MXPA99006001A

MXPA99006001A - Pesticidal 1-arylpyrazoles

Info

Publication number: MXPA99006001A
Application number: MXPA/A/1999/006001A
Authority: MX
Inventors: Doyle Lowder Patrick; Treadway Manning David; Chene Alain; Wyatt Newsome Peter; Wu Taiteh; Charles Ray Nicholas; Lantz Phillips Jennifer
Original assignee: Basf Aktiengesellschaft*
Priority date: 1996-12-24
Filing date: 1999-06-24
Publication date: 2000-02-02

Abstract

The invention relates to novel 1-arylpyrazole oxime derivatives, of general formula (I) or (I bis). These compounds are found to be generally safe systemic insecticides for control of arthropod, nematode, helminth or protozoan pests including compositions andderivatives thereof.

Description

1-ARILPIAZOLES PESTICIDES FIELD OF THE INVENTION The present invention relates to novel oximes of 1-arylpyrazolecarboxaldehyde, compositions, and derivatives thereof. It refers to its systemic, unexpected and useful insecticidal activity. The invention particularly pertains to compositions of such compounds and methods, which use said compounds, for the control of pests of arthropods, nematodes, helminths or protozoa. In particular to the application of such compounds or compositions in methods for agricultural use, particularly as pesticides to control arthropods, especially insects by systemic action. The invention also relates to 1-arylpyrazole hydrazones.

- BACKGROUND OF THE INVENTION The control of insects, nematodes or helminths by means of active material having a 1-arylpyrazole group have been described by many patents or patent applications such as International Patent Publication No. WO 93/06089 (and US Patent No. 5,451,598, equivalent), WO 94/21606 and WO 87/03781 as well as in European Patent Publications Nos. 0295117, 659745, 679650, 201852 and 412849, German Patent No. DE19511269 and US Patent No. 5,232,940. Other compounds are described in WO 92/13451, August 20, 1992, from Schering Agrochemicals Ltd., which describes 5-chloro-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- (4 , 5-dicyano-lH-imadazol-2-yl) -3-hydroxyiminomethyl-lH-pyrazole as an intermediate, also with activity against a single species Lucilia sericata, blue sleep fly. This Schering reference seems to be the only reference describing the 1-arylpyrazole-oxime compounds as insecticides.

DESCRIPTION OF THE INVENTION It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation. A second object of the present invention is to provide pesticidal compositions and pesticidal methods of using the pyrazole compounds pesticides against arthropods, especially insect pests, plant nematodes, or helminths or protozoa, particularly in veterinary medicine, forestry, agricultural crops or horticulture, or breeding of domestic animals, or in public health. A third object of the present invention is to provide many active compounds, with broad spectrum pesticidal activity, as well as also compounds with special selective activity, for example, aficide, miticide, foliar insecticide, soil insecticide, and ne aicide, systemic activity , antialimentation or pesticide for seed treatments. A fourth object of the present invention is to provide compounds with substantially improved and faster activity, especially against insects and more particularly insects in their larval stages. A fifth object of the present invention is to provide compounds with greatly improved penetration (higher and faster) in pest species when applied topically and thereby providing improved movement of the compounds to the site (s) of pesticide action within the pest.

Another object of the present invention is to provide compounds with high activity and improved safety for the user and the environment. These and other objects of the invention will become readily apparent from the detailed description of the present invention. These objects are fulfilled in whole or in part by the present invention.

BRIEF DESCRIPTION OF THE INVENTION This invention describes new systemic chemical compositions and methods for treating plants with compositions having systemic netocidal or insecticidal activity of the following formula (I): 0) where X is -S (0) mR6 or R7. Y is hydrogen, alkenyl of 3 to 6 carbon atoms, alkynyl, formyl, alkylcarbonyl, cycloalkylcarbonyl, halocycloalkylcarbonyl, aroyl, arylalkylcarbonyl, Alkylsulfonyl, ariÍsulfonilo, haloalkylcarbonyl, aminoalkylcarbonyl, alkylaminoalkylcarbonyl, dialkylaminoalkylcarbonyl, alkoxyalkylcarbonyl, ariloxialquilcarbonilo, alquiltioalquilcarbonilo, alquiÍsulfonilalquiIcarbonilo, ariltioalquilcarbonilo, N-alkylcarbamoyl, N- arylcarbamoyl, N-alquiltiocarbamoilo, N- arylthiocarbamoyl, hidroxiarilalquilcarbonilo alpha-, hydroxyalkylcarbonyl, carboxialquiIcarbonilo, alkoxycarbonylalkylcarbonyl, - P (= 0) (O-Alkyl) 2, -P (= S) (0-alkyl) 2, -P (= 0) (S-alkyl) 2, -P (= S) (S-alkyl) 2 , trialkylsilyl, alkylcarbonylaminoalkylcarbonyl, alkylcarbonyloxyalkylcarbonyl, aryl, pyridinyl, pyrimidinyl, -C (= 0) S-alkyl, -C (= 0) S -aryl, -C (= 0) S-alkylaryl, alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, alkylsulfonylalkoxycarbonyl, arylthioalkoxycarbonyl, alkoxycarbonyl, aryloxycarbonyl and aryloxycarbonylalkylcarbonyl; or alkyl or haloalkyl, optionally substituted by alkoxy, alkoxycarbonyl, carboxy, cyano, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio, nitro, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, amino, alkylamino, dialkylamino, hydroxy,. alkylcarbonylamino or alkylcarbonyloxy; Z is hydrogen, halogen, -C (0) R7-, -S (0) nRe -C (0) 0R9, alkyl, haloalkyl, -OR9, -N = C (Rio) (Ru), alkenyl hydrazino, alkylthiocarbonyl, 1H-pyrrol-1-yl or lH-pyrazol-1-yl, -CHO, -CH = NOH, amino, Ri2NH- or R? 3R14N-: Ri is hydrogen, alkyl or -NR? 5R? 6; R2 is hydrogen or halogen; R3 and R5 are hydrogen, halogen or alkyl; R4 is halogen, haloalkyl, haloalkoxy, Ri7S (0) p- or SF5; R6 is alkyl or haloalkyl, alkenyl or haloalkenyl, alkynyl or haloalkynyl or cycloalkyl having from 3 to 5 carbon atoms; R7 is alkyl or haloalkyl; R8 is R7 or phenyl; R9 and Rio are hydrogen, alkyl or haloalkyl; Ru is alkyl, haloalkyl, alkoxy, or a phenyl group which is optionally substituted by one or more groups selected from hydroxy, halogen, alkoxy, cyano, R7 or -S (0) qR7; R12, Ris and RI to which they are identical or different, are R7S (0) r-, formyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl of 3 to 6 carbon atoms or -C (O) alkyl wherein the alkyl and alkenyl portions are optionally substituted by one or more Ri8: or R13 and Ri4 are joined or linked so that together they form a divalent radical having 4 to 6 atoms in the chain, this divalent radical is alkylene, alkyleneoxyalkylene or alkylene aminoalkylene, preferably to form a morpholino, pyrrolidine, piperidine or piperazine ring; R15 and Ri6 are independently hydrogen or alkyl; Ri7 represents haloalkyl; Ris is cyano, nitro, alkoxy, haloalkoxy, -C (0) R7, R8S (0) s-, -C (0) 0Rg, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; , n, p, q, r and s represents zero, one or two; M is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; geometric isomers, tautomeric forms and pesticidally active salts thereof. By the term "pesticidally acceptable salts" is meant salts, anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are soluble in water. Suitable acid addition salts formed from the compounds of the formula (I) containing an amine group, include salts with inorganic acids for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids for example acetates. Suitable base addition salts, formed from compounds of formula (I) containing a carboxylic acid group, include alkali metal salts (eg, sodium or potassium), ammonium salts and organic amine salts (e.g. diethanolamine or morpholine). The compounds of the formula (I) wherein Ri represents -R? 5R? 6 in which R? 6 represents hydrogen and R? 5 represents hydrogen or alkyl may exist in tautomeric forms as shown in formulas (la) and ( Ib). Such tautomerism is well known as described in S. Patai (The Chemistry of Functional Groups: Amidines and Imidates, Vol.2, 1991, pages 276-277). It will be understood that all tautomeric forms are included by the present invention.

Ja) (Ib) Unless otherwise specified the alkyl, alkoxy and alkylthio groups have from one to six (preferably one to four) carbon atoms, the alkenyl groups have from two to six (preferably two to four) carbon atoms and the groups alkynyl have from three to six (preferably three or four) carbon atoms. The cycloalkyl groups have from 3 to 8 carbon atoms, preferably 5 to 7 carbon atoms. By the term "aryl" is meant mono or polycyclic aromatic portions, preferably including phenyl, pyridyl, pyrimidinyl, furyl and naphthyl groups. It will be understood that the rings formed by the divalent alkylene radicals which include the nitrogen atoms to which they generally attach or bind are rings with 5, 6 and 7 elements. In the present invention, some words are used in a specific sense: The term "aminocarbonyl" means a carbamoyl radical, ie, a radical of the formula -C (0) NH2. Similarly, the term "alkylaminocarbonyl" means an alkylcarbamoyl radical, ie, a radical of the formula -C (O) -NH-alkyl; and the term "dialkylaminocarbonyl" means a dialkylcarbamoyl radical, ie, a radical of the formula -C (0) -N (alkyl) 2 in which the alkyl portions may be the same or different. The term "aminosulfonyl" means a sulphamoyl radical, ie, -S02NH2. Similarly, the term "alkylaminosulfonyl" means an alkylsulfamoyl radical, that is, a radical of the formula -S02NH-alkyl; while the term "dialkylaminosulfonyl" means a dialkylsulfamoyl radical, which has the formula -S02N (alkyl) 2 wherein the alkyl portions may be the same or different. The term "halo" before the designation of a radical means that this radical is partially or completely halogenated, that is, substituted by F, Cl, Br, or I, in any combination, preferably by F or Cl.

The term "halogen" means F, Cl, Br or I. When the name or name of any substituent is repeated, the same meaning is maintained unless otherwise specified. The term "aroyl" designates an aromatic carbonyl radical, ie, aryl-C (0) -, which is preferably a benzoyl optionally substituted by one or more alkyl, alkoxy or halogen groups. Compounds in which Z is amino, Ri2NH- or Ri3R? 4N- are preferred. Compounds in which X is -S (0) mR6 are preferred. Ri is preferably amino or hydrogen; R6 is preferably alkyl; especially preferred are methyl and ethyl; R3 and R5 are preferably hydrogen; R4 is preferably haloalkyl, haloalkoxy or SF5; especially preferred is trifluoromethyl. M is preferably C-halo, or N, Y is preferably hydrogen or alkoxycarbonyl. Preferred phenyl groups and pyridyl groups comprising the radicals R 2 to R 5 and M in the formula (I) are: 2,6-dichloro-4-trifluoromethylphenyl; 2,6-dichloro-4-trifluoromethoxyphenyl; 2-bromo-6-chloro-4-trifluoroethylphenyl;; 2-bromo-6-chloro-4-trifluoromethoxyphenyl; 2,6-difluoro-4-trifluoromethylphenyl; 2-chloro-4-trifluoromethylphenyl; 3-chloro-5-trifluoromethyl-2-pyridinyl; 3-chloro-5-trifluoromethoxy-2-pyridinyl; 2-bromo-6-fluoro-4-difluoromethylphenyl; 2-chloro-6-fluoro-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethoxyphenyl; and 2,6-dichloro-4-pentafluorothiophenyl. A preferred class of compounds of formula (I) are those wherein: X is -S (0) mR6; And it's hydrogen; alkyl having 1 to 4 carbon atoms (including linear, branched and cyclic) optionally substituted by aminocarbonyl, alkylsulfonyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, cyano or nitro; alkenyl of 3 to 4 carbon atoms; alkynyl of 3 to 5 carbon atoms; alkylcarbonyl; optionally substituted aroyl, arylalkylcarbonyl; alkylsulfonyl; alkoxycarbonylalkylcarbonyl; haloalkylcarbonyl; N-alkylcarbamoyl; alkoxycarbonyl; aryloxycarbonyl; alkoxyalkylcarbonyl; alpha-hydroxyarylalkylcarbonyl; hydroxyalkylcarbonyl; aminoalkylcarbonyl; C (= 0) S-alkyl and trialkylsilyl; Z is amino, RX2NH-, R? 3R? 4N-, halogen or methyl; Ri is hydrogen, methyl, amino or methylamino; R2 is F, Cl, Br or H; R3 and R5 are hydrogen; R4 is CF3, CF30, CHF2, CF3S (0) p, CF2C1, CFC12, CF2C10, CFC120, Cl, Br, or F; R6 is methyl or ethyl optionally substituted by F, Cl or Br; M is CCl, CF, CBr, or N; R12, R13 and R? are CF3S (0) r-, alkynyl or alkoxycarbonyl; or alkyl, alkenyl of 3 to 6 carbon atoms or -C (O) alkyl wherein the alkyl and alkenyl portions are optionally substituted by one or more Ris; and R 18 is cyano, nitro, alkoxy, haloalkoxy, -C (0) R7, R8S (0) s-, -C (0) 0R9, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl. A class of compounds of the formula (I), further preferred, are those in which: Y represents hydrogen: an alkyl group of 1 to 3 carbon atoms optionally substituted by cyano, carbamoyl, carboxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl; trialkylsilyl; acetyl; propionyl substituted by alkoxycarbonyl; benzoyl optionally substituted by alkyl; alkoxycarbonyl; or N-alkylcarbamoyl; Z represents amino, Ri2NH-, R? 3R? N-, -CHO, -CH = N0H, halogen or methyl; Ri represents hydrogen, methyl, amino or methylamino; R2 represents chlorine, bromine or hydrogen; R3 and R5 represent hydrogen; R4 represents CF3 or OCF3; R6 optionally represents ethyl or halogenated methyl; R7 represents CF3; R 12, Ri 3 and Ri represent alkynyl; or methyl or ethyl optionally substituted by R8S (0) s-, cyano or aminocarbonyl; R8 represents alkyl or phenyl; and M represents C-Cl, C-Br or N. According to another aspect of the invention, Y can be a sugar portion, preferably Y is a ring containing 4, 5 or 6 carbon atoms and which is interrupted by an oxygen atom, the carbon atoms substituted by one or more hydroxy groups, one or more CH2OH groups or one or more OC (O) alkyl groups.

The present invention also provides arylpyrazoles of the following formula (Ia): (Ia) wherein: A is -NR26-: Yi is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, -S (0) aR28, - P (0) R29R30 , -P (S) R29R3o, SKR31) (R32) (R33), -C (0) R27, -C (S) R27, cyano or nitro; R19 is hydrogen, alkyl, haloalkyl, or -NR34R35; R20 is -S (0) bR36 or R37; R2? is hydrogen, halogen, -C (0) R38, -S (0) cR39, alkyl, haloalkyl, -OR0, -N = C (R4?) (R2), alkenyl, -NR43R44, lH-pyrrol-1-yl, lH-pyrazol-1-yl, or -CH = NOH; R22, R23 and R25 are independently selected from hydrogen, halogen or alkyl; R24 is halogen, haloalkyl, haloalkoxy, -S (0) dR4s or SF5; R26 is hydrogen or substituted or unsubstituted alkyl; R27 is hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aryl, -OR46, -NR47R48, or -SR9; R28 is substituted or unsubstituted alkyl or substituted or unsubstituted aryl; R29 and R30 are independently selected from alkoxy and thioalkoxy; R31, R32 and R33 are independently selected from alkyl, haloalkyl and aryl; R34 and R35 are independently selected from hydrogen or substituted or unsubstituted alkyl; R36 is alkyl, alkenyl, alkynyl, or cycloalkyl of 3 to 6 carbon atoms each of which is optionally substituted by one or more halogens; R37 is alkyl or haloalkyl; R38 is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy; R39 is alkylhaloalkyl or aryl; R40 and R41 are independently selected from hydrogen, alkyl and haloalkyl; R42 is alkyl, haloalkyl, alkoxy or phenyl each of which is optionally substituted by one or more groups selected from hydroxy, halogen, alkoxy, -CN, alkyl, -S (0) ealkyl; R43 and R44 are independently selected from hydrogen, NH2, -S (O) fR50, -C (0) R5 ?, substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl or alkynyl; R43 and R44 can together form a divalent alkylene radical which can be interrupted by one or more heteroatoms, preferably selected from hydrogen, nitrogen and sulfur; R 45 is haloalkyl; R6 and R9 are independently selected from substituted or unsubstituted alkyl and substituted or unsubstituted aryl; R7 and R48 are independently selected from hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted aryl; or R47 and R48 can together form a divalent alkylene radical which can be interrupted by one or more heteroatoms preferably selected from oxygen, nitrogen and sulfur; R50 is substituted or unsubstituted alkyl; R51 is hydrogen, alkyl, haloalkyl, aryl, alkenyl, -OR52, -SR53, or -NR54R55 R52 and R53 are independently selected from alkyl and haloalkyl; R54 and R55 are independently selected from hydrogen, alkyl, haloalkyl and aryl; a, b, c, d, e and f independently represent zero, one or two; Mi is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; or a pesticidally acceptable salt thereof. A preferred group of compounds of the formula (Ia) are those with one or more of the following characteristics wherein: A is -NR26-; Yi is hydrogen, alkyl, or -C (0) R27; R19 is hydrogen or NH2; R20 is -S (0) bR36; R21 is -NR43R; R22 is halogen; R23 and R25 are hydrogen; R 24 is haloalkyl; R 27 is alkyl or O-alkyl; or M is C-halo.

Another preferred group of the compounds of the formula (Ia) are those wherein: A is -NR26-; Yi is hydrogen, alkyl, or -C (0) R27; RIA is hydrogen or NH2; R20 is -S (0) bR36; R2? is -NR43R44; R22 is halogen; R23 and R25 are hydrogen; R 24 is haloalkyl; R 27 is alkyl or O-alkyl; and M is C-halo. In the compounds of the formula (Ia), preferably by the term "substituted" is meant one or more of the following substituents: halogen, hydroxy, alkylthio, cyano, carboxy, -C (O) alkyl, -C (0) Oalkyl, -C (0) NH 2, -C (O) NHalkyl, -C (0) N (alkyl) 2. aryl, nitro, azido, amino, alkylamino, dialkylamino, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, aryloxy, arylthio, alkylcarbonylamino, alkylcarbonyloxy or aryloxycarbonyl. Among the compounds of the general formula (I) or (Ia) the following compounds are particularly preferred, which provide particularly useful or beneficial control of insect species by systemic action. The numerous compounds are for reference purposes only. 1) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime; 2) 1- [2,6-Dichloro-4- (trifluoromethyl) phenyl] -5-ethylamino-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime; 3) oxime of 1- [2,6-Dichloro-4- (trifluoromethyl) phenyl] -5-methylamino-4-methylsulfinyl-1H-pyrazole-3-carboxydehyde; 5-Amino-l- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulphinyl-1H-pyrazole-3-carboxydehyde oxime; 6) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylthio-1H-pyrazole-3-carboxaldehyde oxime; 7) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-difluoromethylthio-1H-pyrazole-3-carboxaldehyde oxime; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carboxaldehyde oxime; O- (methyl) oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylthio-1H-pyrazole-3-carboxaidehido; 10) O- (acetyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; go O- (methylbenzoyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 12 'O- (methoxycarbonyl) oxime 5-A? Nino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 13) O- [2- (ethoxycarbonyl) propionyl] oxime of 5-Amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 14) O- (acetyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carboxaldehyde; 15) O- (methoxycarbonyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carboxaldehyde; 16] 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-1H-pyrazole-3-carboxaldehyde oxime; 17: 0- (methyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; 18) 0- (N-methylcarbamoyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 19) O- (carboxymethyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; 2o: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime; 2i: O- (tert-butyldimethylsilyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 22: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formyl-N-hydroxy-4-trifluoromethylthio-lH-pyrazole-3-carboximidamide; 23) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-5-hydroxyiminomethyl-4-trifluoromethylthio-1H-pyrazole-3-carboximidamide; 24) 0- (isopropyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; 25: O- (ethoxycarbonylmethyl) oxime 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylisulfinyl-1H-pyrazole-3-carboxaldehyde; 26) O- (5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde O- (aocarbonylmethyl) oxime; 27) O- [2- (ethylsulfonyl) ethyl] oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 28 O- (2-cyanoethyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 29] 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylthio-lH-pyrazole-3-carboxaldehyde oxime; 30: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime; 31) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylsulfonyl-lH-pyrazole-3-carboxaldehyde oxime; 32: 5-amino-l- [3-chloro-5- (trifluoromethyl) -2-pyridyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde oxime; 33) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylthio-5-methyl-1H-pyrazole-3-carboxaldehyde oxime; 34) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-5-methyl-lH-pyrazole-3-carboxaldehyde oxime; 35: 1- [2-chloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylsulfonyl) ethylamino] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime; 36) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-dimethylamino-4-methylthio-lH-pyrazole-3-carboxaldehyde oxime; 37) 5-amino-l- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -4-ethylsulphinyl-1H-pyrazole-3-carboxaldehyde oxime; 38 oxime of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethyl-1H-pyrazole-3-carboxaldehyde; 39: 3-acetyl-5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole oxime; 40) 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-trifluoro-methylsulfinyl-lH-pyrazole-3-carboximidamide; 4 i: 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-methoxy-4-trifluoro-methylsulfinyl-1H-pyrazole-3-carboximidamide; 42) 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-ethylsulfinyl-lH-pyrazole-3-carboximidamide; 43: 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-ethylthio-lH-pyrazole-3-carboximidamide; 44) 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 45) 5-amino-l- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -N-hydroxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 6: 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] - N -hydroxy-4-methylsulfonyl-1H-pyrazole-3-carboximidamide; 47) 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-methylthio-lH-pyrazole-3-carboxy-idamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-ethylsulfonyl-1H-pyrazole-3-carboximidamide; 49) 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-methoxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; SW; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-methoxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 51] 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4- [2- (fluoroethyl) sulfinyl] -IH-pyrazole-3-carboximidamide; 52) 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4- [2- (fluoroethyl) sulfonyl] -IH-pyrazole-3-carboximidamide; 53) 5-amino-l- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] -4-ethylsulfinyl-N-hydroxy-1H-pyrazole-3-carboximidamide; 54) 5-amino-l- [3-dichloro-5- (trifluoromethyl) -2-pyridinyl] -4-methylsulfinyl-N-hydroxy-1H-pyrazole-3-carboximidamide; 55) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-5-methylamino-4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 56) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-ethylamino-N-hydroxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 57: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylsulfonyl) ethylamino] -N-hydroxy-4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 58) 5- [2- (cyano) ethylamino] -1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 59) 5- (aminocarbonylmethylamino) -1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 60) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [2- (phenylsulfonyl) ethylamino] -N-hydroxy-1H-pyrazole-3-carboximidamide; 61) 5-amino-l- [2,6-dibromo-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N-hydroxy-lH-pyrazole-3-carboximidamide; 62: 1- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl] -5-ethylamino-4-methylsulfinyl-N-hydroxy-lH-pyrazole-3-carboximidamide; 63: 5-amino-l- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 64) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-5- [2- (methylsulfinyl) ethylamino] -N-hydroxy-lH-pyrazole-3-carboximidamide; 65: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-5- [2- (methylsulfinyl) ethylamino] -N-hydroxy-lH-pyrazole-3-carboximidamide; 66) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-5- [2- (ethylsulfinyl) ethylamino] -N-hydroxy-lH-pyrazole-3-carboximidamide; 67) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [(prop-2-ynyl) amino] -N-hydroxy-1H-pyrazole-3-carboximidamide; and 68) 5-amino-l- [2-chloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N-hydroxy-lH-pyrazole-3-carboximidamide; Other compounds of formula (I) or (bis) that are provided by the present invention include: 69] 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N-amino-lH-pyrazole-3-carboximidamide; 70) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N- (isopropylcarbonyl) amino-lH-pyrazole-3-carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N- (n-heptylcarbonyl) amino-lH-pyrazole-3-carboximidamide; 72) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N- (ethoxycarbonyl) amino-lH-pyrazole-3-carboximidamide; 73) 5-Amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylsulfini-1-N-amino-1H-pyrazole carboximidamide; 74) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulphinyl-N-amino-lH-pyrazole carboximidamide; 75: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylsulfinyl-N-acetylamino-1H-pyrazole carboximidamide; 76) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (1-methyletenylcarbonylamino) -lH-pyrazole carboximidamide; 77) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (tert-butylcarbonylamino) -1H-pyrazole carboximidamide; 78) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (2-methyletenylcarbonylamino) -lH-pyrazole carboximidamide; 79. 5-Amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (ethylcarbonylamino) -lH-pyrazole carboximidamide; 80) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (propylcarbonylamino) -1H-pyrazole carboximidamide; 81) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (1-ethylpropylcarbonylamino) -lH-pyrazole carboximidamide; 82) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (butylcarbonylamino) -1H-pyrazole carboximidamide; 83: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (pentylcarbonylaird.no) -1H-pyrazole carboximidamide; 84 '5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (hexylcarbonylamino) -1H-pyrazole carboximidamide; 85: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-N-acetylamino-iH-pyrazole carboximidamide; 86) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N-chloroacetylamino-lH-pyrazole carboximidamide; 87) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N- (tridecylcarbonylamino) -1H-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N- (n-propoxycarbonylamino) -1H-pyrazole carboximidamide; 89: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 4-methylsulfinyl-N- (1,1-dimethylpropyloxycarbonylamino) -lH-pyrazole carboxyimidamide; 90) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (terbutyloxycarbonylamino) -1H-pyrazole carboximidamide; 91) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (acetyloxy) -lH-pyrazole carboximidamide; 92) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-N- (acetyloxy) -lH-pyrazole carboximidamide; 93) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (ethylcarbonyloxy) -lH-pyrazole carboximidamide; 94) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (propylcarbonyloxy) -lH-pyrazole carboximidamide; 95) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (methyletenylcarbonyloxy) -1H-pyrazole carboximidamide; 96) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (benzyloxy) -lH-pyrazole carboximidamide; 97 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methylamino-4-methylsulfinyl-N- (acetyloxy) -1H-pyrazole carboximidamide; 98) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-N- (acetyloxy) -lH-pyrazole carboximidamide; 99) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (heptylcarbonyloxy) -lH-pyrazole carboximidamide; 100) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-N- (heptylcarbonyloxy) -lH-pyrazole carboximidamide; ? o ?: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfenyl-N- (acetyloxy) -lH-pyrazole carboximidamide; 102) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfenyl-N- (heptylcarbonyloxy) -lH-pyrazole carboximidamide; 103: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylsulfinyl-N- (acetyloxy) -1H-pyrazole carboximidamide; 104) 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formylamino-4-ethylsulphenyl-N- (acetyloxy) -1H-pyrazole carboximidamide; 105) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (hexylcarbonyloxy) -lH-pyrazole carboximidamide; 106) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (pentylcarbonyloxy) -lH-pyrazole carboximidamide; 107: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (butylcarbonyloxy) -IH-pyrazole carboximidamide; ios: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfenyl-N- (cyclopentylcarbonyloxy) -1H-pyrazole carboximidamide; 109) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (cyclopentylcarbonyloxy) -1H-pyrazole carboximidamide; 110) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (tert-butylcarbonyloxy) -1H-pyrazole carboximidamide; m: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (isopropylcarbonyloxy) -1H-pyrazole carboximidamide; 112: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formylamino-4-ethylsulphinyl-N- (acetyloxy) -1H-pyrazole carboximidamide; 113) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (chloroacetyloxy) -lH-pyrazole carboximidamide; 114 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (bromoacetyloxy) -lH-pyrazole carboximidamide; 115) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (1-ethylpropylcarbonyloxy) -1H-pyrazole carboximidamide; 116) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- [(3-acetyloxy) phenylcarbonyloxy] -lH-pyrazole carboximidamide; 117) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-trifluoromethylsulfonyl-1H-pyrazole-3-carboximidamide; 118 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-trifluoromethylsulfenyl-lH-pyrazole-3-carboximidamide; 119] 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N- (methoxycarbonylamino) -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde hydrazone; 120) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N- (methylsulfonylamino) -4-ethylsulfinyl-lH-pyrazole-3-carboxaldehyde hydrazone; 121 '5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-amino-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde hydrazone; 122) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-amino-4-trifluoromethylsulfenyl-lH-pyrazole-3-carboxaldehyde hydrazone; 123: 5-Amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] N-amino-4-methylsulfenyl-lH-pyrazole-3-carboximidamide; 124) 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] N- (furylcarbonylamino) -4-methylsulfinyl-1H-pyrazole-3-carboximidamide; or 125) DETAILED DESCRIPTION OF THE INVENTION METHODS OR PROCEDURES FOR SYNTHESIS The compounds of the formula (I) can be prepared according to the manufacturing methods described in International Patent Publications Nos. WO 94/21606 and WO 93/06089 or International Patent Publication No. WO 87/03781 as well as in European Patent Publication No. 0295117 and US Patent No. 5,232,940 to Hatton et al. Those skilled in the art will choose the appropriate initial reagent in these known methods and adapt these known methods to the reagent to obtain the corresponding desired products. It is understood that in the description of the following procedures the sequences for the introduction of the various groups on the pyrazole ring can be operated in a different order and that suitable protecting groups may be required when it is evident to those skilled in the art. . In the following description of the procedures when the symbols that appear in formulas are not specifically defined, it is understood that they are "co or were previously defined" according to the first definition of each symbol in the specification. According to a further feature of the present invention, the compounds of the formula (I) wherein R 2, R 3, R 4, R 5, M, X, Y and Z are as defined above and Ri represents amino (mainly compounds of the formula (la) or (Ib) in which R15 represents hydrogen), can be prepared by the reaction of a compound of the formula (II): with a compound of the formula (III) NH2OY (III) in which Y was previously defined. The reaction was generally effected using an acid salt of the compound (III) for example the hydrochloride salt and in the presence of a base for example pyridine or an alkali metal carbonate (such as sodium carbonate) or an alkali metal acetate (such as sodium acetate) or ammonium acetate in a solvent such as methanol and / or water at a temperature from 0 ° C to 100 ° C. According to a further feature of the present invention, the compounds of the general formula (I) wherein R 2, R 3, R, R 5, M, X, Y and Z are as defined above and Ri represents amino, can be prepared by the reaction of a compound of the formula (IV): wherein R represents alkyl, with a compound of the formula (III) in which R is alkyl and Y is defined above. The reaction was generally carried out using an acid salt of the compound (III) for example the hydrochloride salt and optionally in the presence of a base for example pyridine or an alkali metal carbonate (such as sodium carbonate) or a metal acetate alkaline (such as sodium acetate) or ammonium acetate in a solvent such as methanol and / or water at a temperature from 0 ° C to 100 ° C. According to a further feature of the present invention, the compounds of the general formula (I) wherein R 2, R 3, R 4, R 5, M, X, Y and Z are as defined above and Ri represents alkylamino or dialkylamino, they can be prepared by the reaction of the corresponding compound of the formula (I) wherein Ri represents amino with an alkylating agent preferably of the formula R-hal in which R represents alkyl and hal is chlorine, bromine or iodine. The reaction is usually carried out in the presence of a strong base such as sodium hydride or potassium t-butoxide in a solvent such as tetrahydrofuran at a temperature from 0 ° C to 100 ° C. According to a further feature of the present invention, the compounds of the general formula (I), wherein R 2, R 3, R 4, R 5, M, X, Y and Z are as defined above and Ri represents hydrogen or alkyl, they can be prepared by the reaction of a compound of the formula (V): (V) wherein Ri represents hydrogen or alkyl, with a compound of the formula (III) in which Y is as defined above and using the same conditions that are employed in the reaction of the compounds of the formula (II) with compounds of Formula (III) above. According to the additional feature of the present invention, the compounds of the general formula (I) wherein R 2, R 3, R 4, R 5 M, X and Z are as defined above, Ri represents hydrogen or alkyl, and Y is as previously defined with the exclusion of hydrogen, formyl, aryl, pyridinyl and pyrimidinyl (the exclusions are for chemical reasons only), can be prepared by the reaction of the corresponding compound of the formula (I) wherein Y represents hydrogen with a reagent of suitable alkylation or acylation or Michael acceptor generally in the presence of a base for example triethylamine in an inert solvent such as dichloroethane at a temperature from 0 ° C to 100 ° C. According to a further feature of the present invention, the compounds of the general formula (I), wherein Z represents R? 2NH- or R? 3R? 4N- in these Ri2, R13 and / or Ri4 represents -C (0) ) alkyl optionally substituted by one or more R? 8 can be prepared by the acylation of the corresponding compound wherein Z represents amino, according to methods described in one or more of International Publications No. WO 94/21606, WO 93/06089 and WO 87/03781, European Patent Publication No. 0295117 and US Patent No. 5,232,940 to Hatton et al. For the synthesis of the 5-alkylamino and dialkylamino compounds wherein Z represents R? 2NH- or Ri3R? 4 - in which Ri2, Ri3 and Ri4 represent alkyl or alkenyl of 3 to 6 carbon atoms optionally substituted by Ris, including the aminocyclic compounds (ie, the compounds in which R13 and Ri4 are joined together) of the formula (I), three basic methods are appropriate. The first method includes direct alkylation of the compounds of the precursor of the formula (I) in which Z represents amino with alkylating agents. The second method involves a two-step sequence, with the formation of the imino ethers, followed by a reduction. The third method of preparation is through a conjugate addition, for example, a Michael type addition. The compounds of the formula (I) wherein Z represents Ri2NH- or R? 3R? 4N Ri3 in which R12, R13 and / or Ri4 are R7S (0) r_, formyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl, and R7 and r are as defined above, can be prepared by the methods described in one or more of International Publications Nos. WO 94/21606, WO 93/06089 and WO 87/03781, European Patent Publication No. 0295117 and North American Patent No. 5,232,940, to Hatton et al. The compounds of the formula (I) in which Z represents hydrogen, halogen, -S (0) nRs, -C (0) R7, -C (0) 0R9, alkyl, haloalkyl, -N = C (Rio) Rn ), alkylthiocarbonyl and amino, Ri2NH- or R? 3R? 4N- can be prepared by methods described in one or more of the International Publications Nos. WO 94/21606, WO 93/06089 and WO 87/03781, European Patent Publications Numbers EP 0295117, EP 511845, EP 403309 and EP 403300, and U.S. Patent No. 5,232,940, to Hatton et al., And German Patent Publication No. DE 19511269.

According to a further feature of the present invention, the compounds of the general formula (I) wherein Z represents 0R9 can be prepared by methods described in US Patent Nos. 5,047,550 and 4,918,085. According to a further feature of the present invention, the compounds of the formula (I) in which the substituent Z is hydrazino, IH-pyrrol-1-yl or lH-pyrazol-1-yl, can be prepared in accordance with The procedures described in EP 0352944. The synthesis of high oxidation states of the compounds of the formula (I), ie the compounds in which n is 1 or 2, can be achieved by oxidation of the corresponding compounds in which m is 0 or 1. The intermediates of the formula (II) can be prepared by known methods (see for example the references listed above). Certain compounds of formula (II) are novel and as such constitute a further feature of the invention. The intermediates of the formula (IV) wherein R represents alkyl, can be prepared by the reaction of compounds of the formula (II) with an alcohol of the formula ROH wherein R is alkyl. The alcohol is usually employed in excess as the solvent but a co-solvent such as tetrahydrofuran may be present. The reaction is generally carried out in the presence of a base such as sodium alkoxide at a temperature from 0 ° C to 100 ° C. The intermediates of the formula (V) wherein Ri represents hydrogen or alkyl, can be prepared by methods known for example as described in WO 8703781 and EP 295117. For example, where Ri represents hydrogen by the reaction of the corresponding compound of the formula (II) with diisobutylaluminum hydride, and wherein Ri represents alkyl by the reaction of the corresponding compound of the formula (II) with an organometallic reagent of the formula RiQ in which Q represents for example Mg-Cl or lithium in an inert solvent such as tetrahydrofuran. The compounds of the formula (IV) are new and as such constitute a further feature of the invention. Certain compounds of the formula (V) are new and as such constitute a further feature of the invention. The intermediates of the formula (III) are known or can be prepared by known methods. According to a further feature of the present invention, the compounds of the general formula (Ia) in which Ri 9 is amino, can be prepared by the reaction of a compound of the formula (II bis): with a compound of the formula (III bis): H2NNR26Y? (III bis) in which Y and A are as defined above. The reaction is generally carried out using an acid salt of A compound of the formula (III bis) for example the hydrochloride salt and in the presence of a base for example pyridine or an alkali metal carbonate (such as sodium carbonate) or an alkali metal acetate (such as sodium acetate) or ammonium acetate in a solvent such as methanol and / or water at a temperature from 0 ° C to 100 ° C. According to a further feature of the present invention, the compounds of the general formula (Ia) wherein R 9 is amino can be prepared by the reaction of a compound of the formula (IV bis): wherein R represents alkyl, with a compound of the formula (III bis). The reaction is generally carried out using an acid salt of a compound of the formula (IIIa), for example the hydrochloride salt, and optionally in the presence of a base (for example pyridine or an alkali metal carbonate such as carbonate). sodium) or an alkali metal acetate (such as sodium acetate or ammonium acetate) in a solvent such as methanol and / or water and generally at a temperature from 0 ° C to 100 ° C.

According to a further feature of the present invention, the compounds of the general formula (Ia) wherein Ri9 represents NR34R35 and wherein one or both of R34 and R35 are substituted or unsubstituted alkyl, can be prepared by the reaction of the corresponding compound of the formula (I) wherein R19 represents amino with an alkylating agent of formula R-hal wherein R represents alkyl and hal is chloro, bromo or iodo, preferably iodo. The reaction is usually carried out in the presence of a strong base such as potassium t-butoxide or sodium hydride in a solvent such as tetrahydrofuran at a temperature from 0 ° C to 100 ° C.

According to a further feature of the present invention, the compounds of the general formula (Ia) with the above definitions wherein R19 represents hydrogen or alkyl can be prepared by the reaction of a compound of the formula (V bis): wherein R 9 represents hydrogen or alkyl, with a compound of the formula (III bis) defined above and using the same conditions that are employed in the reaction of the compounds of the formula (II bis) with compounds of the formula III a) above. According to a further feature of the invention, the compounds of the general formula (Ia) wherein Y is -S (0) a'R28, -P (0) R29R3 ?, -P (S) R29R3o, -Yi (R3?) (R32) (R33) -C (0) R27, -C (S) R27, cyano or nitro can be prepared by the reaction of a compound of the formula (Ia) wherein Yi is hydrogen , with sulfonylating, sulfonylation, sulfonation, phosphorylation, thiofosphorylation, silylation, acylation or ioatilation reagents, respectively, generally in the presence of a base such as triethylamine or sodium carbonate and generally in a solvent at a temperature generally in the range -100 to 100 ° C. According to a further feature of the invention for the synthesis of 5-alkylamino and dialkylamino compounds of the formula (Ia) wherein R2i represents R43NH- or R3R4 N- in which R3 and R represent substituted or unsubstituted alkyl or alkenyl of 3 to 6 carbon atoms substituted or unsubstituted, three basic methods are appropriate. The first method includes direct alkylation of precursor compounds of the formula (Ia) in which R2i represents amino with alkylating agent. The second method involves a two-step sequence, with the formation of the imino ethers, followed by a reduction. The third method of preparation is through a conjugate addition, for example, a Michael type addition. The compounds of the formula (II bis) wherein R2, R3, R, Rs Re and M are the substituents described above, can be prepared by methods described in one or more of the following: WO 94/21606, WO 93/06089, WO 87/03781, WO 97/22593; European Patent Publications EP 0295117, EP 0511845, EP 0403309, EP 0403300, EP 352944, EP 780378; U.S. Patent Nos. 5,232,940, 5,047,550, 4,918,085; German Patent Publication No. 19511269; or by methods known to the person skilled in the art. The synthesis of the higher oxidation states of the compounds of the formula (Ia), ie the compounds in which a, b, c, d, eof are 1 6 2, can be achieved by oxidation of the corresponding compounds in which that variable is 0 or 1. The intermediates of the formula (II bis) can be prepared by known methods (see for example the references listed above).

REPRESENTATIVE COMPOUNDS OF THE INVENTION The compounds of TABLE 1 are illustrative of some of the preferred compounds of the general formula (I) wherein R3 and R5 represent hydrogen and can be prepared by the synthesis methods or procedures described herein, by the appropriate selection of reagents, conditions and methods, which are commonly known and are apparent to one skilled in the art. In Table 1 Me means methyl, Et means ethyl and where the subscripts are omitted they must be present, for example CH2 means CH2 • TABLE 1 fifteen twenty DESCRIPTION OF THE PREFERRED MODALITIES DETAILED EXAMPLES OF THE SYNTHESIS OF COMPOUNDS The following EXAMPLES 1 to 17 and REFERENCE EXAMPLES 1 to 24, illustrate detailed methods of synthesis and the physical properties of the representative pesticidal compounds of the formula (I) (and their chemical intermediates) according to the invention. These example compounds and other preparations in a similar manner, following the detailed procedures or other methods or methods described herein, are shown in Tables 2. In addition, one or more spectroscopic analyzes (IR, H1 or F19 NMR, MS, etc.). ) have been made in each compound for the characterization and confirmation of the chemical structure. In the following Tables Me means methyl, Et means ethyl, 2-Tolyl means 2-methylphenyl and C2H means ethynyl.

EXAMPLE 1 A mixture of 5-amino-l- [2,6-dichloro-4-. { trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (2.74 g), hydroxylamine hydrochloride (0.99 g) and pyridine (1.68 g) was stirred in methanol at 46 ° C for 2.8 hours, evaporated, washed (water) and crystallized from ethanol to give 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde oxime (1.74 g) ) as a white solid pf 219-221 ° C (decomposition). Compound 1 In a manner similar to that employed previously, the following compounds shown in Table 2 were also prepared.

TABLE 2 EXAMPLE 2 A mixture of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylthio-lH-pyrazole-3-carboxaldehyde (0.66 g), methoxyamine hydrochloride (0.2 g) and pyridine were stirred at room temperature for 26 hours. The pyridine was evaporated and the residue was dissolved in ethyl acetate / acetonitrile, washed with 1% aqueous HCl, dried (MgSO 4) and evaporated. The residue was purified by column chromatography on silica gel, eluted with hexane / ethyl acetate, to give 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-O-methyloxime. -trifluoromethylthio-lH-pyrazole-3-carboxaldehyde (0.3 g) as a white solid pf 129-131.5 ° C. Compound 9. - •• EXAMPLE 3 Acetyl chloride (0.27 ml) was added to a solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde oxime (1.0 g) ) and triethylamine (0.56 ml) in tetrahydrofuran at 0 ° C and the mixture was stirred for 1 hour. The solvent was evaporated and the residue was chromatographed on silica gel eluting with 3: 1 dichloromethane / ethyl acetate to give 0- (acetyl) oxime of 5-amino-1- [2,6-dichloro-4- ( trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (0.83 g) as an orange solid pf 130-134 ° C. Compound 10. In a manner similar to that previously employed, the following compounds shown in Table 3 were also prepared.

TABLE 3 EXAMPLE 4 A mixture of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde oxime (1.38 g), 30% hydrogen peroxide (1.38) ml), sodium tungstate dihydrate (0.17 g) in methanol / acetic acid, stirred at 20 ° C overnight, then at 50 ° C for 4 hours, and again at 20 ° C overnight. The water was added and the solid filtrate was washed with water and dried to give 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-1H-pyrazole-3-oxime. carboxaldehldo (0.93 g) pf 209.5-211 ° C (decomposition). Compound 16 EXAMPLE 5 A solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) -phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde (0.15 g) oxime in ethanol was added to a solution of Sodium ethoxide (0.025 g) in ethanol at 20 ° C, followed by iodomethane (0.023 ml). The reaction was monitored by HPLC and for the next 24 hours three additional equivalents of iodomethane were added. Then the reaction mixture was concentrated and partitioned between dichloromethane and water. The organic layer was washed with water, dried (MgSO4) and concentrated. This was then combined with the crude product of another identical preparation and subjected to chromatography on a column of silica gel, eluting with hexane / ethyl acetate, to give O- (methyl) oxime of 5-amino-1- [2 , 6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (0.06 g) as a yellow solid pf 80 ° C. Compound 17 EXAMPLE 6 A mixture of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde oxime (1.5 g), methyl isocyanate (0.705 g), and dibutyl diacetate (2 drops) was stirred in dichloromethane at 20 ° C in a sealed bottle or flask for 2 days. The mixture was partitioned between water and dichloromethane, the organic layer was dried (Na 2 SO) and evaporated and the residue was crystallized from ethyl acetate / hexane to give O- (N-methylcarbamoyl) oxime 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (1.22 g) mp 146-147 ° C. Compound 18 EXAMPLE 7 A mixture of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde (5.15 g) and carboxymethoxylamine semichlorohydrate (5.83 g) was stirred at 20 ° C in pyridine / methanol for 17 hours. The methanol was evaporated and the residue was washed with water and subjected to flash column chromatography on silica gel, eluting with acetic acid / ethyl acetate (1: 9) to give O- (carboxymethyl) oxime 5-amino- l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (1.44 g). The mass spectroscopy analysis of the product indicated a molecular weight of 458. Compound 19.

EXAMPLE 8 Tert-butyl nitrite (1.25 g) was added to 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde oxime (2.0 g) in tetrahydrofuran and stirred 4.5 hours. After evaporation the resulting orange solid was triturated with carbon tetrachloride to give 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde oxime (0.24 g) pf 239-240 ° C. Compound 20 EXAMPLE 9 A solution of tert-butyldimethylsilyl chloride (0.8 g) in N, -dimethylformamide (DMF) was added to a stirred solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] oxime. 4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (2.0 g) in (DMF), followed by the dropwise addition of an imidazole solution (0.72 g) in DMF for 7 minutes. The mixture was heated at 50 ° C for 3.5 hours and then kept at 20 ° C for 18 hours. The mixture was diluted (water), extract (methyl tert-butyl ester) and the organic phase was washed again with NaHCO 3 solution, 5% HCl solution and with NaHCO 3 solution, dried (MgSO 4), filtered and It vanished. The residue was purified by flash chromatography on silica gel to give O- (tert-butyldimethylsilyl) oxime of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole -3-carboxaldehyde (0.76 g) as a light yellow solid mp 150-154 ° C. Compound 21 EXAMPLE 10 To a stirred solution of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formyl-4-trifluoromethylthio-lH-pyrazole-3-carbonitrile (3.0 g) in ethanol was added a solution of Hydroxylamine hydrochloride (0.46 g) and sodium carbonate (0.9 g) in water. After 1 hour the mixture was poured into water, extracted (ethyl ether), dried (sodium sulfate) and evaporated. Purification by column chromatography on silica gel gave l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formyl-N-hydroxy-4-trifluoromethylthio-lH-pyrazole-3-carboximidamide (0.255) g), pf 72-75 ° C. Compound 22. The following compounds shown in -Table 4 were prepared in a similar manner.

TABLE 4 EXAMPLE 11 A mixture of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formyl-4-trifluoromethylthio-lH-pyrazole-3-carbonitrile (1.0 g), hydroxylamine hydrochloride (0.48 g) and trihydrate of Sodium acetate (0.94 g) in ethanol was heated under reflux for one hour. After cooling to 20 ° C the mixture was concentrated and partitioned between water and ether. The organic phase was washed (brine), dried (magnesium sulfate) and evaporated to give 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-5-hydroxyiminomethyl-4-trifluoromethylthio -lH-pyrazole-3-carboximidamide (0.5 g), mp 68-72 ° C. Compound 23 EXAMPLE 12 A suspension of sodium ethoxide (0.34 g) in ethanol was added to a stirred solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole oxime. 3-carboxaldehyde (2.0 g) in ethanol, then 2-iodopropane (1 ml) was added and the mixture was stirred overnight at 20 ° C and evaporated. The residue (in dichloromethane) was washed with water, dried (magnesium sulfate), concentrated and purified by chromatography on silica gel to give O (isopropyl) oxime of 5-amino-1- [2,6-dichloro -4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (0.35 g), m.p. 128-130 ° C. Compound 24. By proceeding in a similar manner, the following compounds were also prepared: 0- (ethoxycarbonylmethyl) oxime of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H- pyrazole-3-carboxaldehyde, Compound 25, pf 127-128 ° C; and 0- (carbamoylmethyl) oxime of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1-H-pyrazole-3-carboxaldehyde, Compound 26, m.p. 165-167 ° C.

EXAMPLE 13 In a manner similar to that employed in Example 12, an ethanol solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3 oxime. carboxaldehyde was reacted with sodium ethoxide and ethyl vinyl sulfone to provide the O- [2- (ethylsulfonyl) ethyl] oxime of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-lH-pyrazole-3-carboxaldehyde pf 144-148 ° C. Compound 27 EXAMPLE 14 In a manner similar to that employed in Example 12, an oxime solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde was reacted with sodium ethoxide and acrylonitrile to give O- (2-cyanoethyl) oxime of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3- carboxaldehyde. Compound 28, as the 85 percent (by weight) component of a mixture containing 8 percent of the oxime starting material. The analysis of the mass spectrum of the product indicated the following: MS m / e = 453 (M +).

EXAMPLE 15 % hydrogen peroxide solution (0.32 ml) was added to a solution of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylthio-lH-pyrazole-3 oxime. -carboxaldehyde (0.8 g) in trifluoroacetic acid at 20 ° C. The reaction solution was partitioned between water and dichloromethane and the organic layer was dried (magnesium sulfate), evaporated and subjected to flash chromatography on silica gel, eluting with dichloromethane / ethyl acetate (3: 1) to give oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde (0.29 g), mp 210-214 ° C. Compound 30 and oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylsulfonyl-1H-pyrazole-3-carboxaldehyde (0.2 g), m.p. 211-212 ° C. Compound 31 EXAMPLE 16 To a stirred solution of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxylic acid methyl ester (1.0 g) in anhydrous methanol was added. he added anhydrous methoxylamine hydrochloride (0.2 g). After 4 hours at 20 ° C, the mixture was evaporated and dichloromethane and water were added. The organic layer was dried (MgSO4), evaporated and chromatographed on a florisil column, eluting with 3: 1 dichloromethane / ethyl acetate to give 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] - N-methoxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide (0.28 g), m.p. 140-145 ° C. Compound 49. By proceeding in a similar manner, the following compounds were prepared: 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-methoxy-4-trifluoromethylsulfinyl-1H-pyrazole-3- carboximidamide, mp 169-170 ° C. Compound 41; and 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-trifluoromethylsulfinyl-1H-pyrazole-3-carboximidamide, m.p. 222-224 ° C. Compound 40 EXAMPLE 17 A solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-methoxy-4-methylsulfinyl-1H-pyrazole-3-carboximidamide (0.5 g) in anhydrous THF was stirred at 0-5 ° C and potassium tert-butoxide (0.13 g) and iodomethane (0.081 ml) were added. After three hours, potassium tert-butoxide (0.068 g) and iodomethane (0.08 ml) were added at 0-5 ° C. The mixture was stirred at this temperature for 16 hours, evaporated and the residue was purified by chromatography on silica gel eluting with 3: 1 dichloromethane / ethyl acetate to give 5-amino-1- [2,6-dichloro-4 - (trifluoromethyl) phenyl] -N-methoxy-N '-methyl-4-methylsulfinyl-lH-pyrazole-3-carboximidamide (0.13 g), m.p. 139-142 ° C. Compound 50 EXAMPLE 18 A mixture of 5-amino-3-cyano-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole (550 g), anhydrous hydrazine (700 g) in absolute ethanol ( 1.55 L), was stirred at room temperature for four hours. Water (6.5 L) was added and the precipitate was filtered and washed with water. After 12 hours another batch of precipitate was filtered. All solids were combined to provide 568 g of Compound 69 as a white solid, m.p. 210 ° C. In a similar manner the following compounds were prepared: Compound 73 p.f. 170 ° C; Compound 74 p.f. 193 ° C.

EXAMPLE 19 The mixture of Compound 69 (1.0 g) and acetic anhydride (327 mg) in p-dioxane (10 ml) was stirred at room temperature for 2 days. The mixture was evaporated and the residue was washed with hexane with a small amount of ethyl acetate and the suspension was filtered to give 1.08 g of Compound 75, m.p. 230 ° C.

Compound 85 was synthesized using a general procedure.

EXAMPLE 20 The mixture of Compound 69 (0.2 g) and propionic anhydride (0.07 ml) in tetrahydrofuran (5 ml) was stirred at room temperature for 6 days. The mixture was evaporated and the residue was purified by chromatography on silica gel to give 70 mg of Compound 79, m.p. 155-162 ° C. In a similar manner, the following compounds are prepared: EXAMPLE 21 The mixture of Compound 69 (0.2 g) and di-t-aildicarbonate (0.13 ml) in tetrahydrofuran (4.5 ml) was stirred at room temperature for 5 days. The mixture was evaporated and the residue was purified by chromatography on silica gel to give 20 mg (0.038 mmol) of Compound 89, m.p. 95-98 ° C. The following compounds were synthesized with the general procedure using an appropriate dicarbonate: Compound 88, p.f. 135 ° C. Compound 90, p.f. 155 ° C. Compound 72, p.f. 196 ° C.

EXAMPLE 22 To a suspension of 5-amino-3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylsulfinylpyrazole (20 g) in methanol (120 ml) was added hydroxylamine hydrochloride (3.99 g), followed by by the addition of triethylamine (8.0 ml). The mixture was stirred at room temperature overnight then evaporated. The residue was partitioned between water and ethyl acetate. The organic layer was washed with water, followed by washing with brine. The organic layer was dried over anhydrous sodium sulfate. The solution was concentrated by evaporation of the solvent. A precipitate formed and was collected by filtration. The solid was washed with a small amount of ethyl acetate to give Compound 44 (16.1 g), m.p. 225-226 ° C.

REFERENCE EXAMPLE 1 The diisobutylaluminum hydride (IM in toluene, 391 ml) was added dropwise over 1.5 hours to 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-3-carbonitrile (50%). g) in dry THF at -20 ° C. The mixture was partially evaporated then cooled by the addition of acetonitrile / water at 0-5 ° C. The aluminum salts were filtered, the filtrate was evaporated and the residue was extracted with dichloromethane. The extract was dried (MgSO4), and evaporated to give 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde (47.1 g). By proceeding in a similar manner the following compounds shown in Table 5 were also prepared.

TABLE 5 (a) SUPELCOSIL LC-18 column of 25.0 cm x 4.6 mm. Eluent: MeCN / H20 (3: 1) in one ml / minute. (b) used without purification in the next step.

REFERENCE EXAMPLE 2 To a solution of 1.4 M of methyllithium (31 ml) in ethyl ether, it was added to a stirred solution of 5-bromo-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-meitthyl-1H- pyrazole-3-carbonitrile (17.67 g) in dry tetrahydrofuran (THF) at -65 ° C for 15 minutes and allowed to warm to 0 ° C for 3 hours. After re-cooling to -65 ° C, methyl iodide (3.06 ml) in THF was added over 3 minutes, the mixture was heated at -20 ° C for 1.5 hours, and then partitioned between aqueous ammonium chloride and dichloromethane. The organic phase was dried (magnesium sulfate), evaporated and purified by flash chromatography on silica gel eluting with hexane / tert-butyl ether methyl to give 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- methyl-4-methylthio-lH-pyrazole-3-carbonitrile (6.2 g) having a purity of 90.7 percent area by HPLC. By proceeding in a similar manner, the following compounds were also prepared: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylthio-5-methyl-1H-pyrazole-3-carbonitrile m.p. 79-82 ° C.

REFERENCE EXAMPLE 3 % Hydrogen peroxide (1.82 ml) was added to a stirred solution of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylthio-lH-pyrazole-3-carbonitrile ( 6.2 g) in methanol, which contains catalyst i-PrOH / H2OS0 (5.31 ml) described by Drabowicz, et al (top) at 0-5 ° C. The mixture was allowed to warm to 20 ° C for 17 hours. Additional hydrogen peroxide (5.46 ml) was added in three portions over the next 24 hours, together with the catalyst (5 ml). After stirring for an additional 60 hours, water was added to give l- [2,6-dichloro-4- (trifluoromethyl) phenyl) -5-methyl-4-methylsulfinyl-lH-pyrazole-3-carbonitrile (6.72 g) as a yellow oil (91.7% purity area by HPLC) having a retention time of 3.61 minutes in 25.0 centimeters by 4.6 millimeters of column SUPELCOSIL LC-18, eluting with CH3CN / H20 (3: 1) solvent to 1 ml /minute. By proceeding in a similar manner, the following compounds were also obtained: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-5-methyl-1H-pyrazole-3-carbonyl-substituted, m.p. 109-115 ° C; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- [2- (fluoroethyl) sulfinyl] -l-H-pyrazole-3-carbonitrile, m.p. 182-183 ° C; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (methylsulfinyl) ethylamino] -4-ethylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 106-108 ° C, from 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (methylthio) ethylamino] -4-ethylsulfinyl-lH-pyrazole-3-carbonityium; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (methylsulfinyl) ethylamino] -4-methylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 114-116 ° C, from 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (methylthio) ethylamino] -4-methylsulfinyl-1H-pyrazole-3-carbonitrile; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylsulfinyl) ethylamino} -4-ethylsulfinyl-lH-pyrazole-3-carbonityl, m.p. 138-140 ° C, from 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylthio) ethylamino] -4-ethylsulfinyl-1H-pyrazole-3-carbonitrile; 5-amino-l- [3-chloro-5- (trifluoromethyl) pyrid-2-yl] -4-et i 1 s? L fi ni 1 -1 H-pi-3-carbon-tri-carbon 1, p.f. 150-152 ° C; Y -amino-l- 2,6-dibromo-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 165-166 ° C.

REFERENCE EXAMPLE 4 90% Tertiary Butyl Nitrite (27.9 mL) was slowly added to a stirred solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylthio-1H-pyrazole-3. -carbonitrile (49.8 g) in bromoform (600 ml) at 0-5 ° C. The mixture was stirred for three hours while heating to 20 ° C evaporated and re-evaporated after the addition of hexane / ethyl acetate (1). : 1) to give 5-bromo-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylthio-lH-pyrazole-3-carbonitrile (32.65g), showing an area of 93.3% purity by HPLC and with a retention time of 11.26 minutes in 25.0 cm by a 4.6 mm SUPELCOSIL LC-18 column, eluting with CH3CN / H20 (3: 1) solvent at 1 ml / minute Proceeding in a similar manner, The following compounds were prepared: 5-bromo-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carbonitrile, mp 134-140 ° C.

REFERENCE EXAMPLE 5 Ozone was pumped through a solution of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (E-2-methoxycarbonyletenyl) -4-trifluoromethylthio-lH-pyrazole-3-carbonitrile (36.6 g) in dichloromethane at -78 ° C for 3 hours. The intensely blue solution was decolorized with oxygen gas, then treated with dimethylsulfide (19 ml) and allowed to warm to 20 ° C for 14 hours. The mixture was then washed with water, dried (magnesium sulfate), filtered and evaporated to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-formyl-4-trifluoromethythio-1H-pyrazole-3-. carbonitrile as white crystals (30.7 g), mp 90 ° C.

REFERENCE EXAMPLE 6 1,8-Diazabicyclo- [5, 4, 0] -undec-7-ene (13 ml) was added to a solution of 5- (2'-bromo-2'-carbomethoxy) ethyl-1- (2, 6 dichloro-4-trifluoromethylphenyl) -4-trifluoromethylthio-lH-pyrazole-3-carbonitrile (45 g) in toluene and stirred for 0.5 hour. The mixture was diluted (ethyl acetate), and washed with water, a solution of hydrochloric acid, a saturated sodium hydrogen carbonate solution and brine. The organic phase was dried (magnesium sulfate), concentrated and triturated with cold pentane to give l- (2,6-dichloro-4-trifluoromethylphenyl) -5- (E-2-methoxycarbonyletenyl) -4-trifluoromethylthio-lH- pyrazole-3-carbonitrile as a white solid (36.6 g), mp 90 ° C.

REFERENCE EXAMPLE 7 A solution of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylthio-1H-pyrazole-3-carbonitrile (100 g) in acetonitrile was added dropwise to a mixture of methyl acrylate. (430 ml), copper (II) bromide (80 g), and 90% tertiary butyl nitrite (51 ml) in acetonitrile at 0 ° C, heated to 20 ° C, and stirred for 12 hours. The mixture was diluted (ether), washed (water), dried (magnesium sulfate) and concentrated. Trituration with hexanes gave 5- (2'-bromo-2'-carbomethoxy) ethyl-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylthio-lH-pyrazole-3-carbonitrile as a white solid ( 72.7 g) pf 122 ° C.

REFERENCE EXAMPLE 8 To a stirred suspension of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carbonitrile (5.0 g) in anhydrous methanol was added a 25% solution. p / p of sodium methoxide (8.95 ml) in methanol, at 20 ° C. The mixture was stirred for 16 hours, cooled to 0 ° C and diluted with anhydrous methanol cooled in ice.

Carbon dioxide was passed into the solution for 15 minutes until a pH of 8 was set. The precipitate was filtered off completely, washed (ethyl acetate) and evaporated to give the 5-amino-1-methyl ester. , 6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboximide (3.65 g), 1 H NMR (CDC13) in ppm: 8.34 (s, 1H9, 7.79 (s, 2H), 5.11 (br, 2H), 3.93 (s, 3H), 2.94 (s, 3H) By proceeding in a similar manner, the following compound was prepared: the methyl ester of 5-amino-1- [2,6-dichloro] -4- (trifluoromethyl) phenyl] -4-trifluoromethylsulfinyl-1H-pyrazole-3-carboxymethic, mp 179-180 ° C.

REFERENCE EXAMPLE 9 To a stirred solution of 4,4'-dithiobis [5-amino-3-cyano-1-. { 2,6-dichloro-4- (trifluoromethyl) phenyl} -lH-pyrazole (1.0 g) in methanol, sodium borohydride (0.03 g) was added. After 7 minutes, l-bromo-2-fluoroethane (0.05 ml) was added. Five additional portions of sodium borohydride (0.15 g) and l-bromo-2-fluoroethane (0.25 ml) were added for 5 hours. The mixture was evaporated, dichloromethane and water were added and the organic phase was dried (MgSO 4) and re-evaporated to give 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- [2 - (fluoroethyl) thio] -lH-pyrazole-3-carbonitrile (1.09 g), m.p. 130-131.5 ° C. By proceeding in a similar manner the following compound was obtained: 5-amino-1- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -4-ethylthio-1H-pyrazole-3-carbonitrile, m.p. 127-128 ° C, 4, 4 '-dithiobis [5-amino-3-cyano-l-. { 2,6-dichloro-4- (trifluoromethoxy) phenyl} -lH-pyrazole used above can be prepared in a manner similar to 4,4'-dithiobis [5-amino-3-cyano-1-. { 2,6-dichloro-4- (trifluoromethyl) phenyl} -lH-pyrazole as described in French Patent Applications Nos. 8816710 and 8913371.

REFERENCE EXAMPLE 10 In a manner similar to that of Example 15, 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- [2- (fluoroethyl) thio] -lH-pyrazole-3 was oxidized. carbonitrile with hydrogen peroxide in a solution of trifluoroacetic acid to give 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- [2- (fluoroethyl) sulfonyl] -lH-pyrazole-3 -carbonitrile, mp 192-193 ° C. By proceeding in a similar manner, the following compounds were prepared: 5-amino-l- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 150-151 ° C. 5-amino-1- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carbonitrile, m.p. 137-138 ° C. 5-amino-1- [2-chloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 146-147 ° C.

REFERENCE EXAMPLE 11 A mixture of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5-amino-1H-pyrazole-3-carbonitrile (5.0 g), trimethyl orthoacetate (100 ml) and toluenesulfonic (0.2 g) in toluene, heated at 145 ° C for 2 hours and then at 130 ° C with methanol distillation. The mixture was evaporated and the residue was purified by column chromatography using 20% ethyl acetate in hexane to give 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [1- (methoxymethylene) amino] -lH-pyrazole-3-carbonitrile (3.31 g), m.p. 164 to 165 ° C.

REFERENCE EXAMPLE 12 To a suspension of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [1- (methoxyethylene) amino] -lH-pyrazole-3-carbonitrile (6.0 g) in methanol, Sodium borohydride (0.79 g) was added in three portions for 15 minutes at 20 ° C, then stirred under nitrogen for 45 minutes. After evaporation, the residue was purified by silica gel column chromatography, eluting with 15% ethyl acetate in methylene chloride, to give 1- [2,6-dichloro-4- (trifluoroemethyl) phenyl] - 4-Methylsulfinyl-5-ethylamino-lH-pyrazole-3-carbonitrile (1.1 g), m.p. 130-131 ° C (decomp). By proceeding in a similar manner, there was prepared: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methylamino-4-methylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 147-150 ° C (decomposition). By proceeding in a similar manner, but replacing sodium borohydride with sodium cyanoborohydride, there was prepared: 1- [2-bromo-6-chloro-4- (trifluoromethyl) 'phenyl] -4-methylsulfinyl-5-ethylamino-1H- pyrazole-3-carbonitrile, mp 125-126.5 ° C.

REFERENCE EXAMPLE 13 A solution of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carbonityl (4.92 g) in triethyl orthoformate (100 ml) was heated under reflux for two hours, then stirred at 20 ° C for 16 hours and evaporated. Trituration with boiling hexane gave 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [(ethoxymethylene) amino] -4-methylsulfinyl-1H-pyrazole-3-carbonitrile (4.05 g), m.p. 93-95 ° C. By proceeding in a similar manner, the following compound was prepared: 1- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl] -5- [1- (methoxyethylene) amino] -4 -methylsulfinyl-lH-pyrazole-3-carbonitrile. This was used directly in the next stage.

REFERENCE EXAMPLE 14 To a suspension of 35% potassium borohydride in oil (0.7 g) in dry N, N-dimethylformamide (DMF) was added a solution of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl) ] -4- (Methylsulfinyl) -lH-pyrazole-3-carbonylurea (10.0 g) in dry DMF as a drop at 4 ° C for 10 minutes. After stirring for 20 minutes, vinylethyl sulfone (3.13 g) in dry DMF was added for 5 hours at 4 ° C. The mixture was stirred overnight under nitrogen with heating at 20 ° C. Ammonium chloride was added at 4 ° C, and the mixture was extracted (ethyl acetate), washed twice with water, dried (sodium sulfate) and evaporated. Crystallization from ethyl acetate / methanol / hexanes gave 1- [2,6-dichloro-4- (trifluoromethyl) phenyl) -5- [2- (ethylsulfonyl) g), m.p. -4- (methylsulfinyl) -lH-pyrazole-3-carbonitrile m.p. 131-132 ° C. By proceeding in a similar manner, the following compounds were prepared: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (cyanoethyl) amino] -4- (methylsulinyl) -lH-pyrazole- 3-carbonitrile, mp 55-57 ° C; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [2- (phenylsulfonyl) ethylamino] -lH-pyrazole-3-carbonitrile, m.p. 138-139 ° C; and 1- [2-chloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylsulfonyl) ethylamino] -4-, ethylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 139-140 ° C.

REFERENCE EXAMPLE 15 To a solution of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carbonitrile (0.5 g) in acetonitrile, 2-bromoacetamide (0.18) was added. g) in water and calcium carbonate (0.13 g). The mixture was heated under reflux for 1.5 hours, cooled to 25 ° C and a solution of sodium hydroxide (0.05 g) in water was added. This was then heated under reflux for one hour, evaporated and the residue purified by preparative thin layer chromatography eluting first with 20% methanol in dichloromethane to give 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [(aminocarbonylmethyl) amino] -lH-pyrazole-3-carbonitrile (0.089 g), m.p. 155-157 ° C.

REFERENCE EXAMPLE 16 To a suspension of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carbonitrile (2 g) in toluene, methyl magnesium bromide ( 7 ml of a 1.4 M solution in toluene / THF). The mixture was stirred at 20 ° C (1 hour) and neutralized with a solution of saturated ammonium chloride. The organic layer was dried (sodium sulfate), evaporated and the residue purified by chromatography using 40% ethyl acetate in hexane to give 3-acetyl-5-amino-1- [2,6-dichloro-4- ( trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole (0.68 g), m.p. 166 ° C.

REFERENCE EXAMPLE 17 To a suspension of 35% potassium hydride in oil (1.4g) in dry N, N-dimethylformamide (DMF) was added a solution of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- amino-4- (ethylsulfinyl) -lH-pyrazole-3-carbonitrile (5.0 g) in dry DMF at 4 ° C and stirred for 40 minutes. 2-Chloroethylmethyl sulfide (1.39 g) was added at 4 ° C and the stirred mixture was allowed to warm to 20 ° C for 40 minutes, then heated at 50 ° C for 4 hours and at 20 ° C for 3 days. The solution of ammonium chloride and ethyl acetate was added and the organic layer was dried (sodium sulfate), evaporated and purified by column chromatography using methyl t-butyl ether in hexane to give 1- [2, 6-dichloro-4- (trifluoromethyl) phenyl] -5- [[-2- (methylthio) ethyl] mino-4- (ethylsulfinyl) -lH-pyrazole-3-carbonitrile (0.26 g), m.p. 126-127 ° C. By proceeding in a similar manner, there were prepared: 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (methylthio) ethylamino] -4-methylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 111-113 ° C. 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylthio) ethylamino] -4-ethylsulfinyl-lH-pyrazole-3-carbonitrile, m.p. 27.5-29 ° C. 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- (2-propynyl) amino-1H-pyrazole-3-carbonitrile, m.p. 140-141 ° C.

REFERENCE EXAMPLE 18 Sulfuryl chloride (1.48 g) was added to the methyl disulfide (3.16 g) in methyl t-butyl ether and stirred for 5 hours to give methylsulfenyl chloride. This was added dropwise for 5 minutes to a solution of 5-amino-l- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl] -1H-pyrazole-3-carbonitrile (4.0 g) heated under reflux in methyl t-butyl ether under nitrogen. After 1 hour the cooled mixture was washed in turn with water, a solution of sodium bicarbonate and water, dried (sodium sulfate) and evaporated. Purification by silica gel chromatography eluting with hexane / ethyl acetate (9: 1) gave 5-amino-l- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl} -4-methylthio-lH-pi razol -3-carboni tri lo (31.5 g), m.p. 178-180 ° C.

By proceeding in the same manner, the following compound was prepared: 5-amino-l- [3-chloro-5- (trifluoromethyl) pyrid-2-yl] -4-ethylthio-lH-pyrazole-3-carbonitrile.

REFERENCE EXAMPLE 19 Stage Bromine (0.5 ml) was added over 10 minutes to a stirred solution of sodium thiocyanate (1.7 g) in anhydrous methanol at -65 ° C. A solution of 5-amino-1- (2-chloro-4- (trifluoromethyl) phenyl] -lH-pyrazole-3-carbonitrile (1.5 g) in anhydrous methanol was added for 10 minutes and the stirred mixture was allowed to warm to 20 minutes. C for 16 hours After pouring the water, the precipitate was collected and dried to give 5-amino-l- [2-chloro-4- (r-trifluoromethyl) phenyl] -4-thiocyanantho-lH-pyrazole-3-carbonitri - or (1.64 g) HPLC (column C-18, eluting with 3: 1 CH3CN / H20 at 1.0 ml / min) showing the compound as a peak of 86.8% area at 5.11 minutes.

Stage 2 Iodomethane (0.7 ml) was injected into a stirred suspension of 5-amino-1- [2-chloro-4- (trifluoroethyl) phenyl] -4-thiocyanato-1H-pyrazole-3-carbonitrile (1.64 g) in methanol at 4 ° C. A 10% aqueous solution of sodium hydroxide (2.8 ml) was added and the reaction mixture was stirred for 1 hour at 4 ° C, poured into water and extracted with dichloromethane and ethyl acetate. The combined organic phase (Na 2 SO 4) was evaporated and purified by flash chromatography on silica gel eluting with 4: 1 hexane / ethyl acetate to give, after trituration with hexane / dichloromethane, 5-amino-1- [2- chloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carbonitrile (0.4 g) mp 129-132 ° C. Proceeding in a similar manner as in stage 1 above, we obtained: A) 5-amino-l- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -4-thiocyanato-1H-pyrazole, which was used in Step 2 with iodomethane to give 5-amino-1 - [ 2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carbonitrile, mp 147-148 ° C.

B) 5-amino-l- [2, -dibromo-4- (trifluoromethyl) phenyl] -4-thiocyanato-lH-pyrazole-3-carbonitrile, which was used directly in step 2 with iodoethane and methanol as solvent for give 5-amino-l- [2,6-dibromo-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carbonitrile, mp 211-214 ° C.

REFERENCE EXAMPLE 20 A suspension of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -lH-pyrazole-3-carbonitrile (9.8 g) and N-iodosuccinimide (8.87 g) was heated to reflux in carbon tetrachloride for 3.5 hours, cooled and washed with a solution of sodium bisulfite, a NaOH solution and water. The dried solution (magnesium sulfate) was evaporated and purified by silica gel chromatography eluting with chloromethane to give 5-amino-l [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-iodo-1H-pyrazole -3-carbonitrile (4.0 g), mp 212-214 ° C.

REFERENCE EXAMPLE 21 -amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-iodo-lH-pyrazole-3-carbonitrile (1.96 g) was stirred with dimethylformamide dimethylacetal (10 ml) at 20 ° C. for 2 hours, then an excess of ice / water was added and the solid was filtered and dried in oven to give 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-iodo-5-N- ( dimethylaminomethyleneamino) -lH-pyrazole-3-carbonitrile (1.53 g), m.p. 177-180 ° C. REFERENCE EXAMPLE 22 Activated cadmium was prepared by washing cadmium with hydrochloric acid (10%), water, methanol and ether and dried. Dibromodifluoromethane (317.2 g) in dry N, N-dimethylformamide (DMF) was added for 1 hour to a mixture of activated cadmium (212.5 g) in dry DMF initially at 0-5 ° C and when started at low 35 ° C with agitation under nitrogen. Hexamethylphosphoramide (11, dry) was added followed by copper (I) bromide (108.5 g) and, after 15 minutes, 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-iodo-5- N- (dimethylamomethyleneamino) lH-pyrazole-3-carbonitrile (100.0 g) and the mixture was heated at 75 ° C for 2 hours. The cooled mixture was filtered (Celite), concentrated, diluted (water) and filtered. The product was washed (hot water) to give 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-N- (dimethylaminomethyleneamino) -4-trifluoromethyl-1H-pyrazole-3-carbonitrile (80.9 g) , pf 156-157 ° C.

EXAMPLE OF REFERENCE 23 A solution of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-N- (dimethylaminomethyleneamino) -4-trifluoromethyl-1H-pyrazole-3-carbonitrile (120.5 g) in tetrahydrofuran and hydrochloric acid (6N) ) was heated to reflux for 24 hours, concentrated and filtered. The solids were mixed with dichloromethane and filtered to give 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethyl-1H-pyrazole-3-carbonitrile (88.2 g), m.p. 191-193 ° C.

REFERENCE EXAMPLE 24 A solution of 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carbonitrile (1.0 g) in tetrahydrofuran was added to the anhydrous sodium hydride ( 0.13 g) stirred under nitrogen in tetrahydrofuran at 4 ° C. After 2 hours, iodomethane (0.34 ml) was added and the mixture was stirred at 20 ° C overnight and treated with an ammonium chloride solution. Extraction (ethyl acetate), drying (sodium sulfate) and evaporation followed by silica gel chromatography eluting with ethyl acetate / dichloromethane (1: 9) to give l- [2,6-dichloro-4-trifluoromethyl] Phenyl] -5-dimethylamino-4-methylthio-IH-pi-3-carbonyl tri (0.5 g), mp 118-119 ° C.

ACARICIDAL, INSECTICIDE, AFICIDAL AND NEMATICIDE USE The following representative assay procedures using compounds of the invention were performed to determine the use and pesticidal activity of the compounds of the invention against: mites, certain insects, including aphids, two species of caterpillars, one fly, and three species of larvae of beetles (a leaf feeder and two root feeders); and nematodes. The specific species tested were as follows: GENRE SPECIES COMMON NAME (ABBREVIATION) Tetranychus urticae Acaro bimoteado spider TSM Aphis nasturtii Aphid cambrón BA Spodoptera eridania Southern caterpillar SAW Epilachna varivestis Mexican beetle MBB of the bean Musca domestica Homemade fly HF Diabrotica u. howardi Root caterpillar of the SCRW southern corn Diabrotica vigifera Root caterpillar of the WCRW northern corn Mloidogyne incognito Nematode of the SRKN node the southern root Aphis gossypii Cotton aphid CA Schiz phis gra inun Green insect (aphid) GB Heliothis virescens TBW tobacco insect caterpillar Formulations: The test compounds were formulated to be used in accordance with the following methods used for each of the test procedures. For trials of mites, aphids, southern caterpillars, Mexican bean beetle, and tobacco insect caterpillar, a solution or suspension was prepared by the addition of 10 mg of the test compound to a solution of 160 mg of dimethylformamide, 838 mg of acetone, 2 mg of a 3: 1 ratio of Triton X-172; Triton X-152 (respectively, mainly low anionic and nonionic emulsifiers, which are each combined or anhydrous mixtures of alkarylaryl polyether alcohols with organic sulfonates), and 98.99 g of water. The result was a concentration of 100 ppm of the test compound.

For the test of house flies, the formulation was initially prepared in a manner similar to the previous one, but in 16.3 g of water with the corresponding adjustment of other components, providing a concentration of 200 ppm. The final dilution with an equal volume of 20% by weight of aqueous sucrose solution gave a concentration of 100 ppm of the test compound. When necessary, sonication was provided to ensure complete dispersion. For trials of caterpillars of the southern and northern corn roots, a solution or suspension was prepared in the same manner as that used for the initial concentration of 200 ppm for the housefly. The aliquots of this 200 ppm formulation were then used by dilution with water in accordance with the required test concentration. For nematodes of the southern root knot for systemic trials, a base solution or suspension was prepared by the addition of 15 mg of the test compound to 250 mg of dimethylformamide, 1250 mg of acetone and 3 mg of the mixed or combined emulsifier of the above reference. The water was then added to provide a test compound concentration of 150 ppm. When necessary, sonication was provided to ensure complete dispersion. For the contact test of the tobacco insect caterpillar, a base solution was prepared by dissolving the compound in acetone and then diluted to provide the dilutions of the required serial concentrations.

Test Procedures: The test compounds formulated above were then evaluated for their pesticidal activity at the specified concentrations, in ppm (parts per million) by weight, in accordance with the following test procedures: Mite bimoteado spider: Leaves infested with nymph and adult states of bimoteado spider mite, obtained from a base crop, were placed in primary leaves of two bean plants that grew in a pot with peat of 6 cm. A sufficient number of mites (150-200) for trials were transferred to the fresh plants in a twenty-four hour period. Potted plants (one peat per compound) were placed on a revolving turntable and the plants were sprayed sufficiently wet to be drained with 100 ml of 100 ppm of the test compound formulation by the use of a DeVilbiss spray gun placed at 40 psig. air pressure. As an untreated control, 100 ml of the DMF-acetone-water emulsifying solution, which does not contain the test compound, was also sprayed on the infested plants. A control treated with a commercially available compound, either dicofol or heritiazox, formulated in the same manner, was tested as a standard or standard. The sprayed plants were maintained for six days, after which a mortality count of the mobile forms was made.

Mitten bitered spider mite (ovicide test): Adult eggs were obtained from the bimoteado spider mite from a base culture. The heavily infested leaves from the base culture were placed in non-infested bean plants. The females were left to oviposit for a period of about 24 hours, after which the leaves of the plants were immersed in a solution of TEPP (tetraethyl diphosphate) so that the mobile forms die and prevent the deposition of additional eggs. This submersion procedure, which was repeated after the plants dried, did not affect the viability of the eggs. Potted plants (one peat per compound) were placed on a revolving turntable and the plants were sprayed wet enough to be drained with 100 ml of 100 ppm of the test compound formulation by the use of a DeVilbiss spray gun placed at 40 psig.pressure of air. As an untreated control, 100 ml of the DMF-acetone-water emulsifying solution, which does not contain the test compound, was also sprayed on infested plants. A control treated with a commercial technical compound, typically demeton, formulated in the same manner, is tested as a standard. The sprayed plants were maintained for seven days after which a mortality count of the egg forms was made together with annotations or residual activity in incubated larvae.

Afido of the cotton or cambrón: nymph and adult states of the cambrón or aphid of the cotton were cultivated in pots of dwarf nasturium or cotton plants, respectively. Potted plants (one per test compound) infested with 100-150 aphids were placed on a rotating rotary table and sprayed with 100 ml of 100 ppm of the test compound formulation by the use of a placed DeVilbiss spray gun. at 40 psig. air pressure. As an untreated control, 100 ml of the DMF-acetone-water emulsifying solution, which does not contain the test compound, was also sprayed on the infested plants. A control treated with a commercially available compound, either malathion or cyhalothrin, formulated in the same manner, was tested as a standard or standard. After spraying, the pots were stored for one day in aphid or three days for the cotton aphid, after which dead aphids were counted.

South caterpillar: Potted bean plants were placed on a revolving rotating table and sprayed with 100 ml of the 100 ppm of the test compound formulation by the use of a DeVilbiss spray gun placed at 40 psig. Air pressure . As an untreated control100 ml of the DMF-acetone-water emulsifying solution, which does not contain the test compound, was also sprayed on the infested plants. A control treated with a commercially available compound, either cypermethrin or sulprofos, formulated in the same manner, was tested as a standard or standard. When dried, the leaves were painted in plastic cups lined with moistened filter paper. Five larvae of southern caterpillars of randomly selected second pupae were introduced into each cup, which were closed and maintained for five days. The larvae, which were unable to move the length of the body, even on stimulation by puncture, were considered dead.

Tobacco insect caterpillar: Cotton plants with pots were placed on a rotating rotary table and sprayed with 100 ml of 100 ppm of the test compound formulation by the use of a DeVilbiss spray gun placed at 40 psig. air. As an untreated control, 100 ml of the DMF-acetone-water emulsifying solution, which does not contain the test compound, was also sprayed on the plants. A control treated with a commercially available compound, either cypermethrin or sulprofos, formulated in the same manner, was tested as a standard or standard. After spraying, the sheets were placed on plates or plastic plates containing a piece of filter paper and moistened dental wicks. A randomly selected second pupa larva of the tobacco was then introduced into each cup, which was closed and held for five days. The larva unable to move the length of its body, even on stimulation by punch, was considered dead.

Mexican Bean Beetle: Potted bean plants were placed on a rotating rotating table and sprayed with 100 ml of 100 ppm of the test compound formulation, sufficient to wet the plants to drain, by the use of a spray gun DeVilbiss placed at 40 psig. Air pressure. As an untreated control, 100 ml of 100 ppm of the DMF-acetone-water emulsifying solution, which does not contain the test compound, was also sprayed on the plants. A control treated with a commercially available compound, either cypermethrin or sulprofos, formulated in the same manner, was tested as a standard or standard. After spraying, the leaves were placed in plastic cups lined with moistened filter paper. Five Mexican beetle larvae of randomly selected second pupal beans were introduced into each of the cups, which were closed and maintained for five days. The larvae, which were not viable to move the length of the body, even on stimulation by puncture, were considered dead.

Home fly: Housefly was bred from four to six days of adulthood, in accordance with the specifications of the Chemical Specialties Manufacturing Association (Blue Book, NcNair-Dorland Co., NY 1954, pages 243-244, 261) under controlled conditions. The flies were immobilized by anesthesia with carbon dioxide and twenty-five immobilized individuals, males and females, were transferred to a cage consisting of a standard food filter or strainer and a wrapping paper cover surface. Ten ml of the 100 ppm of the test compound formulation were added to a souffle cup containing an absorbent cotton pad. As an untreated control, 10 ml of a sucrose solution of the DMF-acetone-water emulsifier, containing the non-tested compound, were applied in a similar manner. A control treated with a commercial technical compound, malathion, formulated in the same manner, was tested as a standard. The cup of bait was introduced into the strainer or food filter before the admission of the anesthetized flies.

After 24 hours, the flies, which showed no signs of movement in stimulation, were considered dead.

Caterpillar of the root of the southern and northern corn: In a cage containing 60 g of sandy clay soil, 1.5 ml of an aqueous formulation consisting of an aliquot of 200 ppm of the test compound formulation, diluted with water so appropriate for the final soil concentration of the compound, was added. of testing. 3.2 ml of water and five pregerminated corn seeds. The cage was shaken vigorously to obtain a uniform distribution of the test formulation. Following this, twenty caterpillar eggs of corn root (or optionally ten larvae of the first chrysalises in the case of CRW) were placed in a cavity, which was made in the soil. Vermiculite (1 ml) was optionally used, in the case of the WCRW tests, and water (1.7 ml) were then added to this cavity. In a similar manner, an untreated control was prepared by applying the same aliquot size of an emulsifying solution-DMF-acetone-water, containing the unreacted compound. Additionally, a control treated with a commercial technical compound (typically selected from terbufos, fonofos, phorate, chlorpyrifos, carbofuran, isazofos, or etoprop), formulated in the same manner as was used as necessary as a standard compound. After 7 days, the living larvae of the root caterpillars were counted using a well-known funnel extraction method "Berlese".

Nematode of the southern root knot: Infected roots of tomato plants, which contain masses of nematode eggs from the southern root knot, were removed from a base crop and cleaned from the soil by shaking and washing with running water. The nematode eggs were separated from the root tissue and rinsed with water. Samples of the egg suspension were placed on a screen or fine screen on a receiving bowl or container, which water level was adjusted by being in contact with the screen. From the bowl or container, immature states were collected on a screen or fine screen. The bottom of a cone-shaped container was filled with ordinary vermiculite and then filled within 1.5 cm of the top with approximately 200 ml pasteurized soil volume. Then in a pin made in the center of the soil in the cone, an aliquot of the 150 ppm of the test compound formulation was pipetted. A control treated with a commercial technical compound, fenamiphos, formulated in a similar manner, was used as a standard. As an untreated control, an aliquot of an emulsifying solution-DMF-acetone-water, containing the unreacted compound, was applied in a similar manner. Immediately after the soil treatment with the test compound, 100 nematodes of the southern root knot of the second juvenile state were added to the top of each. After 3 days, a single healthy tomato seed was transplanted into the cone. The cone containing the infested soil and the tomato seed was kept in the nursery for 3 weeks. At the end of the trial, the roots of the tomato seed were removed from the cone and evaluated by exacerbation on a variant scale relative to the untreated control as follows: 1. severe exacerbation, equal to an untreated control 3. slight exacerbation 4. very light exacerbation 5. no exacerbation, that is, complete control.

These results were converted to an ED3 or ED5 value, (effective dose to provide an exacerbation range of 3 to 5).

Southern caterpillars in tomato - systemic evaluation. This test was carried out in conjunction with the evaluation of the nematode of the southern root knot (discussed above). Tomato plants, grown in the soil (at a screening rate of the initial compound test of 6.6 ppm of the soil concentration or approximately 150 ppm of the solution concentration), for evaluation of the nematode, were used for evaluation of root compound updates and systemic transport subsequent to tomato foliage. At the end of the nematode test, 21 days after the treatment, the foliage of the tomato was excised, placed in a plastic container, and infested with larvae of second caterpillars of the southern caterpillar. After about 5 days, the larva was examined for the percentage of mortality.

The cotton aphid and the caterpillar of the tobacco insect (in cotton) and green insect and insect caterpillar (in sorghum) - systemic evaluation: A 7.0 ml aliquot of 150 ppm of the nematode test solution was applied to release the equivalent of 10.0 ppm of the soil concentration dose as a 6 cm soak of the peat containing cotton and sorghum plants. The cotton plants were previously infested with cotton aphids, approximately two days before treatment and with the green worm one day before treatment. After maintaining the plants for approximately three days, the plants were evaluated for aphid activity. Again, at six days, the plants were valued for the activity of the aphid and the cotton aphids and green worms were counted and their mortality valued. The foliage portions of cotton and sorghum were excised, placed in separate plastic containers, and infested with second cocoon larvae of the tobacco insect caterpillar. The potted plants were soaked in sulfotepp to put the remaining aphids and return to the nursery to grow again. Thirty days after treatment, the foliage was excised and fed to the caterpillar of the tobacco worm. Mortality was assessed six days after the infestation.

Cotton aphid and southern caterpillar (in cotton) and green caterpillar and southern caterpillar (in sorghum) - systemic evaluation: A base solution or suspension prepared to release 5 ml of a soil concentration dose of 20 ppm (and dilutions Subsequent) such as 6 cm peat soaks containing sorghum and cotton plants. The cotton plants were previously infested with cotton aphids for approximately two days before treatment and the green worm, one day before treatment. After maintaining the plants for approximately three days, the plants were evaluated for aphid activity. Again, at six days, the plants were valued for the aphidic activity and the cotton aphids and green worms were counted and mortality was assessed. The foliage portions of cotton and sorghum were excised, placed in separate plastic containers, and infected with larvae from second caterpillars of southern caterpillars. The potted plants were submerged in sulfotepp to kill the remaining aphids and return the green worms to growth again. Thirty days after treatment, the remaining foliage was excised and fed to the southern caterpillar. Mortality was assessed six days after the infestation.

Cotton aphid and southern caterpillar (in cotton and oats) - seed treatment: Technical material was applied to the seed of oats and cotton by placing the compound and the seed in a cage of appropriate size in a ball mill. In test the material applied to the seed was by weight. The seeds were planted then. When they germinated and emerged, the plants were infested at the appropriate intervals with host insects. Mortality was assessed in those insects. Caterpillar of the worm insect - contact evaluation: The following method of topical application provided an assessment of the toxicity of the contact of a compound to the caterpillar larva of the tobacco insect. The solution of the test compound at sequential dilution concentrations of two folds from 10 down to 0.16 μg / μl was applied by unb microinjector in 1 μl portions replicated on the back of approximately 20 mg caterpillar larvae of the tobacco insect. This equivalent to applied doses of 500 down to 8 μl / g of body weight. A control treated with acetone, without any test trial was also applied. A control with a commercial technical compound, cypermethrin, or thiodicarb, also in acetone, was used as a standard. The treated larvae were placed, individually, in separate plastic petri dishes, containing an untreated cotton sheet and moistened dental floss. The treated larva was maintained at approximately 27 ° C and at 50% relative humidity. The percentage of mortality was assessed at 1 and 4 after treatment.

All numbers of compounds from 1 to 118 of the invention, showed the insecticidal activity in one or more of the methods of the previous evaluation, with particularly good activity in the systemic assays. Compounds METHODS AND COMPOSITIONS The present invention provides a method for the systemic control of arthropods at a site, especially some insects or mites, which feed on the above soil portions of plants. Control of such leaf pests can be provided directly by foliar application or by application by, for example, soil spray or granular application to plant roots or plant seeds, with systemic translocation subsequent to the anterior portions of the soil. the plants. Such systemic activity includes insect control. They reside not only at the point of application, but at a remote part of the plant, for example, by translocation from one side of a leaf to the other or from a treated leaf to an untreated leaf. Examples of classes of pests or insect pests which can be systemically controlled by the arylpyrazoles of the invention include the Homoptera order (drillers-suckers), Hemiptera order (drillers-suckers) and Thysanoptera order. The invention is especially suitable for aphids and thrips.

As is evident for the pesticidal uses mentioned above, the present invention provides pesticidically active arylpyrazoles and methods of using such arylpyrazoles for the control of a number of pest species which include: arthropods, especially insects or mites: plant nematodes, or pests of helminths or protozoa. The arylpyrazoles of the formula (I) or pesticide-acceptable salts thereof are advantageously used in practical applications, for example, in agricultural or horticultural crops, forestry, veterinary medicine or livestock management, or in public health. From this point, hereafter, when the term "arylpyrazoles of the formula (I)" is used J this term embraces arylpyrazoles of the formula (I) and their pesticide-acceptable salts. The term "arylpyrazoles of formula (I)" embraces an arylpyrazole of the formula (I) and a pesticide-acceptable salt thereof. The present invention therefore provides a method of pest control at a locus or site, which comprises the treatment of the site (eg by application or administration) with an effective amount of an arylpyrazole of the formula (I) or a salt of the same pesticide acceptable, wherein the substituent groups are as defined hereinbefore.

The site includes, for example, the pest itself or the place (plant, animal, field, structure, forest, orchard, canals, establishments, soil, plant or animal product, or the like) where the pest resides or is fed. The arylpyrazoles of this invention can also be used for the control of soil insects, such as caterpillars of the corn root, termites (especially for protection of structures) rootworm, wire worms, root weevils, borer of the stem, cutworm, aphids of the root, or worms. They can also be used to provide activity against pathogenic plant nematodes, such as root knot, Cist, daggers, lesions or nematodes of the bulb or stem, or against mites. For the control of soil pests, for example caterpillars of the maize root, the arylpyrazoles are advantageously applied or incorporated at an effective rate in the soil in which the crops to be planted or the seeds or roots of the crops are planted. growing plants. In the area of public health, arylpyrazoles are especially used in the control of many insects, especially flies of garbage or other pests of Diptera, such as houseflies, barn flies, soldier flies, horn flies, horseflies, blowflies , jején, certain dipterans, whitefly or mosquitoes.

The arylpyrazoles of the invention can be used in the following applications and in the following pests include arthropods, especially insects or mites, nematodes or helminths or protozoan pests. In the protection of stored products, for example cereals, including grain or flour, peanuts, animal fodder, woods, or good household goods, for example carpets and textiles, the arylpyrazoles of the invention are employed against the attack of arthropods, more especially beetles, including weevils, moths or mites, for example Ephestia spp. (flour moths) Anthrenus spp. (carpet beetle), Tribolium spp. (flour beetle) Sitophilus spp. (grain weevil) or Acarus spp. (Mites) . In the control of cockroaches, ants or termites or pests of similar arthropods in infested industrial or domestic establishments, or in control of mosquito larvae in channels, wells, reservations or other streams or water ponds. For the treatment of foundations, structures or soil, in the prevention of attack in constructions by termites, for example. Reticulitermes spp., Heterotermes spp., Coptotermes spp. In agriculture against adults, larvae and eggs of Lepidoptera (butterflies and moths) for example Heliothis spp. Such as Heliothis virescens (tobacco worm caterpillar), Heliothis armígera and Heliothis zea. Against adults and larvae of Coleoptera (beetles) for example, Anthonomus spp., For example grandis (cotton boll weevil), Leptinotarsa decemlineata (Colorado potato beetle), Diabrotica spp, (caterpillar of the root of corn). Against Heteroptera (Hemiptera and Homoptera), for example, Psylla spp., Bemisia spp., Trialeurodes spp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp., Nephotettix spp. (coopers of the rice leaf), Nilaparvata spp.

Against Diptera for example, Musca spp., Against Thysanoptera such as Thrips tabaci. Against Orthoptera such as Locusta and Schistocerca spp., (Locusts and crickets) for example Gryllus, spp, and Acheta spp. For example, Blatta orientalis, Periplaneta americana, Blattella germanica, Locusta migratoria micratorioides, and Schistocerca gregaria. Against Collembora for example, Periplantea spp. and Blattela spp, (cockroaches). Against Isoptera for example, Coptotermes spp. (termites). Against arthropods of agricultural significance such as Acari (mites) for example, Tetranychus spp., And Panonychus spp.

Against nematodes which attack plants or trees of agricultural, forestry or hirticultural importance either directly or by bacterial, viral or microplasma expansion or fungal diseases of the plants. For example, nematodes of root knots, such as Meloidogyne spp. (for example M. incognita). In the field of veterinary medicine or livestock management or in the maintenance of public health against arthropods, helminths or protozoa which are internally or externally parasitic on vertebrates, particularly warm-blooded vertebrates, for example, domestic animals, example, cattle, sheep, goats, horses, pigs, poultry, dogs or cats, for example Acariña, including mites or ticks (for example Ixodes spp., Boophilus spp., for example Boophilus microplus, Rhipicephalus spp., example Rhipicephalus appendiculatus Ornithodorus spp. (for example Orhithodorus moubata) and mites (for example Damaiinia spp.) Diptera (for example Aedes spp., Anopheles spp., Musca spp., Hypoderma spp.); Hemiptera; Dictyoptera (e.g. Periplaneta spp., Blatella spp.); Hymenoptera, for example against infections of the gastrointestinal tract caused by caterpillars of parasitic nematodes, for example, members of the family of Trichlostronglydae; in the control and treatment of protozoan diseases caused by, for example, Eimeria spp .; for example Trypanosoms cruzi, Leishaminia spp.; Plasmodium spp.; Babebis spp; Trichomonadidae spp .; Toxoplasma spp .; and Theileria spp. In practical use for the control of arthropods, especially insects or mites, or pests of plant nematodes, one method, for example, comprises applying to the plants or the medium in which they grow an effective amount of arylpyrazoles of the invention. . For such a method, the active arylpyrazole is generally applied to sites, in which the arthropod or nematode infestation is controlled at an effective ratio in the range of about 5 to about 1 kg of the active arylpyrazole per hectare of the site to be treated. . Under ideal conditions, depending on the pest to be controlled, a lower proportion can offer adequate protection. Otherwise, bad weather, adverse conditions, pest resistance or other factors may require that the active ingredient be used at higher rates. The optimum proportion will commonly depend on a number of factors, for example, the type of pest to be controlled, the type or growth status of the infested plant, the line space or also the method of application. More preferably, the effective ratio range of the active arylpyrazole is from about 50 kg / ha to about 400 g / ha.

When a pest is born in the soil, the active arylprazole in general, in a formulated composition, is evenly distributed over the area to be treated (i.e., for example by band or disseminated band treatment) in any convenient manner and is applied to proportions from 5 to about 1 kh ai / ha, preferably from about 50 to about 250 ai / ha. When applied as a submerged root for planting or drip irrigation to plants of the liquid solution or suspension containing from about 0.075 to about 1000 mg ai / 1. Preferably from about 25 to about 200 mg ai / 1. The application can be made if desired, to the field or to the growth area of crops in general or in close proximity to the seed or plant to be protected from attack. The active component can be washed in the soil by atomization with water over the area or can be left to the natural action of rain. During or after the application, the formulated arylpyrazoles can, if desired, be mechanically distributed in the soil, for example by disc plowing, by the use of drag chains. The application may be prior to planting, when planting, after planting but before germination takes place, or after germination. The arylpyrazoles of the invention and the methods of pest control here, are of particular value in the protection of fields, forages, plantations, nurseries, orchards, or vines, ornamentals, or plantation or forest tree crops, for example.; cereals (such as wheat or rice), cotton, vegetables (such as peppers), harvested fields (such as sugar beet, soybeans or turnip seed oil), meadows or fodder crops (such as corn or sorghum) , orchards or groves (such as stone or stone fruits or citrus fruits), ornamental plants, flowers or vegetables or shrubs under glass or in gardens or parks, or forest trees (whether deciduous or ever green) in forests, plantations or nurseries They are also valuable in the protection of woods (establishments, cut, converted, stored or structural woods) from the attack, for example, of sawfly or beetles or termites. They have applications in the protection of stored products such as grains, fruits, nuts, spices or tobacco, anyway full, ground or arylpyrazole in products from the attack of moths, beetles, mites or grain weevil. Also protected are stored animal products such as skins, hair, wool or feathers in natural or converted form (for example as carpets or textiles) from the attack of the moth or beetle as well as from stored meat, fish or grain from the attack of the beetle, mite or fly. Additionally, the arylpyrazoles of the invention and the methods of use thereof, are of particular value in the control of arthropods, helminths or protozoa, which are harmful to, or extend or act as vectors of domestic animal diseases, by example those mentioned above, and more especially in the control of ticks, mites, lice, fleas, weevils, or insects, or harmful flies or iliases. The arylpyrazoles of the invention are particularly used in the control of arthropods, helminths or protozoa which are present in domestic host animals or which feed on or in the skin or suck the animal's blood, for which reason the purpose may be administered orally, parenterally, percutaneously or topically. In addition, the arylpyrazoles of the invention can be used for coccidiosis, a disease caused by infections from protozoan parasites of the genus Eimeria. It is an important potential cause of economic loss in domestic animals and particularly those reached or maintained under intensive conditions. For example, cattle, sheep, pigs or rabbits may be affected, but the condition is especially important in poultry, particularly in chicks. The administration of a small amount of an arylpyrazole of the invention, preferably by a combination with foods is effective in preventing or greatly reducing the incidence of coccidiosis. The arylpyrazoles are effective against both, the fecal form and the intestinal forms. In addition, the arylpyrazoles of the invention can also be exerted in an inhibitory effect on oocytes by greatly reducing the number and sporulation of those produced. Diseases in poultry are generally spread by birds, piercing the infectious organism in ejections in contaminated baits, soil, food or water to drink. The condition is manifested by hemorrhage, accumulation of blood in the stool, passage of blood to ejections, weakening, digestive disturbances. The diseases offer terms in the death of the animal, but the bird that survives, has severe infections and its market value, is substantially reduced as a result of the infection. The compositions described herein for application to the growth harvests or gro sites of the crops or as a seed coat can in general, be alternatively employed for topical application to animals or in the protection of stored, good domestic, appropriate products. or general areas of the environment. Suitable means of applying the arylpyrazoles of the invention include: gro crops such as leaf sprays, powders, granules, nebulisers or foams, or also as suspensions of encapsulated or finely divided compositions such as soil or root treatments by dipping, powders , granules, fumes or foams; to crop seeds via application as seed coatings by liquid suspensions or powders; to animals infested by exposure to arthropod, helminth or protozoan infestation, by parenteral, oral or topical application of compositions in which the active ingredient presents an immediate and / or prolonged action for a period of time against arthropods, helminths - or protozoans , for example by incorporation into foods or orally ingestible pharmaceutically suitable formulations, edible baits, licking salts, food supplements, by or in formulations, sprays, solutions, humectants, sprays, thrown jets, powders, fats, shampoos, creams, greasy waxes or cattle self-treatment systems. to the environment in general or to specific places where pests can attack, including stored products, woods, good domesticated, or domestic or industrial establishments, such as atomizers, foggers, dust, fumes, greasy waxes, lacquers, granules or baits, or feeders of defiles or streams of water, walls, reservoirs or other streams or water ponds; to domestic animals in the food and control of feeding the larva of the fly in faeces. In practice, the arylpyrazoles of the invention are most frequently part of the compositions. These compositions can be used to control: arthropods, especially pests of mites, nematodes, or helminths or protozoa. The compositions can be of any type known in the art, suitable for application to the desired pest in any establishment, to the interior or exterior area or by internal or external administration to vertebrates. These compositions contain at least one arylpyrazole of the formula ( I) or a salt of the same pesticide acceptable, as described earlier, as the active ingredient in combination or in association with one or more compatible components which are for example, solid or liquid carriers or diluents, adjuvants, activating agents of the surface, or the like, appropriate for the intended use and which are agronomically or medically acceptable. These compositions can be prepared by any manner known in the art, in similar forms or as part of this invention. These compositions may also contain other classes of ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, sprays (especially for acaricidal use), stabilized, preservatives (especially preservatives by molding), sequence agents, or similar, as well as other active ingredients with pesticidal properties (particularly insecticides, miticide, nematicide or fungicide) or with plant growth regulating properties. More generally, the pyrazoles used in the invention can be combined with all the solid or liquid additives corresponding to the usual formulation techniques. Compositions suitable for applications in agriculture, horticulture or the like, include formulations suitable for use as, for example, sprays, powders, granules, nebulizers, foams, emulsions, or the like.

The effective dose used of the arylpyrazoles employed in the invention may vary within a broad range, particularly depending on the nature of the pest to be eliminated or the degree of infestation, for example, of crops with these pests. In general, the compositions according to the invention usually contain from about 0.05 to about 95% (by weight) of one or more active ingredients according to the invention, from about 1 to 95% of one or more liquid solid carriers and, optionally, from about 0.1 to about 50% of one or more other compatible components, such as surface activating agents or the like. In the present count, the term "carrier" denotes an organic or inorganic ingredient, natural or synthetic, with which the active ingredient is combined to facilitate its application, for example, to the plant, seeds or soil. This carrier is, therefore, generally inert and may be acceptable (for example agronomically acceptable particularly for the treated plant). The carrier can be a solid, for example, clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, (for example, ammonium salts), natural minerals of the earth, such as kaolin, clays, talc, chalk , quartz, atapoulgite, montmorillonite, bentonite or diatomaceous earth or synthetic earth minerals such as silica, alumina, or silicates, especially aluminum or magnesium silicates. The following are suitable as solid carriers for granules; fractionated or chopped natural rocks such as calcite, marble, pumice, sepiolite and doilomite; synthetic granules of organic or inorganic flours; granules of organic material such as sawdust, coconut shells, corn cobs or tobacco stems; diatomaceous tricalcium phosphate, powdered bark or absorbent black carbon; water soluble polymers, resins, waxes; or solid fertilizers. Such compositions may, if desired, contain one or more compatible humectants, dispersants, emulsifiers or coloring agents, which when solid, can serve as diluents. The carrier can also be liquid for example; water, alcohols, particularly butanol, or glycol, as well as ethers or esters, particularly methyl glycol acetate; ketones, particularly acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone; petroleum fractions such as aromatic or paraffinic hydrocarbons, particularly xylenes or alkyl naphthalenes; vegetable or mineral oils, chlorinated aromatic hydrocarbons, particularly trichloroethane or methylene chloride; chlorinated aromatic hydrocarbons, particularly chlorobenzenes; highly polar or water soluble solvents, such as dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; liquefied gases; or the like or a mixture thereof. The surface activating agent may be an emulsifying agent, a dispersing agent or a wetting agent of the ionic or non-ionic type or a mixture of such surface active agents. These include, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of denolsulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty esters or fatty amines, substituted phenols (particularly alkylphenols or arylphenols), salts of sulphonic acid esters, taurine derivatives (particularly alkyl taurates), alcohol phosphoric esters or polycondensates of fillet oxide with phenols, ethers of fatty acids with polyols, or sulfate, sulfonate or functional phosphate derivatives of the above arylpyrazoles. The presence of at least one surface activating agent is in general essential when the ingredient and / or the inert carrier are only slightly soluble in water or are not soluble in water and the carrier agent of the composition for the application is aqueous.

The compositions of the invention may additionally contain other additives such as adhesives or colorants. Adhesives such as carboxymethylcellulose or synthetic or natural polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol or polyvinyl acetate, natural phospholipids, such as cephalins or lecithins, or synthetic phospholipids can be used in the formulations . It is possible to use oxidizers such as inorganic pigments, for example: iron oxides, titanium oxides or Prussian Blue; organic dyes, such as alizarin dyes, azo dyes or metal phthalocyanine dyes; or trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum or zinc salts. Compositions containing arylpyrazoles of the formula (I), or pesticidally acceptable salts thereof, which can be applied to control arthropod, plant, helminth or protozoan nematodes, may also contain synergists (e.g. piperonyl or sesamex), stabilizing substances, other insecticides, acaricides, plant nematocides, antifungal or anticoccidial, fungicides (agriculture or veterinary appropriate, eg bena ilo and iprodione), bactericides, arthropod or vertebrate attractants or repellents or pheromones, deodorants, flavoring agents, dyes, or auxiliary therapeutic agents, for example trace elements. These can be designed to improve potency, persistence, safety, absorption where desired, spectrum of controlled pests or to improve the composition to perform other useful functions in the same animal or area treated. Examples of other pesticidally active arylpyrazoles which can be included in or used in conjunction with the compositions of the present invention are: acephate, chlorpyrifos, demeton-S-methyl, disulfoton, ethoprofos, fenitrothion, fenamiphos, fsnofos, isazofos, isofenfos, malathion, monocrotophos, parathion, phorate, fosalone, pirimiphos-methyl, terbufos, triazophos, cyfluthrin, cypermethrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, tefluthrin, aldicarb, carbosulfan, methomyl, oxa.mil, pirimicarb, bendiocarb, teflubenzuron, dicofol, endosulfan, lindane, benzoximate, cartap, cyhexatin, tetradifon, avermectins, ivermectins, milbemycins, thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole. For their application in agriculture, the arylpyrazoles of the formula (I), or pesticidally acceptable salts thereof, therefore, are generally in the form of compositions, which are in various solid or liquid forms. The solid forms of the compositions which can be used are very fine powders (with an arylpyrazole content of the formula (I), or a salt thereof that is pesticidally acceptable or acceptable as pesticides, varying up to 80%), powders or wettable granules (including water-dispersible granules), particularly those obtained by extrusion, compaction or impregnation of a granular carrier, or formation of granules from a powder (the content of the arylpyrazole of the formula (I), or a salt of the same pesticidally acceptable, in these wettable or wettable powders or granules that are between approximately 0.5 and approximately 80%). Homogenous or heterogeneous solid compositions containing one or more arylpyrazoles of the formula (I), or pesticidally acceptable salts thereof, for example granules, pellets, tablets or capsules, can be used to treat stagnant water or to run or circulate during a period of time. A similar effect can be achieved using supplies of dispersible water concentrates that run off or continuous, or intermittent, as described herein. /. * Liquid compositions, for example, include aqueous or non-aqueous solutions or suspensions (such as emulsifiable concentrates), emulsions, flowing products, dispersions or solutions) or aerosols. Liquid compositions also include, in particular, emulsifiable concentrates, dispersions, emulsions, fluids, aerosols, wettable powders (or powder for dispersion), dry fluids or pastes as forms of compositions which are liquid or are proposed to form liquid compositions when they apply, for example as aqueous sprays (including lower or ultra-lower volume) or as mists or aerosols. The liquid compositions, for example, in the form of emulsifiable or soluble concentrates more frequently comprise about 5 to about 80% by weight of the active ingredient, while the emulsions or solutions which are ready for the application contain, in its case, approximately 0.01 to approximately 20% of the active ingredient. In addition to the solvent, the emulsifiable or soluble concentrates may contain, when required, about 2 to about 50% of the suitable additives, such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives. Emulsions of any required concentration, which are particularly suitable for application, for example, to plants, can be obtained from these concentrates by dilution with water. These compositions are included within the scope of the compositions which may be employed in the present invention. The emulsions can be in the water-in-oil or oil-in-water form and they can have a thickness consistency. The liquid compositions of this invention may be used, in addition to normal applications in agriculture, for example to treat substrates or sites infested or exposed to arthropod infestation (or other pests controlled by arylpyrazoles of this invention) including premises , outdoor or indoor storage or processing areas, containers or equipment or stagnant or circulating water. All these aqueous dispersions or emulsions or spray mixtures can be applied, for example, to crops by any suitable means, mainly by spraying, at speeds which are generally of the order of about 100 to approximately 1,200 liters of spray mixture per hectare. , but it can be higher or lower (for example, lower or ultra-lower volume) depending on the need or application technique. The arylpyrazoles or compositions in accordance with the - - invention are conveniently applied to vegetation and in particular to roots or leaves that have pests to be eliminated. Another method of applying the arylpyrazoles or compositions according to the invention is by chemical irrigation, that is, the addition of the formulation containing the active ingredient to irrigate water. This irrigation can be irrigation by aviation for foliar pesticides or it can be irrigation of the ground or underground irrigation for the soil or systematic pesticides.

Concentrated suspensions, which can be applied by spraying, are prepared in order to produce a stable fluid product which is not stable (finely ground) and usually contains from about 75% by weight of active ingredient, from about 0.5% to about 30% surface active agents, from about 0.1 to about 10% of thixotropic agents, from about 0 to about 30% of appropriate additives, such as anti-foam agents, corrosion inhibitors, stabilizers, penetrating agents , adhesives and, as the carrier, water or an organic liquid in which the active agent is poorly soluble or insoluble. Some solids - organic or inorganic salts can be dissolved in the carrier to help prevent their placement or as antifreeze for water.

Water-soluble powders (or spray powders) are usually prepared so as to 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 water soluble agent, from about 3 to about 10% of a dispersing agent, and when necessary, from about 0 to about 80% of one or more stabilizers or / and other additives, such as penetrating agents, adhesives, anti-coagulating agents, colorants, or the like. To obtain these water-soluble powders, the active ingredient (s) is (are) carefully mixed in a suitable mixer with additional substances which can be impregnated onto the porous filler and milled by the use of a mill or other appropriate mill. This produces water-soluble powders, the solubility in water and the usability of this are advantageous. These can be suspended in water to give them any desired concentration and this suspension can be used very advantageously in particular for application to foliar plants. "Water-dispersible granules (WG)" (granules which readily disperse in water) have compositions which are substantially closed ... from water-soluble powders. These can be prepared by granulating the formulations described by the water soluble powders, either by a wet route (by contacting finely divided active ingredients with the inert fillers and a small amount of water, for example, from 1 to 20 % by weight, or with an aqueous solution of a binder or dispersing agent, followed by drying and sieving), or by a dry route (compaction followed by sieving).

The proportions and concentrations of the formulated compositions may vary according to the method of application or the nature of the compositions or the use thereof. Generally speaking, compositions for application in the control of arthropod pests, plant nematodes, helminths or protozoa usually contain from about 0.00001% up to about 95%, more particularly from about 0.0005% up to about 50% by weight of one or more arylpyrazoles of the formula (I), or pesticide-acceptable salts thereof, or of the total active ingredients (i.e. the arylpyrazole of the formula of the formula (I) or a pesticide-acceptable salt thereof, together with: other substances toxic to arthropods or plant nematodes, anthelmintic, anticoccideliodos, synergistic, trace elements or stabilizers). The compositions currently used and their application rates are selected to obtain the desired effect (s) by the farmer, livestock producer, physician or veterinarian using it, the pest control operator or another skilled person. in the technique.

Solid or liquid compositions for topieal application to animals, timber, stored products or necessary products usually contain from about 0.00005% to about 90%, more particularly from about 0.001% to about 10% by weight of one or more arylpyrazoles of formula (I) or pesticide-acceptable salts thereof. To be administered orally or parentally to the animals, which includes liquid or solid compositions percutanerosli, they usually contain from about 0.1% to about 90% by weight one or more arylpyrazoles of formula (I) or pesticide-acceptable salts thereof. Medicated forages typically contain from about 0.001 to about 3% by weight of one or more arylpyrazoles of formula (I) or pesticide acceptable salts thereof. Concentrations or supplements for mixing with forages normally contain from about 5% to about 90%, preferably from about 5% to about 50% by weight of one or more arylpyrazoles of formula (I) or pesticidally acceptable salts of the same. The mineral salts for licking normally contain from about 0.1% to about 10% by weight with one or more arylpyrazoles of formula (I) or pesticide-acceptable salts thereof.

The liquid or powder compositions for applications to cattle, goats, establishments or areas to the open field can contain from around - ¬ 0. 0001% up to about 15% more especially from about 0.005% to about 2.0 5 by weight, of one or more arylpyrazoles of formula (I) or pesticide acceptable salts thereof. Appropriate concentrations in the water treatment are between about 0.0001 ppm and about 20 ppm, more particularly about 0.001 ppm up to about 5.0 ppm. of one or more arylpyrazoles of formula (I), or pesticidically acceptable salts thereof, and can be used therapeutically in fish cultures with appropriate exposure times. The edible baits may contain from about 0.01% to about 5%, preferably from about 0.01% to about 1.0% by weight, one or more arylpyrazoles of formula (I) or pesticide acceptable salts thereof.

When administered to vertebrates parentally, orally or by precutaneous or other means, the doses of arylpyrazoles of the formula (I), or pesticide-acceptable salts thereof, depend on the species, age, or health of the vertebrates and on the nature and degree of your current or potential infestation of arthropod, helminth or protozoan pests. A single dose of about 0.1 to about 100 mg, preferably about 2.0 to about 20.0 mg, by weight in Kg of the animal's body or doses of about 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg per weight in Kg of the body of the animal per day, for sustained medication, are generally suitable for oral or parenteral administration. For the use of sustained release formulations or devices, the daily dose required over a period of months can be combined with and administered to animals on a single occasion.

The following compositions EXAMPLES 2A for use against pests of arthropods, mites or insects, plant nematodes, or helminths which comprises, as an active ingredient, arylpyrazoles of the formula (I), or pesticide-acceptable salts thereof, such as those described in the preparatory examples. The composition described in EXAMPLES 2a-2M can each be diluted to give a sprayable composition at appropriate concentrations for use in the field. The generic chemical descriptions of the ingredients (for which all the following percentages are in percent by weight), used in the composition of examples 2a-2M exemplified below.

Brand Name Chemical Description Ethylan BCP Nonylphenol Condensate Ethylene Oxide Soprophor BSU Tristyrylphenol Condensate Ethylene Oxide Arylan CA A solution of 70% calcium dodecylbenzenesulfonate Solvesso 150 Aromatic solvent Light Cyan Arylan CA Sodium dodecylbenzenesulfonate Darvan No2 Sodium lignosulfonate Celite PF Synthetic magnesium silicate carrier Sorpopon T36 Sodium salts of carboxylic acids Rhodigel 23 Xanthan polysaccharide gum Bentone 38 Organic derivative of magnesium montmorillonite Aerosil Microfine silicon dioxide EXAMPLE 2A A water soluble concentrate is prepared with the following composition: Active ingredient 7% Ethylan BCP 10% N-methylpyrrolidone 83% The active ingredient was added to a solution of Ethylan BCP dissolved in a portion of N-methylpyrrolidone by heating and stirring until dissolved. The resulting solution is made up to a volume with the solvent remaining.

EXAMPLE 2B An emulsifiable concentrate (EC) is prepared with the following composition: Active ingredient 25% (max.) Soprophor 10% Arylan CA 5% N-methylpyrrolidone 50% Solvesso 150 10% The first three components are dissolved in N-methylpyrrolidone and then Solvesso 150 is added to these to give the final volume.

EXAMPLE 2C A powder mixable with water (for its acronym in English WP) is prepared with the following composition: Active ingredient 40% Arylan S 2% Darvan No2 5% Celite PF 53% The ingredients are mixed and pulverized in a hammer mill to a powder with a particle size of less than 50 microns. 2D EXAMPLE A flowing aqueous formulation is prepared with the following composition: Active ingredient 40. 00% Ethylan BCP 1. 00% Sopropon T360. 0 20% Ethylene glycol 5 00% Rhodigel 230. 0. 15% Water 53.65% The ingredients are thoroughly mixed and pulverized in a ball mill until an average particle size of less than 3 microns is obtained.

EXAMPLE 2E An emulsifiable suspension concentrate is prepared with the following composition: Active Ingredient 30.00Í Ethylan BCP 10.0% Bentone 38 0.5% Solvesso 150 59.5% The ingredients are thoroughly mixed and pulverized in a balls mill until an average particle size of less than 3 microns is obtained.

EXAMPLE 2F A water dispersible granule is prepared with the following composition: Active ingredient 30% Darvan No 2 15% Arylan S Celite PF 47% The ingredients are mixed, micronized in an energy mill by fluid and then granulated in a rotary granulator by spraying with water (up to 10%). The resulting granules are dried in a fluidized bed dryer until excess water is removed.

EXAMPLE 2G A medicinal powder is prepared with the following composition: Active ingredient 1 to 10% Superfine talcum powder 99 to 90% The ingredients are mixed tightly and further pulverized as necessary to obtain a fine powder. This powder can be applied to a site of infestation by arthropods, for example waste or residual powders, stored products or home furnishings or animals infested by, or at risk of infestation by, arthropods to control arthropods by oral ingestion. Suitable means for distributing the medicinal powder to the site of infestation by arthropods, include mechanical blowers, livestock self-treatment devices or manual shakers.

EXAMPLE 2H An edible bait is prepared with the following composition: Active ingredient 0.1 to 1.0. Wheat flour 80% Melasa 19.9 to 19í The ingredients are closely mixed and formed as required up to a bait form. This edible bait can be distributed to sites, for example domestic or industrial premises, for example, kitchens, hospitals or warehouses, or outdoor areas, infested by arthropods such as ants, grasshoppers, cockroaches or flies, to control the arthropods by oral ingestion.

EXAMPLE 21 A solution formulation is prepared with the following composition: Active ingredient 15% Dimethyl sulfoxide 85% The active ingredient was dissolved in dimethyl sulfoxide with mixing and / or heating as required. This solution can be applied percutaneously as an application to domestic animals infested by arthropods or, after sterilization by filtration through a polytetrafluoroethylene membrane (0.22 micrometer pore size), by parenteral injection, at a percentage of application from 1.2 up to 12 ml of solution per 100 kg of body weight of the animal.

EXAMPLE 2J A mixable powder is prepared with the following composition: Active ingredient 50% Ethylan BCP 5% Aerosil 5% Celite PF 40% The Ethylan BCP was absorbed onto the Aerosil which was then mixed with the other ingredients and pulverized in a hammer mill to give a miscible powder, which can be diluted in water at a concentration from 0.001% up to 2% by weight of the active arylpyrazole and can be applied to a site of infestation by arthropods, for example, larva diptera or plant nematodes, by dew, or in domestic animals infested by, or at risk of infection by arthropods, helminths or protozoa, by dew or dipping , or by oral administration in drinking water, to control arthropods, helminths or protozoa.

EXAMPLE 2K A slow release pill composition is formed from granules containing the following components in varying percentages (similar to those described by the previous compositions) depending on the need: Active ingredient Density agent Slow release agent Binder The ingredients are mixed tightly, formed into granules which are compressed into a pill with a specific gravity of 2 or more. These can be administered orally to ruminant domestic animals for retention within the reticulum-rumen to give a constant slow release of active arylpyrazole over a prolonged period of time to control infestation by arthropods, helminths or protozoa of ruminant domestic animals.

EXAMPLE 2L A slow release composition in the form of granules, pellets, tablets or the like can be prepared with the following compositions: Active ingredient 0.5 to 25% Polyvinyl chloride 75 to 99.5% Dioctyl phthalate (plasticizer) The components are mixed and then shaped into suitable shapes by melt extrusion or molding. These compositions are useful, for example, for adding to stagnant water or for making necklaces or earplugs for fixing to domestic animals to control pests by slow release.

EXAMPLE 2M A dispersible granulate in water is prepared with the following compositions: Active ingredient 85% (max.) Polyvinylpyrrolidone 5% Attapulgite clay 6% Sodium lauryl sulfate 2% Glycerin 2% The ingredients are mixed as a 45% suspension with water and milled in moisture to a particle size of 4 microns, then spray dried until the water is removed. While the present invention has been described with specific and illustrative details and has been described with preferred particularity, it is susceptible to changes, modifications or alterations, obvious to one skilled in the art, without departing from the scope and spirit of the invention, which is defined by the claims appended thereto. While the invention has been described in terms of several preferred embodiments, one skilled in the art will appreciate that various modifications, substitutions, omissions or changes can be made without departing from the spirit of the same. Accordingly, it is intended that the scope of the present invention be limited only by the scope of the following claims including equivalents thereof.

It is noted that in relation to this date the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property

Claims

1. A compound that has the formula: () wherein: X is -S (0) mR6 or R7, Y is hydrogen, alkenyl C-3 to C-6, alkynyl, formyl, alkylcarbonyl, cycloalkylcarbonyl, halocicloalquilcabo, aroyl, arylalkylcarbonyl, alkylsulfonyl, arylsulfonyl, haloalkylcarbonyl, aminoalkylcarbonyl, alkylaminoalkylcarbonyl, dialkylaminoalkylcarbonyl, alkoxyalkylcarbonyl, ariloxialquilcarbo, alquiltioalquilcarbo, alquilsulfolquiIcarbo, ariltioalquilcarbo, N-alkylcarbamoyl, N- arylcarbamoyl, N-alquiltiocarbamoilo, N-arylthiocarbamoyl, alpha-hidroxiarilalquilcarbo, hydroxyalkylcarbonyl, carboxyalkylcarbonyl, alkoxycarbonylalkylcarbonyl, -P (= 0) (O-alkyl ) 2, -P (= S) (0-alkyl) 2, -P (= 0) (S-alkyl) 2 '-P (S) (S-alkyl) 2, trialkylsilyl, alquilcarbominoalquilcarbo, alquilcarboxialquilcarbo, aryl, pyridinyl, pyrimidinyl, -C (= 0) S-alkyl, -C (= 0) S-aryl, -C (= 0) S-alkylaryl, alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, alkylsulfonyl-alkoxycarbonyl , arylthioalkoxycarbonyl, alkoxycarbonyl, aryloxycarbonyl and aryloxycarbonylalkylcarbonyl; or alkyl or haloalkyl both are unsubstituted or substituted by alkoxy, alkoxycarbonyl, carboxy, cyano, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio, nitro, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, amino, alkylamino, dialkylamino, hydroxy, alkylcarbonylamino or alkylcarbonyloxy; is hydrogen, halogen, -C (0) R7, -S (0) nR8r -C (0) 0R9, alkyl, haloalkyl, -0R9, -N = C (Rio) (Rn), alkenyl, hydrazino, alkylthiocarbonyl, lH-pyrrol-1-yl or 1H-pyrazol-1-yl, -CHO, -CH = N0H, amino, Ri2NH- or R? 3R14N-; Ri is hydrogen, alkyl or - RisRie / R2 is hydrogen or halogen; R3 and R5 are hydrogen, halogen or alkyl; R4 is halogen, haloalkyl, haloalkoxy, R? 7S (0) p- or SF5; Re is alkyl or haloalkyl, alkenyl or haloalkenyl, alkynyl or haloalkynyl or cycloalkyl having from 3 to 5 carbon atoms; R7 is alkyl or haloalkyl; R8 is R7 or phenyl; Rg and Rio are hydrogen, alkyl or haloalkyl; Rn is alkyl, haloalkyl, alkoxy, or a phenyl group which is unsubstituted or substituted by one or more groups selected from hydroxy, halogen, alkoxy, cyano, R7 or -S (0) qR; R 2 R 13 and Ri 4, which are identical or different, are R 7 S (0) r-, formyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl of 3 to 6 carbon atoms or -C (O) alkyl wherein the alkyl and the alkenyl portions are substituted or unsubstituted by one or more Ri8; or 13 and i4 are joined or linked so that together they form a divalent radical having from 4 to 6 atoms in the chain, this divalent radical is alkylene, alkyleneoxyalkylene or alkylene aminoalkylene; Ris and Rie are independently hydrogen or alkyl; Ri7 is haloalkyl; Ris is cyano, nitro, alkoxy, haloalkoxy, -C (0) R7, R8S (0) s, -C (0) 0Rg, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; , n, p, q, r and s are independently zero, one or two; M is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; or a geometric isomer, tautomeric form or pesticidally active salt thereof.

2. A compound of formula (I) according to claim 1, characterized in that: X is -S (0) mR6; And it's hydrogen; alkyl having 1 to 4 carbon atoms, cycloalkyl having from 1 to 4 carbon atoms both of which are unsubstituted or substituted by aminocarbonyl, alkylsulfonyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, cyano or nitro; alkenyl of 3 to 4 carbon atoms; alkynyl of 3 to 5 carbon atom; alkylcarbonyl; substituted or unsubstituted aroyl, arylalkylcarbonyl; alkylsulfonyl; alkoxycarbonylalkylcarbonyl; haloalkylcarbonyl; N-alkylcarbamoyl; alkoxycarbonyl; aryloxycarbonyl; alkoxyalkylcarbonyl; alpha-hydroxyarylalkylcarbonyl; hydroxyalkylcarbonyl; aminoalkylcarbonyl; -C (= 0) S-alkyl and Trialkylsilyl; Z is amino, R? 2NH-, R13R14N-, halogen or methyl; Ri is hydrogen, methyl, amino or methylamino; R2 is F, Cl, Br or H; R3 and R5 are hydrogen; IOR4 is CF3, CF3O, CHF2, CF3S (0) p, CF2C1, CFC12, CF2C10, CFC120, Cl, Br, or F; R6 is methyl or ethyl optionally substituted by F, Cl or Br; M is CCl, CF, CBr, or N; R12, R13 and R14 are CF3S (0) r-r alkynyl or alkoxycarbonyl; or alkyl, alkenyl of 3 to 6 carbon atoms or -C (O) alkyl wherein the alkyl and alkenyl portions are substituted or unsubstituted by one or more Ria; and R18 is cyano, nitro, alkoxy, haloalkoxy, -C (0) R7, R8S (0) s-, -C (0) OR9, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl.

3. The compound of formula (I) according to claim 1 or 2, characterized in that it is: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime; oxime of 1- [2,6-Dichloro-4- (trifluoromethyl) phenyl] -5-ethylamino-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; 10 [2,6-Dichloro-4- (trifluoromethyl) phenyl] -5-methylamino-4-methylsulfinyl-1H-pyrazole-3-carboxydehyde oxime; 5-Amino-l- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -4-methylsulfinyl-lH-15 pyrazole-3-carboxaldehyde oxime; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-1H-pyrazole-3-carboxydehyde oxime; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylthio-1H-pyrazole-3-carboxaldehyde oxime; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-difluoromethylthio-1H-pyrazole-3-carboxaldehyde oxime; 25-oxime 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carboxaldehyde; O- (methyl) oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethylthio-1H-pyrazole-3-carboxaidehyde; O- (acetyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; O- (methylbenzoyl) oxime 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; O- (methoxycarbonyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 15 O- [2- (Ethoxycarbonyl) propionyl] oxime of 5-Amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-lH-pyrazole-3-carboxaldehyde; O- (acetyl) oxime 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carboxaldehyde; O- (methoxycarbonyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-lH-pyrazole-3-carboxaldehyde; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-1H-pyrazole-3-carboxaldehyde oxime; O- (methyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; O- (N-methylcarbamoyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 0- (carboxymethyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-10 pyrazole-3-carboxaldehyde; oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; O- (tert-butyldimethylsilyl) oxime of 5-Amino-l-15 [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formyl-N-hydroxy-4-trifluoromethylthio-lH-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-5-hydroxyiminomethyl-4-trifluoromethylthio-lH-pyrazole-3-carboximidamide; O- (isopropyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-25 pyrazole-3-carboxaldehyde; O- (ethoxycarbonylmethyl) oxime 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; O- (aminocarbonylmethyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; O- [2- (ethylsulfonyl) ethyl] oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 10 O- (2-cyanoethyl) oxime of 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylthio-lH-15 pyrazole-3-carboxaldehyde; oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-methyl-4-methylsulfonyl-1H-pyrazole-3-carboxaldehyde; oxime of 5-amino-l- [3-chloro-5- (trifluoromethyl) -2-pyridyl] -4-methylsulfinyl-lH-pyrazole-3-carboxaldehyde; 25 oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylthio-5-methyl-1H-pyrazole-3-carboxaldehyde; oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulphinyl-5-methyl-lH-pyrazole-3-carboxaldehyde; oxime of 1- [2-chloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylsulfonyl) ethylamino] -4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde; oxime of 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-dimethylamino-4-methylthio-lH-pyrazole-3-carboxaldehyde; oxime 5-amino-l- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -4-ethylsulfinyl-1H-pyrazole-3-carboxaldehyde; 15-oxime 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-trifluoromethyl-1H-pyrazole-3-carboxaldehyde; oxime of 3-acetyl-5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-1H-20 pyrazole; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-trifluoro-methylsulfinyl-lH-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -25 N-methoxy-4-trifluoro-methylsulfinyl-lH-pyrazole-3-carboximidamide; 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] N -hydroxy-4-ethylsulfinyl-lH-pyrazole-3-carboximidamide; 5-a ino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] N-hydroxy-4-ethylthio-lH-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] 'N -hydroxy-4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -N-hydroxy-4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] • N-hydroxy-4-methylsulphonyl-lH-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] • N -hydroxy-4-methylthio-lH-pyrazole-3-carboximidamide; 20 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] • N -hydroxy-4-ethylsulfonyl-1H-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] • N-methoxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-methoxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4- [2- (fluoroethyl) sulfinyl] -IH-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4- [2- (fluoroethyl) sulfonyl] -lH-pyrazole-3-carboximidamide; 5-amino-l- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] -4-ethylsulfinyl-N-hydroxy-1H-pyrazole-3-carboximidamide; 5-amino-l- [3-dichloro-5- (trifluoromethyl) -2-pyridinyl] -4-methylsulfinyl-N-hydroxy-1H-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-5-methylamino-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-ethylamino-N-hydroxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -5- [2- (ethylsulfonyl) ethylamino] -N-hydroxy-4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 5- [2- (cyano) ethylamino] -1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-methylsulfinyl-1H-pyrazole-3-carboximidamide; 5- (aminocarbonylmethylamino) -1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-ethylsulphinyl-1H-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [2- (phenylsulfonyl) ethylamino] -N-hydroxy-lH-pyrazole-3-carboximidamide; 5-amino-l- [2,6-dibromo-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N-hydroxy-lH-pyrazole-3-carboximidamide; 1- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl] -5-ethylamino-4-methylsulfinyl-N-hydroxy-lH-pyrazole-3-carboximidamide; 5-amino-l- [2-bromo-6-chloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-lH-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulphinyl-5- [2- (methylsulfinyl) ethylamino] -N-hydroxy-lH-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [2- (methylsulfinyl) ethylamino] -N-hydroxy-lH-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-5- [2- (ethylsulfinyl) ethylamino] -N-hydroxy-lH-pyrazole-3-carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-5- [(prop-2-ynyl) amino] -N-hydroxy-1H-pyrazole-3-carboximidamide; and 5-amino-l- [2-chloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N-hydroxy-lH-pyrazole-3-carboximidamide;

4. A pesticidal composition characterized in that it comprises: (a) a compound of formula (I) (i) wherein: X is -S (0) mR6 or R7, Y is hydrogen, C-3 to C-6 alkenyl, alkynyl, formyl, alkylcarbonyl, aroyl, arylalkylcarbonyl, alkylsulfonyl, arylsulfonyl, haloalkylcarbonyl, aminoalkylcarbonyl, alkylaminoalkylcarbonyl, dialkylaminoalkylcarbonyl, alkoxyalkylcarbonyl, aryloxyalkylcarbonyl, alkylthioalkylcarbonyl, alkylsulfonylalkylcarbonyl, arylthioalkylcarbonyl, N-alkylcarbamoyl, N-arylcarbamoyl, N-alkylthiocarbamoyl, N-arylthiocarbamoyl, alpha-hydroxyarylalkylcarbonyl, hydroxyalkylcarbonyl, carboxyalkylcarbonyl, alkoxycarbonylalkylcarbonyl, -P (= 0) (0-alkyl) 2, P (= S) (O-alkyl) 2, -P (= 0) (S-alkyl) 2, -P (S) (S-alkyl) 2, trialkylsilyl, alkylcarbonylaminoalkylcarbonyl, alkylcarbonyloxyalkylcarbonyl, aryl, pyridinyl, pyrimidinyl, -C (= 0) S-alkyl, -C (= 0) S-aryl, -C (= 0) S-alkylaryl, alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, alkylsulfonylalkoxycarbonyl, arylthioalkoxycarbonyl, alkoxycarbonyl, aryloxycarbonyl and aryloxycarbonylalkylcarbonyl; or alkyl or haloalkyl both are substituted or unsubstituted by alkoxy, alkoxycarbonyl, carboxy, cyano, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio, nitro, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, amino, alkylamino, dialkylamino, hydroxy, alkylcarbonylamino or alkylcarbonyloxy; is hydrogen, halogen, -C (0) R7-, -S (0) nR8, -C (0) OR9, alkyl, haloalkyl, -OR9, -N = C (Rio) (Rn), alkenyl, hydrazino, alkylthiocarbonyl , lH-pyrrol-1-yl or 1H-pyrazol-1-yl, -CHO, -CH = NOH, amino, R12NH- or R13R14N-; Ri is hydrogen, alkyl or -NR? 5R? 6; R2 is hydrogen or halogen; R3 and R5 are hydrogen, halogen or alkyl; R4 is halogen, haloalkyl, haloalkoxy, R? 7S (0) p- or SF5; Re is alkyl or haloalkyl, alkenyl or haloalkenyl, alkynyl or haloalkynyl or cycloalkyl having from 3 to 5 carbon atoms; R7 is alkyl or haloalkyl; R8 is R7 or phenyl; R9 and Rio are hydrogen, alkyl or haloalkyl; R11 is alkyl, haloalkyl, alkoxy, or a phenyl group which is unsubstituted or substituted by one or more groups selected from hydroxy, halogen, alkoxy, cyano, R7 or -S (0) qR7; R12 / R13 and R ?, which are identical or different, are R7S (0) r-, formyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl of 3 to 6 carbon atoms or -C (O) alkyl wherein the alkyl and the alkenyl portions are substituted or unsubstituted by one or more R? 8; or R13 and Ri4 are joined or linked so that together they form a divalent radical having from 4 to 6 atoms in the chain, this divalent radical is alkylene, alkyleneoxyalkylene or alkylene aminoalkylene; Ris and Rie are independently hydrogen or alkyl; R7 is haloalkyl; Ris is cyano, nitro, alkoxy, haloalkoxy, -C (0) R7, R8S (0) s, -C (0) OR9, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; m, n, p, q, r and s are independently zero, one or two; M is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; or a geometric isomer, tautomeric form or pesticidally active salt thereof; Y (b) An inert carrier acceptable in agriculture for these.

5. A method for the control of pests of a site, characterized in that it comprises applying to said site an effective amount of pesticide of a compound of formula (I) (i) wherein: X is -S (0) mR6 or R7, Y is hydrogen, C-3 to C-6 alkenyl, alkynyl, formyl, alkylcarbonyl, aroyl, arylalkylcarbonyl, alkylsulfonyl, arylsulfonyl, haloalkylcarbonyl, aminoalkylcarbonyl, alkylaminoalkylcarbonyl, dialkylaminoalkylcarbonyl, alkoxyalkylcarbonyl, aryloxyalkylcarbonyl, alkylthioalkylcarbonyl, alkylsulfonylalkylcarbonyl, arylthioalkylcarbonyl, N-alkylcarbamoyl, N-arylcarbamoyl, N-alkylthiocarbamoyl, N-arylthiocarbamoyl, alpha-hydroxyarylalkylcarbonyl, hydroxyalkylcarbonyl, carboxyalkylcarbonyl, alkoxycarbonylalkylcarbonyl, -P (= 0) (O-alkyl) 2 , P (= S) (0-alkyl) 2, -P (= 0) (S-alkyl) 2, -P (S) (S-alkyl) 2, trialkylsilyl, alkylcarbonylaminoalkylcarbonyl, alkylcarbonyloxyalkylcarbonyl, aryl, pyridinyl, pyrimidinyl, -C (= 0) S-alkyl, -C (= 0) S-aryl, C (= 0) S-alkylaryl, alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, alkylsulfonylalkoxycarbonyl, arylthioalkoxycarbonyl, alkoxycarbonyl, aryloxy bonyl and aryloxycarbonylalkylcarbonyl; or alkyl or haloalkyl both are substituted or unsubstituted by alkoxy, alkoxycarbonyl, carboxy, cyano, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio, nitro, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, amino, alkylamino, dialkylamino, hydroxy, alkylcarbonylamino or alkylcarbonyloxy; Z is hydrogen, halogen, -C (0) R7-, -S (0) nR8, -C (0) 0R9, alkyl, haloalkyl, -0R9, -N = C (Rio) (Rn5, alkenyl, hydrazino, alkylthiocarbonyl , IH-pyrrol-l-yl or 1H-pyrazol-1-yl, -CHO, -CH = N0H, amino, Ri2NH- or R13R14N-;> RI is hydrogen, alkyl or -NR? 5R? 6; R2 it is hydrogen or halogen; R3 and R5 are hydrogen, halogen or alkyl; R is halogen, haloalkyl, haloalkoxy, R? 7S (0) p- or SF5; R6 is alkyl or haloalkyl, alkenyl or haloalkenyl, alkynyl or haloalkynyl or cycloalkyl having from 3 to 5 carbon atoms; R7 is alkyl or haloalkyl; Rs is R? or phenyl; R9 and Rio are hydrogen, alkyl or haloalkyl; R11 is alkyl, haloalkyl, alkoxy, or a phenyl group which is unsubstituted or substituted by one or more groups selected from hydroxy, halogen, alkoxy, cyano, R7 or -S (0) qR7; R12, R13 and R14, which are identical or different, are R7S (0) r-, formyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl of 3 to 6 carbon atoms or -C (0) alkyl wherein the alkyl and the alkenyl portions are substituted or unsubstituted by one or more R? 8; or R13 and R14 are joined or linked so that together they form a divalent radical having from 4 to 6 atoms in the chain, this divalent radical is alkylene, alkyleneoxyalkylene or alkylene aminoalkylene; R15 and R1 are independently hydrogen or alkyl; Ri7 is haloalkyl; Ris is cyano, nitro, alkoxy, haloalkoxy, -C (0) R7, R8S (0) s, -C (0) OR9, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; m, n, p, q, r and s are independently zero, one or two; M is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; or a geometric isomer, tautomeric form or pesticidally active salt thereof.

6. A process for preparing a compound of formula (I) as defined in claim 1, characterized in that it comprises: (a) when R2, R3, R, R5, M, X, Y and Z are as defined in claim 1 and Ri represents amino, a compound of formula (II) reacts: with a compound of formula (III) NH2OY (lili wherein Y is as defined in claim 1; (b) when R2, R3, R4, R5, M, X, Y and Z are as defined in claim 1 and Ri represents amino, a compound of formula (IV) reacts: wherein R represents alkyl, with a compound of formula (III) in which R is alkyl and Y is as defined in claim 1; (c) when R2, R3, R, R5, M, X, Y and Z are as defined in claim 1 and Ri represents alkylamino or dialkylamino, the corresponding compound of formula (I) reacts where Ri represents amino with a alkylating agent preferably of formula R-hal wherein R represents alkyl and hal is Cl, Br or I; (d) when R2, R3, R, R5, M, X, Y and Z are as defined in claim 1 and Ri represents hydrogen or alkyl, a compound of formula (V) reacts: wherein Ri represents hydrogen or alkyl with a compound of formula (III) in which Y is as defined above; (e) when R2, R3, R4, R5, M, X, Y and Z are as defined in claim 1 and Ri represents hydrogen or alkyl, and Y is as defined in claim 1 with the exclusion of hydrogen, formyl, aryl, pyridinyl and pyrimidyl, the corresponding compound of formula (I) reacts where Y represents hydrogen with an appropriate alkylation reagent or acylation or Michael acceptor. (f) when Z is Ri2NH- or R? 3R? N- in which Ri2, R 13 and R 1 are alkyl or alkenyl of 3 to 6 carbon atoms optionally substituted by R 8, including the aminocyclic compounds of formula (I), by alkylating a compound of formula (I) in which Z represents amino; followed by the formation of the imino ether or by the reduction of the imino ether; or by Michael's addition; (g) when m is 1 or 2, by oxidizing the corresponding compound of formula (I) in which m is 0 or 1.

7. A compound of formula (I ^ bisi) characterized in that: A is -NR26-: Yi is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, -S (0) aR28, -P (O) R29R30, -P (S) R29R30 / -Si (Rs?) (R32) (R33) r -C (0) RZ7 f -C (S) R2, cyano or nitro; R? 9 is hydrogen, alkyl, haloalkyl, or -NR34R35; R2i is hydrogen, halogen, -C (0) R38, -S (0) CR39, alkyl, haloalkyl, -OR40, -N = C (R4i) (R42), alkenyl, NR43R44, IH-pyrrol-1-yl, lH-pyrazol-1-yl, or CH = NOH; xj. R22 / - R23 and R25 are independently selected from hydrogen, halogen or alkyl; R2 is halogen, haloalkyl, haloalkoxy, -S (0) Rs or SF5; R26 is hydrogen or substituted or unsubstituted alkyl; R27 is hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aryl, -OR46, -NR47R48, or -SR4g; R28 is substituted or unsubstituted alkyl or substituted or unsubstituted aryl; R29 and R30 are independently selected from alkoxy and thioalkoxy; R31, R32 and R33 are independently selected from alkyl, haloalkyl and aryl; R34 and R35 are independently selected from hydrogen or substituted or unsubstituted alkyl; R3 € is alkyl, alkenyl, alkynyl, or cycloalkyl of 3 to 6 carbon atoms each of which is optionally substituted by one or more halogens; R37 is alkyl or haloalkyl; R3-3 is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy; R39 is alkyl haloalkyl or aryl; Ro and R4? are selected independently from hydrogen, alkyl, and haloalkyl, "- 42 is alkyl, haloalkyl, alkoxy, or phenyl each of which is optionally substituted by one or more groups selected from hydroxy, halogen, alkoxy, -CN, alkyl, -S (0) ealkyl; R43 and R44 are selected independently of hydrogen, NH2, -S (0) fR50, -C (0) R5 ?, substituted or unsubstituted alkyl substituted or unsubstituted alkenyl or alkynyl, or R3 and R can together form a divalent alkylene radical which can be interrupted by one or more heteroatoms, preferably selected from hydrogen, nitrogen and sulfur, R45 is haloalkyl, R46 and R49 are independently selected from the substituted or unsubstituted alkyl and aryl substituted or unsubstituted; R7 and R48 are selected independently from hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted aryl, or R7 and R48 can together form a divalent alkylene radical which is It can be interrupted by one or more heteroatoms; R50 is substituted or unsubstituted alkyl; R51 is hydrogen, alkyl, haloalkyl, aryl, alkenyl, -OR52, -SR53, or -NR54R5S; R52 and R53 are independently selected from alkyl and haloalkyl; R54 and R55 are independently selected from hydrogen, alkyl, haloalkyl and aryl; a, b, c, d, e and f independently represent zero, one or two; Mi is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; or a pesticidally acceptable salt thereof.

8. A compound according to claim 7, characterized in that the compound of formula (Ia) has one or more of the following characteristics:

A is -NR26-; Yi is hydrogen, alkyl or -C (0) R27; R19 is hydrogen or NH; R20 is -S (0) bR36; R21 is -NR43R4; R22 is halogen; R23 and R25 are hydrogen; R2 is haloalkyl; R2 is alkyl or O-alkyl; or M is C-halo. and 9. A compound according to claims 1, 2, 3, 7 or 8, characterized in that the compound of formula (I) or (Ia) is: 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (acetyloxy) -lH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-N- (acetyloxy) -IH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (ethylcarbonyloxy) -IH-pyrazole carboximidamide; 5-Amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (propylcarbonyloxy) -IH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (methyletenylcarbonyloxy) -lH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (benzyloxy) -IH-pyrazole carboximidamide; 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] ^ - 5-methylamino-4-methylsulfinyl-N- (acetyloxy) -lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-N- (acetyloxy) -lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (heptylcarbonyloxy) -lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-N- (heptylcarbonyloxy) -lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) enyl] -4- methylsulfenyl-N- (acetyloxy) -IH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4-. { trifluoromethyl) phenyl] -4-methylsulfenyl-N- (heptylcarbonyloxy) -IH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- trifluoromethylsulfinyl-N- (acetyloxy) -lH-pyrazole carboximidamide; - [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formylamino-4-ethylsulphenyl-N- (acetyloxy) -lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (hexylcarbonyloxy'-IH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- ( trifluoromethyl) phenyl] -4- methylsulfinyl-N- (pentylcarbonyloxy) -lH-pyrazole carboxymidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (butylcarbonyloxy) - IH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfenyl-N- (cyclopentylcarbonyloxy) -IH-pyrazole carboximidamide; -Amino-l- [2, 6 dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (cyclopentylcarbonyloxy) -lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4-. {trifluoromethyl) phenyl] -4-methylsulfinyl -N- (tert-butylcarbonyloxy) -IH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (isopropylcarbonyloxy) -lH-pyrazole carboximidamide; - [2,6-dichloro-4- (trifluoromethyl) phenyl] -5-formylamino-4-ethylsulfinyl-N- (acetyloxy) -IH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (chloroacetyloxy) -lH-pyrazole carboximidamide; f "-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (bromoacetyloxy) -IH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro- 4- (trifluoromethyl) phenyl] -4- methylsulfinyl-N- (1-ethylpropylcarbonyloxy) -IH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl- N- [(3-acetyloxy) phenylcarbonyloxy] -1H-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-trifluoromethylsulfonyl-1H-pyrazole-3 - carboximidamide, or 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -N-hydroxy-4-trifluoromethylsulfenyl-1H-pyrazole-3-carboximidamide;

10. A compound according to claim 7 or 8, characterized in that the compound of formula (Ia) is: 5-7? Mino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N-amino-lH-pyrazole-3-carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (isopropylcarbonyl) amino-lH-pyrazole-3-carboximidamide; "5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-N- (n-heptylcarbonyl) amino-lH-pyrazole-3-carboximidamide; -Amino-l- [2 , 6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (ethoxycarbonyl) amino-lH-pyrazole-3-carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl) ] -4- trifluoromethylsulfini1-N-amino-lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- ethylsulfini1-N-amino-lH-pyrazole carboximidamide; -Amino -l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- trifluoromethyl-N-acetylamino-1H-pyrazole carboxyimidamide; -Amino-l- [2,6-dichloro-4-trifluoromethyl] phenyl] -4- methylsulfinyl-N- (1-methyletenylcarbonylamino) -1H-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-N- (tert-butylcarbonylamino) - lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4- methylsulfinyl-N- (2-methyletenylcarbonylamino) -1H-pyrazole carboximidamide; -Amino-l- [2, 6-dichloro-4- (trifluoromethyl) phenyl] -4- - methylsulfinyl-N- (ethylcarbonylaminess) -lH-pyrazole carboximidamide; -Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (propylcarbonylamino) -lH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (1-ethylpropylcarbonylamino) -1H-pyrazole carboximidamide; 5-Amino-1- [2,6-dichloro-4-. { trifluoromethyl) phenyl] -4- methylsulfinyl-N- (butylcarbonylamino) -IH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (pentylcarbonylamino) -lH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (hexylcarbonylamino) -lH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-N-acetylamino-lH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N-chloroacetylamino-IH-pyrazole carboximidamide; 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-ethylsulfinyl-N- (tridecylcarbonylamino) -lH-pyrazole carboximidamide; "X 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (n-propoxycarbonylamino) -lH-pyrazole carboximidamide; 5-Amino-l- [2, 6 -dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfinyl-N- (1,1-dimethylpropyloxycarbonylamino) -IH-pyrazole carboximidamide, or 5-Amino-l- [2,6-dichloro-4- (trifluoromethyl) phenyl) ] -4- methylsulfinyl-N- (tertbutyloxycarbonylamino) -1H-pyrazole carboximidamide;

11. A pesticidal composition characterized in that it comprises: [a) a compound of formula (Ia) where: A is -NR26-: Yi is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, -S (0) aR28, -P (O) R29R30, -P (S) R29R3o, - Si (R3?) (R32) (R33), -C (0) R27, -C (S) R27, cyano or nitro; Rig is hydrogen, alkyl, haloalkyl, or -NR34R35; R20 is -S (0) bR36 or R37; R2? is hydrogen, halogen, -C (0) R38, -S (0) cR39, alkyl, haloalkyl, -OR40, -N = C (R?) (R2), alkenyl, NR3R44, lH-pyrrol-1-yl, IH-pyrazole-1-yl, or CH = NOH; R22, R23 and 25 are independently selected from hydrogen, halogen or alkyl; R24 is halogen, haloalkyl, haloalkoxy, -S (0) dR4s or SF5; R26 is hydrogen or substituted or unsubstituted alkyl; R27 is hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aryl, -OR46, -NR47R8, or -SR49; R28 is substituted or unsubstituted alkyl or substituted or unsubstituted aryl; R29 and R30 are independently selected from alkoxy and thioalkoxy; R31, R32 and R33 are independently selected from alkyl, haloalkyl and aryl; R34 and R35 are independently selected from hydrogen or substituted or unsubstituted alkyl; R36 is alkyl, alkenyl, alkynyl, or cycloalkyl of 3 to 6 carbon atoms each of which is optionally substituted by one or more halogens; R37 is alkyl or haloalkyl; R38 is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy; R39 is alkyl haloalkyl or aryl; R40 and R41 are independently selected from hydrogen, alkyl and haloalkyl; R42 is alkyl, haloalkyl, alkoxy or phenyl each of which is optionally substituted by one or more groups selected from hydroxy, halogen, alkoxy, -CN, alkyl, -S (O) ealkyl; R43 and R44 are independently selected from hydrogen, NH2, -S (O) fR50, -C (0) R5, substituted or unsubstituted alkyl, alkenyl or substituted or unsubstituted alkynyl; or R43 and R44 can together form a divalent alkyl radical which can be interrupted by one or more heteroatoms, preferably selected from hydrogen, nitrogen and sulfur; / R 45 is haloalkyl; R46 and R9 are independently selected from the substituted or unsubstituted alkyl and substituted or unsubstituted aryl; R7 and R48 are independently selected from hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted aryl; or R47 and R48 can together form a divalent alkylene radical which can be interrupted by one or more heteroatoms; R50 is substituted or unsubstituted alkyl; R5? is hydrogen, alkyl, haloalkyl, aryl, alkenyl, -OR52? -SR53, or -NR54R55; R52 and R53 are independently selected from alkyl and haloalkyl; R54 and R55 are independently selected from hydrogen, alkyl, haloalkyl and aryl; a, b, c, d, e and f independently represent zero, one or two; i is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; or a pesticidally acceptable salt thereof; Y (b) An acceptable carrier in agriculture for this one.

12. A method for the control of pests in a site, characterized in that it comprises applying to said site an effective amount of pesticide of a compound of formula (Ia): wherein A is -NR26-: Yi is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, -S (0) aR2s, -P. { O) R29R30, -P (S) R29R3o, -Si (R3?) (R32) (R33), -C (0) R27, -C (S) R27, cyano or nitro; Ri9 is hydrogen, alkyl, haloalkyl, or -NR34R35; R21 is hydrogen, halogen, -C (0) R38, -S (0) cR39, alkyl, haloalkyl, -OR40, -N = C (R4?) (R2), alkenyl, -NR43R44 f lH-pyrrole-1- ilo, lH-pyrazol-1-yl, or -CH = NOH; R22r R23 and R25 are independently selected from hydrogen, halogen or alkyl; R24 is halogen, haloalkyl, haloalkoxy, -S (0) dR4s or SF5; R26 is hydrogen or substituted or unsubstituted alkyl; R 27 is hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aryl, -OR46, -NR47R48i or -SR49; R28 is substituted or unsubstituted alkyl or substituted or unsubstituted aryl; R29 and R30 are independently selected from alkoxy and thioalkoxy; R31, R32 and R33 are independently selected from alkyl, haloalkyl and aryl; R34 and R35 are independently selected from hydrogen or substituted or unsubstituted alkyl; R36 is alkyl, alkenyl, alkynyl, or cycloalkyl of 3 to 6 carbon atoms each of which is optionally substituted by one or more halogens; R37 is alkyl or haloalkyl; R38 is hydrogen, alkyl, ha-Aoalkyl, alkoxy or thioalkoxy; R39 is alkyl haloalkyl or aryl; Ro and R? they are selected independently from hydrogen, alkyl and haloalkyl; R42 is alkyl, haloalkyl, alkoxy or phenyl each of which is optionally substituted by one or more groups selected from hydrsxy, halogen, alkoxy, -NC, alkyl, -S (O) ealkyl; R3 and R4 are independently selected from hydrogen, NH2, -S (O) fR50, -C (0) R5 ?, substituted or unsubstituted alkyl substituted or unsubstituted alkenyl or alkynyl; or R43 and R44 can together form a divalent alkylene radical which can be interrupted by one or more heteroatoms, preferably selected from hydrogen, nitrogen and sulfur; R 45 is haloalkyl; R4e and R49 are independently selected from the substituted or unsubstituted alkyl and substituted or unsubstituted aryl; R47 and R48 are selected independently from hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted aryl; or R and R48 can together form a divalent alkylene radical which can be interrupted by one or more hetero atoms; Rsc is substituted or unsubstituted alkyl; Rsi is hydrogen, alkyl, haloalkyl, aryl, alkenyl, -0R52, -SR53, or -NRsR55; R52 and R53 are independently selected from alkyl and haloalkyl; R54 and R55 are independently selected from hydrogen, alkyl, haloalkyl and aryl; a, b, c, d, e and f independently represent zero, one or two; Mi is C-halo, C-CH3, C-CH2F, C-CH2C1, C-N02, or N; or a pesticidally acceptable salt thereof. ?