WO2004105488A1 - Hydrazone derivatives for combatting harmful insects and arachnids - Google Patents

Hydrazone derivatives for combatting harmful insects and arachnids Download PDF

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Publication number
WO2004105488A1
WO2004105488A1 PCT/EP2004/005681 EP2004005681W WO2004105488A1 WO 2004105488 A1 WO2004105488 A1 WO 2004105488A1 EP 2004005681 W EP2004005681 W EP 2004005681W WO 2004105488 A1 WO2004105488 A1 WO 2004105488A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
phenyl
halogen
haloalkyl
independently
Prior art date
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PCT/EP2004/005681
Other languages
French (fr)
Inventor
Michael Hofmann
Markus Kordes
Udo Lang
Ernst Baumann
Wolfgang Von Deyn
Michael Puhl
Thomas Schmidt
Gerd Steiner
Michael F. Treacy
Deborah L. Culbertson
Toni Bucci
Shieh Hong-Ming
Lester L. Maravetz
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Basf Aktiengesellschaft
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Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to JP2006529926A priority Critical patent/JP2006528955A/en
Priority to MXPA05012226A priority patent/MXPA05012226A/en
Priority to AU2004243492A priority patent/AU2004243492A1/en
Priority to EP04734834A priority patent/EP1631143A1/en
Priority to US10/557,881 priority patent/US20070066627A1/en
Priority to BRPI0410626-1A priority patent/BRPI0410626A/en
Publication of WO2004105488A1 publication Critical patent/WO2004105488A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/86—Hydrazides; Thio or imino analogues thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more 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
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen
    • 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
    • C07D405/12—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 chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • Hydrazone derivatives for combatting harmful insects and arachnids Hydrazone derivatives for combatting harmful insects and arachnids
  • the present invention relates to a method for combating harmful insects and arachnids.
  • WO 87/66133 describes acyl hydrazones which are useful for killing internal parasites, such as nematodes, trematodes and cestodes, affecting warm-blooded animals and humans.
  • US 3066023 discloses aroylhydrazones as components of a photoconducting insulating layer in a material for xerography.
  • WO 99/01423 discloses the preparation of aroylhydrazones which are useful as gluca- gon antagonists or inverse agonists.
  • EP-A 322691 discloses aroylhydrazones as precursors for the preparation of 1- acylpyrazolines.
  • Ar is a cyclic radical selected from phenyl, naphthyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic radical may be fused to 1 or 2 phenyl rings, and where the cyclic radical may have 1 , 2, 3, 4 or 5 substituents R a which are selected, independently of one another, from halogen, cyano, nitro, C C 10 -alkyl, C C 10 -haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 - halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 - haloalkynyl, CrC 10 -alkoxy, d-Cio-
  • R b which are selected, independently of one another, from halogen, cyano, nitro, C C ⁇ o-alkyl, C C 10 -haloalkyl, C 3 -C 10 - cylcoalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 - alkynyl, C 3 -C 10 -haloalkynyl, d-do-alkoxy, d-do-haloalkoxy, C 2 -C 10 -alkenyloxy,
  • X is CO or SO 2 ;
  • R 1 is H, Ci-Cio-alkyl, CrC 10 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C ⁇ 0 -halocycloalkyl, C 2 - C 10 -alkenyl, C 2 -C ⁇ o-haloalkenyl, C 2 -C 10 -alkynyl, C 2 -C 10 -haloalkynyl or phenyl which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, CrC 10 -alkyl, d-Cio-haloalkyl, C 3 -C ⁇ o-cylcoalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C ⁇ 0 -haloalkenyl, C 2 - C ⁇ o-alkynyl, C 3
  • R 2 and R 3 are independently of one another H, halogen, cyano, d-do-alkyl, C C 10 - haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C ⁇ o- haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 -haloalkynyl, d-Cio-alkoxy, d-Cio-haloalkoxy,
  • R 4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl or furyl, thienyl, where the aromatic radical may carry 1 , 2, 3, 4 or 5 substituents R c which are selected, independently of one another, from halogen, cyano, nitro, d-do-alkyl, C Cio-haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 -halocycIoalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 - haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 -haloalkynyl, CrC 10 -alkoxy, C C 10 -haloalkoxy, d-do-alkenyloxy, C 2 -C 10 -haloalkenyloxy, C 2 -C ⁇ 0 -alkynyloxy
  • R 5 R 6 N-CO- and phenoxy which may be substituted by 1 , 2, 3, 4 or 5 substituents R d which are selected, independently of one another, from halogen, cyano, nitro, d-Cio-alkyl, d-do-haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 - alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 -haloalkynyl, CrC 10 -alkoxy, C r do-haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 10 -haloalkenyloxy, C 2 -C 10 -alkynyloxy, C 3 -
  • R 2 and R 4 together with the carbon atoms to which they are bound form a phenyl ring or a 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the phenyl ring and the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring, and where the phenyl ring and the 5- or 6-membered heterocyclic ring and/or the phenyl ring to which they are fused may carry 1 , 2, 3 or 4 substituents R e , which are selected, independently of one another, from halogen, cyano, nitro, C C ⁇ o- alkyl, C C 10 -haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -do-haloalkenyl, C
  • R 5 and R 6 independently of one another are H or d-do-alkyl
  • n O or l
  • the present invention therefore relates to a method for combating harmful insects and arachnids, which comprises contacting the insects or the arachnids, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the insects or arachnids grow or may grow, or the materials, plants, seeds, soil, surfaces or spaces to be protected against attack or infestation by insects or arachnids with a pesticidally effective amount of a hydrazone compound of the formula I.
  • the invention especially relates to a method for protecting crops from attack or infestation by insects or arachnids, which comprises contacting a crop with a pesticidally effective amount of a compound of the formula I as defined above.
  • Suitable compounds of the general formula I encompass all possible stereoisomers (cis/trans isomers) which may occur and mixtures thereof.
  • Suitable compounds also encompass possible enantiomers and racemic mixtures.
  • Salts of the compounds of the formula I which are suitable for the use according to the invention are especially agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question.
  • Suitable salts include adducts of compounds I with maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • salts include those that can form with, for example, amines, metals, alkaline earth metal bases or quaternary ammonium bases, including zwitterions.
  • Suitable metal and alkaline earth metal hydroxides as salt formers include the salts of barium, aluminum, nickel, copper, manganese, cobalt zinc, iron, silver, lithium, sodium, potassium, magnesium or calcium.
  • Additional salt formers include chloride, sulfate, acetate, carbonate, hydride, and hydroxide.
  • Desirable salts include adducts of compounds I with maleic acid, dimaleic acid, fumaric acid, difumaric acid, and methane sulfonic acid.
  • the term "5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S" as used herein refers to both aromatic and non-aromatic rings such as saturated or partially unsaturated radicals having from 1 to 4, preferably 1 ,2, or 3 heteroatoms as ring members.
  • heteroaromatic rings examples include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl or isoxazolyl.
  • the 5- or 6-membered heteroaromatic ring is fused to 1 or 2 phenyl rings, this refers e.g. to quinolinyl, isoquinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzthiazolyl, benzoxazolyl, benzimidazolyl, dibenzopyrrolyl, dibenzofu- ranyl or dibenzothienyl.
  • non-aromatic rings are pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, dioxolanyl, dioxolenyl, thiolanyl, dihydrothiophenyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thia- zolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl,
  • the 5- or 6-membered heterocyclic non-aromatic radical is fused to a phenyl group, this refers to e. g. dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroisochinolinyl, chromenyl, chromanyl and the like.
  • 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring refers e.g.
  • the 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which may be fused to a phenyl ring contains a carbonyl group as a ring member, this refers to e. g. pyrroli- donyl, pyrazolidonyl, pyrazolonyl, oxazolidonyl, pyridonyl, pyronyl, indoxylyl, oxindolyl, cumarinyl, chromenonyl (chromonyl) and the like.
  • Halogen will be taken to mean fluoro, chloro, bromo and iodo.
  • d-do-alkyl refers to a branched or unbranched saturated hydrocarbon group having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, 1- methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1- dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1,1-dimethylbutyl, 1 ,2-dimethylbutyI, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbuty
  • d-C ⁇ 0 -haloalkyl refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example d-C 4 -haloalkyl, such as chloromethyl, bromomethyl, dichloro- methyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro
  • C C 10 -alkoxy and “d-Cio-alkylthio” refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group.
  • Examples include d-C 4 - alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, futher d-C 4 -alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
  • C C 10 -haloalkoxy and " C r C 10 -haloalkylthio” refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C C 2 -haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro
  • C 2 -C ⁇ 0 -alkenyl intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3- butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2- propenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl
  • C 2 -C 10 -haloalkenyl intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • C 2 -d 0 -alkenyloxy intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, for example ethenyloxy, propenyloxy and the like.
  • C 2 -C 10 -haloalkenyloxy intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • C 2 -C 10 -alkynyl refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
  • C 3 -C 10 -haloalkynyl refers to a branched or unbranched un- saturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
  • C 2 -C 10 -alkynyloxy refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, the alkynyl group being bonded through oxygen linkages at any bond in the alkynyl group.
  • C 3 -C 10 -haloalkynyloxy refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, the group being bonded through oxygen linkages at any bond in the alkynyl group, where some or all of the hydrogen atoms in these group may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
  • C 3 -C 10 -cycloalkyl refers to a monocyclic 3- to 10-membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl and cyclodecyl.
  • C 3 -C 10 -halocycloalkyl refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloro-, dichloro- and trichlorocyclopropyl, fluoro-, difluoro- and trifluorocyclopropyl, chloro-, dichloro-, trichloro, tetrachloro-, pentachloro- and hexachlorocyclohexyl and the like.
  • Ar is a cyclic radical selected from phenyl, naphthyl, a 5- or 6-membered heterocyclic radical with 1 to 3 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic radical may be fused to 1 or 2 phenyl rings and where the cyclic radical is unsubstituted or substituted as defined above, i.e. by 1, 2, 3, 4 or 5 of the above mentioned radicals R a .
  • Ar is a cyclic radical selected from phenyl, triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl, isoxazolyl, naphthyl, quinolinyl, isoquinolinyl, indolyl, indazolyl, benzofuryl, benzthienyl, benzthiazolyl, benzoxazolyl, benzimidazolyl, chromenyl, chromenonyl, dibenzopyranyl or fluorenyl and where the cyclic radical is unsubstituted or substituted as defined above.
  • Ar is a cyclic radical selected from phenyl, tri
  • Ar is a cyclic radical selected from thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, tria- zolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, phenyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, naphthyl, dibenzopyranyl, indolyl, benzimidazolyl, benzofuryl, benzoxazolyl, benzothienyl, benzthiazolyl or chrome- nonyl and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or 5 of the above mentioned radicals R a .
  • Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, phenyl, pyridyl, pyrazinyl, naphthyl, dibenzopyranyl, indolyl or benzothieny and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or 5 of the above mentioned radicals R a .
  • Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, phenyl, pyridyl, pyrazinyl, naphthyl, indolyl or benzothienyl, especially thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, phenyl, pyridyl, pyrazinyl, naphthyl or indo- lyl and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or 5 of the above mentioned radicals R a .
  • Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, phenyl, isoxazolyl or pyridyl and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or
  • the cyclic radical mentioned for Ar is unsubstituted or carries 1 , 2, 3 or 4 substituents R a , in particular 1 , 2 or 3 and more preferably 1 or 2 substituents R a .
  • Preferred substituents R a are selected, independently of one another, from halogen, cyano, nitro, Ci-Cio-alkyl, d-do-haloaikyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 -halocycloalkyl, C do-alkoxy, d-Cio-haloalkoxy, C C 10 -alkylthio, C C 10 -haloalkylthio, d-C 10 - alkylsulfonyl, d-C 10 -haloalkylsulfonyl, hydroxy, phenyl, phenoxy, NR 5 R 6 , d-do- alkoxycarbonyl, CrC 10 -haIoalkoxycarbonyl, CrC 10 -alkylcarbonyl, C r C 10 - haloalkylcarbonyl and NR 5 R 6 -CO-.
  • substituents R a are selected, independently of one another, from halogen, hydroxy, d-C 4 -alkyl, C C -haloalkyl, d-C 4 -alkoxy, C C 4 -haloalkoxy, phenyl, which is unsubstituted or substituted by by 1 to 3 substituents R b which are in particular selected, independently of one another, from halogen, C C 4 -alkyl, C C 4 -haloalkyl and d-C 4 -alkoxy, especially by halogen, and phenoxy which is unsubstituted or substituted by 1 to 3 substituents R which are in particular selected, independently of one another, from halogen, CrC 4 -alkyl, C C 4 -haloalkyl and C C 4 -alkoxy, especially by C C 4 - haloalkyl.
  • R a are selected, independently of one another, from halogen, C C 4 -alkyl, CrC 4 -haloalkyl, C r C 4 -alkoxy and C C 4 -haloalkoxy.
  • substituents R a are selected, independently of one another, from fluorine, chlorine, bromine, C C 4 -alkyl, C C 4 -alkoxy, in particular methoxy, C C 4 - haloalkoxy, in particular difluoromethoxy or trifluoromethoxy and CF 3 .
  • R 2 is H, d-Cio-alkyl, d-do-haloalkyl, halogen, phenyl or cyano.
  • R 2 is H, C C 10 -alkyl, , in particular C C 4 -alkyl, halogen, phenyl or cyano.
  • R 2 is H, d-do-alkyl, in particular C C 4 -alkyl or halogen, e.g. methyl, ethyl, isopro- pyl, fluorine, chlorine or bromine.
  • R 2 is C C -alkyl, in particular methyl or ethyl.
  • R 3 is H, d-C 4 -alkyl, d-C -haloalkyl, halogen or phenyl.
  • R 3 is H, d-C 4 -alkyl, halogen or phenyl, especially H or halogen.
  • R 4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl, furanyl, thienyl or benzofuryl where the aromatic radical is unsubstituted or substituted as defined above, i.e. by 1 , 2, 3, 4 or 5 of the above mentioned radicals R G .
  • the aromatic radical as mentioned for R 4 may be unsubstituted or may carry 1 to 5, preferably 1 to 4, more preferably 1 to 3 and in particular 1 or 2 substituents R c .
  • Preferred substituents R c are selected, independently of one another, from hydroxy, halogen, cyano, nitro, C ⁇ -C 10 -alkyl, C r C 10 -haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 - halocycloalkyl, C C 10 -alkoxy, d-Cio-haloalkoxy, d-do-alkylthio, d-Cio-haloalkylthio, d-do-alkylsulfonyl, C C 10 -haloalkylsulfonyl, NR 5 R 6 , C C 10 -alkoxycarbonyl, C C 10 - haloalkoxycarbonyl, R
  • substituents R G are selected, independently of one another, from halogen, d-C 4 -alkyl, C C 4 -haloalkyl, C C 4 -alkoxy, d-d-haloalkoxy, C C 4 -alkylthio, d-C 4 -haloalkylthio, cyano, nitro, NR 5 R 6 and phenoxy which may be substituted by d- C -haloalkyl.
  • R c are selected, independently of one another, from halogen, d-C -alkyl, C C 4 -haloalkyl, d-C 4 -alkoxy, C C -haloalkoxy and C C 4 - haloalkylthio, e.g. from fluorine, chlorine, methyl, ethyl, propyl, isopropyl, butyl, fluoro- methyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy and trifluoromethylthio.
  • R c are selected, independently of one another, from halogen, C C 4 -alkyl and d-C 4 -haloalkyl.
  • R 4 is phenyl, which carries 1 , 2 or 3 of the aforementioned substituents R c , then at least one of the substituents is preferably located in the 2, 4 and/or 6-postion.
  • Examples of paricularly preferred substituted phenyl are those mentioned in tables 2 and 3 as radicals R 4 .
  • R 2 and R 4 together with the carbon atoms to which they are bound form a phenyl ring or a 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring, and where the 5- or 6-membered heterocyclic ring and/or the phenyl ring to which it is fused may carry 1 , 2, 3 or 4 of the aforementioned substituents R e .
  • the substituents R e are selected, independently of one another, from halogen, d-C 4 -alkyl, C r C -haloalkyl, d-C 4 -alkoxy, d-C 4 - haloalkoxy, C C 4 -alkylthio, C r C 4 -haloalkylthio, cyano, nitro, phenyl, which is unsubstituted or is substituted by 1 , 2 or 3 substituents R f which are selected, independently of one another, from C r C 4 -alkyl, C C 4 -haloalklyl C C -alkoxy and halogen, and phenoxy which is unsubstituted or substituted by 1 to 3 substituents which are selected, independently of one another, from d-C 4 -alkyl, C r C 4 -haloalklyl, d-C 4 -alkoxy and halogen, and where the 5-
  • R 3 is either H or is one of the above-mentioned substituents of the moiety formed by R 2 and R 4 together with the carbon atoms to which they are bound.
  • substituents R e are selected, independently of one another, from halogen, d-C 4 -alkyl, d-C 4 -haloalkyl, C C 4 -haloalkoxy, d-C 4 -haloalkylthio, cyano, nitro, phenyl, which is unsubstituted or is substituted by 1 , 2 or 3 substituents which are selected, independently of one another, from d-C 4 -haloalklyl and halogen, and phenoxy which is unsubstituted or substituted by d-C 4 -haloalklyI.
  • the substituents R e are selected, independently of one another, from halogen, C C 4 -alkyl, C C 4 -haloalkyl, d- C 4 -alkoxy, d-C 4 -haloalkoxy, C C 4 -haloalkylthio, cyano and nitro. More preferably substituents R e are selected, independently of one another, from C C 4 -alkyl, C ⁇ -C 4 - haloalkyl and halogen.
  • radicals R b , R d and R f are selected from halogen, C C 4 -alkyl, C C 4 -haloalkyl, d-C 4 -haloalkoxy, CrC 4 -haloalkylthio, cyano and nitro, especially from halogen, C ⁇ -C 4 -alkyl, d-C 4 -alkoxy, d-C 4 -haloalkyl, C C 4 -haloalkoxy.
  • R a , R 1 and R 3 are as defined herein,
  • n 0, 1, 2 or 3
  • R 2a is H or d-C 4 alkyl
  • R 4a is phenyl, which may carry 1 , 2, 3 or 4 substituents R c as defined herein,
  • R 2a is C C 4 alkyl and additionally one of the following provisions i) to iv) are met, the compounds la are new and thus are part of the present invention: i) m is not 0 or ii) R 4a carries at least one substituent R G being different from hydrogen iii) or R 1 is different from hydrogen, iv) or R 2a is different from methyl.
  • R a in formula la has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred.
  • R a is Halogen, in particular F, CI or Br, d-d-alkyl, in particular methyl or ethyl, phenyl, difluoromethyl, trifluoromethyl or d-C 4 -alkoxy, in particular methoxy.
  • R 1 and R 3 have, independently of each other, one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. Most preferred are compounds la, wherein R 1 and R 3 are hydrogen.
  • the substituent R c has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred.
  • R c is selected from F, CI, methoxy or methyl.
  • substituted phenyl is selected from one of the meanings given for R 4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-triflu
  • R is most preferably methyl or ethyl.
  • n, X, R ⁇ R 2 , R 3 and R 4 are as defined herein, and
  • Ar is isoxazolyl, which may carry 1 or 2 substituents R a as defined herein.
  • Ar does not carry an optionally substituted phenyl group as a radical R a if Ar is substituted 4-isoxazolyl these compounds are new and are also part of the present invention.
  • n, X, R a , R 1 , R 2 , R 3 and R 4 have, independently of each other, one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred.
  • the variables R 1 , R 2 , R 3 and R a have the meanings outlined below:
  • R 1 is H
  • R 2 is H or d-C 4 alkyl most preferably methyl or ethyl
  • R 3 is H
  • R 4 is phenyl, which may carry 1 , 2, 3 or 4 substituents R c as defined herein,
  • the substituent R c has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred.
  • R c is selected from F, CI, methoxy or methyl.
  • substituted phenyl is selected from one of the meanings given for R 4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-triflu
  • n, X, R 1 , R 2 , R 3 and R 4 are as defined in claim 1 ,
  • Ar is pyrazolyl which carries a substituent R a2 on the pyrazol nitrogen atom, and which may additionally carry 1 or 2 substituents R a as defined in claim 1 , wherein R a2 is selected from d-Cio-alkyl, C C ⁇ o-haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 - halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 - haloalkynyl, phenyl and benzyl, wherein phenyl and benzyl may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents R b as defined in claim 1
  • n, X, R a , R b , R 1 , R 2 , R 3 and R 4 have, independently of each other, one of the meanings which are indi- cated as being preferred, more preferred, particularly preferred or especially preferred.
  • R a2 is preferably selected from d-C 6 -alkyl, C 3 -C 6 -cycloalkyl or phenyl. In a particularly preferred embodiment R a2 is d-C 4 -alkyl.
  • R 1 is H
  • R 2 is H or C ⁇ -C 4 alkyl most preferably methyl or ethyl
  • R 3 is H, and R 4 is phenyl, which may carry 1 , 2, 3 or 4 substituents R c as defined herein,
  • the substituent R° has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred.
  • R c is selected from F, CI, methoxy or methyl.
  • substituted phenyl is selected from one of the meanings given for R 4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-trifluorome
  • R a , R 1 and R 3 are as defined herein,
  • n 1 , 2 or 3
  • R 2d is H or C C 4 alkyl
  • R 4d is phenyl, which may carry 1 , 2, 3 or 4 substituents R G as defined herein,
  • R a in formula Id has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred.
  • R a is Halogen, in particular F, CI or Br, d-C 4 -alkyl, in particular methyl or ethyl, phenyl, difluoromethyl, trifluoromethyl or d-C -alkoxy, in particular methoxy.
  • R a is halogen, especially fluorine.
  • R 1 and R 3 have, independently of each other, one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. Most preferred are compounds la, wherein R 1 and R 3 are hydrogen.
  • the substituent R c has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred.
  • R c is selected from F, CI, methoxy or methyl.
  • substituted phenyl is selected from one of the meanings given for R 4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-triflu
  • the compounds of the formula I may be readily synthesized using techniques generally known by synthetic organic chemists. Exemplary synthesis methods are described for example in WO 87/06133.
  • acyl hydrazides can be reacted with aldehydes or ketones to form acyl hydrazones:
  • Cinnamic aldehydes and analogous ketones can be obtained according to a literature procedure (Organikum, Johann Ambrosius Barth Verlag, Heidelberg, 1996, pp. 493- 495) from benzaldehydes and aliphatic ketones or aldehydes.
  • carboxylic acid esters Ar-(CH 2 ) n -COOR a
  • Ar-(CH 2 ) n -COY halogen
  • carboxylic acids Ar-(CH 2 ) n -COOH
  • a coupling reagent such as DCC or DIC (according to Guan, Green, Bergstrom, J. Comb. Chem. 2000, 2, 297-300), and subsequent removal of the protecting group (Messina, Botta, Corelli, Paladino, Tetrahedron Asymm. 2000, 11 , 4895-4901 ; Greene, Wuts, Protective Groups in Organic Synthesis, 2nd edition, 1991 , pp. 309):
  • R a C C 10 -alkyl
  • the preparation of the compounds of formula I may lead to them being obtained as isomer mixtures (stereoisomers, enantiomers). If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.
  • the compounds of the general formula I are used for controlling harmful insects and arachnids.
  • they are used for controlling the following animal pests:
  • insects from the order of the lepidopterans for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, A ⁇ tographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unip ⁇ ncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosell ⁇ s, Eupoecilia ambig ⁇ ella, Evetria bo ⁇ - liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo
  • beetles Coldeoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibi- alis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12- punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hir
  • dipterans dipterans
  • Aedes aegypti Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycor
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Hymenopterans e.g. Athalia rosae, Atta cephalotes, Atia sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta,
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor, homopterans (Homoptera), e.g.
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris
  • Acyrthosiphon onobrychis Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysa
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis,
  • orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus,
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melan
  • Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • Arachnids Acarina
  • Argasidae e.g. of the families Argas
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
  • the compounds of the formula I are preferably used for controlling pests of the orders Lepidoptera, Thysanoptera, Homoptera and Acarina and more preferably for controlling insects of the orders Lepidoptera and Homoptera.
  • the compounds of formula (I) may be used to protect growing plants and crops from attack or infestation by insects or arachnids by contacting the plant/crop with a pesti- cidally effective amount of compounds of formula (I).
  • crop refers both to growing and harvested crops.
  • the insect, arachnid, plant and/or soil or water in which the plant is growing can be contacted with the present compound(s) I or composition(s) containing them by any application method known in the art.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the insect, arachnid, and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the insect, arachnid, and/or plant).
  • insects or arachnids may be controlled by contacting the target pest, its food supply or its locus with a pesticidally effective amount of compounds of formula (I).
  • the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
  • “Locus” means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
  • the rate of application of the compounds and/or compositions of this invention may be in the range of about 0.1 g to about 4000 g per hectare, desirably from about 25 g to about 600 g per hectare, more desirably from about 50 g to about 500 g per hectare.
  • the typical rate of application is of from about 1 g to about 500 g per kilogram of seeds, desirably from about 2 g to about 300 g per kilogram of seeds, more desirably from about 10 g to about 200 g per kilogram of seeds.
  • Customary application rates in the protection of materials are, for example, from about 0.001 g to about 2000 g, desirably from about 0.005 g to about 1000 g, of active compound per cubic meter of treated material.
  • the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, microemulsions, suspensions, flowable concentrates, dusts, powders, pastes and granules.
  • the use form depends on the particular purpose; in any case, it should guarantee a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by extending the active ingre-h with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent.
  • auxiliary solvents e.g. water is used as the diluent.
  • Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g.
  • ethanolamine, dimethylformamide and water
  • carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly-disperse silica, silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
  • ground natural minerals e.g. kaolins, clays, talc, chalk
  • ground synthetic minerals e.g. highly-disperse silica, silicates
  • emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquor
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of ligno- sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthalenesulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octyl- phenol, nonylphenol, alkyl
  • Substances which are suitable for the preparation of directly sprayable solutions, emul- sions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • benzene toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexa- none, chlorobenzene, isophorone, strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.
  • strongly polar solvents e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.
  • Powders, materials for scattering and dusts can be prepared by mixing or concomi- tantly grinding the active substances with a solid carrier.
  • Granules e.g. coated granules, compacted granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,
  • compositions of the present invention include a formula I compound of this invention (or combinations thereof) admixed with one or more agronomi- cally acceptable inert, solid or liquid carriers.
  • Those compositions contain a pesticidally effective amount of said compound or compounds, which amount may vary depending upon the particular compound, target pest, and method of use.
  • the formulations comprise of from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient.
  • the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • V. 80 parts by weight of a compound of formula I are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient).
  • the active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, scattering or pouring.
  • the use forms depend entirely on the intended purposes; in any case, this is intended to guarantee the finest possible distribution of the active ingredients according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active ingredient concentrations in the ready-to-use products can be varied within substantial ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
  • the active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • compositions to be used according to this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • agents can be admixed with the agents used according to the invention in a weight ratio of 1:10 to 10:1. Mixing the compounds I or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
  • Organophosphates Acephate, Azinphos-methyl, Chlorpyrifos, Chlorfenvinphos, Diazi- non, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Triazophos, Trichlorfon;
  • Pyrethroids Bifenthrin, Cyfluthrin, Cypermethrin, Deltamethrin, Esfenvalerate, Ethofen- prox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda-Cyhalothrin, Permethrin, Si- lafluofen, Tau-Fluvalinate, Tefluthrin, Tralomethrin, Zeta-Cypermethrin;
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: Chlorflua- zuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novalu- ron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen;
  • HPLC column RP-18 column(Chromolith Speed ROD from Merck KgaA, Germany).
  • each of the compounds listed in table 4 show insecitcidal activity against at least one of the mentioned insect species or against an aphid species when applied in low application rates, e.g. at an application rate of 500 ppm or lower.
  • the active compounds were formulated for testing the activity against insects and arachnids as a 10.000 ppm solution in a mixture of 35% acetone and water, which was diluted with water, if needed.
  • a Sieva lima bean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood.
  • the leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 2nd instar cater- pillars.
  • 5 days observations are made of mortality, reduced feeding, or any interference with normal molting.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Cotton plants at the cotyledon stage were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Pepper plants in the 2 nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour photoperiod) at about 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Nasturtium plants grown in Metro mix in the 1 st leaf-pair stage were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete coverage of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality was determined after 3 days.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Selected cotton plants were grown to the cotyledon state (one plant per pot).
  • the cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry.
  • Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced.
  • the insects were colleted using an aspirator and an 0.6 cm, non-toxic Tygon ® tubing (R-3603) connected to a barrier pipette tip.
  • the tip, containing the collected insects was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding.
  • the cups were covered with a reusable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Sieva lima bean plants with primary leaves expanded to 7-12 cm were infested by plac- ing on each a small piece from an infested leaf (with about 100 mites) taken from the main colony. This was done at about 2 hours before treatment to allow the mites to move over to the test plant to lay eggs. The piece of leaf used to transfer the mites was removed. The newly-infested plants were dipped in the test solution and allowed to dry. The test plants were kept under fluorescent light (24 hour photoperiod) at about 25 °C and 20 - 40% relative humidity. After 5 days, one leaf was removed and mortality counts were made.
  • Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions.
  • the test com- pound was diluted to a concentration of 500 ppm (wt compound: vol diluent) in a 1 :1 mixture of acetone: water, plus 0.01% Kinetic ® surfactant.
  • Thrips potency of each compound was evaluated by using a floral-immersion technique.
  • Plastic petri dishes were used as test arenas. All petals of individual, intact or- chid flowers were dipped into treatment solution for approximately 3 seconds and allowed to dry for 2 hours. Treated flowers were placed into individual petri dishes along with 10 - 15 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 4 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish. The level of thrips mortality was extrapolated from pre- treatment thrips numbers.

Abstract

The present invention relates to a method for combatting insects or arachnids which comprises contacting the insects or the arachnids, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the insects or the arachnids are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from insect or arachnid attack or infestation with a pesticidally effective amount of a compound of the general formula (I) or a salt thereof wherein: Ar is a cyclic radical, n is 0 or 1, X is CO or SO2 and R1 to R4 are as defined in claim 1.

Description

Hydrazone derivatives for combatting harmful insects and arachnids
The present invention relates to a method for combating harmful insects and arachnids.
In spite of commercial pesticides for controlling harmful insects and arachnids available today, damage to crops, both growing and harvested, and other nuisance, such as transmission of diseases, caused by insects and arachnids still occur. Therefore, there is continuing need to provide compounds which are useful for combating harmful insects and arachnids.
It is therefore an objective of the present invention to provide compounds which are useful for combating harmful insects and arachnids.
R. J. Cremlyn (J. Chem Soc. C 1967, 77-81) describes that certain sulfanil hydrazides show fungicidal activity.
WO 87/66133 describes acyl hydrazones which are useful for killing internal parasites, such as nematodes, trematodes and cestodes, affecting warm-blooded animals and humans.
US 3066023 discloses aroylhydrazones as components of a photoconducting insulating layer in a material for xerography.
WO 99/01423 discloses the preparation of aroylhydrazones which are useful as gluca- gon antagonists or inverse agonists.
EP-A 322691 discloses aroylhydrazones as precursors for the preparation of 1- acylpyrazolines.
The inventors of the present application surprisingly found that compounds of formula
Ar— (CH2)n— X—
Figure imgf000002_0001
wherein:
Ar is a cyclic radical selected from phenyl, naphthyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic radical may be fused to 1 or 2 phenyl rings, and where the cyclic radical may have 1 , 2, 3, 4 or 5 substituents Ra which are selected, independently of one another, from halogen, cyano, nitro, C C10-alkyl, C C10-haloalkyl, C3-C10-cylcoalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, CrC10-alkoxy, d-Cio-haloalkoxy, C2-Cι0-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d-C^-alkylthio, d- do-haloalkylthio, CrC o-alkylsuIfinyl, d-do-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC10-haloalkylsulfonyl, hydroxy, NR5R6, C C10-alkoxycarbonyl, C C 0-haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, C C10-alkylcarbonyl, CrC10-haloalkylcarbonyl, R5R6N-
CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be substituted by 1, 2, 3, 4 or 5 substituents Rb which are selected, independently of one another, from halogen, cyano, nitro, C Cιo-alkyl, C C10-haloalkyl, C3-C10- cylcoalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, d-do-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy,
C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d- o-alkylthio, CrC10-haloalkylthio, CrC^-alkylsulfinyl, d-Cio-haloalkylsulfinyl, C C10- alkylsulfonyl, CrC10-haloalkylsulfonyl, hydroxy, NR5R6, C C10-alkoxycarbonyl, CrCio-haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, Cι-Cι0-alkylcarbonyl, d-Cio-haloalkylcarbonyl and
R5R6N-CO-;
X is CO or SO2;
R1 is H, Ci-Cio-alkyl, CrC10-haloalkyl, C3-C10-cycloalkyl, C3-Cι0-halocycloalkyl, C2- C10-alkenyl, C2-Cιo-haloalkenyl, C2-C10-alkynyl, C2-C10-haloalkynyl or phenyl which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, CrC10-alkyl, d-Cio-haloalkyl, C3-Cιo-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-Cι0-haloalkenyl, C2- Cιo-alkynyl, C3-Cι0-haloalkynyl, CrC10-alkoxy, C C10-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d- do-alkylthio, d-Cio-haloalkylthio, Crdo-alkylsulfinyl, d-Cio-haloalkylsulfinyl, d- do-alkylsulfonyl, C C10-haloalkylsulfonyl, hydroxy, NR5R6, C C10- alkoxycarbonyl, d-Cio-haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, CrC10-alkylcarbonyl, d-Cio-haloalkylcarbonyl and
R5R6N-CO-;
R2 and R3 are independently of one another H, halogen, cyano, d-do-alkyl, C C10- haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-Cιo- haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, d-Cio-alkoxy, d-Cio-haloalkoxy,
C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-Cιo- haloalkynyloxy, d-C10-aIkylthio, d-do-haloalkylthio, hydroxy-d-Cι0-alkyl, C C10-alkoxy- d-C10-alkyl, halo-d-C1(ralkoxy-d-C1(ralkyl, d-C10-alkoxycarbonyI- d-Cio-alkyl, halo-d-Cio-alkoxycarbonyl-d-Cio-alkyl or phenyl which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, d-C10-alkyl, CrC10-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haIoalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, d-Cio-alkoxy, C1-C10-haloalkoxy, C2-C10-alkenyloxy, C2-do- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d-Cio-alkylthio, C Cio-haloalkylthio, C C10-alkylsulfinyl, CrC10-haloaIkylsulfinyl, C C10- alkylsulfonyl, CrCιo-haloalkylsulfonyl, hydroxy, NR5R6, d-C10-alkoxycarbonyl, d-C10-haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, d-C10-alkylcarbonyl, d-Cio-haloalkylcarbonyl and R5R6N-CO;
R4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl or furyl, thienyl, where the aromatic radical may carry 1 , 2, 3, 4 or 5 substituents Rc which are selected, independently of one another, from halogen, cyano, nitro, d-do-alkyl, C Cio-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycIoalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, C C10-haloalkoxy, d-do-alkenyloxy, C2-C10-haloalkenyloxy, C2-Cι0-alkynyloxy, C3-C10- haloalkynyloxy, C Cι0-alkylthio, C C10-haloalkylthio, d-do-alkylsulfinyl, d-Cι0- haloalkylsulfinyl, d-do-alkylsulfonyl, C C^-haloalkylsulfonyl, hydroxy, NR5R6, d-Cio-alkoxycarbonyl, d-do-haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C 0-haloalkenyloxycarbonyl, C C10-alkylcarbonyl, CrC10-haloalkylcarbonyl,
R5R6N-CO- and phenoxy which may be substituted by 1 , 2, 3, 4 or 5 substituents Rd which are selected, independently of one another, from halogen, cyano, nitro, d-Cio-alkyl, d-do-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, Cr do-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-
C10-haloalkynyloxy, d-do-alkylthio, d-Cicrhaloalkylthio, C C10-alkylsulfinyl, C do-haloalkylsulfinyl, C Cι0-alkylsulfonyl, d-do-haloalkylsulfonyl, hydroxy, NR5R6, CrC10-alkoxycarbonyl, d-Cio-haloalkoxycarbonyl, C2-C10- alkenyloxycarbonyl, C2-Cι0-haloalkenyloxycarbonyl, Crdo-alkylcarbonyl, d-Cι0- haloalkylcarbonyl and R5R6N-CO; or
R2 and R4 together with the carbon atoms to which they are bound form a phenyl ring or a 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the phenyl ring and the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring, and where the phenyl ring and the 5- or 6-membered heterocyclic ring and/or the phenyl ring to which they are fused may carry 1 , 2, 3 or 4 substituents Re, which are selected, independently of one another, from halogen, cyano, nitro, C Cιo- alkyl, C C10-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-do-haloalkenyl, C2-C10-alkynyl, C2-Cι0-haloalkynyl, d-do-alkoxy, CrC10- haloalkoxy, C2-Cι0-alkenyloxy, C2-Cι0-haloalkenyloxy, C2-Cι0-alkynyloxy, C2-C10- haloalkynyloxy, d-do-alkylthio, CrCι0-haloalkylthio, C C10-alkylsulfinyl, d-do- haloalkylsulfinyl, CrCio-alkylsulfonyl, d-do-haloalkylsulfonyl, hydroxy, NR5R6, d-C-io-alkoxycarbonyl, d-C10-haloalkoxycarbonyl, C2-Cι0-alkenyloxycarbonyl, C2-Cιo-haloalkenyloxycarbonyl, CrC10-alkylcarbonyl, C Cι0-haloalkylcarbonyl,
R5R6N-CO and phenoxy which may be substituted by 1 , 2, 3, 4 or 5 substituents Rf which are selected, independently of one another, from halogen, cyano, nitro, d-Cio-alkyl, d-do-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, C Cio-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3- do-haloalkynyloxy, Cι-C10-alkyIthio, d-do-haloalkylthio, d-Cio-alkylsulfinyl, d- do-haloalkylsulfinyl, d-do-alkylsulfonyl, d-Cio-haloalkylsuifonyl, hydroxy, NR5R6, Cι-C10-alkoxycarbonyl, d-do-haloalkoxycarbonyl, C2-Cιo- alkenyloxycarbonyl, C2-d0-haloalkenyloxycarbonyl, C Cιo-alkylcarbonyl, C C-io- haloalkylcarbonyl and R5R6N-CO, and where the 5- or 6-membered heterocyclic ring may contain 1 carbonyl group as a ring member;
R5 and R6 independently of one another are H or d-do-alkyl; and
n is O or l
or salts thereof are useful for combating insects and arachnids.
The present invention therefore relates to a method for combating harmful insects and arachnids, which comprises contacting the insects or the arachnids, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the insects or arachnids grow or may grow, or the materials, plants, seeds, soil, surfaces or spaces to be protected against attack or infestation by insects or arachnids with a pesticidally effective amount of a hydrazone compound of the formula I.
The invention especially relates to a method for protecting crops from attack or infestation by insects or arachnids, which comprises contacting a crop with a pesticidally effective amount of a compound of the formula I as defined above.
Suitable compounds of the general formula I encompass all possible stereoisomers (cis/trans isomers) which may occur and mixtures thereof. Stereoisomeric centers are e.g. the carbon atom of te hydrazone group (N=C) and the carbon atom carrying the radicals R3 and R4. Suitable compounds also encompass possible enantiomers and racemic mixtures.
Salts of the compounds of the formula I which are suitable for the use according to the invention are especially agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question.
Examples of suitable salts include adducts of compounds I with maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid. Moreover, included as "salts" are those that can form with, for example, amines, metals, alkaline earth metal bases or quaternary ammonium bases, including zwitterions. Suitable metal and alkaline earth metal hydroxides as salt formers include the salts of barium, aluminum, nickel, copper, manganese, cobalt zinc, iron, silver, lithium, sodium, potassium, magnesium or calcium. Additional salt formers include chloride, sulfate, acetate, carbonate, hydride, and hydroxide. Desirable salts include adducts of compounds I with maleic acid, dimaleic acid, fumaric acid, difumaric acid, and methane sulfonic acid. The term "5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S" as used herein refers to both aromatic and non-aromatic rings such as saturated or partially unsaturated radicals having from 1 to 4, preferably 1 ,2, or 3 heteroatoms as ring members.
Examples for heteroaromatic rings are triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl or isoxazolyl.
If the 5- or 6-membered heteroaromatic ring is fused to 1 or 2 phenyl rings, this refers e.g. to quinolinyl, isoquinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzthiazolyl, benzoxazolyl, benzimidazolyl, dibenzopyrrolyl, dibenzofu- ranyl or dibenzothienyl.
Examples for non-aromatic rings are pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, dioxolanyl, dioxolenyl, thiolanyl, dihydrothiophenyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thia- zolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl and thiazinyl.
If the 5- or 6-membered heterocyclic non-aromatic radical is fused to a phenyl group, this refers to e. g. dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroisochinolinyl, chromenyl, chromanyl and the like.
The term "5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring" as used herein refers e.g. to pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxa- zolyl, isothiazolyl, isoxazolyl, quinolinyl, isoquinolinyl, indolyl, indazolyl, benzofuryl, benzthienyl, benzthiazolyl, benzoxazolyl, benzimidazolyl or chromenyl and further to the radicals as exemplified for the 5- or 6-membered heterocyclic non-aromatic rings and for the non-aromatic rings fused to a phenyl group.
If the 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which may be fused to a phenyl ring contains a carbonyl group as a ring member, this refers to e. g. pyrroli- donyl, pyrazolidonyl, pyrazolonyl, oxazolidonyl, pyridonyl, pyronyl, indoxylyl, oxindolyl, cumarinyl, chromenonyl (chromonyl) and the like.
"Halogen" will be taken to mean fluoro, chloro, bromo and iodo.
The term "d-do-alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, 1- methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1- dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1,1-dimethylbutyl, 1 ,2-dimethylbutyI, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2- ethylhexyl, nonyl and decyl and their isomers. d-C4-alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethyIethyl.
The term "d-Cι0-haloalkyl" as used herein refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example d-C4-haloalkyl, such as chloromethyl, bromomethyl, dichloro- methyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like.
Similarly, "C C10-alkoxy" and "d-Cio-alkylthio" refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group. Examples include d-C4- alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, futher d-C4-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
Accordingly, the terms "d-C10-haloalkoxy" and " CrC10-haloalkylthio" refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro- 2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy, further d-C2-haloalkyIthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichloro- fluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro- 2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2- trichloroethylthio and pentafluoroethylthio and the like.
The term "C2-Cι0-alkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3- butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2- propenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2- propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1-ethyl-1 -propenyl, 1-ethyl- 2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1- pentenyl, 2-methyl-1-pentenyl, 3-methyl-l-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2- pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3- pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4- pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl- 2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1,2- dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3- butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3- dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1- ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3- butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1- propenyl and 1-ethyl-2-methyl-2-propenyl;
The term "C2-C10-haloalkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
Similarly, the term "C2-d0-alkenyloxy" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, for example ethenyloxy, propenyloxy and the like.
Accordingly, the term "C2-C10-haloalkenyloxy" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
The term "C2-C10-alkynyl" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
The term "C3-C10-haloalkynyl" as used herein refers to a branched or unbranched un- saturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond. The term "C2-C10-alkynyloxy" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, the alkynyl group being bonded through oxygen linkages at any bond in the alkynyl group.
Similarly, the term "C3-C10-haloalkynyloxy" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, the group being bonded through oxygen linkages at any bond in the alkynyl group, where some or all of the hydrogen atoms in these group may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
The term "C3-C10-cycloalkyl" as used herein refers to a monocyclic 3- to 10-membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl and cyclodecyl.
The term "C3-C10-halocycloalkyl" as used herein refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloro-, dichloro- and trichlorocyclopropyl, fluoro-, difluoro- and trifluorocyclopropyl, chloro-, dichloro-, trichloro, tetrachloro-, pentachloro- and hexachlorocyclohexyl and the like.
With respect to the use according to the invention of the compounds of formula I, particular preference is given to the following meanings of the substituents, in each case on their own or in combination:
Preference is given to the use of compounds of formula I, wherein Ar is a cyclic radical selected from phenyl, naphthyl, a 5- or 6-membered heterocyclic radical with 1 to 3 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic radical may be fused to 1 or 2 phenyl rings and where the cyclic radical is unsubstituted or substituted as defined above, i.e. by 1, 2, 3, 4 or 5 of the above mentioned radicals Ra.
Particular preference is given to the use of compounds of formula I, wherein Ar is a cyclic radical selected from phenyl, triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl, isoxazolyl, naphthyl, quinolinyl, isoquinolinyl, indolyl, indazolyl, benzofuryl, benzthienyl, benzthiazolyl, benzoxazolyl, benzimidazolyl, chromenyl, chromenonyl, dibenzopyranyl or fluorenyl and where the cyclic radical is unsubstituted or substituted as defined above. Furthermore, particular preference is given to the use of compounds of formula I, wherein
Ar is a cyclic radical selected from thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, tria- zolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, phenyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, naphthyl, dibenzopyranyl, indolyl, benzimidazolyl, benzofuryl, benzoxazolyl, benzothienyl, benzthiazolyl or chrome- nonyl and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or 5 of the above mentioned radicals Ra.
Moreover, particular preference is given to the use of compounds of formula I, wherein Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, phenyl, pyridyl, pyrazinyl, naphthyl, dibenzopyranyl, indolyl or benzothieny and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or 5 of the above mentioned radicals Ra.
Even more particular preference is given to the use of compounds of formula I, wherein Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, phenyl, pyridyl, pyrazinyl, naphthyl, indolyl or benzothienyl, especially thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, phenyl, pyridyl, pyrazinyl, naphthyl or indo- lyl and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or 5 of the above mentioned radicals Ra.
Special preference is given to the use of compounds of formula I, wherein Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, phenyl, isoxazolyl or pyridyl and where the cyclic radical is unsubstituted or substituted by 1 , 2, 3, 4 or
5 of the above mentioned radicals Ra. However, compounds, wherin Ar is optionally substituted phenyl are also highly preferred.
Preferably, the cyclic radical mentioned for Ar is unsubstituted or carries 1 , 2, 3 or 4 substituents Ra, in particular 1 , 2 or 3 and more preferably 1 or 2 substituents Ra.
Preferred substituents Ra are selected, independently of one another, from halogen, cyano, nitro, Ci-Cio-alkyl, d-do-haloaikyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C do-alkoxy, d-Cio-haloalkoxy, C C10-alkylthio, C C10-haloalkylthio, d-C10- alkylsulfonyl, d-C10-haloalkylsulfonyl, hydroxy, phenyl, phenoxy, NR5R6, d-do- alkoxycarbonyl, CrC10-haIoalkoxycarbonyl, CrC10-alkylcarbonyl, CrC10- haloalkylcarbonyl and NR5R6-CO-.
Particularly preferred substituents Ra are selected, independently of one another, from halogen, hydroxy, d-C4-alkyl, C C -haloalkyl, d-C4-alkoxy, C C4-haloalkoxy, phenyl, which is unsubstituted or substituted by by 1 to 3 substituents Rb which are in particular selected, independently of one another, from halogen, C C4-alkyl, C C4-haloalkyl and d-C4-alkoxy, especially by halogen, and phenoxy which is unsubstituted or substituted by 1 to 3 substituents R which are in particular selected, independently of one another, from halogen, CrC4-alkyl, C C4-haloalkyl and C C4-alkoxy, especially by C C4- haloalkyl.
More preferred substituents Ra are selected, independently of one another, from halogen, C C4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and C C4-haloalkoxy.
Especially preferred substituents Ra are selected, independently of one another, from fluorine, chlorine, bromine, C C4-alkyl, C C4-alkoxy, in particular methoxy, C C4- haloalkoxy, in particular difluoromethoxy or trifluoromethoxy and CF3.
Preference is given to the use of compounds of formula I, wherein R1 is H, d-C4-alkyl or C C4-haloalkyl.
Particular preference is given to the use of compounds of formula I, wherein R1 is H or methyl, most preferably H.
Preference is given to the use of compounds of formula I, wherein R2 is H, d-Cio-alkyl, d-do-haloalkyl, halogen, phenyl or cyano.
Particular preference is given to the use of compounds of formula I, wherein R2 is H, C C10-alkyl, , in particular C C4-alkyl, halogen, phenyl or cyano.
Furthermore, particular preference is given to the use of compounds of formula I, wherein R2 is H, d-do-alkyl, in particular C C4-alkyl or halogen, e.g. methyl, ethyl, isopro- pyl, fluorine, chlorine or bromine. Most preferably R2 is C C -alkyl, in particular methyl or ethyl.
Preference is given to the use of compounds of formula I, wherein R3 is H, d-C4-alkyl, d-C -haloalkyl, halogen or phenyl.
Particular preference is given to the use of compounds of formula I, wherein R3 is H, d-C4-alkyl, halogen or phenyl, especially H or halogen.
Preference is given to the use of compounds of formula I, wherein
R4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl, furanyl, thienyl or benzofuryl where the aromatic radical is unsubstituted or substituted as defined above, i.e. by 1 , 2, 3, 4 or 5 of the above mentioned radicals RG.
Particular preference is given to the use of compounds of formula I, wherein R4 is phenyl where phenyl is unsubstituted or substituted as defined above.
The aromatic radical as mentioned for R4 may be unsubstituted or may carry 1 to 5, preferably 1 to 4, more preferably 1 to 3 and in particular 1 or 2 substituents Rc. Preferred substituents Rc are selected, independently of one another, from hydroxy, halogen, cyano, nitro, Cι-C10-alkyl, CrC10-haloalkyl, C3-C10-cylcoalkyl, C3-C10- halocycloalkyl, C C10-alkoxy, d-Cio-haloalkoxy, d-do-alkylthio, d-Cio-haloalkylthio, d-do-alkylsulfonyl, C C10-haloalkylsulfonyl, NR5R6, C C10-alkoxycarbonyl, C C10- haloalkoxycarbonyl, R5R6N-CO- and phenoxy which may be substituted by C C4- haloalkyl.
Particularly preferred substituents RG are selected, independently of one another, from halogen, d-C4-alkyl, C C4-haloalkyl, C C4-alkoxy, d-d-haloalkoxy, C C4-alkylthio, d-C4-haloalkylthio, cyano, nitro, NR5R6 and phenoxy which may be substituted by d- C -haloalkyl.
More preferred substituents Rcare selected, independently of one another, from halogen, d-C -alkyl, C C4-haloalkyl, d-C4-alkoxy, C C -haloalkoxy and C C4- haloalkylthio, e.g. from fluorine, chlorine, methyl, ethyl, propyl, isopropyl, butyl, fluoro- methyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy and trifluoromethylthio.
Especially preferred substituents Rcare selected, independently of one another, from halogen, C C4-alkyl and d-C4-haloalkyl.
If R4 is phenyl, which carries 1 , 2 or 3 of the aforementioned substituents Rc, then at least one of the substituents is preferably located in the 2, 4 and/or 6-postion. Examples of paricularly preferred substituted phenyl are those mentioned in tables 2 and 3 as radicals R4.
Alternatively, preference is given to the use of compounds of formula I, wherein
R2 and R4 together with the carbon atoms to which they are bound form a phenyl ring or a 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring, and where the 5- or 6-membered heterocyclic ring and/or the phenyl ring to which it is fused may carry 1 , 2, 3 or 4 of the aforementioned substituents Re. Preferably, the substituents Re are selected, independently of one another, from halogen, d-C4-alkyl, CrC -haloalkyl, d-C4-alkoxy, d-C4- haloalkoxy, C C4-alkylthio, CrC4-haloalkylthio, cyano, nitro, phenyl, which is unsubstituted or is substituted by 1 , 2 or 3 substituents Rf which are selected, independently of one another, from CrC4-alkyl, C C4-haloalklyl C C -alkoxy and halogen, and phenoxy which is unsubstituted or substituted by 1 to 3 substituents which are selected, independently of one another, from d-C4-alkyl, CrC4-haloalklyl, d-C4-alkoxy and halogen, and where the 5- or 6-membered heterocyclic ring may contain 1 carbonyl group as a ring member.
In this alternative, particular preference is given to the use of compounds of formula I, wherein R2 and R4 together with the carbon atoms to which they are bound form a phenyl, benzofuranyl, benzothienyl, indolyl, chromenyl, chromenonyl, pyrazolyl orfu- ranyl moiety, and where the moiety may carry 1 , 2, 3 or 4 substituents of the aforementioned substiuents Re.
Furthermore, particular preference is given to the use of compounds of formula I, wherein R2 and R4 together with the carbon atoms to which they are bound form a phenyl, benzofuranyl, benzothienyl or chromenyl moiety, and where the moiety may be substituted by 1 , 2 o33 substituents Re.
Even more preference is given to the use of compounds of formula I, wherein R2 and R4 together with the carbon atoms to which they are bound form a benzofuranyl or benzothienyl moiety.
In this alternative, R3 is either H or is one of the above-mentioned substituents of the moiety formed by R2 and R4 together with the carbon atoms to which they are bound.
In particular substituents Re are selected, independently of one another, from halogen, d-C4-alkyl, d-C4-haloalkyl, C C4-haloalkoxy, d-C4-haloalkylthio, cyano, nitro, phenyl, which is unsubstituted or is substituted by 1 , 2 or 3 substituents which are selected, independently of one another, from d-C4-haloalklyl and halogen, and phenoxy which is unsubstituted or substituted by d-C4-haloalklyI. Preferably, the substituents Re are selected, independently of one another, from halogen, C C4-alkyl, C C4-haloalkyl, d- C4-alkoxy, d-C4-haloalkoxy, C C4-haloalkylthio, cyano and nitro. More preferably substituents Re are selected, independently of one another, from C C4-alkyl, Cι-C4- haloalkyl and halogen.
Particularly preferred radicals Rb, Rd and Rf are selected from halogen, C C4-alkyl, C C4-haloalkyl, d-C4-haloalkoxy, CrC4-haloalkylthio, cyano and nitro, especially from halogen, Cι-C4-alkyl, d-C4-alkoxy, d-C4-haloalkyl, C C4-haloalkoxy.
A very preferred embodiment of the invention relates to the use of pyridyl compounds of the general formula la
Figure imgf000013_0001
wherein Ra, R1 and R3 are as defined herein,
m is 0, 1, 2 or 3,
R2a is H or d-C4 alkyl and
R4a is phenyl, which may carry 1 , 2, 3 or 4 substituents Rc as defined herein, In case R2a is C C4 alkyl and additionally one of the following provisions i) to iv) are met, the compounds la are new and thus are part of the present invention: i) m is not 0 or ii) R4a carries at least one substituent RG being different from hydrogen iii) or R1 is different from hydrogen, iv) or R2a is different from methyl.
In formula la preference is given to compounds wherein m is 0, 1 or 2.
Preferably Ra in formula la has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. Most preferably Ra is Halogen, in particular F, CI or Br, d-d-alkyl, in particular methyl or ethyl, phenyl, difluoromethyl, trifluoromethyl or d-C4-alkoxy, in particular methoxy.
Amongst the compounds of the formula la those are preferred wherein R1 and R3 have, independently of each other, one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. Most preferred are compounds la, wherein R1 and R3 are hydrogen.
Preferably, the substituent Rc, if present, has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. In particular Rc is selected from F, CI, methoxy or methyl. In particular substituted phenyl is selected from one of the meanings given for R4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-trifluoromethoxyphenyl, 3- trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2-trifluoromethylphenyl, 3- trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-difluoromethoxyphenyl, 3- difluoromethoxyphenyl, 4-difluormethoxyphenyl. However, compounds la, wherein R4a is unsubstituted phenyl, are also highly preferred.
In formula la R is most preferably methyl or ethyl.
Another very preferred embodiment of the invention relates to the use of isoxazol compounds of the general formula lb
Figure imgf000014_0001
wherein n, X, R\ R2, R3 and R4 are as defined herein, and
Ar is isoxazolyl, which may carry 1 or 2 substituents Ra as defined herein.
Provided that Ar does not carry an optionally substituted phenyl group as a radical Ra if Ar is substituted 4-isoxazolyl these compounds are new and are also part of the present invention.
Amongst the compounds of the formula lb those are preferred wherein n, X, Ra, R1, R2, R3 and R4 have, independently of each other, one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. In particular the variables R1, R2, R3 and Ra have the meanings outlined below:
R1 is H,
R2 is H or d-C4 alkyl most preferably methyl or ethyl,
R3 is H, and
R4 is phenyl, which may carry 1 , 2, 3 or 4 substituents Rc as defined herein,
Preferably, the substituent Rc, if present, has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. In particular Rc is selected from F, CI, methoxy or methyl. In particular substituted phenyl is selected from one of the meanings given for R4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-trifluoromethoxyphenyl, 3- trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2-trifluoromethylphenyl, 3- trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-difluoromethoxyphenyl, 3- difluoromethoxyphenyl, 4-difluormethoxyphenyl. However, compounds la, wherein R4 is unsubstituted phenyl, are also highly preferred.
In formula lb X is preferably C=O and n is preferably 0.
Another very preferred embodiment of the invention relates to the use of pyrazol compounds of the general formula lc
Figure imgf000015_0001
wherein n, X, R1, R2, R3 and R4 are as defined in claim 1 ,
Ar is pyrazolyl which carries a substituent Ra2 on the pyrazol nitrogen atom, and which may additionally carry 1 or 2 substituents Ra as defined in claim 1 , wherein Ra2 is selected from d-Cio-alkyl, C Cιo-haloalkyl, C3-C10-cylcoalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, phenyl and benzyl, wherein phenyl and benzyl may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined in claim 1
The compounds of the formula lc are new and thus are also part of the present invention.
Amongst the compounds of the formula lc those are preferred wherein n, X, Ra, Rb, R1, R2, R3 and R4 have, independently of each other, one of the meanings which are indi- cated as being preferred, more preferred, particularly preferred or especially preferred.
Ra2 is preferably selected from d-C6-alkyl, C3-C6-cycloalkyl or phenyl. In a particularly preferred embodiment Ra2 is d-C4-alkyl.
In particular the variables R1, R2, R3 and R4 have the meanings outlined below:
R1 is H,
R2 is H or Cι-C4 alkyl most preferably methyl or ethyl,
R3 is H, and R4 is phenyl, which may carry 1 , 2, 3 or 4 substituents Rc as defined herein,
Preferably, the substituent R°, if present, has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. In particular Rc is selected from F, CI, methoxy or methyl. In particular substituted phenyl is selected from one of the meanings given for R4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-trifluoromethoxyphenyl, 3- trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2-trifluoromethylphenyl, 3- trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-difluoromethoxyphenyl, 3- difluoromethoxyphenyl, 4-difluormethoxyphenyl. However, compounds la, wherein R4 is unsubstituted phenyl, are also highly preferred.
In formula lc X is preferably C=O and n is preferably 0. A very preferred embodiment of the invention relates to the use of phenyl compounds of the general formula Id
Figure imgf000017_0001
wherein Ra, R1 and R3 are as defined herein,
m is 1 , 2 or 3,
R2d is H or C C4 alkyl and
R4d is phenyl, which may carry 1 , 2, 3 or 4 substituents RG as defined herein,
In formula Id preference is given to compounds wherein m is 1 or 2.
Preferably Ra in formula Id has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. Most preferably Ra is Halogen, in particular F, CI or Br, d-C4-alkyl, in particular methyl or ethyl, phenyl, difluoromethyl, trifluoromethyl or d-C -alkoxy, in particular methoxy. Most preferably at least one radical Ra is halogen, especially fluorine.
Amongst the compounds of the formula Id those are preferred wherein R1 and R3 have, independently of each other, one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. Most preferred are compounds la, wherein R1 and R3 are hydrogen.
Preferably, the substituent Rc, if present, has one of the meanings which are indicated as being preferred, more preferred, particularly preferred or especially preferred. In particular Rc is selected from F, CI, methoxy or methyl. In particular substituted phenyl is selected from one of the meanings given for R4 in tables 3 or 4, in particular from 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 3- fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-trifluoromethoxyphenyl, 3- trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2-trifluoromethylphenyl, 3- trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-difluoromethoxyphenyl, 3- difluoromethoxyphenyl, 4-difluormethoxyphenyl. In formula Id R2d is most preferably methyl or ethyl.
As far as the specific stereoisomers are concerned, preference is given to the use of compounds of formula I wherein the conformation at the C/N double bond is E. Prefer- ence is also given to the use of mixture of E/Z isomers referring to the C/N double bond, wherein the E isomer is predominating.
Preference is further given to the use of compounds of formula I wherein R2 and R4 are bound cis to each other. Preference is also given to mixtures of the cis/trans isomers, referring to the position of R2 and R4 towards each other, wherein the cis isomer is predominating.
The compounds of the formula I may be readily synthesized using techniques generally known by synthetic organic chemists. Exemplary synthesis methods are described for example in WO 87/06133.
For instance, suitable acyl hydrazides can be reacted with aldehydes or ketones to form acyl hydrazones:
Ar-(CH2)n-CO-NH-NH2 +
Figure imgf000018_0001
Cinnamic aldehydes and analogous ketones can be obtained according to a literature procedure (Organikum, Johann Ambrosius Barth Verlag, Heidelberg, 1996, pp. 493- 495) from benzaldehydes and aliphatic ketones or aldehydes.
The sulfonyl hydrazones (X = SO2) can be obtained in an analogous way starting from the corresponding sulfonic acid hydrazides (e.g. Munshi, Shah, Trivedi, Indian J. Chem. 1963, 1, 318-320):
Figure imgf000018_0002
If not commercially available, the starting materials (acyl hydrazides) can be prepared according to literature procedures (e.g. Khan, Siddiqui, Bhatt, Oriental Journal of Chemistry 2002, 18, 163-164) e.g. from carboxylic acid esters (Ar-(CH2)n-COORa) or other acid derivatives such as Ar-(CH2)n-COY (Y = halogen) which are reacted with hydrazine to form the corresponding acyl hydrazides. Alternatively, carboxylic acids (Ar-(CH2)n-COOH) can be reacted with protected hydrazine in the presence of a coupling reagent such as DCC or DIC (according to Guan, Green, Bergstrom, J. Comb. Chem. 2000, 2, 297-300), and subsequent removal of the protecting group (Messina, Botta, Corelli, Paladino, Tetrahedron Asymm. 2000, 11 , 4895-4901 ; Greene, Wuts, Protective Groups in Organic Synthesis, 2nd edition, 1991 , pp. 309):
Ar-(CH2)n-COORa + NH2-NH2 *~ Ar-(CH2)n-CO-NH-NH2
Ar-(CH2)n-COOH + NH2-NHP* ^ Ar-(CH2)n-CO-NH-NHP* ^ Ar-(CH2)n-CO-NH-NH2
* P = protective group; Ra = C C10-alkyl
The sulfonyl hydrazides (X = SO2) can be obtained in an analogous way starting from the corresponding sulfonic acid derivatives, e.g. from the corresponding sulfonic acid (Ar-(CH2)n-SO2OH) or another derivative such as the sulfonic acid halogenide (Ar- (CH2)n-SO2Y; Y = halogen): (e.g. El-Maghrabi, Mohamed, J. Chem. Tech. Biotechnol. 1983, 33A, 25-32)
Ar-(CH2)n-S02OH + NH2-NHP* — - Ar-(CH2)n-S02-NH-NHP* - Ar-(CH2)n-S02-NH-NH2
* P = protective group; Ra = Ci-Cio-alkyl
If individual compounds I are not obtainable by the route described above, they can be prepared by derivatization of other compounds I or by customary modifications of the synthesis routes described.
The preparation of the compounds of formula I may lead to them being obtained as isomer mixtures (stereoisomers, enantiomers). If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.
According to the present invention, the compounds of the general formula I are used for controlling harmful insects and arachnids. In particular, they are used for controlling the following animal pests:
insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Aυtographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipυncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellυs, Eupoecilia ambigυella, Evetria boυ- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera eridania, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumato- poea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibi- alis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12- punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hip- pocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl- lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria,
dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hyso- cyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa,
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atia sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta,
heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor, homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactu- cae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus as- calonicus, Myzus cerasi, Myzus persicae, Myzus varians, Nasonovia ribis-nigri, Nila- parvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii.
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis,
orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus,
Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
The compounds of the formula I are preferably used for controlling pests of the orders Lepidoptera, Thysanoptera, Homoptera and Acarina and more preferably for controlling insects of the orders Lepidoptera and Homoptera.
The compounds of formula (I) may be used to protect growing plants and crops from attack or infestation by insects or arachnids by contacting the plant/crop with a pesti- cidally effective amount of compounds of formula (I). The term "crop" refers both to growing and harvested crops.
The insect, arachnid, plant and/or soil or water in which the plant is growing can be contacted with the present compound(s) I or composition(s) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the insect, arachnid, and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the insect, arachnid, and/or plant).
Moreover, insects or arachnids may be controlled by contacting the target pest, its food supply or its locus with a pesticidally effective amount of compounds of formula (I). As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
In general, for use in treating crop plants, the rate of application of the compounds and/or compositions of this invention may be in the range of about 0.1 g to about 4000 g per hectare, desirably from about 25 g to about 600 g per hectare, more desirably from about 50 g to about 500 g per hectare. For use in treating seeds, the typical rate of application is of from about 1 g to about 500 g per kilogram of seeds, desirably from about 2 g to about 300 g per kilogram of seeds, more desirably from about 10 g to about 200 g per kilogram of seeds. Customary application rates in the protection of materials are, for example, from about 0.001 g to about 2000 g, desirably from about 0.005 g to about 1000 g, of active compound per cubic meter of treated material.
The compounds I can be converted into the customary formulations, e.g. solutions, emulsions, microemulsions, suspensions, flowable concentrates, dusts, powders, pastes and granules. The use form depends on the particular purpose; in any case, it should guarantee a fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, e.g. by extending the active ingre- dient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly-disperse silica, silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose. Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of ligno- sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthalenesulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octyl- phenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide conden- sates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropyl- ene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emul- sions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexa- none, chlorobenzene, isophorone, strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for scattering and dusts can be prepared by mixing or concomi- tantly grinding the active substances with a solid carrier.
Granules, e.g. coated granules, compacted granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Such formulations or compositions of the present invention include a formula I compound of this invention (or combinations thereof) admixed with one or more agronomi- cally acceptable inert, solid or liquid carriers. Those compositions contain a pesticidally effective amount of said compound or compounds, which amount may vary depending upon the particular compound, target pest, and method of use.
In general, the formulations comprise of from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are exemplary formulations: I. 5 parts by weight of a compound according to the invention are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight of the active ingredient.
II. 30 parts by weight of a compound of formula I are mixed intimately with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This gives a formulation of the active ingredient with good adhesion properties (comprises 23% by weight of active in- gredient).
III. 10 parts by weight of a compound of formula I are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 9% by weight of active ingredient).
IV. 20 parts by weight of a compound of formula I are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 16% by weight of active ingredient).
V. 80 parts by weight of a compound of formula I are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient).
VI. 90 parts by weight of a compound of formula I are mixed with 10 parts by weight of N-methyl-a-pyrrolidone, which gives a solution which is suitable for use in the form of microdrops (comprises 90% by weight of active ingredient).
VII. 20 parts by weight of a compound of formula I are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
VIII.20 parts by weight of a compound of formula I are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-a-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mix- ture in 20000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.
The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, scattering or pouring. The use forms depend entirely on the intended purposes; in any case, this is intended to guarantee the finest possible distribution of the active ingredients according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active ingredient concentrations in the ready-to-use products can be varied within substantial ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even the active ingredient without additives.
Compositions to be used according to this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
These agents can be admixed with the agents used according to the invention in a weight ratio of 1:10 to 10:1. Mixing the compounds I or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
The following list of pesticides together with which the compounds of formula I can be used, is intended to illustrate the possible combinations, but not to impose any limitation: Organophosphates: Acephate, Azinphos-methyl, Chlorpyrifos, Chlorfenvinphos, Diazi- non, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Triazophos, Trichlorfon;
Carbamates: Alanycarb, Benfuracarb, Carbaryl, Carbosulfan, Fenoxycarb, Furathio- carb, Indoxacarb, Methiocarb, Methomyl, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Triazamate;
Pyrethroids: Bifenthrin, Cyfluthrin, Cypermethrin, Deltamethrin, Esfenvalerate, Ethofen- prox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda-Cyhalothrin, Permethrin, Si- lafluofen, Tau-Fluvalinate, Tefluthrin, Tralomethrin, Zeta-Cypermethrin;
Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: Chlorflua- zuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novalu- ron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen;
Various: Abamectin, Acequinocyl, Amitraz, Azadirachtin, Bifenazate, Cartap, Chlor- fenapyr, Chlordimeform, Cyromazine, Diafenthiuron, Dinetofuran, Diofenolan, Ema- mectin, Endosulfan, Ethiprole, Fenazaquin, Fipronil, Formetanate, Formetanate hydro- chloride, Hydramethylnon, Imidacloprid, Indoxacarb, Pyridaben, Pymetrozine, Spino- sad, Sulfur, Tebufenpyrad, Thiamethoxam, and Thiocyclam.
The present invention is now illustrated in further detail by the following examples.
1. Synthesis Examples
1.1 Preparation of the starting materials
The products were characterized by coupled High Performance Liquid
Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.
HPLC column: RP-18 column(Chromolith Speed ROD from Merck KgaA, Germany).
Elution: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0.1% TFA in a ratio of from 5:95 to 95:5 in 5 minutes at 40 °C. MS: Quadrupol electrospray ionisation, 80 V (positiv modus)
1.1.1 Preparation of 4-methylthiophene carboxylic acid hydrazide
A mixture of 142.2 mg (1 mmol) 4-methylthiophene carboxylic acid, 158.6 mg (1.2 mmol) Boc-protected hydrazine and 518 mg (1 mmol) N-cyclohexyl-N'-methyl- polystyrene carbodiimide in 8 ml dichloromethane was stirred at room temperature overnight. After filtration, 400 mg 4-benzyloxybenzaldehyde polystyrene were added and stirred overnight. After filtration and evaporation of the solvent, 130 mg (0.51 mmol, 51 %) of Boc-protected acyl hydrazide were obtained (retention time (RT) = 2.339 min, m/z = 279 [M+Na]+). Subsequently, 3 ml of trifluoroacetic acid/dichloromethane 1:1 were added. After 2 h the solvent was removed in vacuo and water was added. The product was isolated by extraction with dichlormethane (3 times) and removal of the solvent. Purity was sufficient for further reactions (RT = 1.132 min, m/z = 157 [M+H]+).
1.2 Preparation of the final hydrazones of formula I
1.2.1 Preparation of furan-2-carboxylic acid [(benzofuran-2-yl)methylene] hydrazide
A mixture of 219.2 mg (1.5 mmol) benzo[b]furan-2-carboxaldehyde and 283.7 mg (2.25 mmol) furan-2-carboxylic acid hydrazide in 4 ml methanol was refluxed for 3 h. After cooling to room temperature a white solid precipitated, which was dried in vacuo. Yield: 398 mg of 95% purity according to 1H NMR
1H NMR (d6-DMSO; 400 MHz); 6.8 (s, 1 H), 7.3 (m, 1 H), 7.4 (m, 1 H), 7.45 (m, 1 H), 7.6 (d, 1H), 7.7 (d, 1H), 8.0 (s, 1H), 8.5 (s, 1H), 12.1 (s, 1H).
The compounds listed in the following tables 1 to 4 were prepared in an analogous way. Each of the compounds listed in table 4 show insecitcidal activity against at least one of the mentioned insect species or against an aphid species when applied in low application rates, e.g. at an application rate of 500 ppm or lower.
Figure imgf000028_0001
Figure imgf000028_0002
Figure imgf000029_0001
X
2: o o
X o
CM
_φ
CD
Figure imgf000029_0002
Figure imgf000030_0001
Figure imgf000031_0002
Table 3
Figure imgf000031_0001
Figure imgf000031_0003
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000060_0002
^ φ
J2 CO
I-
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
ε
Figure imgf000066_0001
II a:
* bt)
2. Examples of action against pests
The action of the compounds of formula I against pests was demonstrated by the following experiments.
2.1 Southern armyworm (Spodoptera eridania), 2nd instar larvae
The active compounds were formulated for testing the activity against insects and arachnids as a 10.000 ppm solution in a mixture of 35% acetone and water, which was diluted with water, if needed.
A Sieva lima bean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood. The leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 2nd instar cater- pillars. At 5 days, observations are made of mortality, reduced feeding, or any interference with normal molting.
In this test, compounds nos. 18, 97, 101, 134, 160, 161, 162, 164, 166, 174, 175, 177, 183, 185, 190, 192, 198, 238, 318, 406, 427 and 445 at 300 ppm showed over 80% mortality in comparison with untreated controls.
2.2 Cotton aphid (aphis gossypii)
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Cotton plants at the cotyledon stage (one plant per pot) were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.
In this test, compounds nos. 8, 67, 70, 71, 120, 121, 126, 130, 131, 156, 157, 159, 181, 194, 202, 203, 207, 236, 240, 277, 314, 319, 392, 394, 395, 398, 399, 429, 442, 444, 447, 450 and 451 at 300 ppm showed over 75% mortality in comparison with untreated controls.
2.3 Green Peach Aphid (Myzus persicae)
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour photoperiod) at about 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days.
In this test, compounds nos. 3, 10, 14, 19, 20, 76, 128, 152, 173, 186, 194, 195, 197, 198, 200, 204, 235, 237, 278, 320, 321, 393, 396, 397, 400, 401, 407, 408, 409, 411 and 453 at 300 ppm showed over 75% mortality in comparison with untreated controls.
2.4 Bean aphid (aphis fabae)
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Nasturtium plants grown in Metro mix in the 1st leaf-pair stage (variety 'Mixed Jewle') were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete coverage of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality was determined after 3 days.
In this test, compounds nos. 18, 69, 71, 126, 157, 159, 168, 169, 170, 171, 184, 191, 196, 199, 202, 210, 253, 436, 442, 444 and 446 at 300 ppm showed over 75% mortality in comparison with untreated controls.
2.5 Silverleaf whitefly (bemisia argentifolii)
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Selected cotton plants were grown to the cotyledon state (one plant per pot). The cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry. Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced. The insects were colleted using an aspirator and an 0.6 cm, non-toxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. The cups were covered with a reusable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about
25 °C and 20-40% relative humidity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants. In this test, compounds nos. 2, 6, 50, 156, 158, 175, 183, 187, 189, 193, 406 and 435 at 300 ppm showed over 80% mortality compared to untreated controls.
2.6 2-spotted spider mite (tetranychus urticae, OP-resistant strain)
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Sieva lima bean plants with primary leaves expanded to 7-12 cm were infested by plac- ing on each a small piece from an infested leaf (with about 100 mites) taken from the main colony. This was done at about 2 hours before treatment to allow the mites to move over to the test plant to lay eggs. The piece of leaf used to transfer the mites was removed. The newly-infested plants were dipped in the test solution and allowed to dry. The test plants were kept under fluorescent light (24 hour photoperiod) at about 25 °C and 20 - 40% relative humidity. After 5 days, one leaf was removed and mortality counts were made.
In this test, compounds nos. 21, 91, 96, 114, 138, 183, 429 and 452 at 300 ppm showed over 75% mortality compared to untreated controls.
2.7 Orchid thrips (dichromothrips corbetti)
Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test com- pound was diluted to a concentration of 500 ppm (wt compound: vol diluent) in a 1 :1 mixture of acetone: water, plus 0.01% Kinetic® surfactant.
Thrips potency of each compound was evaluated by using a floral-immersion technique. Plastic petri dishes were used as test arenas. All petals of individual, intact or- chid flowers were dipped into treatment solution for approximately 3 seconds and allowed to dry for 2 hours. Treated flowers were placed into individual petri dishes along with 10 - 15 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 4 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish. The level of thrips mortality was extrapolated from pre- treatment thrips numbers.
In this test, compounds nos. 103, 105 and 144 at 500 ppm showed over 95% mortality compared to untreated controls.

Claims

We claim:
1. A method for combating insects or arachnids which comprises contacting the insects or the arachnids, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the insects or the arachnids are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from insect or arachnid attack or infestation with a pesticidally effective amount of a compound of the general formula I or a salt thereof
Figure imgf000070_0001
wherein:
Ar is a cyclic radical selected from phenyl, naphthyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic radical may be fused to 1 or 2 phenyl rings, and where the cyclic radical may have 1 , 2, 3, 4 or 5 substituents Ra which are selected, independently of one another, from halogen, cyano, nitro, d-do-alkyl, d-Cι0- haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyI, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-Cι0-alkynyl, C3-C 0-haloalkynyl, d-do-alkoxy, d-C10- haloalkoxy, C2-Cι0-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-Cι0-haloalkynyloxy, Cι-C10-alkylthio, C do-haloalkylthio, C C10- alkylsulfinyl, Cι-C10-haloalkylsulfinyl, Cι-C10-alkylsulfonyl, C C10- haloalkylsulfonyl, hydroxy, NR5R6, CrC10-alkoxycarbonyl, d-do- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C 0- haloalkenyloxycarbonyl, CrC10-alkylcarbonyl, d-C^-haloalkylcarbonyl, R5R6N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be substituted by 1 , 2, 3, 4 or 5 substituents Rb which are selected, independently of one another, from halogen, cyano, nitro, d-C10- alkyl, d-C,o-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, C C10- alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-
C10-alkynyloxy, C3-Cι0-haloalkynyloxy, C1-C10-alkylthio, d-do-haloalkylthio, d-Cio-alkylsulfinyl, d-Cio-haloalkylsulfinyl, CrC10-alkylsulfonyl, d-do- haloalkylsulfonyl, hydroxy, NR5R6, C C10-alkoxycarbonyl, C C10- haloalkoxycarbonyl, C2-Cι0-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, d-do-alkylcarbonyl, d-C1Crhaloalkylcarbonyl and
R5R6N-CO-;
X is CO or SO2;
R1 is H, d-Cio-alkyl, C C10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl,
C2-Cιo-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C2-C10-haloalkynyr or phenyl which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, d-do-alkyl, d- do-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2- do-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, C C10-alkoxy, C C10- haloalkoxy, C2-C10-alkenyloxy, C2-Cι0-haloalkenyloxy, C2-C10-alkynyloxy,
C3-C10-haloalkynyloxy, d-do-alkylthio, d-do-haloalkylthio, C C10- alkylsulfinyl, CrC10-haloalkylsuIfinyl, d-do-alkylsulfonyl, d-C-io- haloalkylsulfonyl, hydroxy, NR5R6, d-C10-alkoxycarbonyl, C Cι0- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C -C10- haloalkenyloxycarbonyl, C C10-alkylcarbonyl, CrC10-haloalkylcarbonyl and
R5R6N-CO-;
R2 and R3 are independently of one another H, halogen, cyano, d-Cio-alkyl, d- C10-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2- do-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, C C10-alkoxy, d-C10- haloalkoxy, C2-Cι0-alkenyloxy, C2-Cι0-haloalkenyloxy, C2-C10-alkynyloxy, C3-Cιo-haloalkynyloxy, d-C10-alkylthio, d-C10-haloalkylthio, hydroxy-C C10-alkyl, d-C10-alkoxy- d-C10-alkyl,
Figure imgf000071_0001
C Cio-alkoxycarbonyl-CrCio-alkyl, halo-d-Cio-alkoxycarbonyl-d-Cio-alkyl or phenyl which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, d-C^-alky!, d- do-haloalkyl, C3-C10-cylcoalkyl, C3-C1o-halocycloalkyl, C2-C10-alkenyl, C2- C10-haloalkenyl, C2-C10-alkynyl, C3-Cι0-haloalkynyl, d-Cio-alkoxy, d-C10- haloalkoxy, C2-C10-alkenyloxy, C2-Cι0-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, C C10-alkylthio, Cι-C10-haloalkylthio, C do- alkylsulfinyl, d-do-haloalkylsulfinyl, Cι-Cιo-alkylsulfonyl, C C10- haloalkylsulfonyl, hydroxy, NR5R6, d-C10-alkoxycarbonyl, C do- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-haloalkenyl- oxycarbonyl, C C10-aIkylcarbonyl, d-C10-haIoalkylcarbonyl and R5R6N-CO;
R4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl, and furyl, thienyl , where the aromatic radical may carry 1 to 5 substituents Rb which are selected, independently of one another, from halogen, cyano, nitro, d- do-alkyl, d-do-haloalkyl, C3-C10-cylcoalkyl, C3-C 0-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-do-alkynyl, C3-C10-haloalkynyl, C1-C10- alkoxy, d-C^-haloalkoxy, C2-Cι0-alkenyloxy, C2-C10-haloalkenyloxy, C2- C10-alkynyloxy, C3-Cι0-haloalkynyloxy, CrC10-alkylthio, C Cio-haloalkylthio, CrCιo-alkylsulfinyl, CrCio-haloalkylsulflnyl, C C10-alkylsulfonyl, C C10- haloalkylsulfonyl, hydroxy, NR5R6, CrC10-alkoxycarbonyl, CrC10- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, C1-Cιo-aIkylcarbonylI CrCio-haloalkylcarbonyl, R5R6N-CO- and phenoxy which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, C Cιo-alkyl, d-do-haloalkyl, C3-C10-cylcoalkyl, C3-C10-halocycloalkyl, C2-Cιo-alkenyl, C2-Cι0-haloalkenyl, C2-Cιo-alkynyl, C3-Cιo-haloalkynyl, d- Cio-alkoxy, Cι-Cι0-haloalkoxy, C2-Cι0-alkenyloxy, C2-C10-haloalkenyloxy, C2-Cιo-alkynyloxy, C3-C10-haloalkynyloxy, d-C10-alkylthio, d-do- haloalkylthio, Cι-C 0-alkylsulfinyl, d-C10-haloalkylsuϊfinyl, C1-C10- alkylsulfonyl, Cι-Cι0-haloalkylsulfonyl, hydroxy, NR5R6, C Cι0- alkoxycarbonyl, Cι-Cιo-haloalkoxycarbonyl, C2-Cιo-alkenyloxycarbonyl, C2- Cio-haloalkenyloxycarbonyl, Cι-Cι0-alkylcarbonyl, C Cio-haloalkylcarbonyl and R5R6N-CO; or
R2 and R4 together with the carbon atoms to which they are bound form a phenyl ring or a 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the phenyl ring and the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring, and where the phenyl ring and the 5- or 6-membered hetero- cyclic ring and/or the phenyl ring to which they are fused may carry 1 , 2, 3 or 4 substituents Re which are selected, independently of one another, from halogen, cyano, nitro, C Cιo-alkyl, Ci-Cio-haloalkyl, C3-Cι0-cylcoalkyl, C3-Cιo-halocycloalkyl, C2-Cι0-alkenyl, C2-Cι0-haloalkenyl, C2-Cι0-alkynyl, C2-C10-haloalkynyl, d-do-alkoxy, Cι-Cι0-haloalkoxy, C2-Cι0-alkenyloxy, C2-Cιo-haloalkenyloxy, C2-Cι0-alkynyloxy, C2-Cιo-haloalkynyloxy, d-do- alkylthio, Ci-Cio-haloalkylthio, Cι-Cιo-alkylsulfinyl, C Cio-haloalkylsulfinyl, C Cιo-alkylsulfonyl, Cι-Cιo-haloalkylsulfonyl, hydroxy, NR5R6, d-C10- alkoxycarbonyl, C Cιo-haloalkoxycarbonyl, C2-Cι0-alkenyloxycarbonyl, C2- C o-haloalkenyloxycarbonyl, CrCio-alkylcarbonyl, Cι-C10-haloalkylcarbonyl, R5R6N-CO and phenoxy which may be substituted by 1 , 2, 3, 4 or 5 substituents Rf which are selected, independently of one another, from halogen, cyano, nitro, d-Cio-alkyl, Cι-C10-haloalkyl, C3-Cι0-cylcoalkyl, C3-Cιo- halocycloalkyl, C2-Cιo-alkenyl, C2-Cι0-haloalkenyl, C2-Cι0-alkynyl, C3-Cι0- haloalkynyl, d-Cio-alkoxy, Cι-C 0-haloalkoxy, C2-Cι0-alkenyloxy, C2-Cι0- haloalkenyloxy, C2-Cι0-alkynyloxy, C3-C10-haloalkynyloxy, C Cιo-alkylthio,
Ci-Cio-haloalkylthio, Cι-Cι0-alkylsulfinyl, CrCio-haloalkylsulfinyl, C1-C10- alkylsulfonyl, Cι-Cιo-haloalkylsulfonyl, hydroxy, NR5R6, C1-C10- alkoxycarbonyl, Cι-Cιo-haloalkoxycarbonyI, C2-C 0-alkenyloxycarbonyl, C2- Cio-haloalkenyloxycarbonyl, CrCio-alkylcarbonyl, C Cι0-haloalkylcarbonyl and R5R6N-CO, and where the 5- or 6-membered heterocyclic ring may contain 1 carbonyl group as a ring member;
R5 and R6 independently of one another are H or Ci-Cio-alkyl; and
n is 0 or 1.
2. The method as claimed in claim 1 , where Ar is a cyclic radical selected from phenyl, naphthyl and a 5- or 6-membered heterocyclic radical with 1 to 3 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic radical may be fused to 1 or 2 phenyl rings, and where the cyclic radical may have 1 , 2, 3 or 4 substituents Ra which are selected, independently of one another, from halogen, hydroxy, C C -alkyl, C C4-haloalkyl, d-C4-alkoxy, CrC4-haloalkoxy, Cι-C4-alkylthio, d-C4-haloalkylthio, phenyl, which is unsubstituted or substituted by 1 , 2 or 3 substituents Rb which are selected, independently of one another, from halogen, C C4-alkyl, C C4- haloalkyl and CrC4-alkoxy, and phenoxy which is unsubstituted or substituted by 1 , 2 or 3 substituents Rb which are selected, independently of one another, from halogen, Cι-C4-alkyl, C C4-haloalkyl and C C4-alkoxy.
3. The method as claimed in claim 2, where
Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, phenyl, pyridyl, pyrazinyl, naphthyl, dibenzopyranyl, indolyl or benzothienyl, and where the cyclic radical may be substituted by 1, 2 or 3 substuituents Ra which are selected, independently of one another, from halogen, hydroxy, Cι-C4-alkyl, CrC4-haloalkyl, C C4- alkoxy, Cι-C4-haloalkoxy, phenyl, which is unsubstituted or substituted by 1 , 2 or 3 substituents Rb which are selected, independently of one another, from halogen, d-C4-alkyl, C -C4-haloalkyl and C C -alkoxy , and phenoxy which is unsubstituted or substituted by 1 , 2 or 3 substituents Rb which are selected, independently of one another, from halogen, Cι-C4-alkyl, C C4- alkoxy and Cι-C4-haloalkyl.
4. The method as claimed in claim 3 where
Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxazolyl, phenyl, pyridyl, pyrazinyl, naphthyl, indolyl or benzothienyl, and where the cyclic radical may be substituted by 1 or 2 substituents Ra which are selected, independently of one another, from halogen, hydroxy, C C4-alkyl, d-C4-haloalkyl, CrC4-alkoxy and Cι-C4-haloalkoxy.
5. The method as claimed in any one of the preceding claims, where
R1 is H, Cι-C4-alkyl or Cι-C -haloalkyl.
6. The method as claimed in claim 5, where R1 is H or methyl.
7. The method as claimed in one of the preceding claims, where R2 and R4 together with the carbon atoms to which they are bound form a phenyl ring or a 5- or 6-membered heterocyclic ring with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, where the 5- or 6-membered heterocyclic ring may be fused to a phenyl ring, and where the 5- or 6-membered heterocyclic ring and/or the phenyl ring to which it is fused may carry 1, 2, 3 or 4 substituents Re which are selected, independently of one another, from halogen, CrC -alkyl, C C4-haloalkyl, Cι-C4- alkoxy, C C -haloalkoxy, d-C4-haloalkylthio, cyano, nitro, phenyl, which is unsubstituted or is substituted by 1 , 2 or 3 substituents which are selected, independently of one another, from Cι-C4-alkyl, Cι-C4-haloalklyl, C C4- alkoxy and halogen; and phenoxy which is unsubstituted or substituted by 1 , 2 or 3 substituents Rf which are selected, independently of one another, from C C4-alkyl, C C4-haloalklyl, Cι-C4-alkoxy and halogen, and where the 5- or 6-membered heterocyclic ring may contain 1 carbonyl group as a ring member.
8. The method as claimed in claim 7, where
R2 and R4 together with the carbon atoms to which they are bound form a phenyl, benzofuranyl, benzothienyl, indolyl, chromenyl, chromenonyl, pyrazolyl or furanyl moiety, and where the moiety may carry 1 , 2, 3 or 4 substituents Re which are selected, independently of one another, from halogen, Cι-C4- alkyl, C C4-haloalkyl, CrC4-haloalkoxy, C C4-haloalkylthio, cyano and nitro.
9. The method as claimed in claim 8, where
R2 and R4 together with the carbon atoms to which they are bound form a phenyl, benzofuranyl, benzothienyl or chromenyl moiety, and where the moiety may be substituted by 1 , 2 or 3 substituents Re which are selected, independently of one another, from Cι-C4-alkyl, C C4-haloalkyl and halogen.
10. The method as claimed in one of claims 1 to 6, where
R2 is H, d-Cio-alkyl, Ci-Cio-haloalkyl, halogen, phenyl or cyano.
11. The method as claimed in one of claims 1 to 6 or 10, where
R3 is H, d-C-4-alkyl, halogen or phenyl.
12. The method as claimed in one of claims 1 to 6, 10 or 11 , where
R4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl, furyl, or thienyl I, where the aromatic radical may carry 1 , 2, 3, 4 or 5 substituents Rc which are selected, independently of one another, from hydroxy, halogen, C C4-alkyl, C C4-haloalkyl, d-C4-alkoxy, C C4-haloalkoxy, d-C4- alkylthio, Cι-C4-haloalkylthio, cyano, nitro, NR5R6 and phenoxy which may be substituted by CrC4-haloalkyl; and
R5 and R6 are defined as in claim 1.
13. The method as claimed in claim 12, where
R4 is phenyl which may 1 , 2, 3, 4 or 5 substituents Rc which are selected, independently of one another, from hydroxy, halogen, d-d-alkyl, d-d-haloalkyl, Cι-C4-alkoxy, C C4-haloalkoxy, Cι-C4-alkylthio, C C4-haloalkylthio, cyano, nitro, NR5R6 and phenoxy which may be substituted by C C4-haloalkyl.
14. The method as claimed in one of claims 1 to 6 or 10 to 12, where
R2 is H, Ci-Cio-alkyl, Ci-Ci0-haloalkyl, halogen, phenyl or cyano;
R3 is H, Cι-C4-alkyl, halogen or phenyl; and
R4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl, furyl, or thienyl, where the aromatic radical may carry 1, 2, 3 or 4 substituents Rc which are selected, independently of one another, from hydroxy, halogen, Cι-C4-alkyl, Cι-C4-haloalkyl, Cι-C4-alkoxy, C C4-haloalkoxy, C C4- alkylthio, Cι-C4-haloalkylthio, cyano, nitro, NR5R6 and phenoxy which may be substituted by Cι-C4-haloalkyl; and
R5and R6are defined as in claim 1.
15. The method as claimed in claim 14, where
R4 is phenyl, which may carry 1 , 2, 3 or 4 substituents Rc which are selected, independently of one another, from halogen, Cι-C4-alkyl, d-C4-haloalkyl, d-C4-alkoxy, C C -haloalkoxy, Cι-C4-alkylthio, C C4-haloalkylthio, cyano, nitro, NR5R6 and phenoxy which may be substituted with Cι-C -haloalkyl.
16. The method as claimed in one of claims 14 or 15, where
R2 is H, C Cιo-alkyl or halogen;
R3 is H or halogen; and
R4 is phenyl which may carry 1 ,2 or 3 substituents Rc which are selected, independently of one another, from halogen, Cι-C4-alkyl, C C4-haloalkyl, d- C4-alkoxy, Cι-C4-haloalkoxy, C C4-alkylthio Cι-C4-haloalkylthio, cyano and nitro.
17. A method for protecting crops from attack or infestation by insects or arachnids comprising contacting a crop with a pesticidally effective amount of a compound of formula I as defined in claim 1.
18. The method as claimed in claim 17, where the compound of the formula I is applied at a rate of from 0.1 g/ha to 4000 g/ha.
19. A pryridyl compound of the general formula la
Figure imgf000076_0001
wherein Ra, R1 and R3 are as defined in claim 1 ,
m is 0, 1 , 2 or 3,
R2a is C C4 alkyl and
R4a is phenyl, which may carry 1 , 2, 3 or 4 radicals Rc as defined in claim 1 ,
provided that either i) m is not 0 or ii) R4a carries at least one substituent Rc being different from hydrogen iii) or R1 is different from hydrogen, iv) or R2a is different from methyl.
20. An isoxazolyl compound of the formula lb
Figure imgf000076_0002
wherein n, X, R1, R2, R3 and R4 are as defined in claim 1,
Ar is isoxazolyl, which may carry 1 or 2 substituents Ra as defined in claim 1 , provided that Ar does not carry an optionally substituted phenyl group if Ar is substituted 4-isoxazolyl.
A pyrazolyl compound of the formula lc
Figure imgf000077_0001
wherein n, X, R1, R2, R3 and R4 are as defined in claim 1,
Ar is pyrazolyl which carries a substituent Ra2 on the pyrazol nitrogen atom, and which may carry 1 or 2 substituents Ra as defined in claim 1 , wherein Ra2 is selected from C C10-alkyl, d-Cio-haloalkyl, C3-C 0-cylcoalkyl, C3- Cio-halocycloalkyl, C2-Cι0-alkenyl, C2-C10-haloalkenyl, C -Cι0-alkynyl, C3- C o-haloalkynyl, phenyl and benzyl, wherein phenyl and benzyl may be un- substituted or substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined in claim 1.
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WO2012051708A1 (en) * 2010-10-21 2012-04-26 The University Of British Columbia Anti-bacterial pyruvate kinase modulator compounds, compositions, uses, and methods
CN103641782A (en) * 2013-12-26 2014-03-19 青岛科技大学 Pyrazol acylhydrazone compounds and application thereof
WO2023010191A1 (en) * 2021-08-02 2023-02-09 Eurofarma Laboratórios S.A. N-acylhydrazone compounds capable of inhibiting nav1.7 and/or nav1.8, processes for the preparation thereof, compositions, uses, methods for treatment using same, and kits
WO2023010192A1 (en) * 2021-08-02 2023-02-09 Eurofarma Laboratórios S.A. N-acylhydrazone compounds capable of inhibiting nav1.7 and/or nav1.8, processes for the preparation thereof, compositions, uses, methods for treatment using same, and kits

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KR20060019558A (en) 2006-03-03
EP1631143A1 (en) 2006-03-08
JP2006528955A (en) 2006-12-28
BRPI0410626A (en) 2006-06-20
CN1842272A (en) 2006-10-04
AR045688A1 (en) 2005-11-09
AU2004243492A1 (en) 2004-12-09
CL2004001296A1 (en) 2005-04-08
ZA200510406B (en) 2008-12-31
MXPA05012226A (en) 2006-02-10

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