective 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 amino group are salts with inorganic acids such as hydrochlorides, phosphates, sulfates and nitrates and salts with organic acids such as acetates. Suitable base salts 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 stated, 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, i.e. a group of formula -C (O) NH2. Similarly, the term alkylaminocarbonyl means an alkylcarbamoyl radical, i.e. a radical of formula -C (O) -NHalkyl, and the term dialkylaminocarbonyl means a dialkylcarbamoyl radical, a radical of the formula -C (O) -N (alkyl) ₂ , wherein the alkyl moieties may be the same or different. The term aminosulfonyl means

J is a sulfamoyl radical, i.e. a group of the formula -SÔ ₂ NH ₂ . Similarly, the term alkylaminosulfonyl means an alkylsulfamoyl radical which is a group of 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 by fluorine, chlorine, bromine or iodine in any combination, preferably fluorine or chlorine. By halogen is meant fluorine, chlorine, bromine or iodine. When the name of any substituent is repeated, it has the same meaning unless otherwise indicated. The term aroyl means a carbonyl aromatic radical, 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 or NR R, wherein each of R ⁶ , R ¹ and R ⁸ , which may be the same or different, is a C 1 -C 3 alkyl, a C 3 alkenyl or a -C (O) alkyl group wherein the alkyl and alkenyl groups the moieties are unsubstituted or substituted by cyano, alkoxy, alkyl-S (O) _p , nitro, alkoxycarbonyl, -C (O) alkyl, aminocarbonyl, al) jylaminocarbonyl, dialkylaminocarbonyl, -COOH, hydroxy or 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 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 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

A!

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 methyl or ethyl,

Z is hydrogen or amino; and

M is CCl, CBr or N.

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

Preferred phenyl or pyridyl groups containing R ¹ to 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-ethylsulfinylpropylamino, bromo, formylamino, chloro, methylamino, methylamino, 2-hydroxyethylamino, 2-hydroxyethylamino, 2-hydroxyethylamino, 2-hydroxyethylamino, 2-etylsulfonyletylaminoskupina, 4-methoxybenzoylamino, 2-cyanoethylamino, 2-metyltioetylaminoskupina, 2-aminokarbonyletylaminoskupina (2-carbamoylethylamino), 2-methylsulphinyl ethylamino, 3-metoxykarbonylpropylamin'oskupina, 2-etylsulfinyletylaminoskupina, 2-methylsulfonylethylamino, cyanomethylamino, 2-etyltioetylaminoskupina, aminocarbonylmethylamino (carbamoylmethylamino), dimethylamino, 2-nitroethylamino, 2-acetylethylamino, methylcarbonylmethylamino (acetylmethylamino), methoxycarbonyl and ethoxycarbonyl.

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

Particularly preferred pyrazole derivatives are designated herein by reference and for identification purposes, which are designated by numbers 1 through

11th

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

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

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

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

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

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

7. 5-Amino-1- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-methylsulphinylpyrazole-3-thiocarboxamide

8. 5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide;

9. 5-Amino-1- (2-chloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide

10. 5-Amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide

11. 5-Amino-1- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide

The 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 I can 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 such as 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 such as sodium, potassium or ammonium . By using a crown ether complexing agent, the reaction can be accelerated.

such as

The reaction of the hydrosulfide salt with 3-cyanopyrazole can be carried out in a biphasic water / solvent system of a phase transfer catalyst such as crown also using ether and with a metal 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 an agent of formula Ph ₂ PS ₂ , as described in Tetrahedron Lett., 24 (20), 2059 (1983).

According to another embodiment of the invention, the compounds R ² , R ³ , R ⁴ , R ⁵ , M and Z are to be prepared by oxidation of the corresponding I, with a mild thioamide inert formula I, wherein R ¹ , meaning and where n is 1 or 2 In general, the formula was to prevent the destruction of sodium periodate in dichloromethane, with the solvent.

a temperature from where n is 0 or 1. Reaction with an oxidizing agent (to provide a functional group) as a solvent,

-40 ° C until boiling point is for example

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 7 ⁸ are alkyl, haloalkyl, -C (O) alkyl, alkoxycarbonyl, formyl, and -S (O) _p alkyl, or R ⁶ and R ⁷ are joined to form a bivalent radical containing 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, 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 at the 2-position with R ⁹ , wherein R ⁹ is cyano, nitro, -S (O) _q R ¹⁰ , -C (O) alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl corresponding compounds, to prepare a general of formula I, by a reaction 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 Ν, Ν-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 ⁸ N-, wherein R ⁷ and R ⁸ is an alkyl or haloalkyl group optionally substituted by 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

R ¹¹ -Y (IV) wherein R ¹¹ is an alkyl or haloalkyl group optionally substituted by one or more R ⁹ and Y is a leaving group, preferably a halogen atom (e.g. chlorine).

I

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

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 can be prepared by reaction of 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 ¹³ CH (Cl) CH 2 - wherein R ¹³ is an alkyl group can be prepared by diazotizing the corresponding compound of formula I wherein Z is amino and then reacting 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 -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,

(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.

According to another embodiment of the invention, compounds of formula I wherein Z is R ¹³ CH = CH- can be prepared by dehydrochlorination of the corresponding compounds of formula I wherein Z is R ¹³ CH (Cl) CH 2 -. 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 ΙΗ-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 I wherein Z is formyl. The reaction is generally carried out using potassium permanganate or chromic acid in a solvent such as water, at a temperature from 0 ^and C to the reflux temperature.

Intermediates of formula VIII may be prepared by reacting the corresponding compound of formula I wherein Z is formyl with an organometallic reagent of formula R ¹⁴ Q, wherein Q is preferably an alkali 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 -100 ° C to 100 ° C.

Certain compounds of formula (II) are novel and are also within the scope of the present invention.

The intermediates of formulas III and IV are known or can be prepared by known methods.

In Table 1, specific compounds of Formula I are illustratively summarized. In this table, the term c-Pr is cyclopropyl and CH 2 CH 2 H is 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 C1 H cf ₃ H CC1 2 scf ₃ nh ₂ C1 H cf ₃ H CC1 3 with ₂ cfci ₂ H C1 H C1 H CC1 4 statues ₃ nh ₂ C1 H cf ₃ H CC1 5 Sat ₂ ch ₃ nh ₂ C1 H cf ₃ H CC1 6 statues ₃ nh ₂ br H cf ₃ H CC1 7 statues ₃ nh ₂ C1 H ocf ₃ H CC1 8 SOC2H5 nh ₂ C1 H cf ₃ H CC1 9 statues ₃ nh ₂ H H cf ₃ H CC1 10 soc ₃ h ₅ nh ₂ br H cf ₃ H CC1 11 soc ₃ h ₅ nh ₂ C1 H ocf ₃ H CC1 12 SC2H5 nh ₂ C1 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 C1 H , cf ₃ i H CF 15 Sat ₂ ch ₃ nh ₂ C1 H cf ₃ o H CC1 16 SOCH3 NHC2H5 C1 H cf ₃ H CC1 17 soc ₃ h ₅ NHCH3 F H cf ₃ ch ₃ CC1 18 SO-c-Pr NHCH2OCH3 br H cf ₃ H CC1 19 SOCH3 NHCH2CONH2 C1 H cf ₃ H N 20 S-i-C3H7 nh ₂ C1 H cf ₃ o H CC1 21 Sat ₂ c ₂ h ₅ NHCHO C1 ch ₃ cf ₃ p H CBr

22 sch ₃ nh ₂ C1 H cf ₃ ch ₃ CF 23 SOCH ₃ NHSO2C2H5 C1 H chf ₂ H CC1 24 SO-c-Pr br F H CCIFz H CF 25 SCH ₂ C ₂ H H C1 H cf ₃ H CBr 26 SOC2H5 ch ₃ C1 H CF ₃ O H CC1 27 SCH ₂ CH = CH ₂ nhnh ₂ br ch ₃ cf ₃ H CC1 28 SOCH3 nh ₂ C1 H cf ₃ H cch ₃ 29 sch ₃ NHSC2H5 C1 H cf ₃ H CC1 30 statues ₃ NHCH ₂ CH ₂ CN C1 H cf ₃ H CC1 31 SO2CH3 NHCH2CH2OCH3 C1 H cf ₃ ch ₃ CC1 32 SO-i-C3H7 nh ₂ C1 H cf ₃ H N 33 SOC ₂ H ₅ COCH3 br H cf ₃ o H CC1 34 SOCH3 NHCH3 C1 H cf ₃ H CC1 35 SOCH3 nh ₂ br H cf ₃ H N 36 SOC ₂ H ₅ NH (CH ₂ ) ₂ CONH ₂ C1 H cf ₃ H CC1 37 SOCH3 ch = ch ₂ F ch ₃ cf ₃ H CF 38 SO2CH3 nh ₂ C1 H , cf ₃ / H cno ₂ 39 SO-c-Pr nhco ₂ ch ₃ C1 H CF ₂ C1 H CC1 40 sch ₃ NHSCC13 C1 H cfci ₂ H CC1 41 SCH ₂ C ₂ H nhch ₂ ch ₂ sch ₃ F H cf ₃ H CC1 42 SOC2H5 NHCH ₂ CH ₂ SOC ₂ H ₅ C1 H cf ₃ H CC1 43 SOC ₂ H ₅ ch ₃ H H cf ₃ H CC1 44 SOC2H5 N _{(CH3) 2} H H cf ₃ H CC1 45 SOCH3 N _{(CH3) 2} C1 H cf ₃ 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-metyltiopyrazol-

3-thiocarboxamide

To a stirred solution of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4-methylthiopyrazole (4.7 g) and 5 drops of 15-crown-5 in degassed N, N-dimethylformamide was added a solution of sodium hydrosulfide hydrate (0.79 g) in degassed water was added over several 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-methylthiopyrazole -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.č. R ¹ R ² R ³ R ⁴ M R ⁵ S (O) _n from mp ° C 2 Cl H cf ₃ H CC1 scf ₃ nh ₂ 182 3 Cl H Cl H CC1 SO ₂ CFC1 ₂ H 180.5 4 Cl H cf ₃ H CC1 statues ₃ nh ₂ 192 5 Cl H cf ₃ H CC1 Sat ₂ ch ₃ nh ₂ 231 6 br H cf ₃ H CC1 statues ₃ nh ₂ 188.5 7 Cl H ocf ₃ H CC1 statues ₃ nh ₂ 137 8 Cl H cf ₃ H CC1 SOC2H5 nh ₂ 167 9 H H cf ₃ H CC1 statues ₃ nh ₂ 153.5 10 br H cf ₃ H CC1 SOC2H5 nh ₂ 113.5 11 Cl H ocf ₃ H CC1 SOC2H5 nh ₂ 102

Comparative Example 1 f

Ί

5-amino-l- (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 is 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), ^T H NMR (CDCl 3): NH ₂ (2H, br s, 3.84 ppm ), 4-H (1H, s, 5.97 ppm), aroma. (LH, s, 7.53 ppm).

Comparative Example 2

5-amino-4-dichlorofluoromethylthio-l- (2,4,6-trichlorophenyl) -3kyanopyrazol

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-l- (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-butyl nitrile (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), m.p. 143.5-145 ° C.

Comparative Example 5

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 (C-18 column, eluting with CH ₃ CN and H 2 O 3: 1 at 1.0 mL / min), the compound showed a peak area of 86.6% at 5.11 min.

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. A 10% aqueous sodium hydroxide solution (2.8 mL) was added and the reaction mixture was stirred at 4 ° C for 1 hour, poured into water and extracted with dichloromethane and ethyl acetate. The dried (Na 2 SO ₄₎ the combined organic phase was evaporated and purified by flash chromatography on silica gel eluting hexane: ethyl acetate 4: 1, is cut with hexane dichloromethane gave 5-amino-l- (2-chloro-4-trifluoromethyl) - 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 was warmed to 20 ° C for 2 hours, then poured onto ice and the solid, washed with water was dried. Flash chromatography on silica gel gave 5-amino-1- (2-chloro-4-trifluoromethyl) -3-cyano-4-methylsulfinylpyrazole (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 biting insects (Lepidoptera).

The following species were tested:

kind of common name in short Aphis gossypii cotton APHIGO Schizapis graminum bed bug TOXOGR Musca domestica housefly , MUSCDO t

Soil irrigation test (systemic effectiveness)

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 turntable and sprayed with 100 ppm of the preparation of a selected compound of formula I. Treated aphid-infected plants are maintained for three days after treatment and then the dead aphids are counted.

Compounds 1 to 11 of the invention exhibit 10 ppm of Aphis gossypii and Schizapis graminum in the systemic test, 100 ppm of Musca domestica and 100 ppm of Aphis gossypii and 100 ppm of Aphis gossypii in the 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. Destruction of these leaf pests can be accomplished 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 aerial 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 systematically destroyed by the compounds of the invention include the Homoptera (stinging-sucking), the Hemiptera (stinging-sucking) and the Thysanoptera. The invention is particularly suitable for aphids and chips.

As is evident from previous pesticidal 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 the formula I or their pesticidally acceptable salts are advantageously used in practice, for example, for agricultural or horticultural crops, in forestry, veterinary medicine or in livestock farming or in health and public hygiene. In this regard, whenever the term compound of formula (I) is used, it is also meant to include pesticidally acceptable salts thereof. 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 of controlling pests at their locus by treating the locus (e.g. by administration or administration) with an effective amount of a compound of formula I or a pesticidally acceptable salt thereof, wherein the substituents in the compound are as defined herein. For example, a locus refers to a pest itself or a site (plant, animal, field, organism, buildings, forest, orchard, waterway, soil, plant or animal product or the like) where insects are kept or nourished.

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 exhibit 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 or should be grown or incorporated therein or to the seeds or 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 standing waters. '

For the treatment of Heterotermes spp., Foundations, termites,

Coptotermes of buildings or soil for example spp. .

for prevention

Reticulitermes spp.

egg spp., such as zea. Against and the seas),

Heliothis and larvae and larvae

Heliothis

Heliothis for example decemlineata (beetles), Leptinotarsa (pests)

In agriculture against adults

Lepidoptera (butterfly)

Heliotis virescens, an adult

Anthonomus spp., For example, Potato tapeworm, Diabrotica spp.

corn). Against Heteroptera (Hemiptera and Homoptera), for example, individuals, for example armigera

Coleoptera grandi s,

corn rootworm

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 Ächeta 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 Coptotermes 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 for agriculture, forestry or horticulture or directly or by the spread of bacterial, viral, mycoplasmic or fungal plant diseases. For example, these nematodes are Meloidogyne spp. (e.g. M. incognita).

In the field of veterinary medicine or animal husbandry, or in health and public hygiene against arthropods, helminths or protozoa which parasitize internally or externally, vertebrates, 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 Ornithodorus 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. against infections of the gastrointestinal tract caused by nematode worms, e.g. Trichostrongylidae, for controlling and treating diseases caused by elements, for example Eimeria spp., For example 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, for example, 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 mode 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 insect is an insect living in the soil, the active compound is usually formulated into a composition which is distributed evenly!

over the surface to be treated (e.g., scattering or stripping) by any suitable method, applying an amount of from about 5 to about 1 kg / ha, preferably from about 50 to about 250 g / ha 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 seedlings or forest trees such as cereals (such as wheat or rice), cotton, vegetables (such as paprika) , field crops (such as sugar beets, soybeans or oilseed rape), pastures or forages (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 evergreen), 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, mammalian annoying flies. In particular, the compounds of the invention are useful for destroying arthropods, helminths or protozoa present in domestic animals or living on their skin or in their skin or sucking the blood of the animals, which are administered orally, parenterally, percutaneously or topically .

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 an animal, but poultry that survive a strong infection have a significantly reduced cost to the market as a result of β

infection. '

The described 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 for the protection of stored products, domestic 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 as suspensions of finely crushed or encapsulated formulations such as soil or root treatment with liquid irrigation, dust, granules, smoke or foam, for crop seeds by application as seed coatings with liquid suspensions or dusting, in animals infected or exposed to arthropods, helminths or elements by parenteral, oral or topical application of compositions in which the active ingredient has immediate and / or prolonged action for a certain period of time on arthropods, helminths or protozoa, for example by incorporation into feed or suitably ingestible pharmaceuticals preparations, edible baits, salt licks, dietary supplements, infusions, sprays, baths, dives, showers, fluid flow, dusting, brushing, shampooing, creams, wax disinfection, or a system operated by the animals themselves , in the environment in general or in specific locations where pests are hiding, including stored products, timber, household goods or domestic or industrial objects such as sprays, mists, dusts, fumes, wax disinfectants, lacquers, granules or bait or slow feeds 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, 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 herein, 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 or surfactants. substances relevant to 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. Typically, 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 1 to about 95% by weight.

0.1 to about 50% of one or more other compatible ingredients, such as surfactants or the like.

By carrier is meant an organic or inorganic component of natural or synthetic origin which, in conjunction with the active ingredient, 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, montmorillonite, bentonite synthetic minerals such as silicates, especially clay granules such as granules of organic materials, nuts, ears of corn, especially suitable are: crushed or calcite, marble, inorganic talc, chalk, quartz, attapulgite, or diatomaceous earth or ground are silica, alumina or magnesium. As solid carriers for fractionated natural rocks, sepiolite and dolomite, synthetic organic meal, granules are sawdust, coconut corn husks or tobacco stems, pumice stone or as diatomaceous earth, calcium phosphate, powdered cork 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, in particular from

chlorobenzenes, water-soluble or strongly polar solvents such as dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone, liquefied gases or the like, or mixtures thereof.

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 of sulfonates taurine (especially alkyltaurates), phosphoric esters of alcohols 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. 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 in the compositions. 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 dyes.

Compositions containing compounds of Formula I or pesticidally acceptable salts thereof that 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 nematicides, anthelmintics, or anti-coccidiosis agents, fungicides (agricultural or veterinary such as 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 efficacy, persistence, safety, absorption, spectrum of insect control, or allow the composition to perform other useful functions in the same animal or area treated.

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, demeton-S-methyl, fenamiphos, monocrotophos, chlorpyrifos, fenitrothion, malathion, pirimiphos-methyl, cypermethrin permethrin, pirimicarb, lindane, avermectins, dichlorvos, phonophos, parathion, terbufos, deltamethrin, tefluthrin, bendiocarb, benzoximate, ivermectins, diaveridine or dimetriadazole.

ethoprofos, isofenphos, phosalone, cyfluthrin, fenvalerate, disulfotone, isazophos, phorate, triazophos, fenpropathrin, carbosulfan, methomyl, oxamyl, endosulfan, tetradifon, trichlorfon, aldicarb, teflubenzurap, thicbolexate, dicofolate

For agricultural application, the formulas I or their pesticidally acceptable salts of the compositions are in forms.

Compounds generally in the form which are present in a variety of solid general or liquid forms are formulations which (containing a compound of formula I acceptable or powdered salts in the range of up to

Powder dispersible or pesticidically wettable powders dispersible with water), in particular by impregnating the granulated powder-based powder (content or granules obtained by the carrier (including extrusion, or

I general

%).

one compound of its pesticidally acceptable salt is

Solid homogeneous or heterogeneous compositions or multiple compounds of Formula I herein between; to about 80%), granules by compression, granulation of formula I of about 0.5 to containing or a pesticidally acceptable salt thereof, for example granules, pellets, briquettes or capsules, can 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, flowables, 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 aerosol.

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 contaminated or susceptible to arthropod infestations (or other pests destroyed by compounds of the invention), including buildings, exterior or interior storage areas or work areas, containers or equipment or standing or running water.

All of these aqueous dispersions or emulsions or spray mixtures can be applied, for example, to the crops by any suitable method, in particular by spraying in amounts 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. volume), depending on need or technique. The compounds or compositions of the invention apply to vegetation and in particular to roots or leaves, the pests are to be eliminated. Another method of the compounds or compositions of the invention is the chemization, addition of a water preparation. This irrigation of pesticides on leaves by spraying on soil or systemic pesticides.

suitably in which application it is containing the active ingredient to irrigation can be carried out by spraying at or spraying the ground or underground

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, penetrating 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. In the preparation of these wettable powders, the active ingredient or ingredients are 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.

The water dispersible granules (WG) (granules that readily disperse in water) have a composition substantially close to that of wettable powders. They may 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 dispersing agent 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 typically 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 pesticidally acceptable salt thereof. or all active ingredients (ie compounds 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 a pesticide thereof acceptable salts. For administration to animals orally or parenterally, including percutaneously, they contain solid or liquid compositions of 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 sol 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 I or a compound thereof pesticidally acceptable salts. Suitable concentrations in the applied waters are between about 0.0001 ppm and about 20 ppm, in particular about 0.001 ppm to about 5.0 ppm, of one or more compounds of Formula I, or a pesticidally acceptable salt thereof, and can be used therapeutically in fish farming with appropriate time. impact effect. 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 the vertebrate by percutaneous or other means, parenterally, orally, or doses of the compounds of formula I or their pesticidally acceptable salts depend on the species, age or health of the vertebrate 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, particularly 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, as described in preparation examples. The compositions described in Examples 2A to 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 P 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

A water-soluble concentrate is prepared having the following composition:

active ingredient 7% Ethylan BCP 10% N-methylpyrrolidone 83% To the Ethylan solution BCP dissolved in part N-methyl-

pyrrolidone, the active ingredient is added under heating and stirring, until

will dissolve. The resulting solution was solvent. adjusts to final volume remaining Example 2B Ready emulsifiable concentrate (EC) with 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 Ready wettable powder (WP) having the following composition: effective component 40% Arylan WITH 2% Darvan No.2 5% Celite PF 53%

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

Example 2D

An aqueous flowing composition having the following composition is prepared:

active ingredient 40,05% Ethylan BCP 1.00% Sopropon T360 0.20% ethylene glycol 5,00% Rhodigel 230 0.15% Water 53, 65%

The ingredients are mixed thoroughly and ground in a bead mill until a median particle size of less than 3 μιη is obtained.

Example 2E

prepare is an emulsifiable concentrate composition: active ingredient 30.0% Ethylan BCP 10.0% bentone 38 0.5% >. Solvesso 150 59.5%

with the following

The ingredients are mixed thoroughly and ground in a bead mill until a median particle size of less than 3 μιη is obtained.

Example 2F

Water-dispersible granules are prepared having the following composition:

active ingredient%

Darvan č.2

Arylan S

Celite PF%

%%

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, landfill, stored products or household goods, or animals infested or susceptible to infestation with 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

A bait is prepared with the following composition:

active ingredient 0.1 to 10% wheat flour 80% molasses 19.9 to 19% Ingredients are thoroughly mixed and shaped to the desired forms of bait. This food bait is distributed to sites

infested with arthropods, such as ants, grasshoppers, cockroaches or flies, such as residential and industrial buildings, such as kitchens, hospitals or warehouses or outdoor 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 (pore size 0.22 μπι), by parenteral injection, in an amount of 1.2 to 12 ml solution per 100 kg animal weight.

Example 2J

A wettable powder is prepared having the following composition:

active ingredient%

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 that 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 domestic animals infested or susceptible to infestation by arthropods, nematodes or

spray elements or immersing or oral administration in drinking water, thus destroyed arthropods, worms or protozoa. Example 2K Ready slowly releasing great pellet of granules

containing the following components in different percentages (similar to those described for the previous compositions), as appropriate:

active ingredient thickening agent slow release agent

The intimately mixed 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 make collars or ear tags for attachment to domestic animals to control pests by slow release.

Example 2M

Dispersible granules are prepared having the following composition:

active ingredient% (max) polyvinylpyrrolidone 5% attapulgite clay 6% sodium lauryl sulphate 2% glycerin 2%

The ingredients are mixed as a 45% slurry in water and wet milled to a particle size of 4 µm 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 may 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 (23)

PATENT CLAIMS 1 wherein R ³ 'is halogen, haloalkoxy. What is claimed is: 1. A compound of formula (I) or a pesticidally acceptable salt thereof 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 ; and R ⁵ is lower alkyl, haloalkyl, alkenyl and alkynyl or a cycloalkyl ring of 3 to 5 carbon atoms Z is hydrogen, halogen, alkyl, formyl, -C (O) -alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylidenamino, 1H-pyrrol-1-yl or 1H-pyrazole -1-yl, 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, A 4Ί alkylthiocarbonyl or aroyl or alkyl group, a C 3 -C 6 alkenyl group or a -C (O) alkyl group wherein the alkyl and alkenyl moieties are optionally substituted by one or more R ⁹ , or R ⁷ and R ⁸ are linked so as to form a divalent radical having 4 to 6 carbon 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, alkoxy, R ¹⁰ S (O) _q -, -C (O) alkyl, aminocarbonyl, dialkylaminocarbonyl, hydroxy, aminosulfonyl, dialkylaminosulfonyl or haloalkoxyalkoxycarbonyl alkyl COOH, halogen, alkylaminosulfonyl R ¹⁰ is lower alkyl or lower haloalkyl, 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. 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. A compound according to claim haloalkyl or 3-chloro-5-trifluoromethyl-2-pyridinyl, 3-chloro-5-trifluoromethoxy-2-pyridinyl, 3,5-dichloro-2-pyridinyl, 2,6-dichloro-4-bromophenyl, A compound according to claim 1 or 2, wherein R ⁵ is an alkyl group. 4-Dichlorofluoromethylsulfonyl-1- (2,4,6-trichlorophenyl) pyrazole-3-thiocarboxamide A compound according to claim 1, 2 or 3 wherein Z is amino, R ⁷ NH- or R ⁸ R ⁹ N-. 5-amino-l- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide. 5-amino-1- (2-bromo-6-chloro-4-trifluoromethylphenyl) -4-ethylsulfinylpyrazole-3-thiocarboxamide; or i 5-amino-l- (2-chloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -4-etylsulfinylpyľazol-3-thiocarboxamide 5-amino-l- (2,6-dichloro-4-trifluoromethoxyphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide 5-amino-l- (2-bromo-6-chloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfonyl-3-thiocarboxamide 5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole-3-thiocarboxamide 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylthiopyrazole-3-thiocarboxamide 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthio-3-thiocarboxamide A compound of formula I according to claim 1, 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 or 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. 6th A and A compound of formula I according to claim 1, wherein: R ¹ is chlorine or bromine, R ² a R ⁴ are hydrogen atoms, R ³ is -CF ₃ , -OCF ₃ or chloro, R ⁵ is methyl or ethyl, FROM is a hydrogen atom, a halogen atom (fluorine, chlorine, bromine), C 1 -C 3 alkyl, haloalkyl (C 1 -C 3), (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 alkyl (C 1 -C 3), (C 3 -C 3) alkenyl or -C (O) alkyl, wherein the 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 halogen (fluorine, chlorine, bromine) and M is CCl, CBr or N. A compound of formula I according to claim 1, 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. A compound of formula I according to claim 1, wherein: T R ¹ is chlorine or bromine, R ² and R ⁴ are hydrogen, R ³ is a -cf ₃ , -OCF ₃ or chlorine, R ⁵ is a methyl or ethyl, FROM is a atom hydrogen or amino; and M is a CC1, CBr or N. The compound of claim 1, wherein the 1-aryl groups 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, 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-metylsulfinyletylaminoskupina, 3-metoxykarbonylpropylaminoskupina, 2-ethyl sulfate inyletylaminoskupina, 2-methylsulfonylethylamino, cyanomethylamino, 2-etyltioetylaminoskupina, aminokarbonylmetylaminoskupina, dimethylamino 2-nitroethylamino; 2-acetylethylamino; tylcarbonylmethylamino, methoxycarbonylamino or ethoxycarbonylamino. The compound of claim 1, wherein the -S (O) _n R ^{5 group} is methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, and isopropylthio. A compound of formula I according to claim 1 which is: A pesticidal composition comprising a pesticidally effective amount of a compound of formula I according to any one of claims 1 to 12 together with an agriculturally acceptable inert carrier. 14. A pesticidal composition according to claim 13 comprising from about 0.05 to about 95% by weight of the compound of formula (I). 15. A pesticidal composition according to claim 13 comprising from about 0.00005 to about 90% by weight of the compound of formula (I). 16. A method of controlling pests at a locus thereof, comprising applying to said locus a pesticidally effective amount of a compound of formula I according to any one of claims 1 to 12 or a composition according to claims 13, 14 or 15. 17. The method of claim 16, wherein the pest is an insect. The method of claim 16, wherein the insect is a mammalian insect. 19. The method of claim 16, wherein the site is a crop area. according to claim 16, 20. The method of applying the compound to up to about 1 kg / ha. where the occurrence is from m, About 5 g The method of claim 16, wherein the locus is an animal. by 22. The method of claim 21, wherein the compound is applied to the locus in an amount of from about 0.1 to about 20 mg per kg of animal body weight per day. A process for the preparation of a compound of formula I as defined in claim 1, characterized in that: (a) reacting a compound of formula II (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 n is 1 or 2, the corresponding compound of formula I wherein n is 0 or 1 is oxidized, (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 ⁹ is cyano, nitro, -S (O) _q R ¹⁰ , -C (O) alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl, alkylates the corresponding compound of formula III with III I, wherein Z is an amino group, 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 is R ⁶ NH- or -NR ⁷ R ⁸ , wherein R ⁶ , R ⁷ and R ⁸ are alkyl or haloalkyl optionally substituted by one or more R ⁹ , alkylates the corresponding compound of formula I wherein Z is amino, by a compound of formula IV R ¹¹ -Y (IV) wherein R ¹¹ is an alkyl or haloalkyl group, optionally substituted with one or more R ⁹ and Y is a leaving group, (e) Z is an alkoxycarbonyl group, esterifying the corresponding compound of formula I wherein Z is carboxy, an alcohol of formula V R ¹² -OH (V) wherein R ¹² is an alkyl group, (f) wherein Z is an alkylthiocarbonyl group, esterifies the corresponding compound of formula I wherein Z is carboxy, by a thiol of formula VI (g) wherein Z is R ¹³ CH (Cl) CH 2 -, where R ¹³ is an alkyl group, diazotizes the corresponding compound of formula I, wherein Z is amino, and then reacts with a compound of formula VII, R ¹³ CH = CH ₂ (VII) R ¹² - SH (VI) wherein R ¹² is an alkyl group, in the presence of a copper salt, (h) wherein Z is -C (O) alkyl, a compound of formula VIII is oxidized to the corresponding (VIII) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and M are as defined in claim 1 and R ¹⁴ is an alkyl group, (i) where Z is R ¹³ CH = CH- and R ¹³ is an alkyl group, the corresponding compound of formula I is dehydrochlorinated wherein Z is R ¹³ CH (Cl) CH ₂ -, and optionally converting the compound of formula I so obtained into a pesticidally acceptable salt thereof.