NZ336420A

NZ336420A - Pesticidal 1-aryl and pyridylpyrazole derivatives

Info

Publication number: NZ336420A
Application number: NZ336420A
Authority: NZ
Inventors: David Treadway Manning; Michael Pilato; Tai-Teh Wu; David William Hawkins
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1996-12-24
Filing date: 1997-12-18
Publication date: 2001-04-27
Also published as: WO1998028279A1; IL130537A0; PL334237A1; KR20000062318A; IL130537A; AP9901586A0; CA2275634A1; SK284351B6; EA199900598A1; ID22807A; JP2001506665A; AU5759898A; AU747450B2; UA67734C2; EA003995B1; BG103592A; AP1004A; SK85699A3; HUP0000464A3; BR9714086A

Abstract

Derivatives of 1-arylpyrazole-3-thiocarboxamide (see formula (I)), wherein R1 is H or halogen; each of R2 and R4, which are identical or different, is H, halogen or alkyl; R3 is halogen, haloalkyl, haloalkoxy or R10S(O)m; preferably, R3 is halogen, haloalkyl or haloalkoxy; R5 is alkyl, haloalkyl, alkenyl and alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; preferably R5 is alkyl; Z is hydrogen, halogen, alkyl, formyl, -C(O)alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylideneamino, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl; or, preferably, Z is amino, R6NH-or R7R8N-; each of R6, R7 and R8, which are identical or different, is alkyl-S(O)p-, formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl containing from 3 to 6 carbon atoms, or -C(O)alkyl wherein the alkyl and alkenyl portions are optionally substituted by one or more R9; or R7 and R8 are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; R9 is cyano, nitro, alkoxy, haloalkoxy, R10S(O)q-, -C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; R10 is lower alkyl or lower haloalkyl; m, n, p and q are 0, 1 or 2; M is C-halo, C-CH3, C-CH2F, C-CH2Cl, C-NO2 or N; and pesticidally active salts thereof. By the term "pesticidally acceptable salts" is meant salts the anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water-soluble. Suitable acid addition salts formed from compounds of 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 salts with bases formed from compounds of formula (I) containing a carboxylic acid group, include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts. The process for preparing compounds of formula (I), and their use as insecticides is also described.

Description

<div class="application article clearfix" id="description"> WO 98/28279 PCT/EP97/07116 -1- PESTICIDAL 1-ARYL AND PYRIDYLPYRAZOLE DERIVATIVES BACKGROUND OF THE INVENTION 1. Field of the Invention 5 The invention relates to new 3-thiocarboxamide derivatives of 1-arylpyrazoles and derivatives thereof. The invention further pertains to compositions of said compounds and methods, using said compounds, for the control of arthropod pests, in particular to the application of said compounds or compositions in agricultural methods of use, particularly as pesticides, for 10 controlling arthropods, especially insects by systemic action. '.sNv* „ 2. Description of the Related Art The control of insects, nematodes or helminths using 1-aiylpyrazoles has been described in International Patent Publications No. WO 93/06089 (and the 15 equivalent U.S. Patent No. 5,451,598), WO 94/21606 and WO 87/03781 as in European Patent Publication Numbers 0295117,659745,679650,201552 and 412849, German Patent No. DE19511269 and U.S. Patent No. 5,232,940. OBJECTS AND SUMMARY OF THE INVENTION 20 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 use of the pesticidal pyrazole 25 compounds against arthropods, especially insects, particularly in agricultural or horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health. A third object of the present invention is to provide very active compounds, with broad spectrum pesticidal activity, asjyell as compounds with 30 selective special activity, e.g. aphicidal, miticidal, foliar insecticfalaJ, soil insecticidal, systemic, antifeeding or pesticidal activity via seed treatment. . A fourth object of the present invention is to provide compounds with substantially enhanced and more rapid activity, especially against insects and more particularly insects in their larval stages. Printed from Mimosa 06/24/1999 10:48:06 page -3- A fifth object of the present invention is to provide compounds with greatly improved (faster and greater) penetration into pest species when topically applied and to thus provide enhanced movement of the compounds to the pesticidal site(s) of action within the pest. These and other objects of the invention shall become apparent from the description of the present invention which follows. The objects are met in whole or in part by the invention. The invention provides insecticidal 1-aiylpyrazoles having the general formula (I): Ri is H or halogen; each of R2 and R4, which are identical or different, is H, halogen or alkyl; R3 is halogen, haloalkyl, haloalkoxy or RioS(0)m; preferably, R3 is halogen, haloalkyl or haloalkoxy; Rj is alkyl, haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; preferably R5 is alkyl; Z is hydrogen, halogen, alkyl, formyl, -C(0)alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylideneamino, lH-pyrrol-l-yl or lH-pyrazol-l-yl; or, preferably, Z is amino, R^NH-or R?RgN-; each ofR«, r7 and Rg, which are identical or different, is alkyl-S(0)p-, formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkylthiocarbonyl or aroyl; or alkyl, alkenyl containing from 3 to 6 carbon atoms, or -C(0)alkyl wherein the alkyl and alkenyl portions are optionally substituted by one or more R9; S *3 (D wherein: intellectual property office of N.Z. 2 4 JAN 2001 RECEIVED or R7 and Rs are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or 5 alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; R$ is cyano, nitro, alkoxy, haloalkoxy, R10-S(O)q-, -C(0)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocaibonyl, -C02H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; 10 Rio is lower alkyl or lower haloalkyl; m, n, p and q are 0, 1 or 2; M is C-halo, C-CH3r C-CH2F, C-CH2C1, C-N02, orN; or a pesticidally acceptable salt of a compound of formula (I); with the exclusion of 1-arylpyrazoles of formula (I) in which: 15 Rj is haloalkyl; and Z is hydrogen, lH-pyrrol-l-yl, amino or R$NH - in which R* is formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl containing 3 to 6 carbon atoms or -C(O) alkyl wherein the alkyl portion is optionally substituted by one or more R, in which R9 is halogen; 20 and the other symbols are as hereinbefore defined. By the term "pesticidally acceptable salts" is meant salts the anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water soluble. Suitable acid addition salts formed from compounds of formula (I) containing an amino group, include salts with 25 inorganic acids for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids for examples acetates. Suitable salts with bases formed from compounds of formula (I) containing a carboxylic acid group, include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts. 30 DETAILED DESCRIPTION OF THE INVENTION Unless otherwise specified alkyl, alkoxy and alkylthio groups have from one to six (preferably one to four) carbon atoms. Alkenyl and alkynyl groups have from two to six (preferably two to four) carbon atoms. In the instant invention, some 35 words are used in a specific sense: The term "aminocarbonyl" means a carbamoyl radical, that is, a radical of the intellectual property office of n.z. 2 k JAN 2001 formula -C(0)NH2. Similarly, the term "alkylaminocarbonyl" means an alkylcarbamoyl radical, that is, a radical of the formula -C(0)-NH-alkyl; and the term "dialkylaminocarbonyl" means a dialkylcarbamoyl radical, that is, a radical of the formula -C(0)-N(alkyl)2 in which the alkyl moieties can be the same or different. The term "aminosulfonyl" means a sulfamoyl radical, that is, -S02NH2. Similarly, the term "alkylaminosulfonyl" means an alkylsufamoyl radical, that intellectual property i office of n.z. 2 i JAN 2001 R E C F I V F n WO 98/28279 PCT/EP97/07116 -4- is, a radical of the formula -S02NH-a]kyl; while the term "dialkylaminosulfonyl" means a dialkylsulfamoyl radical, which has the formula -S02N(alkyl)2 wherein the alkyl moieties can be the same or different. The term "halo" before the name of a radical means that this radical is 5 partially or completely halogenated, that is to say, substituted by F, CI, Br, or I, in any combination, preferably by F or CI. The term "halogen" means F, CI, Br or I. When the name of any substituent is repeated, it keeps the same meaning unless otherwise specified. The term "aroyl" designates a carbonyl aromatic radical, that is, aryl-C(O)-, which is preferably a benzoyl optionally substituted 10 by one or more alkyl or halogen groups. A particularly preferred class of compounds of formula (I) are those wherein: Ri is F, CI, Br or H; 15 R2 and R4 are H; R3 is -CF3, -OCF3, -CHF2, -S(0)mCF3, -CFC12, -CF2C1, -OCF2Cl, -OCFCl2, CI, Br or F; R5 is methyl or ethyl; Z is H, halogen (F, CI, Br), Q-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl; or 20 amino, -NHRg or -NR7R8, wherein each of R«, R7 and Rg, which are identical or different, is C1-C3 alkyl, C3 alkenyl or -C(0)alkyl wherein the alkyl and alkenyl portions are unsubstituted or substituted with cyano, alkoxy, alkyl-S(0)p-, nitro, alkoxycarbonyl, -C(0)alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO 2H, hydroxy or halogen (F, CI, Br); and 25 M is CC1, CF, CBr or N. A further especially preferred class of compounds are those wherein: Ri is CI or Br; R2 and R4 are H; R.3 is -CF3, -OCF3 or CI; 30 R5 is methyl or ethyl; Z is H, halogen (F, CI, Br), C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl; or amino, -NHRg or -NR7R8, wherein each of R6, R7 and Rg, which are identical or different, is C(-C3 alkyl, C3 alkenyl or -C(0)alkyl wherein the alkyl or alkenyl portions are unsubstituted or substituted with cyano, alkoxy, a!kyl-S(0)p-, nitro, Printed from Mimosa 06/24/1999 10:48:06 page -6- 6 420 alkoxycarbonyl, -C(0)alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -CO 2H, hydroxy or halogen (F, CI, Br); and M is CCI, CBr orN. A further especially preferred class of compounds are those wherein: 5 Ri is CI or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or CI; Rj is methyl or ethyl; Z is H or amino; and 10 M is CCI, CBr or N. I A further especially preferred class of compounds are those wherein: Ri is CI or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or CI; 15 R5 is methyl or ethyl; Z is H or amino; and Mis CCI, CBr or N. For the above preferred compounds, there are optimum combinations of substituent groups. 20 Preferred phenyl groups or pyridyl groups comprising the R1-R4 and M radicals in formula (I) are: 2,6-dichloro-4-trifluoromethylphenyl; 2,6-dichloro-4-trifluoromethoxyphenyl; 2-bromo-6-chloro-4-trifluoromethylphenyl; 2-bromo-6-^ chloro-4-trifluoromethoxyphenyl; 2,6-difluoro-4-trifluoromethylphenyl; 2- chloro-4-trifluoromethylphenyl; 2,6-dichloro-3-methyl-4-trifluoromethylphenyl; 25 3-chloro-5-trifluoromethyl-2-pyridinyl; 3-chloro-5-trifluoromethoxy-2-pyridinyl; 3,5-dichloro-2-pyridinyl; 2,6-dichloro-4-bromophenyl; 2,4,6-trichlorophenyl; 2-bromo-6-fluoro-4-difluoromethylphenyl; 2-chIoro-6-fluoro-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethoxyphenyl; and 2-bromo-4-trifluoromethylphenyl. 30 Further preferred Z substituents in formula (I) are: acetylamino; amino; 2-n-butoxypropionylamino; methyl; hydroxyacetylamino; ethyl; 3-ethylsulfinylpropylamino; bromo; formylamino; chloro; methylamino; ethylamino; 2-hydroxyethylamino; 2-methoxyethylamino; methylsulfonylamino; 2-ethylsulfonylethylamino; 4-methoxybenzoylamino; 2-cyanoethylamino; 2-35 methylthioethylamino; 2-aminocarbonylethylamino C2-carbamovlethvIamino'): 2- intellectual property o/fice of n.z. 2 4 JAN 2001 WO 98/28279 PCT/EP97/07116 methylsulfinylethylamino; 3-methoxycarbonylpropylamino; 2-ethylsulfinylethylamino; 2-methylsulfonyIethylamino; cyanomethylamino; 2-ethylthioethylamino; aminocarbonylmethylamino (carbamoylmethylamino); dimethylamino; 2-nitroethylamino; 2-acetylethylamino; methylcarbonylmethylamino (acetylmethylamino); methoxycarbonyl; and ethoxycarbonyl. Further preferred -S(0)„Rs substituents in formula (I) are: methylthio; methylsulfinyl; methylsulfonyl; ethylsulfinyl; ethylsulfonyl; ethylthio; cyclopropylsulfinyl; cyclopropylthio; cyclopropylsulfonyl; isopropylsulfinyl; isopropylsulfonyl; and isopropylthio. Particularly preferred pyrazole derivatives include the following, the numbers 1-11 being assigned to these compounds for reference and identification purposes. 1. 5-amino-1 -(2,6-dichloro-4-trifluoromethyIpheny I)-4-methylthiopyrazole-3-thiocarboxamide 2. 5-amino-1 -(2,6-dichloro-4-trifluoromethy Ipheny l)-4-trifluoromethylthiopyrazole-3-thiocarboxamide 3. 4-dichlorofluoromethylsulfonyl-1 -(2,4,6-trichlorophenyl)pyrazole-3-thiocarboxamide 4. 5-amino-1 -(2,6-dichIoro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazoie-3-thiocarboxamide 5. 5-amino-1 -(2,6-dichloro-4-trifluoromethylphenyl)-4-methylsuIfonylpyrazole-3-thiocarboxamide 6. 5-amino-1 -(2-bromo-6-chloro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide 7. 5-amino-1 -(2,6-dichloro-4-trifluoromethoxyphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide 8. 5-amino-l-(2,6-dichloro-4-trifluoromethylphenyl)-4-ethylsulfinylpyrazole-3-thiocarboxamide 9. 5-amino-l-(2-chloro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide 10. 5-amino-l-(2-bromo-6-chloro-4-trifhioromethylphenyl)-4-ethylsulfinylpyrazole-3-thiocarboxamide 11. 5-amino-1 -(2,6-dichloro-4-trifluoromethoxyphenyl)~4-ethylsulfinylpyrazole-3-thiocarboxamide. Printed from Mimosa 06/24/1999 10:48:06 page -8- WO 98/28279 PCT/EP97/07116 -7- METHODS OR PROCESSES OF SYNTHESIS The compounds of general formula (I) can be prepared by the application or adaptation of known methods (i.e., methods heretofore used or described in the chemical literature including the Chemical Abstracts) employing 3-cyano-l-phenylpyrazoles or 3-cyano- l-(2-pyridinyl)pyrazole intermediates of known formula or can be prepared by methods or processes similar to those described in EP 0295117, EP 0234119, WO 87/03781, EP 0500209 and EP 780378. According to a feature of this invention compounds of formula (I) may be prepared by the reaction of a compound of formula (II): wherein Rj, R2, R3, R», Rs, M and Z are defined above with an alkali or alkaline earth metal hydrosulfide, such as lithium, potassium, calcium or preferably sodium hydrosulfide, in an inert solvent for example N,N-dimethylformamide, pyridine, dioxan, tetrahydrofuran, sulfolane, dimethyl sulfoxide, methanol or ethanol at a temperature from -35°C to 50°C preferably 0°C to 30°C. Optionally the hydrosulfide may be generated in situ by treatment with H2S in the presence of an organic base, such as a metal alkoxide or trialkylamine or an inorganic base, such as an alkaline or alkaline earth metal hydroxide or a carbonate, such as sodium, potassium or ammonium carbonate. The use of a metal complexing agent, such as a crown ether, can be of benefit in accelerating the reaction. The reaction of hydrosulfide salt with the 3-cyanopyrazole can also be conducted in a two-phase water/organic solvent system using a phase transfer catalyst such as a crown ether or a tetraalkylammonium salt such as tetra-n-butylammonium bromide or benzyltrimethylammonium chloride. Organic solvents suitable for use in a two-phase system with water include benzene, toluene, dichloromethane, 1-chlorobutane and methyl tertiary-butyl ether. *3 0D Printed from Mimosa 06/24/1999 10:48:06 page -9- WO 98/28279 PCT/EP97/07116 -8- Compounds of formula (I) may also be prepared from compounds of formula (II) by treatment with the reagent PI12PS2, as described in Tet. Lett., 24 (20), 2059 (1983); According to a further feature of the invention compounds of general formula (I) wherein Rj, R2, R3, R4, R5, M and Z are as defined above and in which n represents 1 or 2 may be prepared by the oxidation of the corresponding compounds of formula (I) in which n represents 0 or 1. The reaction should be performed with a mild oxidising agent (to prevent destruction of the thioamide functional group) such as sodium periodate in an inert solvent for example methylene chloride at a temperature from -40°C to the reflux temperature of the solvent. According to a further feature of the present invention compounds of general formula (I) wherein Z represents hydrogen, halogen, alkyl, haloalkyl, amino, R^NH or R7R8N- wherein R6, R7 and/or Rg represent alkyl, haloalkyl, -C(0)alkyl, alkoxycarbonyl, formyl and-S(O) palkyl; or R$ and R7 are joined so as together form a divalent radical having 4 to 6 atoms in the chain, may be prepared by 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 EP 511845, Hatton et al U.S. Patent No. 5,232,940, and German Patent Publication No. DE 19511269. According to a further feature of the invention compounds of general formula (I) wherein Ri, R2, R3, R4, R5 and M are as defined above and Z represents R^NH- wherein R« represents ethyl substituted at the 2-position by R9 wherein R9 represents cyano, nitro, -S(0)qRio, -C(0)alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl, may be prepared by the reaction of the corresponding compound of formula (I) wherein Z is amino with a compound of formula (HI): R9-CH=CH2 (m) wherein R9 is defined above. The reaction may be performed preferably in the presence of a base such as sodium hydride, an alkali metal hydroxide for example potassium hydroxide, or a tetraalkylammonium hydroxide for example N-benzyltrimethylammonium hydroxide in a solvent such as N,N-dimethylformamide, tetrahydrofuran, toluene, ethanol or water, and at a temperature from -20°C to the reflux temperature. Printed from Mimosa 06/24/1999 10:48:06 page -10- WO 98/28279 PCT/EP97/07U6 -9- According to a further feature of the invention compounds of general formula (I) wherein R|, R2, R3, R4, R5 and M are as defined above and Z represents -NHRe or -NR7R8 wherein R7 and Rg represent alkyl or haloalkyl optionally substituted by one or more R9, may be prepared by the reaction of the corresponding compound of formula (I) wherein Z is amino with a compound of formula (IV): Rn-Y (IV) wherein Rn is alkyl or haloalkyl optionally substituted by one or more R9 and Y represents a leaving group, preferably halogen (for example chlorine). The reaction may be performed in the presence of a base such as potassium hydroxide, potassium methoxide, sodium hydride or triethylamine in an inert solvent such as N,N-dimethylformamide, tetrahydrofuran, toluene or ether, and at a temperature from -20°C to the reflux temperature. According to a further feature of the present invention compounds of general formula (I) wherein Z represents alkoxycarbonyl may be prepared by the reaction of the corresponding compound of formula (I) in which Z is carboxy with an alcohol of formula (V): R12OH (V) wherein R12 is alkyl. The above reaction is preferably performed in the presence of an acid catalyst such as sulphuric acid generally in the presence of excess of the alcohol or optionally in a co-solvent at a temperature from 0°C to the reflux temperature. Alternatively the reaction may be performed using a coupling reagent such as dicyclohexylcarbodiimide (DCC) in an inert solvent. According to a further feature of the present invention compounds of general formula (I) wherein Z represents alkylthiocarbonyl may be prepared by the reaction of the corresponding compound of formula (I) in which Z is carboxy with an thiol of formula (VI): R12SH (VI) wherein R12 is alkyl. The reaction may be performed using a coupling reagent such as dicyclohexylcarbodiimide (DCC) in an inert solvent. According to a further feature of the present invention compounds of general formula (I) wherein Z represents R|3CH(C1)CH2- wherein R13 represents alkyl may be prepared by the diazotisation of the corresponding compound of formula (I) in which Z represents amino followed by reaction with a compound of formula (VII): Printed from Mimosa 06/24/1999 10:48:06 page -11- WO 98/28279 PCT/EP97/07116 -10- R,3CH=CH2 (VII) The reaction is generally carried out using an alkyl nitrite such as tert-butyl nitrite in the presence of a copper salt such as copper (II) chloride in a solvent such as acetonitrile at a temperature from -10°C to 50°C. According to a further feature of the present invention compounds of general formula (I) wherein Z represents -C(0)alkyl may be prepared by the oxidation of the corresponding compound of formula (VIII): S cm 10 wherein Ri, R2, R3, R4, R5 and M are as defined above and Rm represents alkyl. The reaction may be performed using for example a mixture of chromic acid and sulphuric acid in a solvent such as water and acetone at a temperature from 0°C to 60°C. Compounds of formula (VIII) are novel and thus constitute a further feature of the present invention. 15 According to a further feature of the invention compounds of formula (I) in which Z represents Ri3CH=CH- may be prepared by the dehydrochlorination of the corresponding compound of formula (I) in which Z represents Ri3CH(CI)CH2-. The reaction is generally performed using a base such as sodium hydroxide or triethylamine in an inert solvent for example 20 dichloromethane or tetrahydrofuran at a temperature from -70°C to the reflux temperature. According to a further feature of the present invention compounds of formula (I) in which the substituent Z is hydrazino, lH-pyrrol-I-yl or 1H-pyrazol-l-yl may be prepared according to the procedures described in EP 25 0352944. Intermediates of general formula (I) wherein Z represents carboxy may be prepared by the oxidation of the corresponding compound of formula (I) in Printed from Mimosa 06/24/1999 10:48:06 page -12- WO 98/28279 PCT/EP97/07116 -11- 5 10 15 20 Printed from Mimosa . 06/24/1999 10:48:06 page -13- which Z represents formyl. The reaction is generally carried out using potassium permanganate or chromic acid in a solvent such as water at a temperature of from 0°C to the reflux temperature. Intermediates of formula (VIII) can be prepared by reaction of the corresponding compounds of formula (I) in which Z represents a formyl group with an organometallic reagent of formula RmQ wherein Q is preferably an alkali or alkaline earth metal for example lithium or a magnesium halide (Grignard) reagent. The reaction may be performed in an inert solvent such as ether or tetrahydrofuran and at a temperature from -78°C to the reflux temperature of the solvent. Intermediates of formula (I) in which Z represents a formyl group may be prepared by the oxidation of the corresponding compound of formula (I) in which Z represents Ri3CH=CH-. The reaction is generally performed using a reagent such as ozone or sodium metaperiodite in an inert solvent for example dichloromethane at a temperature from -100°C to 100°C. Certain compounds of formula (II) are novel and as such form a further feature of the present invention. Intermediates of formula (HI) and (TV) are known or may be prepared by known methods. Illustrative specific compounds of formula (I) of the invention are set forth in Table 1 below. In the Table c-Pr means cyclopropyl and CH2C2H means a propargyl group. WO 98/28279 PCT/EP97/07116 -12- TABLE 1 Cmpd No. RsS(0)n Z ri r2 r3 R, M 1 SCH3 nh2 CI H cf3 H CCI 2 SCFj nh2 CI h cf3 H CCI 3 SO2CFCI2 h CI H CI h CCI 4 SOCHj nh2 CI H cf3 H CCI 5 SO2CH3 nh2 CI H cf3 h CCI 6 SOCH3 nh2 Br H cf3 h cci 7 soch3 NHi a h ocf3 H ca 8 SOC2H5 NH2 CI H cf3 H CCI 9 SOCHj nh2 H h CFj H ca 10 SOC2Hs nh2 Br h cf3 H CCI 11 SOC2H5 nh2 CI H OCF3 h CCI 12 sc2h5 nh2 CI H cf3 H CCI 13 sch2ch=ch2 nh2 Br H cf3 . H ca 14 SOC2H5 NHCOCH3 CI H cf3 H CF 15 so2ch3 NH2 CI H cf3o H CCI 16 SOCH3 NHC2H5 CI H cf3 H CCI 17 SOC2H5 NHCH3 F H cf3 CH3 CCI 18 SO-c-Pr NHCH20CH3 Br H cf3 H cci 19 SOCH3 NHCH2CONH2 CI H cf3 H N 20 S-i-C3H7 NH2 CI H cf3o H CCI 21 S02C2Hs NHCHO CI ch3 cf3s H CBr Printed from Mimosa 06/24/1999 10:48:06 page -14- WO 98/28279 PCT/EP97/07116 -13- Cmpd No. r5s(0)„ z ri r2 R3 R4 M 22 sch. nh2 ci h cf3 ch3 cf 23 SOCHj nhso2c2h5 ci h chf2 h CCI 24 SO-c-Pr Br f h ccif2 h cf 25 sch2c2h h CI h cf3 h CBr 26 soc2h5 ch3 CI h CF3O h ca 27 sch2ch=ch2 nhnh2 Br ch3 cf3 h cci 28 SOCH3 nh2 CI h cf3 h cch3 29 sch3 nhsc2h5 CI h cf3 h cci 30 SOCH3 nhch2ch2cn CI h cf3 h cci 31 so2ch3 nhch2ch2och3 CI H cf3 ch3 cci 32 SO-i-C3H7 nh2 CI H cf3 h N 33 soc2h5 COCHj Br H cf3o H cci 34 SOCH3 nhch3 ci H cf3 H cci 35 SOCH3 nh2 Br H cf3 H N 36 soc2h5 nh(ch2)2conh2 ci H cf3 H cci 37 SOCH3 ch=ch2 f ch3 cf3 H cf 38 S02CH3 nh2 CI h cf3 H CN02 39 SO-c-Pr NHC02CH3 CI H cf2ci H cci 40 sch3 nhscc13 ci h cfc12 H cci 41 sch2c2h NHCH2CH2SCH3 f h cf3 H cci 42 soc2h5 NHCH2CH2SOC2H5 ci h cf3 H cci 43 SOC2H5 ch3 H h cf3 H cci Printed from Mimosa 06/24/1999 10:48:06 page -15- WO 98/28279 PCT/EP97/07116 -14- Cmpd No. RsS(0)n Z Ri Rz r3 R4 M 44 SOC2H5 N(CH3)2 H H cf3 H CCI 45 SOCH3 N(CH3)2 CI H cf3 H CBr The invention is illustrated by the following examples, which are not considered as limiting the invention but are given to better enable use of it. 5 EXAMPLE 1 5-Amino-l-(2.6-dichloro-4-trifluoromethv]phenvl)-4-methvlthiopvrazole-3-thiocarboxamide To a stirred solution of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-methylthiopyrazole (4.7 g) and 5 drops of 15-crown-5 in degassed N,N-10 dimethylformamide was added, over a few minutes, a solution of sodium hydrosulfide hydrate (0.79 g) in degassed water. The mixture was stirred at 20°C for 18 hours, evaporated and the residue purified by flash chromatography on silica gel, eluting with 2:1 hexane/acetone to give 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylthiopyrazole-3-thiocarboxamide (0.38 g), 15 m.p. 161 °C. Compound 1. In a manner similar to that employed above, Compound numbers 2 to 11 of general formula (I) shown in Table 2 below were also prepared. Printed from Mimosa 06/24/1999 10:48:06 page -16- WO 98/28279 PCT/EP97/07116 -15- TABLE 2 Cmpd No. R. r2 r3 r4 m Rs s(0)n z m.p.°C 2 CI h cf3 h cci scf3 nh2 182 3 ci h CI h CCI so2cfci2 h 180.5 4 ci h cf3 h CCI SOCHj nh2 192 5 ci h cf3 h cci so2ch3 nh2 231 6 Br h cf3 h CCI SOCHj nh2 188.5 7 ci h OCFj h cci SOCHj nh2 137 8 ci h cf3 h cci SOC2Hs nh2 167 9 h h cf3 h cci SOCHj nh2 153.5 10 Br h cf3 h cci SOC2Hs nh2 113.5 11 ci h ocf3 h CCI SOC2Hs nh2 102 REFERENCE EXAMPLE 1 5 5-Amino-l-(2.4.6-trichlorophenvlV3-cvanopvrazole Sodium nitrite (27.6 g) was added slowly to concentrated sulphuric acid (106 ml) and the mixture allowed to cool to 30° C. To the stirred mixture was added acetic acid (216 ml) over 30 minutes, which was cooled to 20° C and a solution of 2,4,6-trichloroaniline (70.7 g) in acetic acid added over 30-minutes, 10 maintaining at 20-25° C. The mixture was heated at 52° C for 30 minutes, then fed over 20 minutes, to a solution of ethyl 2,3-dicyanopropionate (52.0 g) in 36% aqueous acetic acid (774 ml), while cooling to 10-15° C. The reaction mixture was allowed to warm to 20° C, diluted (water) and extracted (dichloromethane). The organic layer was then washed with dilute ammonium 15 hydroxide solution and stirred with 29% ammonium hydroxide solution for a 17- hours. The organic phase was washed with water then with hydrochloric acid (IN),dried (MgS04) and evaporated. Crystallization from toluene afforded 5-amino-l-(2,4,6-trichlorophenyl)-3-cyanopyrazole (32.82 g), *H NMR (CDCI3): NH2 (2H, br s, 3.84 ppm), 4-H (1H, s, 5.97 ppm), arom.(2H, s, 7.53 ppm). Printed from Mimosa 06/24/1999 10:48:06 page -17- WO 98/28279 PCT/EP97/07116 -16- REFERENCE EXAMPLE 2 5-Amino-4-dichlorofIuoromethvlthio-l-(2.4.6-trichlorophenvn-3-cvanopvrazole To a stirred solution of 5-amino-l-(2,4,6-trichlorophenyl)-3-cyanopyrazole (8.0 g, 0.028 mol) in acetic acid (70 ml) was fed dichlorofluoromethylsulfenyl chloride (4.4 ml) over 5-minutes. The mixture was allowed to stir at 20°C for 65-hours, then poured into water and extracted (dichloromethane). The organic phase was washed with cold sodium bicarbonate solution then water, dried (MgSC>4) and evaporated. Column chromatography on silica gel eluting with 3:1 dichloromethane/hexane, afforded 5-amino-4-dichlorofluoromethylthio-1 -(2,4,6-trichlorophenyl)-3-cyanopy razole (6.06 g), m.p.l89-191°C. REFERENCE EXAMPLE 3 4-Dichlorofluoromethvlthio-l-(2.4.6-trichlorophenvl')-3-cvanoovrazole A solution of 5-amino-4-dichlorofluoromethylthio-l-(2,4,6-trichlorophenyl)-3-cyanopyrazole (2.19 g)and tert-butyl nitrite (90%, 4.1 ml) in tetrahydrofuran was heated under reflux for 3.5 hours and evaporated. The residue was purified by flash-chromatography on silica gel, eluting with dichloromethane to give 4-dichlorofluoromethylthio-l-(2,4,6-trichlorophenyl)-3-cyanopyrazole (1.56 g), m.p.l06-108°C. REFERENCE EXAMPLE 4 4-Dichlorofluoromethvlsulfonvl-3-cvano-l-(2.4.6-trichloroohenvl)pvrazole A solution of 4-dichlorofluoromethylthio-3-cy ano-1 -(2,4,6-trichlorophenyl)pyrazole (0.80 g) and 3-chloroperbenzoic acid (80%, 0.86 g) in chloroform was heated under reflux for 2 hours, cooled, diluted (ethyl acetate) and washed in sequence with 10% sodium hydrogen sulfite, 2N NaOH, water and brine. The dried (MgSCty) solution was evaporated and purified by flash- chromatography on silica gel eluting with dichloromethane to give 4-dichlorofluoromethy lsulfonyl-1 -(2,4,6-trichlorophenyI)-3 -cyanopy razole (0.41 g), m.p.l43.5-145°C. Printed from Mimosa 06/24/1999 10:48:06 page -18- WO 98/28279 PCT/EP97/07116 -17- REFERENCE EXAMPLE 5 5-Amino-l-(2-chloro-4-trifluoromethvlphenvl')-3-cvano-4-methvlsulfinvlpvrazole Step 1 5 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-l-(2-chloro-4-trifluoromethylphenyI)-3-cyanopyrazole (1.5 g) in anhydrous methanol was added over 10-minutes and the stirred mixture allowed to wann to 20° C over 16-hours. After pouring into water the precipitate was 10 collected and dried to give 5-amino-l-(2-chloro-4-trifluoromethylphenyl)-3- cyano-4-thiocyanatopyrazole (1.64 g). HPLC (C-18 column, eluting with 3:1 CH3CN/H2O at 1.0 ml/min.) showed the compound as a peak of 86.6% area at 5.11 minutes. Step 2 15 Iodomethane (0.7 ml) was injected into a stirred suspension of 5-amino- l-(2-chloro-4-trifluoromethylphenyl)-3-cyano-4-thiocyanatopyrazole (1.64 g), in methanol at 4° C. A 10% aqueous solution of sodium hydroxide (2.8 ml) was added and the reaction mixture stirred for 1 hour at 4° C, poured into water and extracted with dichloromethane and ethyl acetate. The dried (Na2S04) 20 combined organic phase 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-trifluoromethylphenyl)-3-cyano-4-methylthiopyrazoIe (0.4 g), m.p.l29-132°C. Step 3 25 To a stirred solution of 5-amino-1 -(2-chloro-4-trifluoromethylphenyl)-3- cyano-4-methylthiopyrazole (3.0 g) in trifluoroacetic acid (20 ml) was added 30% hydrogen peroxide (0.5 ml) with cooling at 4° C. The mixture was brought to 20° C over 2 hours, then poured onto ice and the solid water-washed and dried. Flash-column chromatography on silica gel gave 5-amino-l-(2-chloro-4-30 trifluoromethylphenyl)-3-cyano-4-methylsulfinylpyrazole (0.69 g) m.p.146- 147°C. Printed from Mimosa 06/24/1999 10:48:06 page -19- WO 98/28279 PCTOP97/07116 -18- REFERENCE EXAMPLE 6 In a manner similar to that employed in Reference Example 5, Steps 1 and 2, the following compounds were also prepared: 5-amino-l-(2,6-dichloro-4-trifluoromethoxyphenyl)-3-cyano-4-5 methylthiopyrazole, m.p. 147-148 0 C, and 5-amino-l-(2-bromo-6-chloro- 4-trifluoromethylphenyl)-3-cyano-4-methylthiopyrazole, m.p. 178-180 0 C. REFERENCE EXAMPLE 7 In a manner similar to that employed in Reference Example 5, Step 3, the following compounds were also prepared: 10 5-amino-1 -(2,6-dichloro-4-trifluoromethoxyphenyl)-3-cy ano-4- methylsulfinylpyrazole, m.p. 137-138 0 C, and 5-amino-l-(2-bromo-6-chloro~4-trifluoromethylphenyl)-3-cyano-4-methylsulfinylpyrazole, m.p. 150-151 °C. BIOLOGICAL EFFICACY 15 The following methods were used to apply the compounds of the invention and to observe the results obtained therewith: a foliar/contact spray on sucking (aphids) or chewing (Lepidoptera) insects. The species tested were as follows: 20 GENUS. SPECIES COMMON NAME ABBREVIATION Aphis gossypii cotton leaf aphid APHtGO Schizaphis graminum greenbug TOXOGR Musca domestica housefly MUSCDO 25 The Soil Drench Test (Systemic Activity) Cotton and sorghum plants were established in pots. One day prior to treatment, each pot was infested with about 25 aphids of a mixed population. Cotton plants were infested with aphids and sorghum plants were infested with the greenbug. The selected compound of formula (I) was applied to the soil 30 surface in a dilution that delivered the equivalent of 10.0 ppm soil concentration by weight. Aphid counts were obtained at 5 DAT (= days after treatment). The number of aphids on the treated plants was compared to the number of those on the untreated control plants. 35 The Housefly Bait/Contact Test (Musca domestica) Printed from Mimosa 06/24/1999 10:48:06 page -20- WO 98/28279 PCT/EP97/07116 -19- About 25 four to six-day-old adult houseflies were anesthetized and placed in a cage with a sugar water bait solution containing the compound. The concentration of the selected compound of formula (I) in the bait solution was 100 ppm. After 24 hours, flies which showed no movement on stimulation were 5 considered dead. Foliar/Contact Test with A. gossypii Aphid-infested cotton plants were placed on a revolving turntable, and sprayed to runoff with a 100 ppm formulation of the selected compound of 10 formula (I). The treated, A. gossypii-infested plants were held for three days after treatment, after which the dead aphids were counted. Compounds 1-11 of the invention showed activity against Aphis gossvpii and Schizaphis eraminum at lOppm in the above systemic test; against Musca 15 domestica at lOOppm in the above bait/contact test; and against Aphis gossvpii at lOOppm in the above foliar/contact test. The present invention provides a method for the systemic control of arthropods at a locus, especially some insects or mites which feed on the above ground portions of plants. Control of such foliar pests may be provided by direct 20 foliar application or by application by for example soil spray or granule application to the plant roots or plant seeds with subsequent systemic translocation to the above ground portions of the plants. Such systemic activity includes the control of insects which 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 25 leaf to the other or from a treated leaf to an untreated leaf. Examples of the classes of insect pests which may be systemically controlled by the compounds of the invention include the Homoptera order (piercing-sucking), Hemiptera order (piercing-sucking), and Thvsanoptera order. The invention is especially appropriate for aphids and thrips. 30 As is evident from the foregoing pesticidal uses, the present invention provides pesticidally active compounds and methods of use of said compounds for the control of a number of pest species which includes: arthropods, especially insects or mites; plant nematodes; or helminth or protozoan pests. The compounds of formula (I) or pesticidally acceptable salts thereof thus are 35 advantageously employed in practical uses, for example, in agricultural or Printed from Mimosa 06/24/1999 10:48:06 page -21- 336420 -20- horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health. From this point forward, whenever the term "compounds of formula (I)" is 5 used this term embraces compounds of formula (I) and their pesticidally acceptable salts. The term "compound of formula (I)" embraces a compound of formula (I) and a pesticidally acceptable salt thereof. The present invention therefore provides a method of control of pests at a locus which comprises the treatment of the locus (e.g., by application or 10 administration) with an effective amount of a 1-arvlpyrazole of formula (I) as hereinbefore defined or a pesticidally acceptable salt of a 1-arylpyrazole of formula (I) with the exclusion of 1-arylpyrazoles of formula (I) in which: R, is haloalkyl; and Z is hydrogen, lH-pyrrol-l-yl, amino or R^NH - in which R* is formyl, 15 alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl containing 3 to 6 carbon atoms or -C(O) alkyl wherein the alkyl portion is optionally substituted by one or more R, in which R, is halogen; and the other symbols are as hereinbefore defined. The locus includes, for example, the pest itself or the place (plant, animal, field, structure, premises, forest, orchard, 20 waterway, soil, plant or animal product, or the like) where the pest resides or feeds. The compounds of this invention may in addition be used to control soil insects, such as com rootworm, termites (especially for protection, of structures), root maggots, wireworms, root weevils, stalkborers, cutworms, root aphids, or grubs. They may also be used to provide activity against plant pathogenic nematodes, such 25 as root-knot, cyst, dagger, lesion, or stem or bulb nematodes, or against mites. For the control of soil pests, for example corn rootworm, the compounds are advantageously applied to or incorporated at an effective rate into the soil in which crops are planted or to be planted or to the seeds or growing plant roots. In the area of public health, the compounds are especially useful in the 30 control of many insects, especially filth flies or other Dipteran pests, such as houseflies, stableflies, soldierflies, homflies, deerflies, horseflies, midges, punkies, blackflies, or mosquitoes. Compounds of the invention may be used in the following applications and on the following pests including arthropods, especially insects or mites, nematodes, 35 or helminth or protozoan pests. intellectual property office of n.z. 2 4 JAN 2001 I R F r IT l er r» 33 6 420 In the protection of stored products, for example cereals, including grain "or flour, groundnuts, animal feedstuffs, timber or household goods, e.g. carpets and textiles, compounds of the invention are useful against attack by arthropods, more especially beetles, including weevils, moths or mites, for example Ephestia spp. (flour moths), Anthrenus spp. (carpet beetles), Tribolium spp. (flour beetles), Sitophilus spp. (grain weevils) or Acarus spp. (mites). intellectual property office of n.z. 2 4 JAN 2001 RECEIVED WO 98/28279 PCT/EP97/07116 -21- In the control of cockroaches, ants or termites or similar arthropod pests in infested domestic or industrial premises or in the control of mosquito larvae in waterways, wells, reservoirs or other running or standing water. For the treatment of foundations, structures or soil in the prevention of the attack on building by termites, for example, Reticulitermes spp., Heterotermes spp., Coptotermes spp.. In agriculture against adults, larvae and eggs of Lepidoptera (butterflies and moths), e.g. Heliothis spp. such as Heliothis virescens (tobacco budworm), Heliothis armigera and Heliothis zea. Against adults and larvae of Coleoptera (beetles) e.g. Anthonomus spp. e.g. erandis (cotton boll weevil), Leptinotarsa decemlineata (Colorado potato beetle), Diabrotica spp. (corn rootworms). Against Heteroptera (Hemiptera and Homoptera) e.g. Psvlla spp., Bemisia spp., Trialeurodes spp., Aphis spp., Mvzus spp., Megoura viciae. Phylloxera spp., Nephotettix spp. (rice leaf hoppers), Nilaparvata spp.. Against Diptera e.g. Musca spp.. Against Thysanoptera such as Thrips tabaci. Against Orthoptera such as Locusta and Schistocerca spp., (locusts and crickets) e.g. Grvllus spp., and Acheta spp. for example, Blatta orientalis. Periplaneta americana. Blatella germanica. Locusta migratoria migratorioides. and Schistocerca gregaria. Against Collembola e.g. Periplaneta spp. and Blattela spp. (roaches). Against Isoptera e.g. Coptotermes spp. (termites). Against arthropods of agricultural significance such as Acari (mites) e.g. Tetranvchus spp., and Panonvchus spp.. Against nematodes which attack plants or trees of importance to agriculture, forestry or horticulture either directly or by spreading bacterial, viral, mycoplasma or fungal diseases of the plants. For example root-knot nematodes such as Meloidogvne spp. (e.g. M. incognita). In the field of veterinary medicine or livestock husbandry or in the maintenance of public health against arthropods, helminths or protozoa which are parasitic internally or externally upon vertebrates, particularly warm-blooded vertebrates, for example domestic animals, e.g. cattle, sheep, goats, equines, swine, poultry, dogs or cats, for example Acarina. including ticks (e.g. Ixodes spp., Boophilus spp. e.g. Boophilus microplus. Rhipicephalus spp. e.g. Rhipicephalus appendiculatusOrnithodorus spp. (e.g. Omithodorus moubata) and mites (e.g. Damalinia spp.); Diptera (e.g. Aedes spp., Anopheles spp., Musca spp., Hvpoderma spp.); Hemiptera.: Dictvoptera (e.g. Periplaneta spp., Printed from Mimosa 06/24/1999 10:48:06 page -23- WO 98/28279 PCT/EP97/07116 -22- Blatella spp.); Hvmenoptera: for example against infections of the gastrointestinal tract caused by parasitic nematode worms, for example members of the family Trichostrongvlidae: in the control and treatment of protozoal diseases caused by, for example, Eimeria spp. e.g. Trvpanosoms cruzi, Leishaminia spp., 5 Plasmodium spp., Babesis spp., Trichomonadidae spp., Toxoplasma spp. and Theileria spp.. In practical use for the control of arthropods, especially insects or mites, or nematode pests of plants, a method, for example, comprises applying to the plants or to the medium in which they grow an effective amount of a compound 10 of the invention. For such a method, the active compound is generally applied to the locus in which the arthropod or nematode infestation is to be controlled at an effective rate in the range of about 5 g to about 1 kg of the active compound per hectare of locus treated. Under ideal conditions, depending on the pest to be controlled, a lower rate may offer adequate protection. On the other hand, 15 adverse weather conditions, resistance of the pest or other factors may require that the active ingredient be used at higher rates. The optimum rate depends usually upon a number of factors, for example, the type of pest being controlled, the type or the growth stage of the infested plant, the row spacing or also the method of application. More preferably an effective rate range of the active 20 compound is from about 50g/ha to about 400 g/ha. When a pest is soil-bome, the active compound generally in a formulated composition, is distributed evenly over the area to be treated (ie, for example broadcast or band treatment) in any convenient manner and is applied at rates from about 5 g to about 1kg ai/ha, preferably from about 50 to about 250 g ai/ha. 25 When applied as a root dip to seedlings or drip irrigation to plants the liquid solution or suspension contains from about 0.075 to about 1000 mg ai/1, preferably from about 25 to about 200 mg ai/1. Application may be made, if desired, to the field or crop-growing area generally or in close proximity to the seed or plant to be protected from attack. The active component can be washed 30 into the soil by spraying with water over the area or can be left to the natural action of rainfall. During or after application, the formulated compound can, if desired, be distributed mechanically in the soil, for example by ploughing, disking, or use of drag chains. Application can be prior to planting, at planting, after planting but before sprouting has taken place, or after sprouting. Printed from Mimosa 06/24/1999 10:48:06 page -24- WO 98/28279 PCT/EP97/07116 -23- The compounds of the invention and methods of control of pests therewith are of particular value in the protection of field, forage, plantation, glasshouse, orchard or vineyard crops, of ornamentals, or of plantation or forest trees, for example: cereals (such as wheat or rice), cotton, vegetables (such as 5 peppers), field crops (such as sugar beets, soybeans or oil seed rape), grassland or forage crops (such as maize or sorghum), orchards or groves (such as of stone or pit fruit or citrus), ornamental plants, flowers or vegetables or shrubs under glass or in gardens or parks, or forest trees (both deciduous and evergreen) in forests, plantations or nurseries. 10 They are also valuable in the protection of timber (standing, felled, converted, stored or structural) from attack, for example, by sawflies or beetles or termites. They have applications in the protection of stored products such as grains, fruits, nuts, spices or tobacco, whether whole, milled or compounded into 15 products, from moth, beetle, mite or grain weevil attack. Also protected are stored animal products such as skins, hair, wool or feathers in natural or converted form (e.g. as carpets or textiles) from moth or beetle attack as well as stored meat, fish or grains from beetle, mite or fly attack. Additionally, the compounds of the invention and methods of use thereof are of 20 particular value in the control of arthropods, helminths or protozoa which are injurious to, or spread or act as vectors of diseases domestic animals, for example those hereinbefore mentioned, and more especially in the control of ticks, mites, lice, fleas, midges, or biting, nuisance or myiasis flies. The compounds of the invention are particularly useful in controlling arthropods, 25 helminths or protozoa which are present inside domestic host animals or which feed in or on the skin or suck the blood of the animal, for which purpose they may be administered orally, parenterally, percutaneously or topically. Furthermore, compounds of the invention may be useful for coccidiosis, a disease caused by infections from protozoan parasites of the genus Eimeria. It 30 is an important potential cause of economic loss in domestic animals and birds, particularly those raised or kept under intensive conditions. For example, cattle, sheep, pigs or rabbits may be affected, but the disease is especially important in poultry, particularly in chickens. Administration of a small amount of a compound of the invention, preferably by a combination with feed is effective in 35 preventing or greatly reducing the incidence of coccidiosis. The compounds are Printed from Mimosa 06/24/1999 10:48:06 page -25- WO 98/28279 PCT/EP97/07116 -24- effective against both the cecal form and the intestinal forms. Furthermore, the compounds of the invention may also exert an inhibiting effect on oocytes by greatly reducing the number and sporulation of those produced. The poultry disease is generally spread by the birds picking up the infectious organism in 5 droppings in or on contaminated litter, ground, food, or drinking water. The disease is manifested by hemorrhage, accumulation of blood in the ceca, passage of blood to the droppings, weakness and digestive disturbances. The disease often terminates in the death of the animal, but the fowl which survive severe infections have had their market value subtantially reduced as a result of the 10 infection. The compositions hereinafter described for application to growing crops or crop growing loci or as a seed dressing may, in general, alternatively be employed for topical application to animals or in the protection of stored products, household goods, property or areas of the general environment. 15 Suitable means of applying the compounds of the invention include: to growing crops as foliar sprays, dusts, granules, fogs or foams or also as suspensions of finely divided or encapsulated compositions as soil or root treatments by liquid drenches, dusts, granules, smokes or foams; to seeds of crops via application as seed dressings by liquid slurries or dusts; 20 to animals infested by or exposed to infestation by arthropods, helminths or protozoa, by parenteral, oral or topical application of compositions in which the active ingredient exhibits an immediate and/or prolonged action over a period of time against the arthropods, helminths or protozoa, for example by incorporation in feed or suitable orally-ingestible pharmaceutical formulations, 25 edible baits, salt licks, dietary supplements, pour-on formulations, sprays, baths, dips, showers, jets, dusts, greases, shampoos, creams, wax smears or livestock self-treatment systems; to the environment in general or to specific locations where pests may lurk, including stored products, timber, household goods, or domestic or 30 industrial premises, as sprays, fogs, dusts, smokes, wax-smears, lacquers, granules or baits, or in tricklefeeds to waterways, wells, reservoirs or other running or standing water; to domestic animals in feed to control fly larvae feeding in their feces; In practice, the compounds of the invention most frequently form parts of 35 compositions. These compositions can be employed to control: arthopods, Printed from Mimosa 06/24/1999 10:48:06 page -26- especially insects or mites; nematodes; or helminth or protozoan pests. The compositions may be of any type known in the art suitable for application to the desired pest in any premises or indoor or outdoor area or by internal or external administration to vertebrates. These compositions contain at least one compound of formula (I) or a pesticidally acceptable salt thereof, such as described earlier, as the active ingredient in combination or association with one or more other compatible components which are for example, solid or liquid carriers or diluents, adjuvants, surface-active-agents, or the like appropriate for the intended use and which are agronomically or medicinally acceptable. These compositions, which may be prepared by any manner known in the art, likewise form a part of this invention. The present invention accordingly provides a pesticidal composition comprising a pesticidally effective amount of a 1-arylpyrazole of formula (I) as hereinbefore defined or a pesticidally acceptable salt of a 1 -arylpyrazole of formula (I); with the exclusion of 1-arylpyrazoles of formula (I) in which: Rs is haloalkyl; and Z is hydrogen, lH-pyrroI-l-yl, amine or RgMH - in which Rg is formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl containing 3 to 6 carbon atoms or -C(O) alkyl wherein the alkyl portion is optionally substituted by one or more R, in which R9 is halogen; and the other symbols are as hereinbefore defined. These compositions may also contain other kinds of ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, spray oils (especially for acardical use), stabilizers, preservative agents (especially mold preservative), sequestering agents, or the like, as well as other known active ingredients with pesticidal properties (particularly insecticidal, miticidal, nematicidal, or fungicidal) or with properties regulating the growth of plants. More generally, the compounds employed in the invention may be combined with all the solid or liquid additives corresponding to the usual techniques of formulation. Compositions, suitable for applications in agriculture, horticulture, or the like include formulations suitable for use as, for example, sprays, dusts, granules, fogs, foams, emulsions, or the like. The effective use doses of the compounds employed in the invention can vary within wide limits, particularly depending on the nature of the pest to be eliminated or degree of infestation, for example, of crops with these pests. In general, the intellectual property office of n.z. 2 k JAN 2001 25a 33 0 (followed by page 26) compositions according to the invention usually contain about 0.05 to about 95% (by weight) of one or more active ingredients according to the invention, about 1 to about 95% of one or more solid or liquid carriers and, optionally, about 0.1 to about 50% of one or more other compatible components, such as surface-active agents or the like. In the present account, 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, to seeds or to the soil. This intellectual PROPERTY office of n.z. 2 4 JAN 2001 RECEIVED WO 98/28279 PCT/EP97/07U6 -26- carrier is therefore generally inert and it must be acceptable (for example, agronomically acceptable, particularly to the treated plant). The carrier may be a solid, for example, clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers (for example ammonium salts), 5 ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceous earth, or ground synthetic minerals, such as silica, alumina, or silicates especially aluminium or magnesium silicates. As solid carriers for granules the following are suitable: crushed or fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite; synthetic 10 granules of inorganic or organic meals; granules of organic material such as sawdust, coconut shells, corn cobs, corn husks or tobacco stalks; kieselguhr, tricalcium phosphate, powdered cork, or absorbent carbon black; water soluble polymers, resins, waxes; or solid fertilizers. Such solid compositions may, if desired, contain one or more compatible wetting, dispersing, emulsifying or 15 colouring agents which, when solid, may also serve as a diluent. The canier may also be liquid, for example: water; alcohols, particularly butanol or glycol, as well as their ethers or esters, particularly methylglycol acetate; ketones, particularly acetone, cyclohexanone, methylethyl ketone, methylisobutylketone, or isophorone; petroleum fractions such as paraffinic or 20 aromatic hydrocarbons, particularly xylenes or alkyl naphthalenes; mineral or vegetable oils; aliphatic chlorinated hydrocarbons, particularly trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons, particularly chlorobenzenes; water-soluble or strongly polar solvents such as dimethylformamide, dimethyl sulphoxide, or N-methylpyrrolidone; liquefied 25 gases; or the like or a mixture thereof. The surface-active agent may be an emulsifying agent, dispersing agent or wetting agent of the ionic or non-ionic type or a mixture of such surface-active agents. Amongst these are e.g., salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, 30 polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty esters or fatty amines, substituted phenols (particularly alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (particularly alkyltaurates), phosphoric esters of alcohols or of polycondensates of ethylene oxide with phenols, esters of fatty acids with polyols, or sulphate, sulphonate or 35 phosphate functional derivatives of the above compounds. The presence of at Printed from Mimosa 06/24/1999 10:48:06 page -28- WO 98/28279 PCT/EP97/07116 -27- least one surface-active agent is generally essential when the active ingredient and/or the inert carrier are only slightly water soluble or are not water soluble and the carrier agent of the composition for application is water. Compositions of the invention may further contain other additives such 5 as adhesives or colorants. Adhesives such as carboxymethylcellulose or natural or synthetic polymers in the form of powders, granules or lattices, such as arabic gum, 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 colorants such as inorganic pigments, for 10 example: iron oxides, titanium oxides or Prussian Blue; organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs; or trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc. Compositions containing compounds of formula (I), or pesticidally 15 acceptable salts thereof, which may be applied to control arthropod, plant nematode, helminth or protozoan pests, may also contain synergists (e.g. piperonyl butoxide or sesamex), stabilizing substances, other insecticides, acaricides, plant nematocides, anthelmintics or anticoccidials, fungicides (agricultural or veterinary as appropriate, e.g. benomyl and iprodione), 20 bactericides, arthropod or vertebrate attractants or repellents or pheromones, deodorants, flavouring agents, dyes, or auxiliary therapeutic agents, e.g. trace elements. These may be designed to improve potency, persistence, safety, uptake where desired, spectrum of pests controlled or to enable the composition to perform other useful functions in the same animal or area treated. 25 Examples of other pesticidally-active compounds which may be included in, or used in conjunction with the compositions of the present invention are: acephate, chlorpyrifos, demeton-S-methyl, disulfoton, ethoprofos, fenitrothion, fenamiphos, fonofos, isazophos, isofenphos, malathion, monocrotophos, parathion, phorate, phosalone, pirimiphos-methyl, terbufos, triazophos, 30 cyfluthrin, cypermethrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, tefluthrin, aldicarb, carbosulfan, methomyl, oxamyl, pirimicarb, bendiocarb, teflubenzuron, dicofol, endosulfan, lindane, benzoximate, cartap, cyhexatin, tetradifon, avermectins, ivermectins, milbemycins, thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole. Printed from Mimosa 06/24/1999 10:48:06 page -29- WO 98/28279 PCT/EP97/07116 -28- For their agricultural application, the compounds of the formula (I), or pesticidally acceptable salts thereof, are therefore generally in the form of compositions, which are in various solid or liquid forms. Solid forms of compositions which can be used are dusting powders 5 (with a content of the compound of formula (I), or a pesticidally acceptable salt thereof, ranging up to 80%), wettable powders or granules (including water dispersible granules), particularly those obtained by extrusion, compacting, impregnation of a granular carrier, or granulation starting from a powder (the content of the compound of formula (I), or a pesticidally acceptable salt thereof, 10 in these wettable powders or granules being between about 0.5 and about 80%). Solid homogenous or heterogenous compositions containing one or more compounds of formula (I), or pesticidally acceptable salts thereof, for example granules, pellets, briquettes or capsules, may be used to treat standing or running water over a period of time. A similar effect may be achieved using trickle or 15 intermittent feeds of water dispersible concentrates as described herein. Liquid compositions, for example, include aqueous or non-aqueous solutions or suspensions (such as emulsifiable concentrates, emulsions, flowables, dispersions, or solutions) or aerosols. Liquid compositions also include, in particular, emulsifiable concentrates, dispersions, emulsions, 20 flowables, aerosols, wettable powders (or powder for spraying), dry flowables or pastes as forms of compositions which are liquid or intended to form liquid compositions when applied, for example as aqueous sprays (including low and ultra-low volume) or as fogs or aerosols. Liquid compositions, for example, in the form of emulsifiable or soluble 25 concentrates most frequently comprise about 5 to about 80% by weight of the active ingredient, while the emulsions or solutions which are ready for application contain, in their case, about 0.01 to about 20% of the active ingredient. Besides the solvent, the emulsifiable or soluble concentrates may contain, when required, about 2 to about 50% of suitable additives, such as 30 stabilizers, surface-active agents, penetrating agents, corrosion inhibitors, colorants or adhesives. Emulsions of any required concentration, which are particularly suitable for application, for example, to plants, may 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 Printed from Mimosa 06/24/1999 10:48:06 page -30- WO 98/28279 PCT/EP97/07116 -29- invention. The emulsions may be in the form of water-in-oil or oil-in-water type and they may have a thick consistency. The liquid compositions of this invention may, in addition to normal agricultural use applications be used for example to treat substrates or sites 5 infested or liable to infestation by arthropods (or other pests controlled by compounds of this invention) including premises, outdoor or indoor storage or processing areas, containers or equipment or standing or running water. All these aqueous dispersions or emulsions or spraying mixtures can be applied, for example, to crops by any suitable means, chiefly by spraying, at rates 10 which are generally of the order of about 100 to about 1,200 liters of spraying mixture per hectare, but may be higher or lower (eg. low or ultra-low volume) depending upon the need or application technique. The compounds or compositions according to die invention are conveniently applied to vegetation and in particular to roots or leaves having pests to be eliminated. Another 15 method of application of the compounds or compositions according to the invention is by chemigation, that is to say, the addition of a formulation containing the active ingredient to irrigation water. This irrigation may be sprinkler irrigation for foliar pesticides or it can be ground irrigation or underground irrigation for soil or for systemic pesticides. 20 The concentrated suspensions, which can be applied by spraying, are prepared so as to produce a stable fluid product which does not settle (fine grinding) and usually contain from about 10 to about 75% by weight of active ingredient, from about 0.5 to about 30% of surface-active agents, from about 0.1 to about 10% of thixotropic agents, from about 0 to about 30% of suitable 25 additives, such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrating agents, adhesives and, as the carrier, water or an organic liquid in which the active ingredient is poorly soluble or insoluble Some organic solids or inorganic salts may be dissolved in the carrier to help prevent settling or as antifreezes for water. 30 The wettable powers (or powder for spraying) are usually prepared so that they contain from about 10 to about 80% by weight of active ingredient, from about 20 to about 90% of a solid carrier, from about 0 to about 5% of a wetting agent, from about 3 to about 10% of a dispersing agent and, when necessary, from about 0 to about 80% of one or more stabilizers and/or other 35 additives, such as penetrating agents, adhesives, anti-caking agents, colorants, or Printed from Mimosa 05/24/1999 10:48:06 page -31- WO 98/28279 PCT/EP97/07116 -30- the like. To obtain these wettable powders, the active ingredient(s) is(are) thoroughly mixed in a suitable blender with additional substances which may be impregnated on the porous filler and is(are) ground using a mill or other suitable grinder. This produces wettable powders, the wettability and the suspendability 5 of which are advantageous. They may be suspended in water to give any desired concentration and this suspension can be employed very advantageously in particular for application to plant foliage. The "water dispersible granules (WG)" (granules which are readily dispersible in water) have compositions which are substantially close to that of 10 the wettable powders. They may be prepared by granulation of formulations described for the wettable powders, either by a wet route (contacting finely divided active ingredient with the inert filler and a little water, e.g. 1 to 20% by weight, or with an aqueous solution of a dispersing agent or binder, followed by drying and screening), or by a dry route (compacting followed by grinding and 15 screening). The rates and concentrations of the formulated compositions may vary according to the method of application or the nature of the compositions or use thereof. Generally speaking, the compositions for application to control arthropod, plant nematode, helminth or protozoan pests usually contain from 20 about 0.00001% to about 95%, more particularly from about 0.0005% to about 50% by weight of one or more compounds of formula (I), or pesticidally acceptable salts thereof, or of total active ingredients (that is to say the compound of formula (I), or a pesticidally acceptable salt thereof, together with: other substances toxic to arthropods or plant nematodes, anthelmintics, 25 anticoccidials, synergists, trace elements or stabilizers). The actual compositions employed and their rate of application will be selected to achieve the desired effect(s) by the farmer, livestock producer, medical or veterinary practitioner, pest control operator or other person skilled in the art. Solid or liquid compositions for application topically to animals, timber, 30 stored products or household goods usually contain from about 0.00005% to about 90%, more particularly from about 0.001% to about 10%, by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof. For administration to animals orally or parenterally, including percutaneously solid or liquid compositions, these normally contain from about 0.1% to about 90% by 35 weight of one or more compounds of formula (I) or pesticidally acceptable salts Printed from Mimosa 06/24/1999 10:48:06 page -32- 10 15 20 • » 30 thereof. Medicated feedstuffs normally contain from about 0.001% to about 3% by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof. Concentrates or supplements for mixing with feedstuffs normally contain from about 5% to about 90%, preferably from about 5% to about 50%, by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof. Mineral salt licks normally contain from about 0.1% to about 10% by weight of one or more compounds of formula (I) or pesticidally acceptable salts thereof. Dusts or liquid compositions for application to livestock, goods, premises or outdoor areas may contain from about 0.0001% to about 15%, more especially from about 0.005% to about 2.0%, by weight, of one or more compounds of formula (I) or pesticidally acceptable salts thereof. Suitable concentrations in treated waters are between about 0.0001 ppm and about 20 ppm, more particularly about 0.001 ppm to about 5.0 ppm, of one or more compounds of formula (I), or pesticidally acceptable salts thereof, and may be used therapeutically in fish farming with appropriate exposure times. Edible baits may contain from about 0.01% to about 5%, preferably from about 0.01% to about 1.0%, by weight, of one or more compounds of formula (I) or pesticidally acceptable salts thereof. When administered to vertebrates parenterally, orally or by percutaneous or other means, the dosage of compounds of formula (I), or pesticidally acceptable salts thereof, will depend upon the species, age, or health of the vertebrate and upon the nature and degree of its actual or potential infestation by arthropod, helminth or protozoan pests. A single dose of about 0.01 to about 100 mg, preferably about 2.0 to about 20.0 mg, per kg body weight of the animal or doses of about 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg, per kg body weight of the animal per day, for sustained medication, are generally suitable by oral or parenteral administration. By use of sustained release fonnulations or devices, the daily doses required over a period of months may be combined and administered to animals on a single occasion. The invention accordingly also provides a method for controlling pests of a vertebrate animal which method comprises administering to the animal a 1-arylpyrazole of formula (I) as hereinbefore defined or a pesticidally acceptable salt thereof in a single dose of 0.1 to 100 mg per kg body weight of the animal or in doses of 0.01 to 20 mg per kg body weight of the animal per day. The following composition EXAMPLES 2A - 2M illustrate compositions for use against arthropods, especially mites or insects, plant nematodes, or helminth or intellectual property office of n.z. 2 4 JAN 2001 3U 33 6 420 protozoan pests which comprise, as active ingredient, compounds of formula (I), or pesticidally acceptable sajts thereof, such as those described in preparative examples. The compositions described in EXAMPLES 2A - 2M can intellectual property office of n.z. 2 k JAN 2001 RECEIVED WO 98/28279 PCT/EP97/07116 -32- each be diluted to give a sprayable compositon at concentrations suitable for use in the field. Generic chemical descriptions of the ingredients (for which all of the following percentages are in weight percent), used in the composition EXAMPLES 2A - 2M exemplified below, are as follows: Trade Name Chemical Description Ethylan BCP Nonylphenol ethylene oxide condensate Soprophor BSU Tristyrylphenol ethylene oxide condensate Arylan CA A 70% w/v solution of calcium dodecylbenzenesulfonate Solvesso 150 Light Cio aromatic solvent Arylan S Sodium dodecylbenzenesulfonate Darvan No2 Sodium lignosulphonate CelitePF Synthetic magnesium silicate carrier Sopropon T36 Sodium salts of polycarboxylic acids Rhodigel 23 Polysaccharide x an than gum Bentone 38 Organic derivative of magnesium montmorillonite Aerosil Microfine silicon dioxide EXAMPLE 2A A water soluble concentrate is prepared with the composition as follows: Active ingredient 7% Ethylan BCP 10% N-methylpyrrolidone 83% 10 To a solution of Ethylan BCP dissolved in a portion of N-methylpyrrolidone is added the active ingredient with heating and stirring until dissolved. The resulting solution is made up to volume with the remainder of the solvent. 15 EXAMPLE 2B An emulsifiable concentrate (EC) is prepared with the composition as follows: Printed from Mimosa 06/24/1999 10:48:06 page -34- WO 98/28279 PCT/EP97/07116 -33- Active ingredient 25%(max) Soprophor BSU 10% Arylan CA 5% N-methylpyrrolidone 50% Solvesso 150 10% The first three components are dissolved in N-methylpyrrolidone and to this is then added the Solvesso 150 to give the final volume. EXAMPLE 2C 5 A wettable powder (WP) is prepared with the composition as follows: •o Active ingredient 40% Arylan S 2% Darvan No2 5% Celite PF 53% The ingredients are mixed and ground in a hammer-mill to a powder with a particle size of less than 50 microns. 10 EXAMPLE 2D An aqueous-flowable formulation is prepared with the composition as follows: Active ingredient 40.00% Ethylan BCP 1.00% Sopropon T360. 0.20% Ethylene glycol 5.00% Rhodigel 230. 0.15% Water 53.65% 15 The ingredients are intimately mixed and are ground in a bead mill until a mean particle size of less than 3 microns is obtained. EXAMPLE 2E Printed from Mimosa 06/24/1999 10:48:06 page -35- WO 98/28279 PCT/EP97/07116 -34- An emulsifiable suspension concentrate is prepared with the composition as follows: Active ingredient 30.0% Ethylan BCP 10.0% Bentone 38 0.5% Solvesso 150 59.5% The ingredients are intimately mixed and ground in a beadmill until a mean particle size of less than 3 microns is obtained. EXAMPLE 2F A water dispersible granule is prepared with the composition as follows: Active ingredient 30% DarvanNo2 15% Arylan S 8% Celite PF 47% The ingredients are mixed, micronized in a fluid-energy mill and then granulated in a rotating pelletizer by spraying with water (up to 10%). The resulting granules are dried in a fluid-bed drier to remove excess water. EXAMPLE 2G A dusting powder is prepared with the composition as follows: Active ingredient 1 to 10% Talc powder-superfine 99 to 90% The ingredients are intimately mixed and further ground as necessary to 20 achieve a fine powder. This powder may be appplied to a locus of arthropod infestation, for example refuse dumps, stored products or household goods or animals infested by, or at risk of infestation by, arthropods to control the arthropods by oral ingestion. Suitable means for distributing the dusting powder to the locus of arthropod infestation include mechanical blowers, handshakers or 25 livestock self treatment devices. Printed from Mimosa 06/24/1999 10:48:06 page -36- WO 98/28279 PCT/EP97/07116 -35- EXAMPLE 2H An edible bait is prepared with the composition as follows: Active ingredient 0.1 to 1.0% Wheat flour 80% Molasses 19.9 to 19% The ingredients are intimately mixed and formed as required into a bait form. This edible bait may be distributed at a locus, for example domestic or industrial premises, e.g. kitchens, hospitals or stores, or outdoor areas, infested by arthropods, for example ants, locusts, cockroaches or flies, to control the arthropods by oral ingestion. EXAMPLE 21 A solution formulation is prepared with a composition as follows: Active ingredient 15% Dimethyl sulfoxide 85% The active ingredient is dissolved in dimethyl sulfoxide with mixing and or heating as required. This solution may be applied percutaneously as a pour-on 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 rate of application of from 1.2 to 12 ml of solution per 100 kg of animal body weight EXAMPLE 2J A wettable powder is prepared with the composition as follows: Active ingredient 50% Ethylan BCP 5% Aerosil 5% Celite PF 40% Printed from Mimosa 06/24/1999 10:48:06 page -37- WO 98/28279 PCT/EP97/07116 -36- The Ethylan BCP is absorbed onto the Aerosil which is then mixed with the other ingredients and ground in a hammer-mill to give a wettable powder, which may be diluted with water to a concentration of from 0.001 % to 2% by weight of the active compound and applied to a locus of infestation by 5 arthropods, for example, dipterous larvae or plant nematodes, by spraying, or to domestic animals infested by, or at risk of infection by arthropods, helminths or protozoa, by spraying or dipping, or by oral administration in drinking water, to control the arthropods, helminths or protozoa. EXAMPLE 2K A slow release bolus composition is formed from granules containing the following components in varying percentages(similar to those described for the previous compositions) depending upon need: Active ingredient Density agent Slow-release agent Binder The intimately mixed ingredients are formed into granules which are compressed into a bolus with a specific gravity of 2 or more. This can be administered orally to ruminant domestic animals for retention within the reticulo-rumen to give a continual slow release of active compound over an extended period of time to control infestation of the ruminant domestic animals by arthropods, helminths or protozoa. EXAMPLE 2L A slow release composition in the form of granules, pellets, brickettes or the like can be prepared with compositions as follows: Active ingredient 0.5 to 25% Polyvinyl chloride 75 to 99.5% Dioctyl phthalate (plasticizer) The components are blended and then formed into suitable shapes by melt-extrusion or molding. These composition are useful, for example, for Printed from Mimosa 06/24/1999 10:48:06 page -38- 15 20 25 WO 98/28279 PCT/EP97/07116 10 -37- addition to standing water or for fabrication into collars or eartags for attachment to domestic animals to control pests by slow release. EXAMPLE 2M A water dispersible granule is prepared with the composition as follows: Active ingredient 85%(max) Polyvinylpyrrolidone 5% Attapulgite clay 6% Sodium Iauryl sulfate 2% Glycerine 2% The ingredients are mixed as a 45% slurry with water and wet milled to a particle size of 4 microns, then spray-dried to remove water. While the invention has been described in terms of various preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions and changes can be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention 15 be limited solely by the scope of the following claims, including equivalents thereof. Printed from Mimosa 06/24/1999 10:48:06 page -39- -38- </div>

Claims

<div class="application article clearfix printTableText" id="claims"> CLAIMS 3 0^2 i. A l-axylpyra2ole of the formula (I): P>5S(0), (I) wherein: 5 Rj is H or halogen; each of R2 and R4, which are identical or different, is H, halogen or alkyl; R3 is halogen, haloalkyl, haloalkoxy, or RI0 S(0)m; Rj is lower alkyl, haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; 10 Z is hydrogen, halogen, alkyl, formyl, -C(0)alkyl, haloalkyl, alkenyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, alkoxyalkylideneamino, lH-pyrrol-1-yl, lH-pyrazol-l-yl, amino, R^NH- or R7 Rj N-; each ofR*, R7 and Rs, which are identical or different, is alkyl-S^),,-, formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, 15 alkylthiocarbonyl, or aroyl; or alkyl, alkenyl containing 3 to 6 carbon atoms, or -C(O) alkyl wherein the alkyl and alkenyl portions are optionally substituted by one or more R,; or R7 and Rs are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or intellectual property office of n.z. 2 k JAN 2001 RECEIVED "39" 35 6^ alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or -piperazine ring; R, is cyano, nitro, alkoxy, haloalkoxy, R10S(O)q, -C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -C02H, 5 halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialky laminosulfonyl; R10 is lower alkyl or lower haloalkyl; m, n, p and q are 0,1 or 2; M is C-halo, C-CH3, C-CH,F, C-CHX1, C-N02 orN; or a pesticidally acceptable salt of a compound of formula (I); 10 with the exclusion of 1 -ary lpyrazoles of formula (I) in which: R5 is haloalkyl; and Z is hydrogen, lH-pyrrol-l-yl, amino or R^NH - in which R6 is formyl, alkynyl containing from 3 to 6 carbon atoms, alkoxycarbonyl, alkyl, alkenyl containing 3 to 6 carbon atoms or -C(O) alkyl wherein the alkyl portion is optionally 15 substituted by one or more R$ in which Rg is halogen; and the other symbols are as hereinbefore defined.
2. A compound according to claim 1, wherein R3 is halogen, haloalkyl or haloalkoxy.
3. A compound according to Claim 1 or 2, wherein R$ is alkyl. 20
4. A compound according to Claim 1, 2 or 3 wherein Z is amino, RfiNH- or RjRgN-.
5. A compound according to Claim 1, in which: R, is F, CI, Br or H; R2 and R4 are H: 25 R3 is-CF3, -OCF3, -CHF2, -S(O) mCF3, -CFC12, -CF2C1, -OCF2Cl, -OCFCl2, Cl, Br or F; Rj is methyl or ethyl; Z is H, halogen (F, Cl, Br), C,-C3 alkyl, CrC3 haloalkyl, C2-C3 alkenyl; or amino, -NHR,s or NR7RS, wherein each of R^, R, and R-, which are identical or different, is 30 CrC3 alkyl, C3 alkenyl or -C(O) alkyl wherein the alkyl or alkenyl portions are intellectual property office of n.z. 2 4 JAN 2001 RECEIVPn '33 6 * unsubstituted or substituted with cyano, alkoxy, alkyl-S(0)p-, nitro, alkoxycarbonyl, -C(O) alkyl, aminocarbonyl, alkylaminocarbonyl; dialkylaminocarbonyl, -C02H, hydroxy or halogen (F,C1, Br); and M is CCI, CF, CBr or N.
6. A compound according to Claim 1, in which: 5 is Cl or Br; R2 and R4 are H; R3 is -CF3, -OCF3 or Cl; Rj is methyl or ethyl; Z is H, halogen (F, Cl, Br), CrC3 alkyl, CrC3 haloalkyl, C2-C3 alkenyl; or amino, -10 NHRs or -NR7RS, wherein each of Rs, R7 and RSl which are identical or different, is Ci-C, alkyl, C3, alkenyl or -C(O) alkyl wherein the alkyl or alkenyl portions are unsubstituted or substituted with cyano, alkoxy, alkyl-S(0)p-, nitro, alkoxycarbonyl, -C(0)alkyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, -C02H, hydroxy or halogen (F, Cl, Br); and M is CCI, CBr or N. 15
7. A compound according to Claim 1, in which: Rt is Cl or Br; R2 and R«, are H; R3 is -CFj, -OCF, or Cl; Rj is methyl or ethyl; 20 Z is H or amino; and M is CCI, CBr orN.
8. A compound according to claim 1, in which: Rj is Cl or Br; R2 and R« are H; 25 R3 is -CF3, -OCF3 or Cl; Rj is methyl or ethyl; Z is H or amino; and - - < ■ ■ * "' ■ " M is CCI, CBr or N.
9. A compound according to Claim 1, wherein the 1-aryl group is: 30 2,6-dichloro-4-trifluoromethylphenyl; 2,6-dichloro-4-trifluoromethoxyphenyl; 2- intellectual property office of n.z. 2 k JAN 2001 ■33 0 -41- bromo-6-chloro-4-trifluoromethylphenyl; 2-bromo-6-chloro-4-trifluoromethoxyphenyl; 2,6-difluoro-4-trifluoromethylphenyl; 2-chloro-4-trifluoromethylphenyl; 2,6-dichloro-3-methyl-4-trifluoromethylphenyl; 3-chloro-5-trifluoromethyl-2-pyridinyl; 3-chloro-5-trifluoromethoxy-2-pyridinyl; 3,5-dichloro-2-pyridinyl; 2,6-dichioro-4-bromophenyI; 2,4,6-trichlorophenyl; 2-bromo-6-fluoro-4-difluoromethylphenyl; 2-chloro-6-fluoro-4-trifluoromethylphenyI; 2,6-dibromo-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethoxyphenyl; or 2-bromo-4-tn fluor omethy Ipheny 1.
10. A compound according to claim 1, wherein Z is acetylamino, amino, 2-n-butoxypropionylamino, methyl, hydroxyacetylamino, ethyl, 3-ethylsulfmylpropylammo, bromo, formylamino, chloro, methylamino, ethylamino, 2-hydroxyethylamino, 2-methoxyethylamino, methylsulfonylamino, 2-ethylsulfonylethylamino, 4-methoxybenzoylamino, 2-cyanoethylamino, 4-methoxybenzylamino, 2-methylthioethylamino, 2-aminocaxbonyIethylamino, 2-methylsulfinylethylamino, 3-ms'hoxycarbonylpropylamino, 2-ethylsulfinylethylamino, 2-methylsulfonylethylamino, cyanomethylamino, 2-ethylthioethylammo, aminocarbonylmethylamino, dimethylamino, 2-nitroethylamino, 2-acetyIethylamino, methylcarbonylmethylamino, methoxycarbonylamino, or ethoxycarbonylamino.
11. A compound according to Claim 1, wherein -S(O) nRs is methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl or isopropylthio.
12. A compound of formula (I) according to Claim 1, which is: 5-amino-1 -(2,6-dichloro-4-trifluoromethylphenyl)-4-methylthiopyrazole-3-thiocarboxamide; 5-amino-l-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylsulfinylpyTazole-3-thiocarboxamide; 5-amino-l-(2,6-dichIoro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide; intellectual property office of n.z. 2 4 JAN 2001 RECEIVED 336 42 5-amino-1 -(2-bromo-6-chloro-4-trifluoromethylphenyl)-4-methylsulfinylpyrazole-3-thiocarboxainide; 5-amino-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide; 5 5-amino-l-(2.6-dichloro-4-trifluoromethyphenyl)-4-ethylsulfinyIpyrazole-3-thiocarboxamide; 5-amino-l-(2-chloro-4-txi fluoromethylphenyl)-4-methylsulfinylpyrazole-3-thiocarboxamide.; 5 -amino-1 -(2-bromo-6-chloro-4-trifluoromethylphenyl)-4-ethylsulfinylpyrazole-3-10 thiocaxboxamide; or 5-ammo-l-(2,6-dichIoro-4-trifluoromethoxyphenyl)-4-ethylsulfinylpyrazole-3-thiocarboxamide.
13. A compound of fonnula (I) as defined in claim 1 which is 5-amino-1 -(2,6-dichloro-4-trifiuoromethylphenyl)-4- 15 trifluoromethylthiopyrazole-3-thiocarboxamide;or 4-dichlorofluoromethylsulfonyl-1 -(2,4,6-trichlorophenyl) pyrazole-3-thiocarboxamide.
14. A pesticidal composition comprising a pesticidally effective amount of a 1-arylpyrazole as claimed in any one of Claims 1 to 13 or a pesticidally 20 acceptable salt of a 1-arylpyrazole of formula (I) as defined in claim 1, in association with an agriculturally acceptable inert carrier thereof.
15. A pesticidal composition according to Claim 14 which contains from about 0.05 to about 95% (by weight) of a compound of fonnula (I).
16. A pesticidal composition according to Claim 14 which contains 25 from about 0.00005 to about 90% (by weight) of a compound of fonnula (I).
17. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a 1-arylpyrazole as claimed in any one of Claims 1 to 13, or a pesticidally acceptable salt of a 1-arylpyrazole of fonnula (I) as defined in claim 1, or a composition according to claim 14, 15, or 16. 30 15.
The method according to Claim 17, wherein said pests are insects. intellectual property ortice of n.z. 2 4 JAN 2001 R E G El V F n -43- <33 6
19. The method according to Claim 17, wherein said insects are sucking insects.
20. The method according tc Claim 17, wherein said locus is a crop area. 5
21. The method according to Claim 17, wherein said compound is applied to said locus at a rate of from about 5g to about 1 kg/ha.
22. The method according to Claim 17, wherein said locus is an animal.
23. The method according to Claim 22, wherein said compound is 10 applied to said locus at a rate of from about 0.1 to 20 mg per kg body weight of the animal per day.
24. A method for controlling pests of a vertebrate animal which method comprises administering to the animal a 1 -arylpyrazole of formula (I) as defined in claim 1 or a pesticidally acceptable jalt thereof in a single dose of 0.1 to 15 100 mg per kg body weight of the animal or in doses of 0.01 to 20 mg per kg body weight of the animal per day.
25. A process for preparing a compound of formula (I) as claimed in Claim lor 13 which comprises: (a) the reaction of a compound of Formula (II): RsS(0)nv. ^CN —r (id 20 wherein R], R2, R3, R», R5, M and Z are as defined in Claim 1, with an alkali or intellectual property office of n.z. 2 4 JAN 2001 R E C E IV F n -44- , alkaline earth metal hydrosulfide; a (b) where Rb R2, R3, R^ R;, M and Z are as defined in Claim 1 and n represents 1 or 2, the oxidation of the corresponding compounds of fonnula (I) in which n represents 0 or 1; 5 (c) where R,, R2, R3, R.- and M are as defined in Claim 1 and Z represents RSNH-wherein R^ represents ethyl substituted at the 2-position by in which R$ represents cyano, nitro, -S(O)qR!0, -C(0)alkyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; the alkylation of the corresponding compound of formula (I) wherein Z is amino with 10 a compound of formula (III): R9 -CH=CH2 (HI) wherein R^ is as defined in Claim 1: (d) where Rh R2, R3, R4, Rj and M are as defined in Claim 1 and Z represents - NHR6 or -NR7R8 wherein R6, R7 and Rs represent alkyl or haloalkyl optionally substituted 15 by one or more R9, the alkylation of the corresponding compound of fonnula (I) wherein Z is amino with a compound of formula (IV): Ru-Y (IV) wherein Rn is alkyl or haloalkyl optionally substituted by one or more R, and Y represents a leaving group; 20 (e) where Z represents alkoxycarbonyl the esterification of the corresponding compound of fonnula (I) in which Z is carboxy with an alcohol of formula (V): Rl2OH (V) wherein R12 is alkyl; (f) where Z represents alkylthiocarbonyl the esterification of the corresponding 25 compound of formula (I) in which X is carboxy with a thiol of fonnula (VI): R12SH (VI) (g) where Z represents Rl3CH(CI)CH2- wherein Ru represents alkyl, the diazotisation of the corresponding compound of formula (I) in which Z represents amino followed by reaction with a compound of formula (VII): 30 R13CH=CH2 (VII) intellectual property 07fice of n.z. 2 4 JAN 2001 RECEIVED -45- 33 It in the presence of a copper salt; (h) where Z represents -C(0)alkyl, the oxidation of the corresponding compound of formula (Vm): RsS(0)n OH I Ru—CH (VIII) 10 wherein Rb R2, R3, Ri, R3 and M are as defined in Claim 1 and R14 represents alkyl; (i) where Z represents Ri3CH=CH- and R13 represents alkyl, the dehydro -chlorination of the corresponding*compound of formula (I) in which Z represents R[3CH(C1)CH2-; optionally followed by the conversion of the compound of formula (I) thus obtained into a pesticidally acceptable salt thereof.
26. A process for preparing a pesticidally acceptable salt of a 1-arylpyrazole of fonnula (I) as defined in claim 1 which comprises the conversion of such a 1-arylpyrazole of formula (I) into a pesticidally acceptable salt thereof.
27. A pesticidal composition according to claim 14 substantially as hereinbefore described.
28. A method as claimed in claim 17 substantially as hereinbefore described.
29. A process as claimed in claim 25 substantially as hereinbefore described. — intellectual property office of n.z. 2 k JAN 2001 </div>