EA003995B1 - Pesticidal 1-aryl and pyridylpyrazole derivatives - Google Patents

Abstract

1. A 1-arylpyrazole of the formula (I): wherein: R1 is H or halogen; each of R2 and R4, which are identical or different, is H, halogen or alkyl; R3 is halogen, haloalkyl, haloalkoxy or R10S(O)m; R5 is lower alkyl, haloalkyl, alkenyl and alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; Z is hydrogen, halogen, alkyl, formyl, -C(O)alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylideneamino, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl, amino, R6NH- OR R7R8N-; each of R6, R7 and R8, which are identical or different, is alkyl-S(O)p-, formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl containing 3 to 6 carbon atoms, or -C(O)alkyl wherein the alkyl and alkenyl portions are optionally substituted by one or more R9; or R7 and R8 are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; R9 is cyano, nitro, alkoxy, haloalkoxy, R10S(O)q, -C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; R10 is lower alkyl or lower haloalkyl; m, n, p and q are 0, 1or 2; M is C-halo, C-CH3, C-CH2F, C-CH2Cl, C-NO2 or N, wherein if not indicated otherwise, said alkyl groups and moieties contain from 1 to 4 carbon atoms, alkenyl and alkynyl groups and moieties contain from 2 to 6 carbon atoms; or a pesticidally acceptable salt thereof; excluding 1-arylpyrazole of the formula (I), in which: R5 is haloalkyl; and Z is H, 1H-pyrrol-1-yl, amino group, or R6NH-, where R6 is formyl, alkynyl, containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl, containing from 3 to 6 carbon atoms or C(O)alkyl, where alkyl portion is optionally substituted by one or more R9, where R9 is halo; and other groups are as defined above. 2. A compound according to Claim 1, wherein R3 is halogen, haloalkyl or haloalkoxy. 3. A compound according to Claim 1 or 2, wherein R5 is alkyl. 4. A compound according to Claim 1, 2 or 3 wherein Z is amino, R6NH- or R7R8N-. 5. A compound according to Claim 1, in which: R1 is F, Cl, Br or H; R2 and R4 are H; R3 is -CF3, -OCF3, -CHF2, -S(O)mCF3, -CFCl2, -CF2Cl, -OCF2Cl, -OCFCl2, Cl, Br or F; R5 is methyl or ethyl; Z is H, halogen (F, Cl, Br), C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl; or amino, -NHR6 or -NR7R8, wherein each of R6, R7 and R8, which are identical or different, is C1-C3 alkyl, C3 alkenyl or -C(O)alkyl wherein the alkyl or alkenyl portions are unsubstituted or substituted with cyano, alkoxy, alkyl-S(O)q-, nitro, alkoxycarbonyl, -C(O)alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, hydroxy or halogen (F, Cl, Br); and M is CCl, CF, CBr or N. 6. A compound according to Claim 1, in which: R1 is Cl or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or Cl; R5 is methyl or ethyl; Z is H, halogen (F, Cl, Br), C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl; or amino, -NHR6 or -NR7R8, wherein each of R6, R7 and R8, which are identical or different, is C1-C3 alkyl, C3 alkenyl or -C(O)alkyl wherein the alkyl or alkenyl portions are unsubstituted or substituted with cyano, alkoxy, alkyl-S(O)p, nitro, alkoxycarbonyl, -C(O)alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, hydroxy or halogen (F, Cl, Br); and M is CCl, CBr or N. 7. A compound according to Claim 1, in which: R1 is Cl or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or Cl; R5 is methyl or ethyl; Z is H or amino; and M is CCl, CBr or N. 8. A compound according to Claim 1, in which: R1 is Cl or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or Cl; R5 is methyl or ethyl; Z is H or amino; and M is CCl, CBr or N. 9. A compound according to 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-chloro4-trifluoromethylphenyl; 2,6-dichloro-3-methyl-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-trichiorophenyl; 2-bromo-6-fluoro-4-difluoromethylphenyl; 2-chloro-6-fluoro-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethylphenyl; 2,6-dibromo4-trifluoromethoxyphenyl; or 2-bromo4-trifluoromethylphenyl. 10. 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-methoxyethylamino, methylsulfonylamino, 2-ethylsulfonylethylamino, 4-methoxybenzoylamino, 2-cyanoethylamino, 4-methoxybenzylamino, 2-methylthioethylamino, 2-aminocarbonylethylamino, 2-methylsulfinylethylamino, 3-methoxycarbonylpropylamino, 2-ethylsulfinylethylamino, 2-methylsulfonylethylamino, cyanomethylamino, 2-ethylthioethylamino, aminocarbonylmethylamino, dimethylamino, 2-nitroethylamino, 2-acetylethylamino, methylcarbonylmethylamino, methoxycarbonylamino, or ethoxycarbonylamino. 11. A compound according to Claim 1, wherein-S(O)nR5 is methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl or isopropylthio. 12. The 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-methysulfonylpyrazole-3-thiocarboxamide; 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole-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-thiocarboxamide; 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-ethylsulfinylpyrazole-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. 13. The compound of formula (I) according to Claim 1, which is: 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole-3-thiocarboxamide; or 4-dichlorofluoromethylsulfonyl-1-(2,4,6-trichlorophenyl)pyrazole-3-thiocarboxamide. 14. A pesticidal composition comprising a pesticidally effective amount of 1-arylpyrazole according to any one of Claims 1 to 13 or a pesticidally acceptable salt 1-arylpyrazole of formula (I) in association with an agriculturally acceptable inert carrier thereof. 15. A pesticidal composition according to Claim 14 which contains from about 0.05 to about 95% (by weight) of a compound of formula (I). 16. A pesticidal composition according to Claim 14 which contains from about 0.00005 to about 90% (by weight) of a compound of formula (I). 17. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of 1-arylpyrazole according to any one of Claims 1 to 13, or a pesticidally acceptable salt 1-arylpyrazole of formula (I) according to any one of claims 14, 15 and 16. 18. The method according to Claim 17, wherein said pests are insects. 19. The method according to Claim 18, wherein said insects are sucking insects. 20. The method according to Claim 17, wherein said locus is a crop area. 21. The method according to Claim 20, wherein said compound is applied to said locus at a rate of from about 5g to about 1 kg/ha. 22. The method according to Claim 17, wherein said locus is an animal. 23. The method according to Claim 22, wherein said compound is applied to said locus at a rate of from about 0.1 to 20mg per kg body weight of the animal per day. 24. A method for controlling pests of vertebrates comprising applying to said animals of 1-arylpyrazole of formula (I) as defined in claim 1 or a pesticidally acceptable salt thereof at a unit dosage of about from 0.1 to 100mg per kg body weight of the animal per day. 25. A process for preparing a compound of formula (I) as defined in Claim 1 which comprises the reaction of a compound of formula (II): where R1, R2, R3, R4, R5, M, n and Z are as defined in Claim 1, with an alkali or alkaline earth metal hydrosulfide. 26. A process for preparing a compound of formula (I), in which Z is alkoxycarbonyl or alkylthiocarbonyl, comprising esterification of the corresponding compound of formula (I) in which Z is carboxy with an alcohol of formula (V): R12OH (V) or an thiol of formula (VI): R12SH (VI) wherein R12 in formulae (V) and (VI) is alkyl. 27. A process for preparing a compound of formula (I), in which Z is -C(O)alkyl, comprising oxidation of the corresponding formula (VIII): where R1, R2, R3, R4, R5, M, n and Z are as defined in Claim 1 and R14 is alkyl. 28. The process according to any one of claims 25-27, further comprising a step of the conversion of the compound thus obtained of formula (I) according to claim 1, selected from: a) the oxidation of the corresponding compounds of formula (I) in which n is 1 or 2; b) the alkylation of the corresponding compound of formula (I) wherein Z is amino with a compound of formula (III): R9-CH=CH2 (III) wherein R9 is as defined in Claim 1 obtaining the compound (I), in which Z is R6NH-, wherein R6 is ethyl substituted at the 2-position by R9 in which R9 is cyano, nitro, -S(O)qR10, -C(O)alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; c) alkylation of the corresponding compound of formul

Description

BACKGROUND OF THE INVENTION

1. The scope of the invention.

The present invention relates to new

3-thiocarboxamide derivative of 1-arylpyrazoles and their derivative. The invention also relates to compositions based on these compounds and methods that use these compounds for controlling arthropod pests, in particular, to the use of these compounds or compositions in agricultural methods, in particular as pesticides, to combat arthropod pests, especially insects, through systemic action.

2. Description of the prior art.

The control of insects, nematodes or helminths using 1-arylpyrazoles is described in publications of international patents Nos. XVO 93/06089 (and corresponding US patent No. 5451596), XVO 94/21606 and XVO 87/03781, as well as in European Patent Publications No. 0295117, 659745, 679650, 201852 and 412849, German patent No. 19511269 and US patent No. 5232940.

Objectives and summary of the invention

An object of the present invention is to provide novel pesticidal compounds of the 1-arylpyrazole family together with methods for their preparation.

A second object of the present invention is to provide pesticidal compositions and methods of using pyrazole compounds with pesticidal properties against arthropods, especially insects, in particular with respect to agricultural or horticultural crops, in forestry, veterinary medicine or cattle breeding, or public health.

A third object of the present invention is to provide very active compounds with a wide spectrum of pesticidal action, as well as compounds with a specific selective action, for example, with acidic, miticidal, insecticidal on leaf cover, soil insecticidal, systemic, nutritional or pesticidal effect provided by seed treatment.

A fourth object of the present invention is to provide compounds with significantly enhanced and faster action, especially against insects and, more specifically, against insects that are in the stage of larvae.

A fifth objective of the present invention is to provide compounds with significantly improved (faster and more significant) penetration into pest species by local (local) application, and thus to provide enhanced promotion of the compound to pesticidal sites within the pest.

These and other objects of the invention will become apparent from the following description of the present invention. The invention will fully or partially satisfy these objectives.

The invention provides 1-arylpyrazoles with insecticidal properties,

where K.1 represents H or halogen;

each of K ₂ and K ₄ , which are the same or different, is H, halogen or alkyl;

K ₃ represents halogen, haloalkyl, haloalkoxy or K ₁₀ 8 (O) _t ;

K ₅ represents lower alkyl, haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing from 3 to 5 carbon atoms;

Ζ represents hydrogen, halogen, alkyl, formyl, -C (O) alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylidenamino, 1H-pyrrole-1yl, 1H-pyrazol-1-yl, amino, Κ ₆ ΝΗ- or Β-Β ₈ Ν-;

each of the radicals K ₆ , K ₇ and K ₈ , which are the same or different, are alkyl-8 (O) _p - formyl containing from 3 to 6 carbon atoms, alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl;

or alkyl containing from 3 to 6 carbon atoms, alkenyl or —C (O) alkyl, in which the alkyl and alkenyl moieties are optionally substituted with one or more K ₉ radicals;

or the K ₇ and K ₈ radicals are connected in such a way that they together form a divalent radical containing from 4 to 6 carbon atoms in a chain, and this divalent radical is alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably with the formation of morpholine, pyrrolidine, piperidine or piperazine cycle;

K ₉ is cyano, nitro, alkoxy, haloalkoxy, K. ₁₀ 8 (O), -. -C (O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;

K ₁₀ represents lower alkyl or lower haloalkyl;

t, n, p and d are 0, 1 or 2;

M represents C-halogen, C-CH ₃ , C-CH ₂ E, C-CH ₂ Cl, C-HO ;. or Ν, and unless otherwise indicated, said alkyl groups and fragments contain from 1 to 6 carbon atoms, lower alkyl groups and fragments contain from 1 to 4 carbon atoms, alkenyl and alkynyl groups and fragments contain from 2 to 6 carbon atoms; or a pesticidally acceptable salt thereof; excluding 1arylpyrazoles of the formula (I) in which: K ₅ is haloalkyl; and

Ζ is hydrogen, 1H-pyrrol1-yl, an amino group or Ρ ₆ ΝΗ-, where K ₆ is formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl containing from 3 to 6 carbon atoms, or —C (O) alkyl, wherein the alkyl portion is optionally substituted with one or more K ₉ , where K ₉ is halogen; and other groups are as defined above.

DETAILED DESCRIPTION OF THE INVENTION

Unless otherwise indicated, the alkyl, alkoxy and alkylthio groups contain from one to six (preferably from one to four) carbon atoms. Alkenyl and alkynyl groups contain from two to six (preferably from two to four) carbon atoms, in the present invention some terms are used in the following specific sense.

The term aminocarbonyl refers to a carbamoyl radical, i.e. a radical of the formula —C (O) XH ₂ . Similarly, the term alkylaminocarbonyl means an alkylcarbamoyl radical, i.e. a radical of the formula —C (O) XN-alkyl; and the term dialkylaminocarbonyl means a dialkylcarbamoyl radical, i.e. a radical of the formula —C (O) X (alkyl) ₂ , in which the alkyl radicals may be the same or different. The term aminosulfonyl means a sulfamoyl radical, i.e. -8Ο ₂ ΝΗ ₂ . Similarly, the term alkylaminosulfonyl refers to an alkylsulfamoyl radical, i.e. a radical of the formula -8O ₂ XH alkyl; while the term dialkylaminosulfonyl means a dialkyl sulfamoyl radical which has the formula -8O ₂ X (alkyl) ₂ in which the alkyl radicals may be the same or different.

The term halogen before the name of the radical means that this radical is partially or fully halogenated, that is, in other words, substituted by atoms E, C1, Br or I in any combination, preferably by atoms E or C1. The term halogen means E, C1, Br or I. In the case where the name of any substituent is repeated, it retains the same meaning, unless otherwise indicated. The term aroyl means a carbonyl aromatic radical, i.e. an aryl-C (O) - radical, which is preferably benzoyl, optionally substituted with one or more alkyl or halogen groups.

Compounds are preferred where

K ₃ represents halogen, haloalkyl or haloalkoxy;

K ₅ is alkyl;

Ζ represents amino, K ₆ BN- or Κ ₇ Κ ₈ Ν-.

Compounds wherein

K represents E, C1, Br or H;

K ₂ and K ₄ represent H;

K ₃ represents —CO ₃ , —OCE ₃ , —CHE ₂ , —8 (O) _t CEc, —CEC12, —CE2C1, —OCE2C1, —OCEC12, C1, Vgili E;

K ₅ is methyl or ethyl;

Ζ represents H, halogen (E, C1, Br), C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl; or amino, -CNA. ₆ or ₇ -ΝΚ Κ _8, wherein each of the radicals Rs, R ₇ and R _8, which are identical or different, represents a _C1-C3 alkyl, _C3 alkenyl or -C (O) alkyl in which the alkyl and alkenyl parts are unsubstituted or substituted with cyano, alkoxy, alkyl-8 (O) _h -, nitro, alkoxycarbonyl, -C (O) alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO ₂ H, hydroxy or halogen (E, C1, Br) ; and

M represents CC1, CE, CBg or Ν.

Compounds wherein

TO.! represents C1 or Br;

K ₂ and K ₄ represent H;

K ₃ is —CO ₃ , —OCE ₃ or C1; K ₅ is methyl or ethyl;

Ζ represents H, halogen (F, C1, Br), _C1-C3 alkyl, C1-C ₃ haloalkyl, C ₂ -C ₃ alkenyl; or amino, -ΝΚΚ or -ΝΚ ₇ Κ _8, wherein each of the radicals Rs, R ₇ and R _8, which are identical or different, represents a _C1-C3 alkyl, _C3 alkenyl or -C (O) alkyl, which alkyl and alkenyl moieties are unsubstituted or substituted with cyano, alkoxy, alkyl-8 (O) _p -, nitro, alkoxycarbonyl, -C (O) alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, hydroxy or halogen (E, C1, Vg); and

M represents CC1, CBr or Ν.

Even more preferred are compounds wherein

TO! represents C1 or Br;

Κ ₂ and Κ ₄ are H;

Κ3 is —CE3, —OCE3 or C1;

Κ ₅ represents methyl or ethyl;

Ζ represents H or an amino group; and

M represents CC1, CBr or Ν.

Particularly preferred compounds wherein

Κι is C1 or Br;

Κ ₂ and Κ ₄ are H;

Κ3 represents -CE3; -OCE3 or C1;

Κ ₅ represents methyl or ethyl;

Ζ represents H or an amino group; and

M represents CC1, CBg or N.

Particularly preferred compounds 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;

group Ζ represents a group of acetylamino, amino, 2-n-butoxypropionylamino, methyl, hydroxyacetylamino, ethyl, 3-ethylsulfinylpropylamino, bromo, formylamino, chloro, methylamino, ethylamino, 2-hydroxyethylamino, 2-methoxyethylamino, methylsulfonylaminoamino, 2; 4-methoxybenzoylamino, 2-cyanoethylamine, 4-methoxybenzylamino, 2-metiltioetilamino, 2-aminokarboniletilamino, 2-metilsulfiniletilamino, 3metoksikarbonilpropilamino, 2-etilsulfiniletilamino, 2-metilsulfoniletilamino, cyanomethylamino, 2-etiltioetilamino, aminokarbonilmetilamino, dimethylamino, 2nitroetilamino, 2-acetylethylamino, methylcarbonylmethylamino, methoxycarbonylamino or ethoxycarbonylamino;

group -8 (O) _p Z ₅ is methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl or isopropylthio.

Most preferred compounds selected from

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-bro m-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 -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, and in particular

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

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

A further aspect of the invention is a process for preparing a compound of formula (I) as defined above, comprising reacting a compound of formula (II)

(“) Where K. ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , M, η and Ζ are defined above, with hydrosulfide of an alkali or alkaline earth metal.

Another aspect of the invention is a method for producing a compound of formula (I) in which Ζ is alkoxycarbonyl or alkylthiocarbonyl, comprising esterifying the corresponding compound of formula (I) in which Ζ is a carboxy group, an alcohol of formula (V)

K42OH (V) or thiol of formula (VI)

K428H (VI), where K. | ₂ in formulas (V) and (VI) is alkyl.

A further aspect of the invention is a process for preparing a compound of formula (I), wherein Ζ is —C (O) alkyl, comprising oxidizing the corresponding compound of formula (VIII)

where K. ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , η and M are defined in claim 1 and Z 1 ₄ is alkyl.

Each of the above methods may further comprise a step of interconverting the obtained compounds of formula (I) selected from

a) oxidizing compound (I) in which η is 0 or 1, to give compound (I) in which η is 1 or 2;

b) alkylating a compound of formula (I), where Ζ is amino, with a compound of formula (III)

K ₉ —CH = CH ₂ (III), where K. _{9 is} defined in claim 1, to obtain compound C), in which Ζ is -Κ ₆ ΝΗ-, where Kb is ethyl substituted at position 2 with a K ₉ group, where K ₉ represents cyano, nitro, -8 (O) _h K ₁₀ , -C (O) alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;

C) alkylation of the corresponding compounds of formula (I), where Ζ represents amino, the compound of formula (IV)

Ki-Υ (IV), where K ₁₁ represents alkyl or halogenated, optionally substituted with one or more K ₉ , and Υ represents a leaving group, to obtain compound (I), in which Ζ represents -ΝΗΚ ₆ or -ΝΚ ₇ Κ ₈ , where K _b , K ₇ and K ₈ are alkyl or halogenated, optionally substituted with one or more K ₉ ;

g) diazotization of the corresponding compound of formula (I), where Ζ is amino, followed by interaction with the compound of formula (VII)

K1cCH = CH2 (VII) in the presence of a copper salt to give compound (I) in which Ζ represents K ₁₃ CH (C1) CH ₂ -, where K ₁₃ is alkyl;

d) dehydrochlorination of the corresponding compound of formula (I), where Ζ represents K ₁₃ CH (C1) CH ₂ -, to obtain compound (I), in which Ζ represents K ₁₃ CH = CH ₂ -, and also the conversion of the compounds of formula ( I) in its pesticidally acceptable salt.

A further aspect of the invention is a pesticidal composition comprising a pesticidally effective amount of 1-arylpyrazole according to the invention or a pesticidally acceptable salt of 1-arylpyrazole of formula (I) as defined above, in combination with an agriculturally inert carrier. In particular, the pesticidal composition of the invention contains from about 0.05 to about 95% by weight of a compound of formula I, preferably from about 0.00005 to about 90% by weight of a compound of formula (I).

A further aspect of the invention is a method for controlling pests in a locus of infection, comprising applying to said locus a pesticidally effective amount of 1-arylpyrazole according to the invention or a pesticidally acceptable salt of 1-arylpyrazole of formula (I) as above or a composition according to the invention.

These pests are insects, preferably sucking insects.

The indicated infection site is an area seeded with cultures and the compound is applied to the specified infection site in an amount of about 5 g to about 1 kg / ha. Said infection site may be an animal, wherein said compound is used in an amount of from about 0.1 to about 20 mg per kg of animal body weight per day.

A preferred method for controlling pests of vertebrate animals involves administering to the animal 1-arylpyrazole of formula (I) as above or its pesticidally acceptable salt in a single dose of 0.1-100 mg per kg of animal body or in doses of 0.01 to 20 mg per kg of animal body per day.

Representative specific compounds of formula (I) according to the present invention are presented in table. 1 below. In the table, c-Pr is cyclopropyl, CH2C2H is a propargyl group, and 1-C ₃ H ₇ is isopropyl.

Table 1

Compound No. Kb8 (O) p Ζ K1 K2 K3 K4 m one 8CH3 νή ₂ C1 N CP3 N CC1 2 8СР3 νή ₂ C1 N CP3 N CC1 3 802СРС12 N C1 N C1 N CC1 4 8OCN3 νή ₂ C1 N CP3 N CC1 5 8O2CH3 νή ₂ C1 N CP3 N CC1 b 8OCN3 νή ₂ Vg N CP3 N CC1 7 8OCN3 νή ₂ C1 N OCP3 N CC1 8 8OS2N5 νή ₂ C1 N CP3 N CC1 nine 8OCN3 νή ₂ N N CP3 N CC1 10 8OS2N5 νή ₂ Vg N CP3 N CC1 eleven 8OS2N5 νή ₂ C1 N OCP3 N CC1 12 8С2Н5 νή ₂ C1 N CP3 N CC1 thirteen 8СЩСН = СН2 νή ₂ Vg N CP3 N CC1 14 8OS2N5 INSOS ₃ C1 N CP3 N SR fifteen 8O2CH3 νή ₂ C1 N SR3O N CC1

sixteen 8OCN3 ΝΙΙΓΙΙ. C1 N CP3 N CC1 17 8OS2N5 1HGNSN ₃ R N CP3 CH3 CC1 eighteen 80s-rg Vg N CP3 N CC1 nineteen 8OCN3 ΝΊΚΊΙΗΌΝΊΠ C1 N CP3 N N twenty 8-1-C3H7 νή ₂ C1 N SR3O N CC1 21 8О2С2Н5 1HGNSO C1 CH3 CP38 N SVG 22 8CH3 νή ₂ C1 N CP3 CH3 SR 23 8OCN3 MN8O2S2N5 C1 N CHP2 N CC1 24 8O-e-Rg Vg R N SS1R2 N SR 25 8С1ПС СН N C1 N CP3 N SVG 26 8OS2N5 CH3 C1 N SR3O N CC1 27 8СЩСН = СН2 ΝΉΝ ^ Vg CH3 CP3 N CC1 28 8OCN3 νή ₂ C1 N 6P3 N CCH3 29th 8CH ₃ 1KHGN8S2N5 C1 N CP3 N CC1 thirty 8OCN3 ^ CH ₂ CH ^ C1 N CP3 N CC1 31 8O2CH3 1HGNSN ₂ CH ₂ OCH ₃ C1 N CP3 CH3 CC1 32 8O-1-C3H7 νπ ₂ C1 N CP3 N N 33 8OS2N5 SOSN3 Vg N SR3O N CC1 34 8OCN3 1HGNSN ₃ C1 N CP3 N CC1 35 8OCN3 νπ ₂ Vg N CP3 N N 36 8OS2N5 Ш1 (С11 _; ) _; SOSP C1 N CP3 N CC1 37 8OCN3 CH = CH2 R CH3 CP3 N SR 38 8O2CH3 νπ ₂ C1 N CP3 N SJO; 39 8O-e-Rg ΝΙΚΌΗΊΗ C1 N SR2S1 N CC1 40 8CH3 1MN8SS13 C1 N CPC12 N CC1 41 8С1НС СН 1KHGNSN2CH28CH3 R N CP3 N CC1 42 8OS2N5 1ХНСН2СН28ОС2Н5 C1 N CP3 N CC1 43 8OS2N5 CH3 N N CP3 N CC1 44 8OS2N5 Ν№) 2 N N CP3 N CC1 45 8OCN3 ν№) 2 C1 N CP3 N SVG

The invention is illustrated by the following examples, which are not considered as limiting the invention, but are given in order to better demonstrate its use.

Example 1. 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthiopyrazole-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 Ν, Ν-dimethylformamide for several minutes a solution of sodium hydrosulfide hydrate (0.79 g) in degassed water was added. The mixture was stirred at 20 ° C for 18 hours, evaporated and the residue was purified by flash chromatography on silica gel, eluting with a 2: 1 hexane / acetone mixture to give 5-amino-1- (2,6-dichloro-4 trifluoromethylphenyl) - 4-methylthiopyrazole-3-thiocarboxamide (0.38 g), T. pl. 161 ° C (compound 1).

Using a method similar to the method used above, compounds Nos. 2 to 11 of general formula (I) were also synthesized, as shown in Table 1. 2 below.

table 2

Connection No. K1 AT 2 IN 3 K-4 M I ₅ 8 (O) _p Ζ Mp, ° C 2 C1 N CP3 N CC1 8СР3 ID ₂ 182 3 C1 N C1 N CC1 8О2СРС12 N 180.5 4 C1 N CP3 N CC1 8OCN3 ID ₂ 192 5 C1 N CP3 N CC1 8O2CH3 ID ₂ 231 6 Vg N CP3 N CC1 8OCN3 ID ₂ 188.5 7 C1 N OCP3 N CC1 8OCN3 ID ₂ 137 8 C1 N CP3 N CC1 8OS2N5 ID ₂ 167 nine N N CP3 N CC1 8OCN3 ID ₂ 153.5 10 Vg N CP3 N CC1 8OS2N5 ID ₂ 113.5 eleven C1 N OCP3 N CC1 8OS2N5 ID ₂ 102

Reference Example 1. 5-amino-1- (2,4,6trichlorophenyl) -3-cyanopyrazole.

Sodium nitrite (27.6 g) was slowly added to concentrated sulfuric acid (106 ml) and the mixture was allowed to cool to 30 ° C. Acetic acid (216 ml) was added to the stirred mixture over 30 minutes, which was cooled to 20 ° C, and a solution of 2,4,6-trichloroaniline (70.7 g) in acetic acid was added over 30 minutes, keeping the temperature at level 20-25 ° C. The mixture was heated to 52 ° C for 30 min, then a solution of ethyl 2,3-dicyanopropionate (52.0 g) in a 36% aqueous solution of acetic acid (774 ml) was fed into it for 20 min, while cooling to 10-15 ° C. The reaction mixture was allowed to warm to 20 ° C, diluted with water and extracted with dichloromethane. Then, the organic layer was washed with a dilute solution of ammonium hydroxide and stirred with a 29% solution of ammonium hydroxide for 17 hours. The organic phase was washed with water, then hydrochloric acid (1N), dried (MgO ₄ ) and evaporated. Crystallization from toluene gave 5-amino-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (32.82 g),

Ή NMR (SBS1 _3): ΝΗ ₂ (2H, brs, 3.84 million ^-1), 4-N (1H, s, 5.97 million ^-1), arom. (2H, s, 7.53 million ^-1).

Reference Example 2. 5-Amino-4-dichlorofluoromethylthio-1 - (2,4,6-trichlorophenyl) -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 dichlorofluoromethylsulfonyl 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 with dichloromethane. The organic phase was washed with a cold solution of sodium bicarbonate, then with water, dried (Md ₈ O ₄ ) and evaporated. Silica gel column chromatography eluting with 3: 1 dichloromethane / hexane gave 5-amino4-dichlorofluoromethylthio-1- (2,4,6-trichlorophenyl) 3-cyanopyrazole (6.06 g), mp 189-191 ° C.

Reference 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-butyl nitrite (90%, 4.1 mmol) in tetrahydrofuran was heated under reflux for 3.5 hours and evaporated. The residue was purified by flash chromatography on silica gel, eluting with dichloromethane to give 4-dichlorofluoromethylthio-1- (2,4,6-trichlorophenyl) -3-cyanopyrazole (1.56 g), mp 106108 ° C.

Reference 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 3chloroperbenzoic acid (80%, 0.86 g) in chloroform was heated under reflux for 2 hours, cooled diluted with ethyl acetate and washed successively with 10% sodium hydrosulfite, 2N. ΝαΟΗ, water and saturated saline. The dried (MdO ₄ ) solution was evaporated and purified by flash chromatography on silica gel, eluting with dichloromethane to give 4-dichlorofluoromethylsulfonyl-1- (2,4,6trichlorophenyl) -3-cyanopyrazole (0.41 g), mp 143.5-145 ° C.

Reference Example 5. 5-Amino-1- (2-chloro-

4-trifluoromethylphenyl) -3-cyano-4-methylsulfinylpyrazole.

Stage 1

Bromine (0.5 ml) was added over 10 min to a stirred solution of sodium thiocyanate (1.7 g) in anhydrous methanol at -65 ° C. A solution of 5-amino-1- (2chloro-4-trifluoromethylphenyl) -3-cyanopyrazole (1.5 g) in anhydrous methanol was added over 10 minutes, and the stirred mixture was allowed to warm to 20 ° C. for 16 hours. After pouring into water the precipitate was collected and dried to give 5-amino-1- (2-chloro-4-trifluoromethylphenyl) -3-cyano-4-thiocyanatepyrazole (1.64 g). HPLC (C-18 column, elution with a mixture of CH ₃ С№Я ₂ О 3: 1 at 1.0 ml / min) showed the compound as a peak with an area of 86.6% at a yield time of 5.11 min.

Stage 2

Iodomethane (0.7 ml) was injected into a stirred suspension of 5-amino-1- (2-chloro-4 trifluoromethylphenyl) -3-cyano-4-thiocyanatepyrazole (1.64 g) in methanol at 4 ° C. A 10% aqueous sodium hydroxide solution (2.8 ml) was added and the reaction mixture was stirred for 1 h at 4 ° C, poured into water and extracted with dichloromethane and ethyl acetate. The dried (No. ₂ 8 O ₄ ) combined organic phase was evaporated and purified by flash chromatography on silica gel, eluting with hexane / ethyl acetate 4: 1 to give, after trituration with hexane / dichloromethane, 5-amino-1- (2-chloro- 4-trifluoromethylphenyl) -3-cyano-4-methylthiopyrazole (0.4 g), mp 129-132 ° C.

Stage 3.

To a stirred solution of 5-amino-1 (2-chloro-4-trifluoromethylphenyl) -3-cyano-4methylthiopyrazole (3.0 g) in trifluoroacetic acid (20 ml) was added 30% hydrogen peroxide (0.5 ml) while cooling up to 4 ° C. The temperature of the mixture was brought to 20 ° C for 2 hours, then it was poured onto ice and the solid phase was washed with water and dried. Silica gel flash column chromatography afforded 5-amino-1 (2-chloro-4-trifluoromethylphenyl) -3-cyano-4-methylsulfinylpyrazole (0.69 g), mp 146-147 ° C.

Reference Example 6

Using a method similar to that used in reference example 5, stages 1 and 2, the following compounds were also obtained:

5-amino-1 - (2,6-dichloro-4-trifluoromethoxylphenyl) -3-cyano-4-methylthiopyrazole, mp 147-148 ° C, and

5-amino-1 - (2-bromo-6-chloro-4-trifluoromethylphenyl) -3-cyano-4-methylthiopyrazole, mp 178-180 ° C.

Reference example 7.

Using a method similar to that used in reference example 5, stage 3, the following compounds were also obtained:

5-amino-1- (2,6-dichloro-4-trifluoromethoxylphenyl) -3-cyano-4-methylsulfinylpyrazole, mp 137-138 ° C, and

5-amino-1 - (2-bromo-b-chloro-4-trifluoromethylphenyl) -3-cyano-4-methylsulfinylpyrazole, mp 150-151 ° C.

Biological effectiveness

In order to apply the compounds of the present invention and to monitor the results obtained, the following methods were used: foliage / contact aerosol (spray solution) against sucking (aphids) or chewing (Lepidoptera) insects.

The tests were carried out on the following types

Rod, species Common name Abbreviation Ar111k dozurtz Cotton aphid ARNWO 8сЫζарЫз dhashshish Aphid ordinary TOXOO Mix Bosheisis Housefly MISBO

Soil test (systemic effect)

Seedlings of cotton and sorghum rooted in pots. One day before treatment, each pot was infected with aphids from the mixed population in an amount of about 25 individuals. Cotton sprouts infected cotton aphids, and sorghum sprouts infected cereal aphids. The selected compounds of formula (I) were applied to the soil surface in such a dilution that gave an equivalent concentration in the soil of 10 ppm ^-1 by weight. Aphids were counted 5 days after treatment. The number of aphids on the treated plants was compared with the number of aphids on the untreated control plants.

Contact Action Bait Test for House Flies (Miesa yoshi Isa)

About 25 individuals of the housefly from 4 to 6 days old were anesthetized and placed in a cage with a bait solution of sugar in water containing the compound. The concentration of the selected compound of formula (I) in the bait solution was 100 ppm ^-1 . After 24 hours, flies that did not exhibit movement upon stimulation were considered dead.

Contact action test on foliage in relation to type A. dosuri

Cotton seedlings infected with aphids were placed on a rotating turntable and sprayed to an excess of the preparation with a composition containing 100 ppm ^{-1 of the} compound of formula (I). Treated plants infected with A. dozurp were kept for 3 days after treatment, after which they counted dead aphids.

Compounds 1-11 of the present invention exhibited activity against ArYz dozzurp Ξΐιίζαρίιίδ dgashshish and at 10 h ^-1 -mln in the above systemic test.; against Mix yoshesis at a concentration of 100 ppm ^-1 in the above contact action bait test; and against Apylz dozurp at a concentration of 100 ppm ^-1 in the above foliage contact action test.

The present invention provides a method for systemic control of arthropods in the affected areas, especially some insects or mites that feed on parts of plants located above the soil. The control of such leaf-damaging pests can be carried out by direct application to the foliage or application, for example, spraying onto the soil or applying granules to the roots or seeds of plants with subsequent systemic transfer to parts of plants located above the ground. Such systemic activity includes the control of insects that are not only in the place of application, but also in the remote parts of the plant, for example, by transferring from one side of the leaf to the other or from the treated leaf to the untreated leaf. Examples of classes of insect pests that can be systematically controlled with the compounds of the present invention include the Noshoroega (piercing-sucking) squad. detachment Neshp1ega (piercing-sucking) and detachment Tyuzapor1ega. The present invention is particularly suitable for controlling aphids and thrips.

As follows from the previous pesticidal use, the present invention provides pesticidally active compounds and methods of using these compounds to control a number of insect species, which includes arthropods, especially insects or mites; plant nematodes; or helminths or protozoa. The compounds of formula (I) or their pesticidally acceptable salts are advantageously used for practical purposes, for example, in agriculture or horticulture, in forestry, veterinary or animal husbandry, or for health purposes. Hereinafter, when the term compounds of formula (I) is used, this term encompasses compounds of formula (I) and their pesticidally acceptable salts. The term compound of formula (I) encompasses a compound of formula (I) and a pesticidally acceptable salt thereof.

Therefore, the present invention provides a pest control method at a lesion site, which comprises treating this site (for example, by applying or administering) an effective amount of a compound of formula (I) or a pesticidally acceptable salt thereof, wherein substituent groups are defined above. The place of application includes, for example, the pests themselves or the place (plant, animal, field, structure, house with an adjacent plot, forest, greenhouse, pond, soil, plant or animal product, etc.) where these pests are located or feed on.

The compounds of the present invention can also be used to control soil insects, such as long-barked flea, termites (especially to protect buildings), root larvae, wireworms, root weevils, grinders, scoops, root aphids or larvae. They can also be used to provide activity against plant pathogenic nematodes, such as gall, cyst, (dagger, in the places of damage), stem or bulb nematodes, or against ticks. To combat soil pests, for example, long-legged flea, compounds are conveniently applied or applied in an effective amount to the soil in which the plants are planted or will be planted, or to the seeds or roots of growing plants.

In the field of health, these compounds are especially useful for controlling many insects, especially dung flies or other insect pests of the diptera group, such as house flies, autumn litter, lions, cow litter, deer horsefly, horse gadfly, small dipteran insects, biting midges, carrion flies or mosquitoes.

The compounds of the present invention can be used in the following applications and for controlling the following pests, including arthropods, especially insects and mites, nematodes or helminths, or protozoan pests.

To protect stored products, such as cereals, including grains or flour, peanuts, livestock products, timber, or home stock, for example carpets and textiles, the compounds of the present invention can be used against attack by arthropods, especially beetles, including weevils, moths and ticks, for example Yerbekba krr. (flour moth), ApLtepik crr. (Anthrenus), Trobit krr. (flour hrushchik), 8bor1y krr. (grain weevil) or Asagik krr. (ticks).

To control cockroaches, ants or termites or similar arthropod pests in infected residential or industrial premises, or to control mosquito larvae in ponds, wells, tanks or other type of standing or running water.

For the treatment of foundations, buildings or soil to prevent attacks on termite structures, for example, WebSyStetek krr., Neetetoegtek krr., Sor1o1ettek krr.

In agriculture, it is against adult individuals, larvae and eggs of Lepidoptera (butterflies and moths), for example, Neobbk krr., Such as Neobobk uieksepk (scoop), Nebobbk agpbdega and Nebok khea. Against adult individuals or larvae of Cepeloridae (beetles), for example, ApLopotik krr., For example, dtapfk (cotton weevil), Larbopatka bezeteaaa (Colorado potato beetle), and Ilabobs krr. (long-louse flea). Against Netsetorite (Net1net apb Notoreta), for example, Rku11a kr., Vetsha kr., Tpa1eitobek kr., ArYk kr., Mukhik kr., Medoiga uy1ae, RNu 11ohega krr., No.rbo1e1bh kr. (psa ba £ grasshoppers), No. 1 aratua1a krr.

Against I1p1eta, for example, Mix krr., Against T11ukaporega. such as Tbprk 1aBacE Against Ogbyur1ega. such as Laricidae apc. 8Syk1osets krr., (locusts and crickets), e.g. Against Co11etloa, for example, Reprotea crp. and B1abe1a crr. (cockroaches).

Against arthropods of importance for agriculture, such as Asap (ticks), for example, Tebapusbik krr., And RapopusNik krr.

Against nematodes, which damage plants and trees and pose a danger to agriculture, forestry or gardening, either directly or by spreading bacterial, viral, mycoplasma or fungicidal diseases of plants. For example, nodule nematodes, such as Me1o1 bodupe crp. (e.g. M. tsodpba).

In the field of veterinary medicine or animal husbandry, or healthcare against arthropods, helminths or protozoa that parasitize inside or on the surface of vertebrate organisms, especially warm-blooded vertebrates, for example, domestic animals, for example cattle, sheep, goats, horses, pigs, birds, dogs or cats, for example, Asappa, including ticks (for example, Nobek krr., Worbbik krr, Worbbik t1stor1ik, Vyr1erba krr. Absha Crr.); I1r1ega (for example, Aebek krr., AporNe1kr krr., Mix krr., Nurobegta krr.); No1r1eta; Ju1uor1ega (for example, Repr1ape1a spr., B1a1e11a spr.); For example, intestinal of the pathway caused by parasitic nematode worms, for example, members of the family TpNeigopduKbae; for the fight and for the treatment of protozoal diseases caused, for example, E1tepa spr., e.g. ., Tochor1azta spr. and TnePepasr.

In practical use for controlling arthropods, especially insects or mites, or nematodes that are pests of plants, the method, for example, involves applying to plants or the environment where they grow, an effective amount of a compound of the present invention. With this method, the active compound is usually applied to the place where it is necessary to fight infection with arthropods or nematodes, in an effective amount in the range from about 5 g to about 1 kg of active compound per hectare of the treated area. Under ideal conditions, depending on the pest to be destroyed, lower doses can provide adequate protection. On the other hand, adverse weather conditions, pest resistance, or other factors may require higher doses of the active ingredient. The optimal amount usually depends on a number of factors, for example, on the type of pest to be destroyed, on the type or stage of development of infected plants, the distance between the rows, and also on the method of application. More preferably, an effective amount of the active compound is in the range of from about 50 to about 400 g / ha.

If the pest is excreted in the ground, the active compound (usually in the composition) is distributed evenly over the surface to be treated (i.e., for example, sprayed over the entire surface or treated in strips) in any convenient way and applied in doses of about 5 g up to about 1 kg ai / ha (ai = active ingredient), preferably from about 50 to about 250 g ai / ha. When applied in the form of soaking the roots of seedlings or drip irrigation of plants, the liquid solution or suspension contains from about 0.075 to about 1000 mg ai / L, preferably from about 25 to about 200 mg ai / L. Application can be carried out, if desired, on the entire surface of the field or area where any crop is grown, or in close proximity to seeds or plants that need protection. The active ingredient can be washed away into the soil by spraying the entire surface with water, or it can be left until the natural effect of rain. During or after application, the compound in the composition can, if desired, be distributed mechanically in the soil, for example, by plowing, disking, or using a chain loop. Application can be made before planting, during planting, after planting, but before the appearance of sprouts, or after the appearance of sprouts.

The compounds of the present invention and the proposed pest control methods here are of particular value in the case of protecting fields, fodder plants, plantations, greenhouses, greenhouses or vineyards, ornamental plants, planting trees or trees in the forest, for example: cereals (such as wheat or rice), cotton, vegetable plants (such as peppers), field crops (such as sugar beets, soybeans or oilseed rape), meadows or crops of fodder plants (such as corn or sorghum), orchards and groves (such as stone fruits or pome fruits or cereals) Trusov), ornamental plants, flowers or vegetables or shrubs under glass or in gardens and parks, or forest trees (both deciduous and evergreen) in forests, plantations or nurseries.

They are also valuable for protecting timber (standing, fallen, processed, stored or in buildings) from attack, such as a sawfly, beetles or termites.

They are used to protect stored products, such as grains, fruits, nuts, spices or tobacco, either whole, or chopped, or converted into products, from the attack of moths, beetles, ticks or barn weevil. Livestock products, such as leather, hair, wool or feathers in natural or processed form (for example, in the form of carpets and textiles), from the attack of moths or beetles, as well as stored meat, fish or grain from the attack of beetles, ticks or flies, are also protected. .

In addition, the compounds of the present invention and methods of its use are of particular value for combating arthropods, helminths or protozoa that infect, spread, or are carriers of diseases of domestic animals, for example, those already mentioned, and more specifically, to combat with ticks, mites, lice, fleas, small diptera insects or biting, annoying or tu1a818 flies. The compounds of the present invention are particularly useful for controlling arthropods, helminths, or protozoa that live in host animals, or that feed on the body or skin, or suck animal blood, and for this purpose they can be administered orally, parenterally, through the skin, or superficially.

In addition, the compounds of the present invention may be useful in controlling coccidiosis, a disease that is caused by infection with protozoan parasites of the genus Elta. It is an important potential cause of economic losses when breeding domestic animals and poultry, especially those that are raised or maintained in intensive conditions. For example, cattle, sheep, pigs or rabbits can be affected, but the disease is especially dangerous for poultry, especially for chickens. Administration of a small amount of a compound of the present invention, preferably in combination with food, effectively prevents or significantly reduces the possibility of coccidiosis. These compounds are effective both against the cecum and intestinal forms. In addition, the compounds of the present invention can also have an inhibitory effect on oocytes, significantly reducing their number and sporulation. Poultry diseases are usually spread by birds that peck infectious organisms in litter in litter, on litter, on the ground, in feed, or in drinking water. The disease is manifested by bleeding, accumulation of blood in the appendix, the appearance of blood in excrement, weakness and digestive upset. The disease often ends in the death of the animal, but the bird that survived after a serious infection loses significantly in market price as a result of the infection.

Compositions, which are further described for application to growing crops or application to areas where crops are grown, or for pelleting seeds, can generally be alternatively used for surface application to animals or for the protection of stored products, household utensils, estates or environmental areas . Suitable agents for applying the compounds of the present invention include:

for growing crops - aerosols, dusts, granules, mists or foams intended for foliage processing, or in the form of a suspension of finely ground or encapsulated compositions in the form of soil or root treatment with liquid irrigation, dusts, granules, fumes or foams; on plant seeds by dragging seeds with liquid suspensions or dusts;

on animals infected or susceptible to infection by arthropods, helminths or protozoa, parenteral, oral administration or surface application of a composition in which the active ingredient exhibits an immediate and / or prolonged action over a period of time against arthropods, helminths or protozoa, for example, by incorporation into food or in suitable pharmaceutical compositions, which are absorbed by oral administration, into edible baits, salt licks, food additives, bulk compositions, prei, baths, showers, washing, spraying, dusts, ointments, shampoos, creams, ointments or waxy body-worn self-treatment systems;

for the environment in general or for specific places where pests can hide, including stored food, lumber, household supplies or residential or industrial premises, in the form of sprays, mists, dusts, fumigations, waxy ointments, varnishes, granules or decoys, or in the form of droppers for reservoirs, wells, reservoirs or other running or standing water;

for pets in the feed to combat the larvae of flies feeding in their feces.

In practice, the compounds of the present invention most often form parts of a composition. These compositions can be used to combat: arthropods, especially insects or ticks; nematodes; or helminths or protozoa. The compositions can be of any type known to those skilled in the art, for use against the desired pest in any room, both inside and outside it, or by internal or external vertebral administration. These compositions contain at least one compound of formula (I) or a pesticidally acceptable salt thereof, such as previously described, as an active ingredient in combination or in combination with one or more of the other compatible components, which are, for example, solid or liquid carriers or diluents, adjuvants, surface active agents or the like, suitable for the intended use, and which are suitable for use in agriculture and medicine. These compositions, which can be obtained by any method known to those skilled in the art, also form part of the present invention.

These compositions may also contain other types of ingredients, such as protective colloids, adhesives, thickeners, thixotropic agents, penetration enhancers, spray oils (especially for acaricidal use), stabilizers, preservatives (especially mold preservatives), sequestering agents or the like , as well as other known ingredients having pesticidal properties (in particular, insecticidal, miticidal, nematicidal or fungicidal) or having the properties of regulating plant growth. In a more general formulation, the compounds used in the present invention can be combined with all solid or liquid additives consistent with conventional methods of preparing the compositions.

Compositions suitable for use in agriculture, horticulture, etc., include compositions suitable for use as, for example, sprays, dusts, granules, mists, foams, emulsions or the like.

Effectively used doses of the compounds used in the present invention can vary within wide limits, in particular depending on the nature of the pest to be destroyed, or the degree of infection, for example, crops, by these pests. Typically, the compositions of the present invention contain from about 0.05 to about 95 wt.% One or more of the active ingredients of the present invention, from about 1 to about 95% of one or more solid or liquid carriers, and optionally from about 0.1 to about 50% of one or more of other compatible components, such as surface active agents or the like.

In this text, the term “carrier” means an organic or inorganic ingredient, natural or synthetic, with which the active ingredient is combined to facilitate its application, for example, to plants, seeds or soil. Therefore, such a carrier is usually inert, and it must be acceptable (for example, agronomically acceptable, especially for processing plants).

Carriers can be solid, for example, clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers (e.g. ammonium salts), ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceous earth, or powdered synthetic minerals such as silica, alumina or silicates, especially silicates of aluminum or magnesium. As solid carriers for granules, crushed or fractionated rocks such as calcite, marble, pumice, sepiolite and dolomite are suitable; synthetic granules of inorganic or organic flour, granules of organic materials such as sawdust, coconut husks, corn cobs, corn husks or tobacco stalks; kieselguhr, tricalcium phosphate, powdery crust or absorbent soot; water soluble polymers, resins, waxes; or solid fertilizers. Such solid compositions may optionally contain one or more compatible wetting, dispersing, emulsifying or coloring agents, which, if they are solid, can also serve as diluents.

Carriers can 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, especially xylenes or alkyl naphthalenes; mineral or vegetable oils; aliphatic chlorinated hydrocarbons, especially trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons, especially chlorobenzenes; water soluble or highly polar solvents such as dimethylformamide, dimethyl sulfoxide or Ν-methylpyrrolidone; liquefied gases; or the like, or mixtures thereof.

The surfactant may be an emulsifying agent, a dispersing agent or a wetting agent of ionic or non-ionic type, or it may be a mixture of such surfactants. Among them may be, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenylsulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids, or fatty esters or fatty amines substituted by phenols (especially alkyl phenols or aryl phenols), salts sulfosuccinic acid, derivatives of taurine (in particular alkyl taurates), phosphoric esters of alcohols or polycondensates of ethylene oxide with phenols, fatty acid esters with polyols, Whether sulphate, sulphonate or phosphate functional derivatives of the above compounds. The presence of at least one surface-active agent is usually essential if the active ingredient and / or inert carrier is only slightly soluble in water, or insoluble in water, and the carrier of this composition for application is water.

The compounds of the present invention may further contain other additives, such as adhesives and dyes. Adhesives such as carboxymethyl cellulose, or natural or synthetic polymers in the form of powders, granules or lattices, such as gum arabic, polyvinyl alcohol or polyvinyl acetate, natural phospholipids such as cephalins or lecithins, or synthetic phospholipids can be used in these compositions. Dyes such as inorganic pigments, for example, iron oxides, titanium oxides or Prussian blue, can be used; organic dyes such as alizarin dye, azo dye or metal phthalocyanine dyes; or micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

Compositions containing compounds of formula (I) or pesticidally acceptable salts thereof that can be used to control arthropods, plant nematodes, helminths or protozoa can also contain synergists (e.g. piperonyl butoxide or sesamex), stabilizers, other insecticides, acaricides, plant nematicides, agents for controlling helminths or coccidiosis, fungicides (for use in agriculture or veterinary medicine, for example, benomyl and iprodion), bactericides, attractants or repellents, or pheromone s for arthropods or vertebrates, deodorants, flavoring agents, colorants or auxiliary therapeutic agents, for example trace elements. Such compositions can be created to increase efficiency, stability, safety, the ability to absorb where necessary, to expand the spectrum of pests that can be combated, or to give the composition the ability to perform other useful functions in relation to the same animals or areas to be treated .

Examples of other pesticidal active compounds that can be included in the compositions or used with the compositions of the present invention are acephate, chlorpyrifos, demeton-8-methyl, disulfotone, etoprofos, phenitrotion, phenamiphos, phonophos, isazophos, isofenfos, malathion, monocrotophos, parathion, phorate, fosalon, pyrimifos-methyl, terboufos, triazophos, cyfluthrin, cypermethrin, deltamethrin, fenpropatrin, fenvalerate, permethrin, teflutrin, aldicarb, carbosulfan, methomil, oxamyl, pyrimicarb, bendiofarub, tepfibrudibar, te, ulfan, lindane, benzoximate, cartap, cyhexatin, tetradifon, avermectins, ivermectin, milbemycins, thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole.

For use in agriculture, the compounds of formula (I) or their pesticidally acceptable salts are usually in the form of various solid or liquid compositions.

Solid forms of compositions that can be used are dusts (containing a compound of formula (I) or a pesticidally acceptable salt thereof, in the range of up to 80%), wettable powders or granules (including water-dispersible granules), in particular those which receive by extrusion, pressing, impregnating a carrier of granules or granulating on the basis of a powder (the content of the compound of formula (I) or its pesticidally acceptable salt in such wettable powders or granules is from about 0.5 to about 80%). Solid homogeneous or heterogeneous compositions containing one or more of the compounds of formula (I) or their pesticidally acceptable salts, for example, granules, tablets, briquettes or capsules, can be used to treat running or standing water for some time. A similar effect can be achieved using a continuous or batch feed of water-dispersible concentrates, as indicated here.

Liquid compositions, for example, include aqueous or non-aqueous solutions or suspensions (such as emulsifiable concentrates, emulsions, flowable compositions, dispersions or solutions) or aerosols. Liquid compositions also include, in particular, emulsifiable concentrates, dispersions, emulsions, flowable formulations, aerosols, wettable powders (or powders for sprays), dry, spillable products or pastes, as forms of compositions that are liquid or intended to form liquid compositions, for application, for example, in the form of water sprays (including small and ultra-small volumes) or in the form of mists or aerosols.

Liquid compositions, for example, in the form of emulsifiable or soluble concentrates, most often comprise from about 5 to about 80% by weight of the active ingredient, although emulsions or solutions ready for use, in their case, contain from about 0.01 to about 20% active ingredient. In addition to the solvent, emulsifiable or soluble concentrates may contain, if necessary, from about 2 to about 50% of suitable additives, such as stabilizers, surfactants, penetration enhancers, corrosion inhibitors, dyes or adhesives. Emulsions of any desired concentration, which are especially suitable for application, for example, to plants, can be obtained from these concentrates by diluting them with water. These compositions are included within the scope of compositions that can be used in the method of the present invention. Emulsions can be of the type water-in-oil or oil-in-water, and they can have a thick consistency.

The liquid compositions of the present invention can be, in addition to conventional agricultural applications, used, for example, for treating substrates or areas infected, or those that can be infected by arthropods (or other pests that can be destroyed using the compounds of the present invention), including buildings, external or internal storage or process areas, containers or equipment, or standing or running water.

All of these aqueous dispersions or emulsions or sprayable mixtures can be applied, for example, to cultivated plants, by any suitable method, mainly by spraying in doses that are usually from about 100 to about 1200 liters of sprayable mixture per hectare, but can be higher or lower (e.g. small or ultra-small volumes), depending on the need or technique used. Compounds or compositions in accordance with the present invention is conveniently applied to the vegetative parts and, in particular, to the roots or leaves on which the pests to be destroyed are located. Another way to apply the compositions or compounds in accordance with the present invention is to apply by chemicalization, in other words, by adding a composition containing the active ingredient to the water of irrigation facilities. Such irrigation can be accomplished by spraying for pesticides on foliage, or it can be ground irrigation for soil or for systemic pesticides.

Concentrated suspensions that can be applied by spraying are prepared in such a way as to obtain a suitable liquid product that does not settle (fine grinding) and usually contains from about 10 to about 75 wt.% Of the active ingredient, from about 0.5 to about 30% of the surface active agent, from about 0.1 to about 10% thixotropic agents, from about 0 to about 30% of suitable additives, such as anti-foaming agents, corrosion inhibitors, stabilizers, penetration enhancers, adhesives and, as a carrier, water or organic a liquid in which the active ingredient is slightly soluble or insoluble. Some organic solids or inorganic salts can be dissolved in the carrier to prevent settling or used as antifreezes for water.

Wettable powders (or spray powders) are usually prepared so that they contain from about 10 to about 80% by weight of the active ingredient, from about 20 to about 90% of a solid carrier, from about 0 to about 5% of a wetting agent, from about 3 to about 10% of a dispersing agent and, if necessary, from about 0 to about 80% of one or more stabilizers and / or other additives, such as penetration enhancing agents, adhesives, anti-clumping agents, dyes, etc. To obtain such wettable powders, an asset This ingredient (s) are thoroughly mixed in a suitable mixer with additional substances that can be impregnated with the porous filler, and ground using a mill or other suitable grinder. As a result, wettable powders are obtained, the wettability and suspendibility of which is an important property. They can be suspended in water to obtain any desired concentration, and this suspension can be used with great success, in particular, for application to foliage of plants.

Water-dispersible granules (AS) (granules that are easily dispersible in water) have compositions that are almost similar to the compositions of wettable powders. They can be obtained by granulation or preparation, as indicated for wettable powders, or by a wet method (by contacting the finely divided active ingredient with an inert filler or a small amount of water, for example, from 1 to 20 wt.%, Or with an aqueous solution of a dispersing agent or a binder, followed by drying and sieving), or by a dry method (by pressing followed by grinding and sieving).

Doses and concentrations of the resulting compositions may vary depending on the method of application or the nature of the composition, or its use. Generally speaking, application compositions for controlling arthropods, plant nematodes, helminths, or protozoan pests typically contain from about 0.00001 to about 95%, more preferably from about 0.0005 to about 50% by weight of one or more of the compounds of formula ( I) or their pesticidally acceptable salts, or all active ingredients (i.e., the compounds of formula (I) or its pesticidally acceptable salt, together with other substances toxic to arthropods or plant nematodes, agents against helminths and coccidiosis, synergists, micro elements or stabilizers). Really used compositions and doses of their application should be chosen to achieve the desired effect (s) for the farmer, the breeder, the doctor or veterinarian, the pest control operator, or other specialists.

Solid or liquid compositions for surface application to animals, timber, stored products or household utensils typically contain from about 0.00005 to about 90%, in particular from about 0.001 to about 10% by weight of one or more of the compounds of formula (I) or its pesticidally acceptable salts. For administration to animals, either orally or parenterally, including through the skin, solid or liquid compositions usually contain from about 0.1 to about 90 wt.% One or more of the compounds of formula (I) or their pesticidally acceptable salts. Medicinal food additives usually contain from about 0.001 to about 3 wt.% One or more compounds of formula (I) or their pesticidally acceptable salts. Concentrates or additives for mixing with food usually contain from about 5 to about 90%, preferably from about 5 to about 50 wt.% Of one or more of the compounds of formula (I) or their pesticidally acceptable salts. Mineral salt salts usually contain from about 0.1 to about 10 wt.% One or more of the compounds of formula (I) or their pesticidally acceptable salts.

Dusts or liquid compositions for application to livestock, goods, premises or external areas may contain from about 0.0001 to about 15%, especially from about 0.005 to about 2 wt.%, One or more of the compounds of formula (I) or their pesticidally acceptable salts. Suitable concentrations in the treated waters are from about 0.0001 to about 20 ppm, especially from about 0.001 to about 5.0 ppm, of one or more of the compounds of formula (I) or their pesticidally acceptable salts, and can be used with therapeutic purposes in fish farming with appropriate exposure time. Edible baits may contain from about 0.01 to about 5%, preferably from about 0.01 to about 1 wt.% Of one or more of the compounds of formula (I) or their pesticidally acceptable salts.

When administered vertebrally parenterally, orally, or through the skin, or in other ways, the doses of the compounds of formula (I) or their pesticidally acceptable salts will depend on the type, age or health status of the vertebrate and on the nature and degree of actual or potential infection by arthropods, helminths or protozoa . A unit dose of from about 0.1 to about 100 mg, preferably from about 2.0 to about 20.0 mg per kg of animal body weight, or a dose of from about 0.01 to about 20.0 mg, preferably from about 0.1 to about 5.0 mg per kg of animal body weight per day for long-term treatment are usually suitable for oral or parenteral administration. Using compositions or devices with delayed release, the daily doses needed for months can be combined and administered to the animal once.

The following compositions of Examples 2A-2M illustrate compositions for use against arthropods, especially ticks or insects, plant nematodes or helminths or protozoa, which include, as an active ingredient, compounds of formula (I) or pesticidally acceptable salts thereof, such as those described in preparative examples. Any compositions presented in examples 2A-2M can be diluted to obtain a sprayable composition in a concentration suitable for use in the field. General chemical descriptions of the ingredients (for which all of the following percentages are indicated as wt.%) Used in the compositions of Examples 2A-2M below are as follows:

Trademark Chemical description E1y1ap HRV Nonylphenol-thylene oxide Condensate 8orgorog V8i Tristyrylphenolethylene oxide Condensate Agu1ap SA 70% w / v calcium dodecylbenzenesulfonate solution 8o1ezzo 150 Light Xiu Aromatic Solvent Agu1ap 8 Sodium dodecylbenzenesulfonate Eaguap No. 2 Sodium Lignosulfonate SESHE RE Synthetic carrier magnesium silicate 8orgorNop T36 Polycarboxylic Acid Sodium Salts P11 <k1 | «e1 23 Polysaccharidxantangam Vep1op 38 Organic Magnesium Montmorillonite Derivative Aegosi Ultra-Fine Silica

Example 2A

Prepare a water-soluble concentrate of the following composition:

Active ingredient 7%

E1yu1ap HRV 10%

Ν-methylpyrrolidone 83%

The active ingredient is added to the E1yy1ap HRV solution dissolved in the Ν-methylpyrrolidone portion by heating and stirring until dissolved. The volume of the resulting solution was adjusted to the desired with the remaining solvent.

Example 2B

An emulsifiable concentrate (EC) of the following composition is prepared:

Active ingredient 25% (max)

8ortoriot V8I 10%

Agu1ap CA 5%

Ν-methylpyrrolidone 50%

8o1ouzzo 150 10%

The first three components are dissolved in п methylpyrrolidone and then 8O1uzezo 150 is added to this to a final volume.

Example 2C.

A wettable powder of the following composition is prepared:

Active ingredient 40%

Agu1ap 8 2%

Iatuap No. 2 5%

SESHE RE 53%

All ingredients are mixed and ground in a hammer mill into a powder with a particle size of less than 50 microns.

Example 2I.

Prepare an aqueous fluid composition of the following composition:

Active ingredient 40.00%

Е1йу1ап HRV 1.00%

8orgoropop T36 0.20%

Ethylene glycol 5%

WBWhde1 23 0.15%

Water 53.65%

All ingredients are thoroughly mixed and ground in a ball mill to an average particle size of less than 3 microns.

Example 2E

An emulsifiable suspension of the following composition is prepared:

Active ingredient 30.0%

Е1йу1ап HRV 10.0%

Vep1op 38 0.5%

8O1Uzzo 150 59.5%

All ingredients are thoroughly mixed and ground in a ball mill to an average particle size of less than 3 microns.

Example 2E

Prepare water-dispersible granules of the following composition:

Active ingredient thirty% Iatuap No. 2 fifteen% Agu1ap 8 8% Ce1ye RE 47%

All ingredients are mixed, finely ground in a liquid mill (Пшб-спсгду Ш111), and then granulated in a rotary translator, spraying with water (up to 10%). The granules obtained are dried in a fluid bed dryer to remove excess water.

Example 26

A powder is prepared for dusting the following composition:

Active ingredient 1 to 10%

Ultra-fine powder of talc from 99 to 90%

The ingredients are thoroughly mixed and then ground, if necessary, until a fine powder is obtained. This powder can be applied to an area infected with arthropods, such as a landfill, food storage or household utensils, or to animals infected or at risk of arthropod infection to control arthropods by oral absorption. Suitable powder spraying agents for dusting an arthropod-infected area include mechanical dusters, hand shakers, or self-processing devices used for livestock.

Example 2H

Prepare an edible bait of the following composition:

Active ingredient 0.1 to 1.0%

Wheat flour 80%

Molasses from 19.9 to 19%

All ingredients are thoroughly mixed and molded into the bait of the desired shape. Edible baits can be placed in various places, in residential or industrial premises, for example, in kitchens, hospitals or storages, or outdoors, infected with arthropods, such as ants, locusts, cockroaches or flies, to control arthropods by oral absorption.

Example 21

Prepare a solution of the following composition:

Active ingredient 15%

Dimethyl sulfoxide 85%

The active ingredient is dissolved in dimethyl sulfoxide with stirring or by heating if necessary. This solution can be applied through the skin, by pouring it on pets infected with arthropods, or after sterilization by filtration through a polytetrafluoroethylene membrane (pore size 0.22 μm), by parenteral injection, at a dose of 1.2 to 12 ml of solution per 100 kg of weight body of the animal.

Example 21

A wettable powder of the following composition is prepared:

Active ingredient fifty% E1y1ap HRV 5% EasyP 5% SESHE RE 40%

E111u1ap HRV is absorbed on Lungi, which is then mixed with other ingredients and ground in a hammer mill to obtain a wettable powder that can be diluted with water to a concentration of 0.001 to 2% by weight of the active compound, and applied to a site infected with arthropods, such as diptera larvae, or plant nematodes, by spraying, or on domestic animals infected or at risk of infection by arthropods, helminths or protozoa, by spraying or by dipping, or by oral administration drinking water to combat arthropods, helminths, or protozoa.

Example 2K.

A composition is prepared in the form of pills with delayed release from granules containing the following components in various percentages (similar to those described for previous formulations), depending on the need:

Active ingredient

Density Agent

Slow Release Agent

Binder.

All thoroughly mixed ingredients are formed into granules that are compressed into capsules with a specific gravity of 2 or higher. They can be administered orally to ruminant pets so that they linger in the reticulo-rumen (first part of the stomach) and provide a constant, slow release of the active compound for a long time to combat infection of ruminant pets with arthropods, helminths or protozoa.

Example 2b

Sustained release compositions may be prepared in the form of granules, tablets, briquettes or the like. the following composition:

Active ingredient 0.5 to 25%

Polyvinyl chloride from 75 to 99%

Dioctyl phthalate (plasticizer)

All components are mixed and then molded into appropriate shapes by melt extrusion or extrusion. These compositions can be used, for example, to be added to stagnant water or to make collars or ear pads for attachment to pets to control pests as a result of slow release.

Example 2M

Prepare water-dispersible granules of the following composition:

Active ingredient 85% (max)

Polyvinylpyrrolidone 5%

Attapulgite clay 6%

Sodium lauryl sulfate 2%

Glycerin 2%

All ingredients are mixed in the form of a 45% suspension with water and wet milled to a particle size of 4 microns, then spray dried to remove water.

Although the present invention has been disclosed in its various preferred embodiments, it should be apparent to those skilled in the art that various modifications, substitutions, omissions and changes can be made without departing from the scope of the invention. Accordingly, it should be considered that the scope of the present invention is limited only by the scope of the attached claims, including its equivalents.

Claims (29)

CLAIM 1. 1-Arylpyrazole of the formula (I) wherein Κι represents H or halogen; each of K ₂ and K ₄ , which are the same or different, is H, halogen or alkyl; K ₃ represents halogen, haloalkyl, haloalkoxy or B ₁₀ 8 (O) _t ; K ₅ represents lower alkyl, haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing from 3 to 5 carbon atoms; Ζ represents hydrogen, halogen, alkyl, formyl, -C (O) alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylidenamino, 1H-pyrrole-1yl, 1H-pyrazol-1-yl, amino, Κ ₆ ΝΗ- or Κ.-Κ. ₈ Ν-; each of the KB, K - and K ₈ radicals, which are the same or different, are alkyl-8 (O) _p - formyl containing from 3 to 6 carbon atoms, alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl containing from 3 to 6 carbon atoms alkenyl or —C (O) alkyl, in which the alkyl and alkenyl moieties are optionally substituted with one or more K ₉ radicals; or the K - and K ₈ radicals are connected in such a way that they together form a divalent radical containing from 4 to 6 carbon atoms in a chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably with the formation of morpholine, pyrrolidine, piperidine or piperazine cycle; K ₉ is cyano, nitro, alkoxy, haloalkoxy, Βι ₀ 8 (Ο) ₄ -, -C (O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO ₂ H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; K ₁₀ represents lower alkyl or lower haloalkyl; t, η, p and s. | equal to 0, 1 or 2; M represents C-halogen, C-CH3, C-CCHR, C-CH2C1, C-ΝΌ, or Ν, and, unless otherwise indicated, said alkyl groups and fragments contain from 1 to 6 carbon atoms, lower alkyl groups and fragments contain from 1 to 4 carbon atoms, alkenyl and alkynyl groups and fragments contain from 2 to 6 carbon atoms; or a pesticidally acceptable salt thereof; excluding 1-arylpyrazoles of formula (I) in which K ₅ is haloalkyl; and Ζ represents hydrogen, 1H-pyrrol1-yl, an amino group or I ₍ CN-. Where K ₆ represents formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl containing from 3 to 6 carbon atoms, or —C (O) alkyl, wherein the alkyl portion is optionally substituted with one or more K ₉ , where K ₉ is halogen; and other groups are as defined above. 2. The compound according to claim 1, in which And ₃ represents halogen, halogenated or halogenated. 3. The compound according to claim 1 or 2, in which K ₅ represents alkyl. 4. The compound according to claim 1, 2 or 3, in which Ζ represents amino, K ^ CN - or Κ.-Κ. ₈ Ν-. 5. The compound according to claim 1, in which K ₁ represents P, C1, Br or H; K ₂ and K ₄ represent H; K ₃ represents —CP ₃ , —OCP ₃ , —CHP ₂ , —8 (O) tCP ₃ , —CPC12, —CP2C1, —OCP2C1, —OCCP12, C1, Br or P; K ₅ is methyl or ethyl; Ζ represents H, halo (F, C1, Br), _C1-C3 alkyl, C1-C ₃ haloalkyl, C ₂ -C ₃ alkenyl; or amino, ^ NK ₆ or -ΝΚ.-Κ. ₈ , where each of the radicals And ₆ , K - and K ₈ , which are the same or different, represents C1-C ₃ alkyl, C ₃ alkenyl or -C (O) alkyl, in which the alkyl and alkenyl parts are not substituted or substituted cyano, alkoxy, alkyl-8 (O) _h -, nitro, alkoxycarbonyl, —C (O) alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO ₂ H, hydroxy or halogen (P, C1, Br); and M represents CC1, CP, CBr or Ν. 6. The compound according to claim 1, in which Κι represents C1 or Br; K ₂ and K ₄ represent H; K ₃ represents —CP ₃ —OCP ₃ or C1; K ₅ is methyl or ethyl; Ζ represents H, halo (F, C1, Br), _C1-C3 alkyl, C1-C ₃ haloalkyl, C ₂ -C ₃ alkenyl or amino, NC ^ ₆ or -ΝΚ-Κ _8, wherein each of the radicals K . _6, K ₈ and K, which are Odin kovymi or different, represents a _C1-C3 alkyl, _C3 alkenyl or -C (O) alkyl in which the alkyl and alkenyl portions are unsubstituted or substituted by cyano, alkoxy, alkyl -8 (O) _p -, nitro, alkoxycarbonyl, -C (O) alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, hydroxy or halogen (E, C1, Br); and M represents CC1, CBr or Ν. 7. The compound according to claim 1, in which Κι represents C1 or Br; Κ2 and Κ4 are H; Κ ₃ represents —CO ₃ , —OCE ₃ or C1; Κ ₅ represents methyl or ethyl; Ζ represents H or an amino group and M represents CC1, CBr or Ν. 8. The compound according to claim 1, in which Κι represents C1 or Br; Κ2 and Κ4 are H; Κ3 represents -CE2; -OCE3 or C1; Κ5 represents methyl or ethyl; Ζ represents H or an amino group and M represents CC1, CBr or Ν. 9. The compound according to claim 1, in which 1aryl group is a 2,6-dichloro-4-trifluoromethylphenyl; 2,6dichloro-4-trifluoromethoxyphenyl; 2-bromo-6chloro-4-trifluoromethylphenyl; 2-bromo-6-chloro-4 trifluoromethoxyphenyl; 2,6-difluoro-4-trifluoromethylphenyl; 2-chloro-4-trifluoromethylphenyl; 2,6dichloro-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; 2chloro-6-fluoro-4-trifluoromethylphenyl; 2,6-dibromo- 4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethoxyphenyl or 2-bromo-4-trifluoromethylphenyl. 10. The compound according to claim 1, in which the group Ζ represents a group of acetylamino, amino, 2-n-butoxypropionylamino, methyl, hydroxyacetylamino, ethyl, 3-ethylsulfinylpropylamino, bromine, formylamino, chlorine, methylamino, ethylamino, 2-hydroxyethylamino, 2 -methoxyethylamino, methylsulfonylamino, 2-ethylsulfonylethylamino; 4-methoxybenzoylamino, 2tsianoetilamino, 4-methoxybenzylamino, 2metiltioetilamino, 2-aminokarboniletilamino, 2-metilsulfiniletilamino, 3-metoksikarbonilpropilamino, 2-etilsulfiniletilamino, 2-metilsulfoniletilamino, cyanomethylamino, 2-etiltioetilamino, aminokarbonilmetilamino, dimethylamino, 2-nitroetilamino, 2atsetiletilamino, metilkarbonilmetilamino, methoxycarbonylamino or ethoxycarbonylamino. 11. The compound according to claim 1, in which the group ZCO) ^ represents methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl or isopropylthio. 12. The compound of formula (I) according to claim 1, which is a 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-ethylsulfinylpyrazole-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. 13. The compound of formula (I) according to claim 1, which is a 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylthiopyrazole-3-thiocarboxamide or 4-dichlorofluoromethylsulfonyl-1- (2,4,6trichlorophenyl) pyrazole-3-thiocarboxamide. 14. A pesticidal composition containing a pesticidally effective amount of 1-arylpyrazole according to any one of claims 1 to 13 or a pesticidally acceptable salt of 1-arylpyrazole of formula (I), as defined in claim 1, in combination with an agriculturally inert carrier. 15. The pesticidal composition according to 14, containing from about 0.05 to about 95 wt.% The compounds of formula I. 16. The pesticidal composition according to 14, containing from about 0.00005 to about 90 wt.% The compounds of formula (I). 17. A method of controlling pests in a locus of infection, which consists in applying to the indicated locus a pesticidally effective amount of 1-arylpyrazole according to any one of paragraphs 113 or a pesticidally acceptable salt of 1arylpyrazole of formula (I), as defined in claim 1, or a composition according to any of paragraphs 14, 15 and 16. 18. The method according to 17, in which these pests are insects. 19. The method of claim 18, wherein said insects are sucking insects. 20. The method according to 17, in which the indicated focus of infection is an area seeded with cultures. 21. The method according to claim 20, in which the specified compound is applied to the specified focus of infection in an amount of from about 5 g to about 1 kg / ha 22. The method according to 17, in which the indicated focus of infection is an animal. 23. The method according to item 22, in which the specified compound is used in an amount of from about 0.1 to about 20 mg per kg of animal body weight per day. 24. A method of controlling vertebrate pests, which comprises administering to an animal 1-arylpyrazole of formula (I) as defined in claim 1, or a pesticidally acceptable salt thereof in a single dose of 0.1-100 mg per kg of animal body or in doses from 0.01 to 20 mg per kg of animal body per day. 25. A method of obtaining a compound of formula (I) according to claim 1, comprising reacting a compound of formula (II) where K _b K ₂ , K ₃ , K ₄ , K ₅ , Μ, η and Ζ are defined in claim 1, with alkaline hydrosulfide or alkaline earth metal. 26. A method of obtaining a compound of formula (I) according to claim 1, in which Ζ represents alkoxycarbonyl or alkylthiocarbonyl, comprising esterification of the corresponding compound of formula (I), in which Ζ is a carboxy group, an alcohol of formula (V) K12OH (V) or thiol of formula (VI) K ₁₂ 8H (VI), where K ₁₂ in formulas (V) and (VI) is alkyl. 27. The method of obtaining the compounds of formula (I) according to claim 1, in which Ζ represents-C (O) alkyl, including the oxidation of the corresponding compounds of formula (VIII) c-CH-A ^ And "a (VII) where K ₂ , K ₃ , K ₄ , K ₅ η and M are defined in paragraph 1 and Κι ₄ is alkyl. 28. The method according to any one of paragraphs.25-27, further comprising the stage of interconversion of the obtained compounds of formula (I) according to claim 1, selected from a) oxidizing compound (I) in which η is 0 or 1, to give compound (I) in which η is 1 or 2; b) alkylating a compound of formula (I), where Ζ is amino, with a compound of formula (III) K ₉ —CH = CH ₂ (III), where K _{9 is} defined in claim 1, to give compound (I) in which Ζ is —Κ ₆ ΝΉ—, where K _b is ethyl substituted at position 2 with group K ₉ , where K ₉ represents cyano, nitro, -8 (O) _h K ₁₀ , -C (O) alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; C) alkylation of the corresponding compounds of formula (I), where Ζ represents amino, the compound of formula (IV) Κ11-Υ (IV), where ц представляет represents alkyl or halogenated, optionally substituted with one or more K ₉ , and Υ represents a leaving group, to give compound (I) in which Ζ represents -ΝΉΚ ₆ or ΝΚ ₇ Κ ₈ wherein K _b , K ₇ and K ₈ are alkyl or haloalkyl optionally substituted with one or more K ₉ ; g) diazotization of the corresponding compound of formula (I), where Ζ is amino, followed by interaction with the compound of formula (VII) K13CH = CH2 (VII) in the presence of a copper salt to give compound (I), wherein Ζ represents K ₁₃ CH (C1) CH ₂ -, where K ₁₃ is alkyl; d) dehydrochlorinating the corresponding compound of formula (I), where Ζ represents K ₁₃ CH (C1) CH ₂ -, to give compound (I), in which Ζ represents K ₁₃ CH = CH ₂ -. 29. The method according to any one of paragraphs.25-28, further comprising converting the compound of formula (I) into its pesticidally acceptable salt.