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USRE37936E1 - Pesticidal 1-polyarylpyrazoles - Google Patents

Pesticidal 1-polyarylpyrazoles Download PDF

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Publication number
USRE37936E1
USRE37936E1 US09/903,990 US90399001A USRE37936E US RE37936 E1 USRE37936 E1 US RE37936E1 US 90399001 A US90399001 A US 90399001A US RE37936 E USRE37936 E US RE37936E
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Prior art keywords
alkyl
haloalkyl
formula
independently
halogen
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US09/903,990
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Jamin Huang
Scot Kevin Huber
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Bayer CropScience Inc USA
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Aventis CropScience USA Inc
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Assigned to RHONE-POULENC AG COMPANY INC. reassignment RHONE-POULENC AG COMPANY INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: RHONE-POULENC INC.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/333—Radicals substituted by oxygen or sulfur atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C07D231/40—Acylated on said nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • the invention relates to new 1-arylpyrazoles and derivatives thereof which have some valuable properties either as pesticides or as intermediates to make other pesticides.
  • the invention further pertains to compositions of said compounds and methods, using said compounds either as intermediates to make other pesticides, or for the control of pests particularly insects, in particular to the application of said compounds or compositions in agricultural methods of use or for animal protection, particularly as pesticides, for controlling arthropods.
  • Another object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole 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, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, 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.
  • a fifth objective 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.
  • the invention thus relates to compounds having the general formula (I):
  • X is N or C—R 2 ;
  • Y is N or C—R 3 ;
  • W is N or C—R 4 ;
  • R 2 and R 3 are independently selected from H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO 2 , —S(O) n R 8 , alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, and dialkylaminosulfonyl;
  • R 4 is H, halogen, alkyl, alkoxy, CN, NO 2 , haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH ⁇ N—OH, —CH ⁇ N—O-alkyl. —CH ⁇ N—O-alkyl, —S(NH 2 )( ⁇ NH), —S(O) n R 8 , mercapto, haloalkylcarbonyl, or a —S—radical so that two molecules are bound together to form a disulfide compound;
  • R 5 is hydrogen, halogen, —NR 9 R 10 , —N ⁇ CR 11 R 19 , —S(O) n R 8 , formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, alkyl, haloalkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl;
  • R 8 is alkyl or haloalkyl, alkenyl or alkynyl, or a cycloalkyl ring containing 3 to 5 carbon atoms;
  • R 11 is H, or alkyl
  • R 19 may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino, or R 19 is phenyl, thienyl, pyridyl or furyl, each of which is unsubstituted or substituted with alkyl, haloalkyl, halogen, NO 2 , CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;
  • R 9 and R 10 independent of one another, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R 8 S(O) n , formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or 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; the alkyl portion of R 9 and R 10 may be substituted by R 7 ;
  • R 7 is cyano, nitro, alkoxy, haloalkoxy, R 8 S(O) n , —C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO 2 H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
  • Z is N or C—R 16 ;
  • n zero, one or two;
  • R 12 , R 13 , R 15 , R 16 are independently selected from hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;
  • R 22 , R 23 , R 24 , R 25 , R 26 are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF 5 , R 8 S(O) n ; preferably R 24 is halogen, haloalkyl or haloalkoxy; or R 22 and R 23 or R 23 and R 24 or R 25 and R 26 may also be together a divinylidene group (—CH ⁇ CH—CH ⁇ CH—) or a methylene diether (—O—CH 2 —O—) or halomethylene diether (—O—CF 2 —O—), so as to form a cyclic ring vicinal to the phenyl ring; or pesticidally acceptable salts
  • 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 suitably acidic group include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts.
  • lower alkyl-S(O) n means a radical of the formula —S(O) n — lower alkyl.
  • R 10 S(O) n means a radical of the formula —S(O) n R 10 .
  • aminocarbonyl means a carbamoyl radical, that is, a radical of the formula —C(O)NH 2 .
  • alkylaminocarbonyl means an alkylcarbomoyl alkylcarbamoyl radical, that is, a radical of the formula —C(O)—NH-alkyl; and the term “dialkylaminocarbonyl” means a dialkylcarbamoyl radical, that is, a radical of the formula —C(O)—N(alkyl) 2 in which the alkyl moieties can be the same or different.
  • aminonosulfonyl means a sulfamoyl radical, that is, —SO 2 NH 2 .
  • alkylaminosulfonyl means an alkylsulfamoyl radical, that is, a radical of the formula —SO 2 NH-alkyl; while the term “dialkylaminosulfonyl” means a dialkylsulfamoyl radical, which has the formula —SO 2 N(alkyl) 2 wherein the alkyl moieties can be the same or different.
  • halo before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br, or I, in any combination, preferably by F or Cl.
  • halogen means F, Cl, Br or I.
  • lower before the name of a radical having a carbon skeleton means that this carbon skeleton has less than 6 carbon atoms. When the name of any substituent is repeated, it keeps the same meaning unless otherwise specified.
  • aryl designates a carbon and/or heteroatom-containing aromatic radical which is preferably phenyl optionally substituted with one or more substituents selected from halogen, methyl and methoxy, especially phenyl, halophenyl, tolyl or xylyl.
  • aroyl designates a carbonyl aromatic radical, that is, aryl-C(O)—, which is preferably a benzoyl, methylbenzoyl, halobenzoyl or xylylcarbonyl radical.
  • acyl designates an alkylcarbonyl radical.
  • the various individual radicals (such as alkyl, alkenyl, alkynyl, alkoxy and alkylene or the like) generally contain up to six carbon atoms.
  • a preferred class of compounds of formula (I) is that wherein
  • X is N
  • Y is C—R 3 ;
  • W is C—R 4 ;
  • R 3 is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO 2 , —S(O) n R 8 , alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl;
  • R 4 is H, halogen, alkyl, alkoxy, CN, NO 2 , haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH ⁇ N—OH, —CH ⁇ N—O-alkyl, —S(NH 2 ) ( ⁇ NH), —S(O) n R 8 , mercapto, haloalkylcarbonyl, or a —S—radical so that two molecules are bound together to form a disulfide compound;
  • R 5 is hydrogen, halogen, —NR 9 R 10 , —N ⁇ CR 11 R 19 , —S(O) n R 8 , formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, lower alkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl, preferably, amino —NR 9 R 10 ;
  • R 8 is alkyl or haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; preferably R 8 is lower alkyl;
  • R 11 is H or alkyl
  • R 19 may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino; or R 19 is phenyl, thienyl, pyridyl or furyl, all of them being optionally substituted with alkyl, haloalkyl, halogen, NO 2 , CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;
  • R 9 and R 10 are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R 8 —S(O) n , formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or 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; the alkyl portion of R 9 and R 10 may be substituted by R 7 ;
  • R 7 is cyano, nitro, alkoxy, haloalkoxy, R 8 S(O) n , —C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO 2 H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
  • Z is N or C—R 16 ;
  • n zero, one or two;
  • R 12 , R 13 , R 15 , R 16 are separately hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;
  • R 22 , R 23 , R 24 , R 25 , R 26 are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF 5 , R 8 S(O) n , preferably R 24 is halogen, haloalkyl or haloalkoxy; or R 22 and R 23 or R 23 and R 24 or R 25 and R 26 may also be together a divinylidene group (—CH ⁇ CH—CH ⁇ CH—) or a methylene diether (—O—CH 2 —O—) or halomethylene diether (—O—CF 2 —O—) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable
  • Another preferred class of the compounds of formula (I) are those with one or more of the following features wherein:
  • X is N or C—R 2 ;
  • Y is N or C—R 3 ;
  • W is N or C—R 4 ;
  • R 3 is CN or halogen
  • R 4 is H, halogen, formyl, or —S(O) n R 8 ;
  • R 5 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, or —NR 9 R 10 ;
  • R 8 is methyl, ethyl, —CF 3 , —CFCl 2 , —CF 2 Cl;
  • R 12 and R 16 are independently selected from F, Cl, Br and H;
  • R 13 and R 15 are H
  • R 24 is —CF 3 , —OCF 3 , —CHF 2 , —S(O) n CF 3 , —CFCl 2 , —CF 2 Cl, —OCF 2 Cl, —OCFCl 2 , Cl, Br or F; or
  • Z is CCl, CF, CBr or N.
  • a further especially preferred class of compounds are those wherein:
  • X is N
  • Y is C—R 3 ;
  • W is C—R 4 ;
  • R 12 and R 16 are Cl or Br
  • R 13 and R 15 are H
  • R 24 is —CF 3 , —OCF 3 or Br
  • R 5 is amino
  • R 9 and R 10 are H, alkyl or alkylcarbonyl
  • R 8 is methyl or ethyl or CF 3 , CCl 2 F, CClF 2 ;
  • R 3 is CN or halogen.
  • preferred S(O) n R 8 substituents in formula (I) are: methyltrio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichloromethylsulfinyl, dichloromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
  • 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 as starting material the compounds of formula (II)
  • halo is a halogen atom, preferably bromine or iodine.
  • the compounds of formula (II) can be prepared by methods or processes similar to those described in International patent applications WO 87/03781, 93/06089, 94/21606, in European patent applications 295117, 403300, 385809, 0500209, 679650, 285,893, and 780,381, U.S. Pat. Nos. 5,232,940, 5,236,938, 5,187,185, 5,223,525 and German Patent application 19511269 or by other methods known to the skilled addressee. The skilled addressee understands and is generally knowledgeable of Chemical Abstracts.
  • a compound of formula (II) is caused to react with a boric acid or ester, preferably in presence of a coupling catalyst, so as to form a compound of formula (III)
  • B(OR 30 ) 2 represents a boric acid or ester group (R 30 is preferably hydrogen, alkyl, or a divalent lower alkylene radical such that two R 30 O radicals may form a cyclic borate ester),
  • R 20 is bromine or iodine or O—SO 2 CF 3 .
  • the first step of this first process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis (triphenylphosphine)palladium(0) or Pd 2 (dibenzylidene acetone) 3 , generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.
  • the boron derivative used as a reactant with the compound of formula (II) is preferably a cyclic diboron ester or acid of formula (R 30 O) 2 B—B(OR 30 ) 2 .
  • the second step of this first process is advantageously conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine) palladium(0) or Pd 2 (dibenzylidene acetone) 3 , generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.
  • an organic solvent for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or
  • a compound of formula (II) is caused to react with a compound of formula (IV):
  • the process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd 2 (dibenzylidene acetone) 3 , generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.
  • an organic solvent for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-meth
  • a compound of formula (II) is caused to react in the presence of a catalyst as described above, with a hexaalkylstannane[(alkyl or cycloalkyl) 3 Sn] 2 so as to form a compound of formula (V):
  • the first step of the process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; at a temperature generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd 2 (dibenzylidene acetone) 3 .
  • an organic solvent for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; at a temperature generally between 50° C. and 150° C.; utilizing as catalysts organic
  • the second step of this second process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; as catalysts, organic derivatives of palladium such as Pd(P-phenyl 3 ) 4 , Pd 2 (dibenzylidene acetone) 3 , Pd(O—CO—CH 3 ) 2 may be cited.
  • an organic solvent for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; as catalysts,
  • the solid was dissolved in 40 ml of dichloromethane at reflux, cooled to room temperature, and treated with tetramethylguanidine (1.6 ml), added dropwise over twenty minutes. After stirring at room temperature overnight, the mixture was cooled in an ice/salt bath and dichlorofluoromethylsulfenyl chloride (1.5 ml) was added. After 1 h, the mixture was diluted with 100 ml of methylene chloride and washed with saturated sodium bicarbonate solution, then with water, then dried over magnesium sulfate.
  • AroCH is [4-OH 3-methoxy phenyl]-CH, so that AroCH ⁇ N— is the group [4-OH3-methoxy phenyl]CH ⁇ N— 4 - OH - 3 - methoxyphenyl] - CH ⁇ N—
  • the present invention provides also a method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a compound of formula (I), or a pesticidal composition comprising a pesticidally effective amount of a compound of formula (I) and a pesticidally acceptable carrier therefor.
  • the invention provides a method for controlling insects at a locus comprising applying to said locus an insecticidally effective amount of a compound of formula (I), or an insecticidally effective amount of an insecticidal composition comprising an insecticidally effective amount of a compound of formula (I) and an agriculturally acceptable inert carrier therefor.
  • the locus to which the pesticidally (especially insecticidally) effective amount is applied is a crop-growing area, that is, an area in which a crop is growing or in which a crop has been planted, or an area in which a crop will be planted/grown.
  • compositions which can be used in the invention for the pesticidal/insecticidal treatment of the invention can comprise from about 0.001 to 95% of the compound of formula (I).
  • the diluted liquid formulations as applied to the locus to be treated or crop, generally comprise from about 0.001 to about 3% of active ingredient of formula (I), preferably from about 0.1 to about 0.5%.
  • the solid formulations as applied to the locus or crop generally comprise from about 0.1 to about 8% of active ingredient of formula (I), preferably from about 0.5 to about 1.5%.
  • the concentrated compositions are the compositions which are commercialized or transported or stored. For application to plants, they are normally diluted in water and applied in such diluted form.
  • the diluted forms are part of the invention as well as the concentrated forms.
  • the concentrated formulations generally comprise from about 5 to about 95% of active ingredient of formula (I), preferably from about 10 to about 50%.
  • insecticidal compositions of the invention can be applied once, or more than once, throughout the whole insect season.
  • Insecticidal compositions according to the invention are usually applied to the locus to be treated or crop area at a rate of from about 0.01 to about 2 kg/ha of active ingredient, preferably from about 0.1 to about 1 kg/ha.
  • the concentrated insecticidal compositions according to the invention can be in the form of a solid, e.g., dusts or granules or wettable powders, or, preferably, in the form of a liquid, such as an emulsifiable concentrate or a true solution.
  • compositions according to the instant invention generally comprise from about 0.5 to about 95% of active ingredient of formula (I).
  • the remainder of the composition up to 100% comprises a carrier as well as various additives such as those hereafter indicated.
  • carrier there is meant herein an organic or inorganic material, which can be natural or synthetic, and which is associated with the active ingredient and which facilitates its application to the locus to be treated or crop.
  • This carrier is thus generally inert and should be agriculturally acceptable, especially on the contemplated or treated locus or crop.
  • the carrier can be solid (clay, silicates, silica, resins, wax, fertilizers, etc.) or liquid (water, alcohols, ketones, oil solvents, saturated or unsaturated hydrocarbons, chlorinated hydrocarbons, liquified petroleum gas, etc.).
  • compositions of the invention can comprise surfactants as well as other ingredients such as dispersants, stickers, antifoam agents, anti-freezing agents, dyestuffs, thickeners, adhesives, protective colloids, penetrating agents, stabilizing agents, sequestering agents, antiflocculating agents, corrosion inhibitors, pigments and polymers.
  • compositions of the invention can comprise all kinds of solid or liquid additives which are known in the art of insecticides and insecticidal treatments.
  • the surfactants can be of the emulsifying or wetting type, ionic or non-ionic.
  • Possible surfactants are salts of polyacrylic or lignosulfonic acids; salts of phenolsulfonic or naphthalenesulfonic acids; polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines or substituted phenols (particularly alkylphenols or arylphenols); ester-salts of sulfosuccinic acids; taurine derivatives, such as alkyl taurates; phosphoric esters; or esters of alcohols or polyoxyethylated phenols.
  • the spraying vehicle is water, the use of at least one surfactant is generally required because the active ingredients are not water-soluble.
  • the method of application of the compositions of the invention is generally the spraying of a mixture which has been previously made, by dilution of more concentrated formulations according to the invention.
  • Solid compositions can be powders for dusting or for dispersion (wherein the content of active ingredient can be up to 100%) and granules, especially extruded or compacted granules, or granules which have been made by impregnation of a powder (the content of active ingredient in such powders being between about 1 and about 80%).
  • Liquid compositions of compositions which have to be liquid when applied include solutions, water-soluble concentrates, emulsifiable concentrates, emulsions, wettable powders or pastes or water-dispersible granules.
  • Emulsifiable concentrates generally comprise from about 10 to about 80% of active ingredient; the emulsions when applied generally comprise from about 0.01 to about 20% of active ingredient.
  • the emulsifiable concentrates can comprise the solvent and, to the extent needed, from about 2 to about 20% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors or other additives already recited.
  • suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors or other additives already recited.
  • the concentrated suspensions can also be applied by spraying and have to be fluid without allowing any solid to separate and fall to the bottom.
  • they comprise from about 1 to about 75% of active ingredient (preferably from about 2 to about 50%), from about 0.5 to about 15% of surfactant, from about 0.1 to about 10% of thickener, from 0 to about 10% of other suitable additives as already indicated, the remainder being water or an organic liquid wherein the active ingredient is insoluble or has a low solubility.
  • the wettable powders generally comprise the active ingredient (from about 1 to about 95%, preferably from about 2 to about 80%), the solid carrier, a wetting agent (from 0 to about 5%), a dispersing agent (from about 3 to about 10%) and, to the extent needed, from 0 to about 10% of other additives such as stabilizers and others as already listed.
  • Dispersible granules are generally made by agglomeration of a powder, followed by an appropriate granulation process.
  • the emulsions herein described can be of the oil-in-water or water-in-oil types. Fluidity of the emulsions can range from low viscosities up to high viscosities approaching those of gels.
  • compositions or formulations one skilled in the art can choose the one most appropriate, according to the specific conditions of the treatment problem.
  • the compounds and compositions of the invention can also be used in admixtures with another pesticide, e.g., an insecticide, acaricide or herbicide.
  • another pesticide e.g., an insecticide, acaricide or herbicide.
  • the compounds of the invention may also be used in controlling pests found in non-agricultural domains.
  • helminths or protozoa which are parasitic internally or externally upon vertebrates, particularly warm-blooded vertebrates, for example man or 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, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. e.g.
  • ticks e.g. Ixodes spp., Boophilus spp. e.g. Boophilus microplus, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. e.g.
  • Rhipicephalus appendiculatus Haemaphysalis spp., Dermacentor spp., Ornithodorus spp. (e.g. Ornithodorus moubata) and mites (e.g. Damalinia spp., Dermahyssus gallinae, Sarcoptes spp. e.g. Sarcoptes scabiei, Psoroptes spp., Chorioptes spp;, Demodex spp., Eutrombicula spp.,); Diptera (e.g.
  • Monomorium pharaonis for example against infections of the gastro-intestinal tract caused by parasitic nematode worms, for example members of the family Trichostrongylidae, Nippostrongylus brasiliensis, Trichinella spiralis, Haemonchus contortus, Trichostrongylus colubriformis, Nematodirus batus, Ostertagis circumcincta, Trichostrongylus axei, Cooperia spp. and Hymenolepis nana; in the control and treatment of protozoal diseases caused by, for example, Eimeria spp. e.g.
  • the compounds of the invention may be useful for coccidiosis, a disease caused by infections from protozoan parasites of the genus Eimeria.
  • Solid or liquid compositions for application topically to animals, timber, 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 general formula (I).
  • these normally contain from about 0.1% to about 90% by weight of one or more compounds of general formula (I).
  • Medicated feedstuffs normally contain from about 0.001% to about 3% by weight of one or more compounds of general formula (I).
  • 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 general formula (I).
  • Mineral salt licks normally contain from about 0.1% to about 10% by weight of one or more compounds of general formula (I).
  • Dusts or liquid compositions for application to livestock, persons, 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 general formula (I).
  • 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 general formula (I) 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 general formula (I).
  • the dosage of compounds of general formula (I) 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 0.1 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.
  • sustained release formulations or devices the daily doses required over a period of months may be combined and administered to animals on a single occasion.
  • Aphid-infested cotton plants were placed on a revolving turntable, and sprayed to runoff with a 100 ppm formulation of the selected compound of formula (I).
  • the treated, A. gossypii-infested plants were held for three days after treatment, after which the dead aphids were counted.
  • Jars are filled with 60 g dry soil homogeneously mixed with 5 ml aqueous solution containing the compound to be tested. After drying, four germinated corn seedlings are placed in the bottom of each jar and the soil is wetted. Then ten newly born larvae are placed in each jar. The jars are stored for six days at 27° C. under 70% of relative humidity. The number of surviving larvae are then counted.
  • the inner wall of a 100 ml jar is covered by shaking 2 ml of pesticidal formulation. Furthermore, a pellet of dog chow is placed into a jar and the pesticidal formulation is absorbed on the pellet, using excess liquid. The jar is then left open up to evaporation of liquid. Cockroach nymphs are placed in the jar and mortality is assessed after five days.
  • Leaves of soybeans were sprayed to run-off with a spray of various concentrations. Then the leaves were allowed to dry, excised, and placed into a container with five larvae. The containers are stored for five days at 25° C. under 50% relative humidity. Mortality ratings are then counted.
  • Test formulation are prepared by mixing 2 microliters of dimethylsulfoxide with 100 microliters of a solution of Escherichia coli (which is food for C. elegans). 98 microliters of this mixture are then mixed with an inoculum solution which consists of mixed life stages of C. elegans (about 50 worms). This new mixture is stored 7 days at 20° C. Mortality is then visually assessed as well as the behavior of the worm. For the mortality, the rating is either 1 (large increase in number of the population, similar to the control which is trebbling in 7 days) or 3 (slight increase of the population, but significantly less increase than the control) or 5 (little to no increase in the population). For the behavior effect, the rating is either 1 (normal motion) or 3 (motion is slower than the control) or 5 (little to no movement).

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Abstract

A compound of formula (I):
Figure USRE037936-20021210-C00001
compositions containing them and methods of use to control pests.

Description

CROSS-REFERENCE TO RELATED APPLICATION
This application claims the priority of U.S. Provisional Patent Application No. 60/030,128, filed Nov. 4, 1996, incorporated by reference herein in its entirety and relied upon.
The invention relates to new 1-arylpyrazoles and derivatives thereof which have some valuable properties either as pesticides or as intermediates to make other pesticides. The invention further pertains to compositions of said compounds and methods, using said compounds either as intermediates to make other pesticides, or for the control of pests particularly insects, in particular to the application of said compounds or compositions in agricultural methods of use or for animal protection, particularly as pesticides, for controlling arthropods.
International Patent Publication No. WO 87/03781 and European Patent Publication No. 295117, 154115, 201852 describe insecticidal 1-(substituted phenyl)pyrazoles. Other prior art is also found in the text of these patent applications or the patents issued therefrom.
International Patent Publications No. WO 93/06089 and WO 94/21606 also describe insecticidal 1-(4-SF5 substituted phenyl) heterocycles which may be pyrroles as well as imidazoles or pyrazoles. The teaching of these patents is not substantially different from International Patent Publication No. WO 87/03781 or from European Patent Publication No. 0295117 as far as pyrazoles are concerned.
It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation.
Another object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole 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, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, 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.
A fifth objective 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 objectives of the invention are met in whole or part and shall become readily apparent from the description of the present invention which follows.
The invention thus relates to compounds having the general formula (I):
Figure USRE037936-20021210-C00002
wherein
X is N or C—R2;
Y is N or C—R3;
W is N or C—R4;
R2 and R3 are independently selected from H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO2, —S(O)nR8, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, and dialkylaminosulfonyl;
R4 is H, halogen, alkyl, alkoxy, CN, NO2, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH═N—OH, —CH═N—O-alkyl. —CH═N—O-alkyl, —S(NH2)(═NH), —S(O)nR8, mercapto, haloalkylcarbonyl, or a —S—radical so that two molecules are bound together to form a disulfide compound;
R5 is hydrogen, halogen, —NR9R10, —N═CR11R19, —S(O)nR8, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, alkyl, haloalkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl;
R8 is alkyl or haloalkyl, alkenyl or alkynyl, or a cycloalkyl ring containing 3 to 5 carbon atoms;
R11 is H, or alkyl;
R19 may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino, or R19 is phenyl, thienyl, pyridyl or furyl, each of which is unsubstituted or substituted with alkyl, haloalkyl, halogen, NO2, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;
R9 and R10 independent of one another, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R8S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or 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; the alkyl portion of R9 and R10 may be substituted by R7;
R7 is cyano, nitro, alkoxy, haloalkoxy, R8S(O)n, —C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
Z is N or C—R16;
n is zero, one or two;
R12, R13, R15, R16, are independently selected from hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;
R22, R23, R24, R25, R26 are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF5, R8S(O)n; preferably R24 is halogen, haloalkyl or haloalkoxy; or R22 and R23 or R23 and R24 or R25 and R26 may also be together a divinylidene group (—CH═CH—CH═CH—) or a methylene diether (—O—CH2—O—) or halomethylene diether (—O—CF2—O—), so as to form a cyclic ring vicinal to the phenyl ring; or pesticidally acceptable 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 suitably acidic group include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts.
In the present invention, some words are used in a specific sense:
The term “lower alkyl-S(O)n” means a radical of the formula —S(O)n— lower alkyl. The term “R10S(O)n” means a radical of the formula —S(O)nR10. The term “aminocarbonyl” means a carbamoyl radical, that is, a radical of the formula —C(O)NH2. Similarly, the term “alkylaminocarbonyl” means an alkylcarbomoyl alkylcarbamoyl radical, that is, a radical of the formula —C(O)—NH-alkyl; and the term “dialkylaminocarbonyl” means a dialkylcarbamoyl radical, that is, a radical of the formula —C(O)—N(alkyl)2 in which the alkyl moieties can be the same or different. The term “aminosulfonyl” means a sulfamoyl radical, that is, —SO2NH2. Similarly, the term “alkylaminosulfonyl” means an alkylsulfamoyl radical, that is, a radical of the formula —SO2NH-alkyl; while the term “dialkylaminosulfonyl” means a dialkylsulfamoyl radical, which has the formula —SO2N(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 partially or completely halogenated, that is to say, substituted by F, Cl, Br, or I, in any combination, preferably by F or Cl. The term “halogen” means F, Cl, Br or I. The term “lower” before the name of a radical having a carbon skeleton means that this carbon skeleton has less than 6 carbon atoms. When the name of any substituent is repeated, it keeps the same meaning unless otherwise specified. The term “aryl” designates a carbon and/or heteroatom-containing aromatic radical which is preferably phenyl optionally substituted with one or more substituents selected from halogen, methyl and methoxy, especially phenyl, halophenyl, tolyl or xylyl. The term “aroyl” designates a carbonyl aromatic radical, that is, aryl-C(O)—, which is preferably a benzoyl, methylbenzoyl, halobenzoyl or xylylcarbonyl radical. The term “acyl” designates an alkylcarbonyl radical. The various individual radicals (such as alkyl, alkenyl, alkynyl, alkoxy and alkylene or the like) generally contain up to six carbon atoms.
A preferred class of compounds of formula (I) is that wherein
X is N;
Y is C—R3;
W is C—R4;
R3 is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO2, —S(O)nR8, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl;
R4 is H, halogen, alkyl, alkoxy, CN, NO2, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH═N—OH, —CH═N—O-alkyl, —S(NH2) (═NH), —S(O)nR8, mercapto, haloalkylcarbonyl, or a —S—radical so that two molecules are bound together to form a disulfide compound;
R5 is hydrogen, halogen, —NR9R10, —N═CR11R19, —S(O)nR8, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, lower alkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl, preferably, amino —NR9R10;
R8 is alkyl or haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; preferably R8 is lower alkyl;
R11 is H or alkyl;
R19 may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino; or R19 is phenyl, thienyl, pyridyl or furyl, all of them being optionally substituted with alkyl, haloalkyl, halogen, NO2, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;
R9 and R10 are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R8—S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or 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; the alkyl portion of R9 and R10 may be substituted by R7;
R7 is cyano, nitro, alkoxy, haloalkoxy, R8S(O)n, —C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
Z is N or C—R16;
n is zero, one or two;
R12, R13, R15, R16, are separately hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;
R22, R23, R24, R25, R26 are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF5, R8S(O)n, preferably R24 is halogen, haloalkyl or haloalkoxy; or R22 and R23 or R23 and R24 or R25 and R26 may also be together a divinylidene group (—CH═CH—CH═CH—) or a methylene diether (—O—CH2—O—) or halomethylene diether (—O—CF2—O—) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable salt thereof.
Another preferred class of the compounds of formula (I) are those with one or more of the following features wherein:
X is N or C—R2;
Y is N or C—R3;
W is N or C—R4;
R3 is CN or halogen;
R4 is H, halogen, formyl, or —S(O)nR8;
R5 is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, or —NR9R10;
R8 is methyl, ethyl, —CF3, —CFCl2, —CF2Cl;
R12 and R16 are independently selected from F, Cl, Br and H;
R13 and R15 are H;
R24 is —CF3, —OCF3, —CHF2, —S(O)nCF3, —CFCl2, —CF2Cl, —OCF2Cl, —OCFCl2, Cl, Br or F; or
Z is CCl, CF, CBr or N.
A further especially preferred class of compounds are those wherein:
X is N;
Y is C—R3;
W is C—R4;
R12 and R16 are Cl or Br;
R13 and R15 are H;
R24 is —CF3, —OCF3 or Br;
R5 is amino;
R9 and R10 are H, alkyl or alkylcarbonyl;
R8 is methyl or ethyl or CF3, CCl2F, CClF2; and
R3 is CN or halogen.
For the above preferred compounds, there are optimum combinations of substituent groups.
Further, preferred S(O)nR8 substituents in formula (I) are: methyltrio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichloromethylsulfinyl, dichloromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
Some compounds are useful as intermediates to make other pesticides, others are useful directly as pesticides. Compounds wherein R23 or R24 or R25 is formyl are preferred as intermediates as well as compounds wherein R5 is H or compounds wherein simultaneously R4 is not halogenated and R22 and R23 and R24 and R25 and R26 are H.
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 as starting material the compounds of formula (II)
Figure USRE037936-20021210-C00003
wherein the various substituents have the same meaning as in formula (I) and halo is a halogen atom, preferably bromine or iodine.
The compounds of formula (II) can be prepared by methods or processes similar to those described in International patent applications WO 87/03781, 93/06089, 94/21606, in European patent applications 295117, 403300, 385809, 0500209, 679650, 285,893, and 780,381, U.S. Pat. Nos. 5,232,940, 5,236,938, 5,187,185, 5,223,525 and German Patent application 19511269 or by other methods known to the skilled addressee. The skilled addressee understands and is generally knowledgeable of Chemical Abstracts.
According to a first method of preparation of compounds of formula (I) from compounds of formula (II), a compound of formula (II) is caused to react with a boric acid or ester, preferably in presence of a coupling catalyst, so as to form a compound of formula (III)
Figure USRE037936-20021210-C00004
wherein the substituents have the same meaning as previously indicated, and B(OR30)2 represents a boric acid or ester group (R30 is preferably hydrogen, alkyl, or a divalent lower alkylene radical such that two R30O radicals may form a cyclic borate ester),
said compound (III) being, in a second step, caused to react with a compound of formula (VI)
Figure USRE037936-20021210-C00005
wherein R20 is bromine or iodine or O—SO2CF3.
The first step of this first process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis (triphenylphosphine)palladium(0) or Pd2 (dibenzylidene acetone)3, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine. The boron derivative used as a reactant with the compound of formula (II) is preferably a cyclic diboron ester or acid of formula (R30O)2B—B(OR30)2.
The second step of this first process is advantageously conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine) palladium(0) or Pd2(dibenzylidene acetone)3, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.
According to another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (IV):
Figure USRE037936-20021210-C00006
wherein the substituents have the same meaning as previously indicated.
The process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd2 (dibenzylidene acetone)3, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.
According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react in the presence of a catalyst as described above, with a hexaalkylstannane[(alkyl or cycloalkyl)3Sn]2 so as to form a compound of formula (V):
Figure USRE037936-20021210-C00007
which in a second step is caused to react with a compound of formula (IV) in the presence of a coupling catalyst.
The first step of the process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; at a temperature generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd2 (dibenzylidene acetone)3.
The second step of this second process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; as catalysts, organic derivatives of palladium such as Pd(P-phenyl3)4, Pd2(dibenzylidene acetone)3, Pd(O—CO—CH3)2 may be cited.
According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (VII)
Figure USRE037936-20021210-C00008
preferably in the presence of a coupling catalyst as described above, and preferably in a solvent as described above, and preferably at a temperature from 50° C. to 150° C.
According to another method of preparation of a compound of formula (I), a compound of formula (VIII):
Figure USRE037936-20021210-C00009
is reacted in a step to form a pyrrole, imidazole, triazole, or pyrazole of formula (I). Such reactions are known and can be found in Katritzky, Rees, and Scriven, Comprehensive Heterocyclic Chemistry II, volumes 2,3,4 1996, Pergamon Press, London.
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.
EXAMPLE 1 Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole
A mixture of 6 g of 5-amino-3-cyano-1-(2,6-dichloro-4-bromophenyl)4-trifluoromethylthiopyrazole 5-amino- 3 -cyano- 1 -( 2,6 -dichloro- 4 -bromophenyl)- 4 -trifluoromethylthiopyrazole (prepared according to procedures reported in U.S. Pat. No. 5,232,940), 4-trifluoromethylphenylboronic acid (5.3 g), K2CO3 (5.8 g), tris(dibenzylidene acetone)dipalladium (0.6 g) and diglyme was heated at 130° C. for 25 hours. After cooling to 20° C., the mixture was poured into water and extracted with diethyl ether. The ether solutions were combined, dried, filtered and the filtrate concentrated and purified by chromatography. The desired product as a solid (3.9 g, mp 181-184° C.) was obtained.
EXAMPLE 2 Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylsulfonyl-5-aminopyrazole
A solution of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole (0.5 g), m-chloroperbenzoic acid (2.2 g) and 1,2-dichloroethane was heated at reflux for 40 hours. After cooling to 20° C., the mixture was dissolved in diethyl ether and washed with sat. aqueous NaHCO3 solution twice, then saturated aqueous NaHSO3 solution twice, dried, filtered, and the filtrate concentrated and purified by chromatography. The desired product as a solid (0.13 g, mp 197-202° C.) was obtained.
EXAMPLE 3 Preparation of 1-[2,6-dichloro-4-(tributyltin)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole
A mixture of 1-(2,6-dichloro-4-bromophenyl)-3-cyano-4-trifluoromethylthio-5-aminopyrazole (5 g), bis-(tributyltin) (6.7 g) tetrakis(tri-phenylphosphine)palladium(0) (1.3 g) and 1-methyl-2-pyrrolidinone was heated to reflux for 75 minutes, cooled to 20° C., poured to water and extracted with methyl t-butyl ether. After concentration to dryness, methylene chloride was added and stirred with saturated aqueous KF solution for 16 hours. More water was added and extracted with methylene chloride. The methylene chloride solutions were combined, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (1.9 g, mp 116-117° C.) was obtained.
EXAMPLE 4 Preparation of 1-[2,6-dichloro-4-(2,3,5,6-tetrafluoropyrid-4-yl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole
A mixture of 1-[2,6-dichloro-4-(tributyltin)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole (0.5 g), 4-bromo-2,3,5,6-tetrafluoropyridine (0.1 mL), tetrakis(triphenylphosphine)palladium(0) (0.1 g) and THF was refluxed for 26 hours. After cooling to 20° C., methylene chloride was added and stirred with saturated aqueous KF solution for 16 hours. The mixture was filtered with diethyl ether and dried, filtered again and the filtrate concentrated and purified via chromatography. The desired product as a solid (87 mg, mp 100-104° C.) was obtained.
EXAMPLE 5 Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-5-aminopyrazole
A mixture of 1-(2,6-dichloro-4-bromophenyl)-3-cyano-5-aminopyrazole (45 g, prepared according to procedures reported in U.S. Pat. No. 5,232,940), 4-trifluoromethylphenylboronic acid (45 g), 2M of Na2CO3 (75 mL), tris(dibenzylideneacetone)dipalladium (6.4 g), toluene and ethanol was heated at 130° C. for 25 hours. After cooling to 20° C., the mixture was poured into water and extracted with diethyl ether. The ether solutions were combined, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (30.6 g, mp 195-199° C.) was obtained.
EXAMPLE 6 Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-bromo-5-aminopyrazole
A mixture of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-5-aminopyrazole (1 g), N-bromosuccinimide (0.5 g) and acetonitrile was stirred at 20° C. for 90 minutes, then concentrated and the residue was mixed with diethyl ether, washed with saturated aqueous NaHCO3 solution, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (1.04 g, mp 178-180° C.) was obtained.
EXAMPLE 7 Preparation of 4-dichlorofluoromethylsulfenyl-1-[2-fluoro-4-(4-trifluoromethylphenyl)phenyl]imidazole
Step A
A solution of 4-bromo-2-fluoroaniline (3.8 g) in 20 ml of triethyl orthoformate was stirred at room temperature. After stirring for 1 h, tetrahydrofuran (40 ml), aminoacetonitrile hydrochloride (2.8 g), and diisopropylamine (5.3 ml) were added and stirring continued for an additional hour. After 1 h, the mixture was poured into 150 ml of ice water and extracted with 150 ml of dichloromethane. The organic solution was washed twice with water and dried over magnesium sulfate. Evaporation of solvents afforded a light purple solid (3.1 g), which was washed with hexane and filtered.
The solid was dissolved in 40 ml of dichloromethane at reflux, cooled to room temperature, and treated with tetramethylguanidine (1.6 ml), added dropwise over twenty minutes. After stirring at room temperature overnight, the mixture was cooled in an ice/salt bath and dichlorofluoromethylsulfenyl chloride (1.5 ml) was added. After 1 h, the mixture was diluted with 100 ml of methylene chloride and washed with saturated sodium bicarbonate solution, then with water, then dried over magnesium sulfate. After filtration and evaporation, chromatography on silica gel afforded 5-amino-4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole (1.285 g).
Step B
1 g of 5-amino-4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole was dissolved in 15 ml of tetrahydrofuran, cooled to 0° C., and treated with t-butylnitrite. After 1 h, the mixture is evaporated. Silica gel chromatography afforded 4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole (0.555 g).
Step C
50 mg of 4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole and 37 mg of trifluoromethylphenylboronic acid in 3 ml of toluene were treated with 0.13 ml of 2M aqueous potassium carbonate and a catalytic amount (about 5 mg) of palladium tetrakis(triphenylphoshine). The mixture was heated at 90° C. for 12 h, then cooled to room temperature and evaporated. Silica gel chromatography afforded 4-dichlorofluoromethylsulfenyl-1-[2-fluoro-4-(4-trifluoromethylphenyl)phenyl]imidazole (27.3 mg, mass spec m/e 438).
In a manner similar to that employed in examples 1 to 7, the following compounds in Tables 1-4 were also prepared. The last column of the table indicates the physical characteristic of the compound obtained from the mass spectrum analysis. It is the m/e value from the mass spectrum of the molecular ion. The number of the compound is for identification only.
N/A=Not Applicable
AroCH is [4-OH 3-methoxy phenyl]-CH, so that AroCH═N— is the group [4-OH3-methoxy phenyl]CH═N— 4-OH- 3 -methoxyphenyl]-CH═N—
TABLE 1
Figure USRE037936-20021210-C00010
CMP. NO R12 R13 R15 R16 R22 R23 R24 R25 R26 R3 R4 R5 m/e
 1 Cl H H Cl (CH═CH)2 H H H CN SCF3 NH2 478
 2 Cl H H Cl H H H H H CN SCF3 NH2 428
 3 Cl H H Cl Me H H H H CN SCF3 NH2 442
 4 Cl H H Cl H NH2 H H H CN SCF3 NH2 443
 5 Cl H H Cl H NO2 H H H CN SCF3 NH2 473
 6 Cl H H Cl H NHAc H H H CN SCF3 NH2 485
 7 Cl H H Cl H CHO H H H CN SCF3 NH2 456
 8 Cl H H Cl H H OMe H H CN SCF3 NH2 458
 9 Cl H H Cl H H SMe H H CN SCF3 NH2 474
10 Cl H H Cl H H F H H CN SCF3 NH2 446
11 Cl H H Cl H F H H H CN SCF3 NH2 446
12 Cl H H Cl H Cl F H H CN SCF3 NH2 480
13 Cl H H Cl H H Cl H H CN SCF3 NH2 462
14 Cl H H Cl H H Br H H CN SCF3 NH2 506
15 Cl H H Cl H Cl H Cl H CN SCF3 NH2 496
16 Cl H H Cl H H CF3 H H CN SCF3 NH2 496
17 Cl H H Cl H CF3 H CF3 H CN SCF3 NH2 564
18 Cl H H Cl (CH═CH)2 H H H CN SMe NH2 424
19 Cl H H Cl H H H H H CN SMe NH2 374
20 Cl H H Cl Me H H H H CN SMe NH2 388
21 Cl H H Cl H NH2 H H H CN SMe NH2 389
22 Cl H H Cl H NO2 H H H CN SMe NH2 419
23 Cl H H Cl H NHAc H H H CN SMe NH2 431
24 Cl H H Cl H H CHO H H CN SMe NH2 402
25 Cl H H Cl H H OMe H H CN SMe NH2 404
26 Cl H H Cl H F H H H CN SMe NH2 392
27 Cl H H Cl H Cl F H H CN SMe NH2 426
28 Cl H H Cl Cl H Cl H H CN SMe NH2 442
29 Cl H H Cl H H CF3 H H CN SMe NH2 442
30 Cl H H Cl H CF3 H CF3 H CN SMe NH2 510
31 Cl H H Cl H Br H H H CN SMe NH2 452
32 Cl H H Cl Me H H H H CN SCF3 Van-CH═N— 576
33 Cl H H Cl H NO2 H H H CN SCF3 Van-CH═N— 607
34 Cl H H Cl H NHAc H H H CN SCF3 Van-CH═N— 619
35 Cl H H Cl H H CHO H H CN SCF3 Van-CH═N— 590
36 Cl H H Cl H H OMe H H CN SCF3 Van-CH═N— 592
37 Cl H H Cl H Cl F H H CN SCF3 Van-CH═N— 614
38 Cl H H Cl Cl H Cl H H CN SCF3 Van-CH═N— 630
39 Cl H H Cl H H CF3 H H CN SCF3 Van-CH═N— 630
40 Cl H H Cl H H CF3 H H CN S(O)2CCl2F NH2 560
41 Cl H H Cl H H CF3 H H CN S(O)2CCl2F NH2 544
42 Cl H H Cl H H CF3 H H CN SCCl2F NH2 528
43 Cl H H Cl H H CF3 H H CN SOCF3 NH2 512
44 Cl H H Cl H H CF3 H H CN S(O)2CF3 NH2 528
45 Cl H H Cl H H CF3 H H PhC(O) SCF3 NH2 575
46 Cl H H Cl (CH═CH)2 H H H CN SCF3 H 463
47 Cl H H Cl H (CH═)2 H H CN SCF3 H 463
47 Cl H H Cl H (CH═CH)2 H H CN SCF3 H 463
48 Cl H H Cl H H H H H CN SCF3 H 413
49 Cl H H Cl H NO2 H H H CN SCF3 H 458
50 Cl H H Cl H H OMe H H CN SCF3 H 443
51 Cl H H Cl H H SMe H H CN SCF3 H 459
52 Cl H H Cl H H F H H CN SCF3 H 431
53 Cl H H Cl H F H H H CN SCF3 H 431
54 Cl H H Cl H Cl F H H CN SCF3 H 465
55 Cl H H Cl H H Cl H H CN SCF3 H 447
56 Cl H H Cl H H Br H H CN SCF3 H 491
57 Cl H H Cl H Cl H Cl H CN SCF3 H 481
58 Cl H H Cl Cl H C H H CN SCF3 H 481
59 Cl H H Cl H H CF3 H H CN SCF3 H 481
60 Cl H H Cl H CF3 H H H CN SCF3 H 481
61 Cl H H Cl H CF3 H CF3 H CN SCF3 H 549
62 Cl H H Cl H Cl H H H CN SCF3 H 447
63 Cl H H Cl H Br H H H CN SCF3 NH2 491
64 Cl H H Cl H H CF3 H H PhC(O) S(O)2CCl2F NH2 639
65 Cl H H Cl H H Br H H CN SCCl2F NH2 538
66 Cl H H Cl Cl H CF3 H Cl CN SCF3 NH2 564
67 Cl H H Cl H H OCF3 H H CN SCF3 NH2 512
68 Cl H H Cl H H CF3 H H PhC(O) S(O)2CClF2 NH2 623
69 Cl H H Cl H H CF3 H H CN H NH2 396
70 Cl H H Cl H H CF3 H H CN Br NH2 474
71 Cl H H Cl H H CF3 H H CN SEt NH2 456
72 Cl H H Cl H H CF3 H H CN SMe NH2 442
73 Cl H H Cl H H CF3 H H CN SCN NH2 453
74 Cl H H Cl H H CF3 H H CN Cl NH2 430
75 Cl H H Cl H H CF3 H H CN SOMe NH2 458
76 Cl H H Cl H H CF3 H H CN S(O)Et NH2 472
77 Cl H H Cl H H Br H H CN S(O)2CCl2F NH2 570
78 Cl H H Cl H H CF3 H H CN S(O)2CH3 NH2 474
79 Cl H H Cl H H CF3 H H CN S(O)2Et NH2 488
80 Cl H H Cl H H CF3 H H CONH2 C(OH) (CF3)2 NH2 580
81 Cl H H Cl H H CF3 H H CN C(OH) (CF3)2 NH2 562
82 Cl H H Cl H H CF3 H H CN H NHAc 438
83 Cl H H Cl H H CF3 H H Ac SMe NH2 459
84 Cl H H Cl H H CF3 H H CN CF(CF3)2 NH2 564
85 Cl H H Cl H H CF3 H H CN SCCl2F H 513
86 Cl H H Cl H H CF3 H H CN S(O)2CCl2F H 545
87 Cl H H Cl H Cl Cl H H CN H NH2 396
88 Cl H H Cl H H OCF3 H H CN H NH2 412
89 Cl H H Cl H H H H H CN H NH2 346
89 Cl H H Cl F H H H H CN H NH2 346
90 Cl H H Cl H H CO2Me H H CN H NH2 386
91 Cl H H Cl H Cl Cl H H CN SCF3 NH2 496
92 Cl H H Cl F H H H H CN SCF3 NH2 446
93 Cl H H Cl H H CO2Me H H CN SCF3 NH2 486
94 Cl H H Cl H H CF3 H H CN SCCl2F Br 591
95 Cl H H Cl H H CF3 H H Ac S(O)2CH3 NH2 491
96 Cl H H Cl Cl H H H Cl CN SCF3 NH2 496
97 Cl H H Cl Cl H Cl H H CN SCF3 NH2 496
98 Cl H H Cl Cl H CF3 H Cl CN SCF3 NH2 564
99 Cl H H Cl CF3 H H H H CN SCF3 NH2 496
100  Cl H H Cl NO2 H CF3 H H CN SCF3 NH2 541
101  Cl H H Cl Me H F H H CN SCF3 NH2 460
102  Cl H H Cl H F H F H CN SCF3 NH2 464
103  Cl H H Cl F H H H F CN SCF3 NH2 464
104  Cl H H Cl H OCF3 H H H CN SCF3 NH2 512
105   Cl H H Cl H H H Cl H CN SCF3 NH2 480
105  Cl H H Cl H F H Cl H CN SCF3 NH2 480
106  Cl H H Cl H CN H H H CN SCF3 NH2 453
107  Cl H H Cl H OMe H H H CN SCF3 NH2 458
108  Cl H H Cl H H CH2CN H H CN SCF3 NH2 467
109  Cl H H Cl H H Ms H H CN SCF3 NH2 506
110  Cl H H Cl H H SO2NH2 H H CN SCF3 NH2 507
111  Cl H H Cl H H NMe2 H H CN SCF3 NH2 471
112  Cl H H Cl OCH2O H H H CN SCF3 NH2 472
113  Cl H H Cl H H CN H H CN SCF3 NH2 453
114  Cl H H Cl H H CN H H CN SCF3 NH2 453
115  Cl H H Cl F H F H H CN SCF3 NH2 464
116  Cl H H Cl H H CONH2 H H CN SCF3 NH2 471
117  Cl H H Cl H Cl CN H H CN SCF3 NH2 487
118  Cl H H Cl H CF3 H H H CN SCF3 NH2 496
119  Cl H H Cl F F F F F CN SCF3 NH2 518
120  Cl H H Cl H H OPh H H CN SCF3 NH2 520
121  Cl H H Cl Cl H CF3 H H CN SCF3 NH2 530
122   Cl H H Cl H OCF2O H H CN SCF3 NH2 508
122  Cl H H Cl H OCF2O H H CN SCF3 NH2 508
123  Cl H H Cl H F NH2 H H CN SCF3 NH2 461
124  Cl H H Cl H CF3 NO2 H H CN SCF3 NH2 541
125  Cl H H Cl OH H H H H CN SCF3 NH2 444
126  Cl H H Cl H H NH2 H H CN SCF3 NH2 443
127  Cl H H Cl H H OH H H CN SCF3 NH2 444
128  Cl H H Cl H CF3 H NH2 NH2 CN SCF3 NH2 526
129  Cl H H Cl H F Me H H CN SCF3 NH2 460
130  Cl H H Cl CN F H H H CN SCF3 NH2 471
131  Cl H H Cl H Me F H H CN SCF3 NH2 460
132  Cl H H Cl Me H H F H CN SCF3 NH2 460
133  Cl H H Cl Ph H H H H CN SCF3 NH2 504
134  Cl H H Cl OH OMe H CHO H CN SCF3 NH2 502
135  Cl H H Cl H Cl Cl H H CN S(O)2CH3 NH2 474
136  Cl H H Cl Cl H H H Cl CN S(O)2CH3 NH2 474
137  Cl H H Cl Cl H Cl H H CN S(O)2CH3 NH2 474
138  Cl H H Cl Cl H CF3 H Cl CN S(O)2CH3 NH2 542
139  Cl H H Cl H H OCF3 H H CN S(O)2CH3 NH2 490
140  Cl H H Cl CF3 H H H H CN S(O)2CH3 NH2 474
141  Cl H H Cl NO2 H CF3 H H CN S(O)2CH3 NH2 519
142  Cl H H Cl Me H F H H CN S(O)2CH3 NH2 438
143  Cl H H Cl H F H F H CN S(O)2CH3 NH2 442
144  Cl H H Cl F H H H F CN S(O)2CH3 NH2 442
145  Cl H H Cl F H H H H CN S(O)2CH3 NH2 424
146  Cl H H Cl H H CF3 H H CN C═NOH NH2 439
147  Cl H H Cl H H CF3 H H CN NO2 NHAc 483
148  Cl H H Cl H H CF3 H H CN NO2 NH2 441
149  Cl H H Cl F H F H H CN S(O)2CH3 NH2 442
150  Cl H H Cl H OCF3 H H H CN S(O)2CH3 NH2 490
151  Cl H H Cl H F H Cl H CN S(O)2CH3 NH2 458
152  Cl H H Cl H H CONH2 H H CN S(O)2CH3 NH2 449
153  Cl H H Cl H CN H H H CN S(O)2CH3 NH2 431
154  Cl H H Cl H H SMe H H CN S(O)2CH3 NH2 452
155  Cl H H Cl H OMe H H H CN S(O)2CH3 NH2 436
156  Cl H H Cl H H CH2CN H H CN S(O)2CH3 NH2 445
157  Cl H H Cl H H Ms H H CN S(O)2CH3 NH2 484
158  Cl H H Cl H H SO2NH2 H H CN S(O)2CH3 NH2 485
159  Cl H H Cl H H NMe2 H H CN S(O)2CH3 NH2 449
160  Cl H H Cl OCH2O H H H CN S(O)2CH3 NH2 450
161  Cl H H Cl H Cl CN H H CN S(O)2CH3 NH2 465
162  Cl H H Cl H H CN H H CN S(O)2CH3 NH2 431
163  Cl H H Cl H H CO2Me H H CN S(O)2CH3 NH2 464
164  Cl H H Cl H CF3 H H H CN S(O)2CH3 NH2 474
165  Cl H H Cl F F F F F CN S(O)2CH3 NH2 496
166  Cl H H Cl H H OPh H H CN S(O)2CH3 NH2 498
167  Cl H H Cl Cl H CF3 H H CN S(O)2CH3 NH2 508
168  Cl H H Cl Cl H SF5 H Cl CN S(O)2CH3 NH2 600
169  Cl H H Cl Cl H OCF3 H Cl CN S(O)2CH3 NH2 558
170   Cl H H Cl H OCF2O H H CN S(O)2CH3 NH2 486
170   Cl H H Cl H OCF2O H H CN S(O)2CH3 NH2 486
171  Cl H H Cl H CO2H OH H H CN S(O)2CH3 NH2 466
172  Cl H H Cl H F OH H H CN S(O)2CH3 NH2 440
173  Cl H H Cl H F NH2 H H CN S(O)2CH3 NH2 439
174   Cl H H Cl H CF3 NH2 H H CN S(O)2CH3 NH2 519
174  Cl H H Cl H CF3 NO2 H H CN S(O)2CH3 NH2 519
TABLE 2
Figure USRE037936-20021210-C00011
CMP. NO R12 R13 R15 R16 R2 R22 R23 R24 R25 R26 R3 R4 R5 m/e
175 Cl H H Cl H (CH—CH)2 H H H SCFCl2 CN Cl 528
175 Cl H H Cl H (CH═CH)2 H H H SCFCl2 CN Cl 528
176 Cl H H Cl Cl H (CH═CH2) H H CN SCFCl2 H 528
176 Cl H H Cl Cl H (CH═CH)2 H H CN SCFCl2 H 528
177 Cl H H Cl Cl H H H H H CN SCFCl2 H 478
178 Cl H H Cl H H H Me H H SCFCl2 CN Cl 492
179 Cl H H Cl H Me H H H H SCFCl2 CN Cl 492
180 Cl H H Cl Cl H NH2 H H H CN SCFCl2 H 493
181 Cl H H Cl H H NO2 H H H SCFCl2 CN Cl 523
182 Cl H H Cl Cl H NHAc H H H CN SCFCl2 H 535
183 Cl H H Cl H CHO H H H H SCFCl2 CN C 506
184 Cl H H Cl H H CHO H H H SCFCl2 CN Cl 506
185 Cl H H Cl Cl H H CHO H H CN SCFCl2 H 506
186 Cl H H Cl H OMe H H H H SCFCl2 CN Cl 508
187 Cl H H Cl H H OMe H H H SCFCl2 CN Cl 508
188 Cl H H Cl Cl H H OMe H H CN SCFCl2 H 508
189 Cl H H Cl Cl H H SMe H H CN SCFCl2 H 524
190 Cl H H Cl H H H F H H SCFCl2 CN Cl 496
191 Cl H H Cl Cl H F H H H CN SCFCl2 H 496
192 Cl H H Cl Cl H Cl F H H CN SCFCl2 H 530
193 Cl H H Cl H H H Cl H H SCFCl2 CN Cl 512
194 Cl H H Cl H H H Br H H SCFCl2 CN Cl 556
195 Cl H H Cl Cl H Cl H Cl H CN SCFCl2 H 546
196 Cl H H Cl H Cl H Cl H H SCFCl2 CN Cl 546
197 Cl H H Cl Cl H H CF3 H H CN SCFCl2 H 546
198 Cl H H Cl Cl H CF3 H H H CN SCFCl2 H 546
199 Cl H H Cl H H CF3 H CF3 H SCFCl2 CN Cl 614
200 Cl H H Cl Cl H Cl H H H CN SCFCl2 H 512
201 Cl H H Cl Cl H Br H H H CN SCFCl2 H 556
202 Cl H H Cl H H H CF3 H H S(O)CFCl2 CN Cl 562
203 Cl H H Cl H H H CF3 H H S(O)CFCl2 CN Cl 578
204 H H H H H H H CF3 H H CHO H H 315
205 H H H Me H H H CF3 H H CHO H H 329
206 Me H H Me H H H CF3 H H CHO H H 343
207 Cl H H H H H H CF3 H H CHO H H 349
208 H Cl H H H H H CF3 H H CHO H H 349
209 Cl H H Me H H H CF3 H H CHO H H 353
210 Cl H H Cl H H H CF3 H H CHO H H 383
211 F H H H H H H CF3 H H CHO H H 333
212 F H H F H H H CF3 H H CHO H H 351
213 H H H CF3 H H H CF3 H H CHO H H 383
214 H H CF3 H H H H CF3 H H CHO H H 383
215 F F F F H H H CF3 H H CHO H H 387
216 Me H H NO2 H H H CF3 H H CHO H H 374
217 H H (CH═CH)2 H H H CF3 H H CHO H H 365
TABLE 3
Figure USRE037936-20021210-C00012
CMP. NO R12 R13 R15 R16 R22 R23 R24 R25 R26 R3 R5 m/3
218 Cl H H Cl H H CF3 H H t-Bu NH2 428
219 Cl H H Cl H H CF3 H H t-Bu H 413
220 Cl H H Cl H H CF3 H H t-Bu Br 491
221 Cl H H Cl H H CF3 H H CF3 NH2 440
222 Cl H H Cl H NO2 H H H CF3 NH2 417
223 Cl H H Cl H F H H H CF3 NH2 390
224 Cl H H Cl H H CF3 H H CF3 Br 503
225 Cl H H Cl H H CF3 H H CF3 H 425
226 Cl H H Cl H (CH═CH)2 H H CF3 NH2 422
227 Cl H H Cl (CH═CH)2 H H H CF3 NH2 422
228 Cl H H Cl Me H H H H CF3 NH2 386
229 Cl H H Cl H OMe H H H CF3 NH2 402
230 Cl H H Cl H H OMe H H CF3 NH2 402
231 Cl H H Cl H H SMe H H CF3 NH2 418
232 Cl H H Cl H H F H H CF3 NH2 390
233 Cl H H Cl H H Cl H H CF3 NH2 406
234 Cl H H Cl H H Br H H CF3 NH2 450
235 Cl H H Cl H Cl H Cl H CF3 NH2 440
236 Cl H H Cl Cl H Cl H H CF3 NH2 440
237 Cl H H Cl H CF3 H H H CF3 NH2 440
238 Cl H H Cl H Cl H H H CF3 NH2 406
239 Cl H H Cl H Br H H H CF3 NH2 450
240 Cl H H Cl (CH═CH)2 H H H CF3 H 407
241 Cl H H Cl H H H H H CF3 H 357
242 Cl H H Cl H H Me H H CF3 H 371
243 Cl H H Cl H NO2 H H H CF3 H 402
244 Cl H H Cl H CHO H H H CF3 H 385
245 Cl H H Cl H OMe H H H CF3 H 387
246 Cl H H Cl H H F H H CF3 H 375
247 Cl H H Cl H H F H H CF3 H 375
248 Cl H H Cl H F H H H CF3 H 375
249 Cl H H Cl H Cl F H H CF3 H 409
250 Cl H H Cl H (CH═CH)2 H H CF3 H 407
251 Cl H H Cl H NHAc H H H CF3 H 414
252 Cl H H Cl CHO H H H H CF3 H 385
253 Cl H H Cl H H CHO H H CF3 H 385
254 Cl H H Cl OMe H H H H CF3 H 387
255 Cl H H Cl H H CF3 H H SMe H 403
256 Cl H H Cl H H CF3 H H SMe NH2 418
257 Cl H H Cl H H CF3 H H SOMe NH2 434
258 Cl H H Cl H H CF3 H H SOMe H 419
259 Cl H H Cl H H CF3 H H SOMe Br 497
260 Cl H H Cl H H CF3 H H SCCl2F H 489
261 Cl H H Cl H H CF3 H H S(O)CCl2F H 505
263 Cl H H Cl H H CF3 H H S(O)2CCl2F H 521
TABLE 4
Figure USRE037936-20021210-C00013
CMP. NO R12 R13 R15 R16 R21 R23 R24 R25 R26 R4 R5 m/e
264 Cl H H Cl H H CF3 H H SCCl 2 F H 488
265 Cl H H Cl H H CF3 H H SCCl 2 F Br 566
266 Cl H H Cl H H CF3 H H SCCl 2 F NH2 503
267 Cl H H Cl H F3 H H SO 2 CCl2F Br 537
268 Cl H H Cl H H CF3 H H SOCCl 2 F H 504
269 Cl H H Cl H H CF3 H H SO2CCl2F H 520
270 H H H F H H CF3 H H SOCCl2F H 454
271 Cl H H Cl Cl H CF3 H Cl SOCCl2F H 572
272 Cl H H Cl H H OCF3 H H SOCCl2F H 520
273 Cl H H Cl H OCF2O H H SOCCl2F H 516
274 Cl H H Cl H H H H H SOCCl2F H 436
275 Cl H H Cl Me H Me Me H SOCCl2F H 478
276 Cl H H Cl Me H H H Me SOCCl2F H 464
277 Cl H H Cl H H t-Bu H H SOCCl2F H 492
278 Cl H H Cl H CF3 H CF3 H SOCCl2F H 572
279 Cl H H Cl H CH2CN H H H SOCCl2F H 475
280 Cl H H Cl H OCH2O H H SOCCl2F H 480
281 Cl H H Cl H F H F H SOCCl2F H 472
282 Cl H H Cl F F NH2 F F SOCCl2F H 523
283 Cl H H Cl NO2 H CF3 H H SOCCl2F H 549
284 Cl H H Cl H H CH2CN H H SOCCl2F H 475
285 Cl H H Cl H H n-Bu H H SOCCl2F H 492
286 Cl H H Cl Cl H Cl H H SOCCl2F H 504
287 Cl H H Cl H NO2 NH2 Me Me SOCCl2F H 524
288 Cl H H Cl Cl H CF3 H H SOCCl2F H 538
289 Cl H H Cl Cl H Cl H Cl SOCCl2F H 538
290 Cl H H Cl F F CF3 F F SOCCl2F H 576
291 Cl H H Cl F F CN F F SOCCl2F H 533
292 Cl H H Cl 5-tetrazolyl H H H H SOCCl2F H 504
293 Cl H H Cl H H CN H H SOCCl2F H 461
294 Cl H H Cl Cl H SF5 H Cl SOCCl2F H 630
295 H H H F H H CF3 H H SCCl2F H 438
296 Cl H H Cl H H CF3 H H SCF3 H 456
297 Cl H H Cl H H CF3 H H SOCF3 H 472
298 Cl H H Cl H H CF3 H H SO 2 CF3 H 488
The present invention provides also a method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a compound of formula (I), or a pesticidal composition comprising a pesticidally effective amount of a compound of formula (I) and a pesticidally acceptable carrier therefor. In a preferred embodiment, the invention provides a method for controlling insects at a locus comprising applying to said locus an insecticidally effective amount of a compound of formula (I), or an insecticidally effective amount of an insecticidal composition comprising an insecticidally effective amount of a compound of formula (I) and an agriculturally acceptable inert carrier therefor. Preferably, the locus to which the pesticidally (especially insecticidally) effective amount is applied is a crop-growing area, that is, an area in which a crop is growing or in which a crop has been planted, or an area in which a crop will be planted/grown.
The compositions which can be used in the invention for the pesticidal/insecticidal treatment of the invention can comprise from about 0.001 to 95% of the compound of formula (I).
The diluted liquid formulations, as applied to the locus to be treated or crop, generally comprise from about 0.001 to about 3% of active ingredient of formula (I), preferably from about 0.1 to about 0.5%.
The solid formulations as applied to the locus or crop generally comprise from about 0.1 to about 8% of active ingredient of formula (I), preferably from about 0.5 to about 1.5%.
The concentrated compositions are the compositions which are commercialized or transported or stored. For application to plants, they are normally diluted in water and applied in such diluted form. The diluted forms are part of the invention as well as the concentrated forms.
The concentrated formulations generally comprise from about 5 to about 95% of active ingredient of formula (I), preferably from about 10 to about 50%.
The insecticidal compositions of the invention can be applied once, or more than once, throughout the whole insect season. Insecticidal compositions according to the invention are usually applied to the locus to be treated or crop area at a rate of from about 0.01 to about 2 kg/ha of active ingredient, preferably from about 0.1 to about 1 kg/ha.
The concentrated insecticidal compositions according to the invention can be in the form of a solid, e.g., dusts or granules or wettable powders, or, preferably, in the form of a liquid, such as an emulsifiable concentrate or a true solution.
The compositions according to the instant invention generally comprise from about 0.5 to about 95% of active ingredient of formula (I). The remainder of the composition up to 100% comprises a carrier as well as various additives such as those hereafter indicated.
By “carrier”, there is meant herein an organic or inorganic material, which can be natural or synthetic, and which is associated with the active ingredient and which facilitates its application to the locus to be treated or crop. This carrier is thus generally inert and should be agriculturally acceptable, especially on the contemplated or treated locus or crop. The carrier can be solid (clay, silicates, silica, resins, wax, fertilizers, etc.) or liquid (water, alcohols, ketones, oil solvents, saturated or unsaturated hydrocarbons, chlorinated hydrocarbons, liquified petroleum gas, etc.).
Among the many additives, the compositions of the invention can comprise surfactants as well as other ingredients such as dispersants, stickers, antifoam agents, anti-freezing agents, dyestuffs, thickeners, adhesives, protective colloids, penetrating agents, stabilizing agents, sequestering agents, antiflocculating agents, corrosion inhibitors, pigments and polymers.
More generally, the compositions of the invention can comprise all kinds of solid or liquid additives which are known in the art of insecticides and insecticidal treatments.
The surfactants can be of the emulsifying or wetting type, ionic or non-ionic. Possible surfactants are salts of polyacrylic or lignosulfonic acids; salts of phenolsulfonic or naphthalenesulfonic acids; polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines or substituted phenols (particularly alkylphenols or arylphenols); ester-salts of sulfosuccinic acids; taurine derivatives, such as alkyl taurates; phosphoric esters; or esters of alcohols or polyoxyethylated phenols. When the spraying vehicle is water, the use of at least one surfactant is generally required because the active ingredients are not water-soluble.
The method of application of the compositions of the invention is generally the spraying of a mixture which has been previously made, by dilution of more concentrated formulations according to the invention.
Solid compositions can be powders for dusting or for dispersion (wherein the content of active ingredient can be up to 100%) and granules, especially extruded or compacted granules, or granules which have been made by impregnation of a powder (the content of active ingredient in such powders being between about 1 and about 80%).
Liquid compositions of compositions which have to be liquid when applied include solutions, water-soluble concentrates, emulsifiable concentrates, emulsions, wettable powders or pastes or water-dispersible granules.
Emulsifiable concentrates generally comprise from about 10 to about 80% of active ingredient; the emulsions when applied generally comprise from about 0.01 to about 20% of active ingredient.
For example, the emulsifiable concentrates can comprise the solvent and, to the extent needed, from about 2 to about 20% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors or other additives already recited.
These concentrates are usually diluted in tank water so as to obtain the dilution appropriate for spraying.
The concentrated suspensions can also be applied by spraying and have to be fluid without allowing any solid to separate and fall to the bottom. Generally they comprise from about 1 to about 75% of active ingredient (preferably from about 2 to about 50%), from about 0.5 to about 15% of surfactant, from about 0.1 to about 10% of thickener, from 0 to about 10% of other suitable additives as already indicated, the remainder being water or an organic liquid wherein the active ingredient is insoluble or has a low solubility.
The wettable powders generally comprise the active ingredient (from about 1 to about 95%, preferably from about 2 to about 80%), the solid carrier, a wetting agent (from 0 to about 5%), a dispersing agent (from about 3 to about 10%) and, to the extent needed, from 0 to about 10% of other additives such as stabilizers and others as already listed.
In order to obtain these wettable powders or dusting powders, it is appropriate to intimately mix the active ingredients and the additives, as by grinding in a mill or similar device.
Dispersible granules are generally made by agglomeration of a powder, followed by an appropriate granulation process.
The emulsions herein described can be of the oil-in-water or water-in-oil types. Fluidity of the emulsions can range from low viscosities up to high viscosities approaching those of gels.
Among these many compositions or formulations, one skilled in the art can choose the one most appropriate, according to the specific conditions of the treatment problem.
The compounds and compositions of the invention can also be used in admixtures with another pesticide, e.g., an insecticide, acaricide or herbicide.
The compounds of the invention may also be used in controlling pests found in non-agricultural domains.
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 man or 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, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. e.g. Rhipicephalus appendiculatus, Haemaphysalis spp., Dermacentor spp., Ornithodorus spp. (e.g. Ornithodorus moubata) and mites (e.g. Damalinia spp., Dermahyssus gallinae, Sarcoptes spp. e.g. Sarcoptes scabiei, Psoroptes spp., Chorioptes spp;, Demodex spp., Eutrombicula spp.,); Diptera (e.g. Aedes spp., Anopheles spp., Dermatobia spp., Haematobia spp., Musca spp., Hippoboscidae spp., Hypoderma spp., Gasterophilus spp., Simulium spp); Stomoxys spp., Hemiptera (e.g. Triatoma spp); Phthirapter (e.g. Damalinia spp., Linognathus spp.); Siphonaptera (e.g. Ctenocephalides spp.); Dictyoptera (e.g. Periplaneta spp., Blatella spp.); Hymenoptera (e.g. Monomorium pharaonis); for example against infections of the gastro-intestinal tract caused by parasitic nematode worms, for example members of the family Trichostrongylidae, Nippostrongylus brasiliensis, Trichinella spiralis, Haemonchus contortus, Trichostrongylus colubriformis, Nematodirus batus, Ostertagis circumcincta, Trichostrongylus axei, Cooperia spp. and Hymenolepis nana; in the control and treatment of protozoal diseases caused by, for example, Eimeria spp. e.g. Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix, Trypanosoms cruzi, Leishaminia spp., Plasmodium spp., Babesis spp., Trichomonadidae spp., Histomanas spp., Giardia spp., Toxoplasma spp., Entamoeba histolytica and Theileria spp.
Furthermore, the compounds of the invention may be useful for coccidiosis, a disease caused by infections from protozoan parasites of the genus Eimeria.
Compositions
Solid or liquid compositions for application topically to animals, timber, 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 general formula (I). For administration to animals orally or parenterally, including percutaneously solid or liquid compositions, these normally contain from about 0.1% to about 90% by weight of one or more compounds of general formula (I). Medicated feedstuffs normally contain from about 0.001% to about 3% by weight of one or more compounds of general formula (I). 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 general formula (I). Mineral salt licks normally contain from about 0.1% to about 10% by weight of one or more compounds of general formula (I).
Dusts or liquid compositions for application to livestock, persons, 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 general formula (I). 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 general formula (I) 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 general formula (I).
When administered to vertebrates parenterally, orally or by percutaneous or other means, the dosage of compounds of general formula (I) 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 0.1 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 formulations or devices, the daily doses required over a period of months may be combined and administered to animals on a single occasion.
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:
GENUS, SPECIES COMMON NAME
Aphis gossypii cotton leaf aphid
Musca domestica housefly
Diabrotica virgifera Western cornrootworm
Periplaneta americana American Cockroaches
Spodoptera eridania Southern armyworm
The Housefly Bait/Contact Test
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 50 ppm. After 24 hours, flies which showed no movement on stimulation were considered dead.
Foliar application (Contact Test) with Aphids
Aphid-infested cotton plants were placed on a revolving turntable, and sprayed to runoff with a 100 ppm formulation of the selected compound of formula (I). The treated, A. gossypii-infested plants were held for three days after treatment, after which the dead aphids were counted.
Application on Western cornrootworm
Jars are filled with 60 g dry soil homogeneously mixed with 5 ml aqueous solution containing the compound to be tested. After drying, four germinated corn seedlings are placed in the bottom of each jar and the soil is wetted. Then ten newly born larvae are placed in each jar. The jars are stored for six days at 27° C. under 70% of relative humidity. The number of surviving larvae are then counted.
Application by contact to Cockroaches
The inner wall of a 100 ml jar is covered by shaking 2 ml of pesticidal formulation. Furthermore, a pellet of dog chow is placed into a jar and the pesticidal formulation is absorbed on the pellet, using excess liquid. The jar is then left open up to evaporation of liquid. Cockroach nymphs are placed in the jar and mortality is assessed after five days.
Application to Southern armyworm
Leaves of soybeans were sprayed to run-off with a spray of various concentrations. Then the leaves were allowed to dry, excised, and placed into a container with five larvae. The containers are stored for five days at 25° C. under 50% relative humidity. Mortality ratings are then counted.
Application to Caenorhabditis elegans (nematode worm)
This test is significant for animal health applications of active ingredient.
Test formulation are prepared by mixing 2 microliters of dimethylsulfoxide with 100 microliters of a solution of Escherichia coli (which is food for C. elegans). 98 microliters of this mixture are then mixed with an inoculum solution which consists of mixed life stages of C. elegans (about 50 worms). This new mixture is stored 7 days at 20° C. Mortality is then visually assessed as well as the behavior of the worm. For the mortality, the rating is either 1 (large increase in number of the population, similar to the control which is trebbling in 7 days) or 3 (slight increase of the population, but significantly less increase than the control) or 5 (little to no increase in the population). For the behavior effect, the rating is either 1 (normal motion) or 3 (motion is slower than the control) or 5 (little to no movement).
All the hereinabove prepared compounds show a positive activity in one or more of these tests (rather good activity on C. elegans).
While the invention has been described in terms of various preferred embodiments, the person skilled in the art 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 be limited solely by the scope of the following claims, including equivalents thereof.

Claims (21)

What is claimed is:
1. A compound of formula (I):
Figure USRE037936-20021210-C00014
wherein:
X is N;
Y is C—R3;
W is C—R4;
R3 is CN;
R4 is —S(O)nR8;
R5 is —NR9R10;
R8 is alkyl, haloalkyl, alkenyl, or alkynyl, or R8 is a cycloalkyl ring having 3 to 5 carbon atoms;
R9 and R10, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R8S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl, the alkyl portions of R9 and R10 being optionally substituted by R7;
R7 is cyano, nitro, alkoxy, haloalkoxy, R8S(O)n, —C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
Z is C—R16;
n is zero, one or two;
R12, R13, R15 and R16, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;
R22, R23, R24, R25, and R26, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF5, or R8S(O)n;
or a pesticidally acceptable salt thereof.
2. A compound according to claim 1, wherein R24 is halogen, haloalkyl or haloalkoxy.
3. A compound according to claim 1, wherein R5 is —NH2.
4. A compound according to claim 1, wherein R8 is lower alkyl or haloalkyl.
5. A compound according to claim 1, having at least one feature selected from the group consisting of:
R8 is methyl, ethyl, —CF3, —CFCl2, or —CF2Cl;
R12 and R16, independently of each other, are F, Cl, Br or H;
R13 and R15 are H;
R24 is —CF3, —OCF3, —CHF2, —S(O)nCF3, —CFCl2, —CF2Cl, —OCF2Cl, —OCFCl2, Cl, Br or F; and
Z is CCl, CF, or CBr.
6. A compound according to claim 2 claim 5, wherein R5 is —NH2.
7. A compound according to claim 1, wherein:
R12 and R16, independently of each other, are Cl or Br;
R13 and R15 are H;
R24 is —CF3, —OCF3 or Br;
R5 is amino;
R9 and R10, independently of each other, are H, alkyl or alkylcarbonyl; and
R8 is methyl, ethyl, CF3, CFCl2 or CF2Cl.
8. A compound according to claim 2 claim 5, wherein:
R12 and R16, independently of each other, are Cl or Br;
R24 is —CF3, —OCF3 or Br;
R5 is amino; and
R9 and R10, independently of each other, are H, alkyl or alkylcarbonyl.
9. A compound according to claim 1, wherein the S(O)nR8 substituent of formula (I) is: methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
10. A compound according to claim 5, wherein the S(O)nR8 substituent of formula (I) is: trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
11. A compound according to claim 7, wherein the S(O)n R8 substituent of formula (I) is: trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
12. A compound according to claim 8, wherein the S(O)nR8 substituent of formula (I) is: trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
13. The compound of formula (I) according to claim 1, which is:
1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole; or
1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylsulfonyl-5-aminopyrazole.
14. A pesticidal composition comprising:
(a) a pesticidally effective amount of a compound of formula (I):
Figure USRE037936-20021210-C00015
wherein:
X is N;
Y is C—R3;
W is C—R4;
R3 is CN;
R4 is —S(O)nR8;
R5 is —NR9R10;
R8 is alkyl, haloalkyl, alkenyl, or alkynyl, or R8 is a cycloalkyl ring having 3 to 5 carbon atoms;
R9 and R10, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R8S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl, the alkyl portions of R9 and R10 being optionally substituted by R7;
R7 is cyano, nitro, alkoxy, haloalkoxy, R8S(O)n, —C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
Z is C—R16;
n is zero, one or two;
R12, R13, R15 and R16, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl;
R22, R23, R24, R25, and R26, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF5, or R8S(O)n;
or a pesticidally acceptable salt thereof.
(b) a pesticidally acceptable carrier therefor.
15. A composition according to claim 14, comprising from 0.001 to 95% of compound of formula (I).
16. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a compound of formula (I):
Figure USRE037936-20021210-C00016
wherein:
X is N;
Y is C—R3;
W is C—R4;
R3 is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN;
R4 is —S(O)nR8;
R5 is —NR9R10;
R8 is alkyl, haloalkyl, alkenyl, or alkynyl, or R8 is a cycloalkyl ring having 3 to 5 carbon atoms;
R9 and R10, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R8S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl, the alkyl portions of R9 and R10 being optionally substituted by R7;
R7 is cyano, nitro, alkoxy, haloalkoxy, R8S(O)n, —C(O) alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO2H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;
Z is C—R16;
n is zero, one or two;
R12, R13, R15 and R16, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl;
R22, R23, R24, R25, and R26, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF5, or R8S(O)n;
or a pesticidally acceptable salt thereof.
17. A method according to claim 16, wherein said pests are insects and wherein said pesticidally effective amount is an insecticidally effective amount.
18. A method according to claim 17, comprising applying to said locus from about 0.01 to about 2 kg/ha of compound of formula (I).
19. A method according to claim 18, comprising applying to said locus from about 0.1 to about 1 kg/ha of compound of formula (I).
20. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a composition as claimed in claim 14.
21. A method according to claim 20, wherein said pests are insects and wherein said pesticidally effective amount is an insecticidally effective amount.
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