AU2004243492A1 - Hydrazone derivatives for combatting harmful insects and arachnids - Google Patents
Hydrazone derivatives for combatting harmful insects and arachnids Download PDFInfo
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- AU2004243492A1 AU2004243492A1 AU2004243492A AU2004243492A AU2004243492A1 AU 2004243492 A1 AU2004243492 A1 AU 2004243492A1 AU 2004243492 A AU2004243492 A AU 2004243492A AU 2004243492 A AU2004243492 A AU 2004243492A AU 2004243492 A1 AU2004243492 A1 AU 2004243492A1
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- haloalkyl
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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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Pyridine Compounds (AREA)
- Indole Compounds (AREA)
- Pretreatment Of Seeds And Plants (AREA)
Description
WO 2004/105488 PCT/EP2004/005681 1 Hydrazone derivatives for combatting harmful insects and arachnids The present invention relates to a method for combating harmful insects and arachnids. 5 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 in sects and arachnids. 10 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 15 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. 20 US 3066023 discloses aroylhydrazones as components of a photoconducting insulat ing layer in a material for xerography. WO 99/01423 discloses the preparation of aroylhydrazones which are useful as gluca 25 gon antagonists or inverse agonists. EP-A 322691 discloses aroylhydrazones as precursors for the preparation of 1 acylpyrazolines. 30 The inventors of the present application surprisingly found that compounds of formula I R1 Ar -(CH 2 )n-X - NH - N== C R3 35 (I) 35 ~R2> = R4 wherein: Ar is a cyclic radical selected from phenyl, naphthyl and a 5- or 6-membered hetero cyclic radical with 1 to 4 heteroatoms which are selected, independently of one 40 another, from 0, N and S, where the 5- or 6-membered heterocyclic radical may be fused to I or 2 phenyl rings, and where the cyclic radical may have 1, 2, 3, 4 or 5 substituents R' which are selected, independently of one another, from halo gen, cyano, nitro, C-C 10 -alkyl, C 1
-C
1 o-haloalkyl, C 3
-C
1 o-cylcoalkyl, C3-C1o halocycloalkyl, C 2
-C
1 o-alkenyl, C 2
-C
1 o-haloalkenyl, C 2
-C
1 o-alkynyl, C 3
-C
10 45 haloalkynyl, C-C 1 o-alkoxy, C-C 1 o-haloalkoxy, C 2
-C
1 o-alkenyloxy, C 2
-C
10
-
WO 2004/105488 PCT/EP2004/005681 2 haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3
-C
1 o-haloalkynyloxy, C-C 1 o-alkylthio, C
C
1 o-haloalkylthio, C-C 1 o-alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, NRR 6 , C-C 1 o-alkoxycarbonyl,
C-C
1 o-haloalkoxycarbonyl, C 2
-C
10 -alkenyloxycarbonyl, C 2
-C
1
O
5 haloalkenyloxycarbonyl, C-C 10 -alkylcarbonyl, C-C 1 o-haloalkylcarbonyl, R 6
R
6
N
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-C 1 o-alkyl, C-C 1 -haloalkyl, C 3
-C
10 cylcoalkyl, C 3
-C
1 o-halocycloalkyl, C 2 -C1 0 -alkenyl, C 2
-C
1 o-haloalkenyl, C 2
-CO
10 alkynyl, C 3
-C
1 o-haloalkynyl, C-C 1 o-alkoxy, C-C 1 o-haloalkoxy, C 2
-C
1 o-alkenyloxy,
C
2
-C
1 o-haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3
-C
1 o-haloalkynyloxy, C-C 1 o-alkylthio,
C-C
1 o-haloalkylthio, C-Clo-alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 10 alkylsulfonyl, Cl-C 1 o-haloalkylsulfonyl, hydroxy, NR 5
R
6 , C-C 10 -alkoxycarbonyl,
C-C
1 o-haloalkoxycarbonyl, C 2 -Clo-alkenyloxycarbonyl, C 2
-C
10 15 haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl; C-C 1 o-haloalkylcarbonyl and RRN-CO-; X is CO or SO 2 ; 20 R' is H, C 1 -o-alkyl, C-C 1 o-haloalkyl, C 3
-C
10 -cycloalkyl, C 3
-C
1 o-halocycloalkyl, C 2 C 10 -alkenyl, C 2
-C
1 o-haloalkenyl, C 2
-C
1 o-alkynyl, C 2 -Clo-haloalkynyl or phenyl which may be substituted by I to 5 substituents which are selected, independ ently of one another, from halogen, cyano, nitro, C-C 1 o-alkyl, C-C 1 o-haloalkyl,
C
3
-C
10 -cylcoalkyl, C 3
-C
1 o-halocycloalkyl, C 2
-C
1 o-alkenyl, C 2
-C
1 o-haloalkenyl, C2 25 C 10 -alkynyl, C 3
-C
1 o-haloalkynyl, C-C 1 -alkoxy, C-C 1 o-haloalkoxy, C 2
-C
1 o alkenyloxy, C 2
-C
1 o-haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3
-C
1 o-haloalkynyloxy, C
C
1 o-alkylthio, Cl-Clo-haloalkylthio, C-C 10 -alkylsulfinyl, Cl-Clo-haloalkylsulfinyl, C
C
1 o-alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, NR 5
R
6 , C 1 rC 10 alkoxycarbonyl, C-C 1 o-haloalkoxycarbonyl, C 2
-C
1 o-alkenyloxycarbonyl, C 2
-C
1
O
30 haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl and
R
5 RN-CO-;
R
2 and R 3 are independently of one another H, halogen, cyano, C-C 1 o-alkyl, C1-010 haloalkyl, C 3
-C
1 o-cylcoalkyl, C 3
-C
1 o-halocycloalkyl, C 2
-C
1 o-alkenyl, C 2
-C
1
O
35 haloalkenyl, C 2
-C
1 o-alkynyl, C 3
-C
1 o-haloalkynyl, C-C 1 o-alkoxy, C-C 1 o-haloalkoxy,
C
2
-C
1 o-alkenyloxy, C 2
-C
1 o-haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3
-C
10 haloalkynyloxy, C-C 1 o-alkylthio, C-C 1 o-haloalkylthio, hydroxy-C-C 1 o-alkyl, C
C
1 0 -alkoxy- C-C 1 o-alkyl, halo-C-C1o-alkoxy-C-C1a-alkyl, C-C 1 o-alkoxycarbonyl
C-C
1 o-alkyl, halo-C-C 1 o-alkoxycarbonyl-C-C 10 -alkyl or phenyl which may be 40 substituted by I to 5 substituents which are selected, independently of one an other, from halogen, cyano, nitro, C-C 1 o-alkyl, C-C 1 o-haloalkyl, C 3
-C
10 -cylcoalkyl,
C
3
-C
1 o-halocycloalkyl, C 2
-C
10 -alkenyl, C 2
-C
1 o-haloalkenyl, C 2
-C
10 -alkynyl, C3-C10 haloalkynyl, Cl-C 10 -alkoxy, C-C 1 o-haloalkoxy, C 2
-C
1 o-alkenyloxy, C 2
-C
10 haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3
-C
1 o-haloalkynyloxy, C-C 1 o-alkylthio, C 45 C 1 O-haloalkylthio, C-C 1 0 -alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 10
-
WO 2004/105488 PCT/EP2004/005681 3 alkylsulfonyl, C 1
-C
1 o-haloalkylsulfonyl, hydroxy, NR 5
R
6 , C 1
-C
1 o-alkoxycarbonyl,
C-C
1 o-haloalkoxycarbonyl, C 2
-C
1 o-alkenyloxycarbonyl, C 2
-C
1 o haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl and
RR
8 N-CO; 5
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 Rc which are se lected, independently of one another, from halogen, cyano, nitro, C-C 1 o-alkyl, C
C
10 -haloalkyl, Cs-C1 0 -cylcoalkyl, C 3
-C
1 o-halocycloalkyl, C 2
-C
10 -alkenyl, C 2
-C
1
O
10 haloalkenyl, C 2
-C
1 o-alkynyl, 0 3 -Co-haloalkynyl, C-C 1 o-alkoxy, C-C 10 -haloalkoxy,
C
2
-C
1 o-alkenyloxy, C 2 -Cio-haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3
-C
1 haloalkynyloxy, C-C 10 -alkylthio, C-C 1 o-haloalkylthio, C-C 1 o-alkylsulfinyl, C-C 1 o haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, NRR,
C-C
1 o-alkoxycarbonyl, C-C 1 o-haloalkoxycarbonyl, C 2
-C
10 -alkenyloxycarbonyl, 15 C 2
-C
1 o-haloalkehyloxycarbonyl, C-C 10 -alkylcarbonyl, C-C 1 o-haloalkylcarbonyl, RRON-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,
C-C
1 O-alkyl, C-C 1 o-haloalkyl, C 3
-C
10 -cylcoalkyl, C 3
-C
1 o-halocycloalkyl, C 2
-C
1
O
alkenyl, C 2
-C
1 o-haloalkenyl, C 2
-C
10 -alkynyl, C 3
-C
1 o-haloalkynyl, C-C 1 o-alkoxy, C 20 C 1 O-haloalkoxy, C-C 1 o-alkenyloxy, C 2
-C
1 o-haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3 C 1 o-haloalkynyloxy, C-C 10 -alkylthio, C 1 -0o-haloalkylthio, C-C 1 o-alkylsulfinyl, C
C
1 o-haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy,
NR
5
R
6 , C-C 1 o-alkoxycarbonyl, C-C 1 o-haloalkoxycarbonyl, C 2
-C
1
O
alkenyloxycarbonyl, C 2
-C
1 o-haloalkenyloxycarbonyl, C-C 1 -alkylcarbonyl, C-C 1 o 25 haloalkylcarbonyl and R 5 RN-CO; or
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 se lected, independently of one another, from 0, N and S, where the phenyl ring 30 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*, which are selected, independently of one another, from halogen, cyano, nitro, C-C 10 alkyl, C-C 1 o-haloalkyl, C 3
-C
10 -cylcoalkyl, C-C 1 o-halocycloalkyl, C 2
-C
10 -alkenyl, 35 C 2
-C
1 o-haloalkenyl, C 2
-C
10 -alkynyl, C 2
-C
1 o-haloalkynyl, C-C 10 -alkoxy, C-C 1 o haloalkoxy, C 2
-C
1 o-alkenyloxy, C 2
-C
1 o-haloalkenyloxy, C 2
C
1 o-alkynyloxy, C 2
-C
1
O
haloalkynyloxy, C-C 10 -alkylthio, CI-C 1 o-haloalkylthio, C-C 1 -alkylsulfinyl, C-C 1 o haloalkylsulfinyl, C-Ca-alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, NR5R 6 ,
C-C
10 -alkoxycarbonyl, C-C 1 o-haloalkoxycarbonyl, C 2
-C
1 o-alkenyloxycarbonyl, 40 C 2
-C
1 o-haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl,
R
5
R
6 N-CO and phenoxy which may be substituted by 1, 2, 3, 4 or 5 substituents R' which are selected, independently of one another, from halogen, cyano, nitro,
C-C
1 o-alkyl, C 1
-C
1 o-haloalkyl, C 3
-C
10 -cylcoalkyl, C 3
-C
1 o-halocycloalkyl, C 2
-C
1 o alkenyl, C 2
-C
1 o-haloalkenyl, C 2
-C
1 o-alkynyl, C 3
-C
1 o-haloalkynyl, C-C 1 o-alkoxy, C 45 C 1 -haloalkoxy, C 2
-C
10 -alkenyloxy, C 2
-C
1 o-haloalkenyloxy, C 2
-C
1 o-alkynyloxy, C 3
-
WO 2004/105488 PCT/EP2004/005681 4
C
1 o-haloalkynyloxy, C-C 1 o-alkylthio, C-C 1 o-haloalkylthio, C-C 10 -alkylsulfinyl, C
C
1 O-haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C-C 10 -haloalkylsulfonyl, hydroxy,
NR
5
R
6 , C-C 1 o-alkoxycarbonyl, C-Cio-haloalkoxycarbonyl, C 2 -C10 alkenyloxycarbonyl, C 2
-C
1 o-haloalkenyloxycarbonyl, C-Clo-alkylcarbonyl, C 1
-C
10 5 haloalkylcarbonyl and R 5
R
6 N-CO, and where the 5- or 6-membered heterocyclic ring may contain 1 carbonyl group as a ring member;
R
5 and R 6 independently of one another are H or C-C 1 o-alkyl; and 10 n is 0 or 1 or salts thereof are useful for combating insects and arachnids. The present invention therefore relates to a method for combating harmful insects and 15 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, sur faces 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 1. 20 The invention especially relates to a method for protecting crops from attack or infesta tion by insects or arachnids, which comprises contacting a crop with a pesticidally ef fective amount of a compound of the formula I as defined above. 25 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 R 3 and R 4 . Suitable compounds also encompass possible enantiomers and racemic mixtures. 30 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 cus tomary method, e.g. by reacting the compound with an acid of the anion in question. 35 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 40 the salts of barium, aluminum, nickel, copper, manganese, cobalt zinc, iron, silver, lith ium, sodium, potassium, magnesium or calcium. Additional salt formers include chlo ride, sulfate, acetate, carbonate, hydride, and hydroxide. Desirable salts include ad ducts of compounds I with maleic acid, dimaleic acid, fumaric acid, difumaric acid, and methane sulfonic acid. 45 WO 2004/105488 PCT/EP2004/005681 5 The term "5- or 6-membered heterocyclic radical with I to 4 heteroatoms which are selected, independently of one another, from 0, N and S" as used herein refers to both aromatic and non-aromatic rings such as saturated or partially unsaturated radicals having from I to 4, preferably 1 ,2, or 3 heteroatoms as ring members. 5 Examples for heteroaromatic rings are triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl or isoxazolyl. 10 If the 5- or 6-membered heteroaromatic ring is fused to I 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. 15 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, 20 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. 25 The term "5- or 6-membered heterocyclic ring with I or 2 heteroatoms which are se lected, independently of one another, from 0, 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 30 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. 35 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. 40 "Halogen" will be taken to mean fluoro, chloro, bromo and iodo. The term "C 1
-C
1 o-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 45 methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1- WO 2004/105488 PCT/EP2004/005681 6 dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4 methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, I-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, I-ethyl-2-methylpropyl, heptyl, octyl, 2 5 ethylhexyl, nonyl and decyl and their isomers. Cr-C 4 -alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl. The term "C 1
-C
10 -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 10 hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C 1
-C
4 -haloalkyl, such as chloromethyl, bromomethyl, dichloro methyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, I-chloroethyl, 1-bromoethyl, I-fluoroethyl, 2 fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2 15 difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. Similarly, "C 1
-C
1 o-alkoxy" and "C 1
-C
1 o-alkylthio" refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or 20 sulfur linkages, respectively, at any bond in the alkyl group. Examples include C 1
-C
4 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, futher C 1
-C
4 -alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio. 25 Accordingly, the terms "C-C 1 o-haloalkoxy" and " C-C 1 o-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 C1-C 2 -haloalkoxy, such as chloromethoxy, 30 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 C-C 2 -haloalkylthio, 35 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 40 trichloroethylthio and pentafluoroethylthio and the like. The term "C 2
-C
10 -alkenyl" as used herein intends a branched or unbranched unsatu rated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any posi tion, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3 45 butenyl, 1-methyl-1 -propenyl, 2-methyl-I -propenyl, 1 -methyl-2-propenyl, 2-methyl-2- WO 2004/105488 PCT/EP2004/005681 7 propenyl; I -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 5 2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1 pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-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 10 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 15 butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-l propenyl and 1-ethyl-2-methyl-2-propenyl; The term "C-C 1 o-haloalkenyl" as used herein intends a branched or unbranched un saturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any 20 position, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Similarly, the term "C 2
-C
1 o-alkenyloxy" as used herein intends a branched or un branched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double 25 bond in any position, the alkenyl group being bonded through oxygen linkages, respec tively, at any bond in the alkenyl group, for example ethenyloxy, propenyloxy and the like. Accordingly, the term "C 2
-C
1 o-haloalkenyloxy" as used herein intends a branched or 30 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, respec tively, 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. 35 The term "C 2
-C
10 -alkynyl" as used herein refers to a branched or unbranched unsatu rated 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 "C 3
-C
1 o-haloalkynyl" as used herein refers to a branched or unbranched un 40 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.
WO 2004/105488 PCT/EP2004/005681 8 The term "C 2
-C
1 o-alkynyloxy" as used herein refers to a branched or unbranched un saturated 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. 5 Similarly, the term "C 3
-C
1 o-haloalkynyloxy" as used herein refers to a branched or un branched 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 10 replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond. The term "C 3
-C
10 -cycloalkyl" as used herein refers to a monocyclic 3- to 10-membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo 15 heptyl, cyclooctyl and cyclodecyl. The term "Ca-C 1 o-halocycloalkyl" as used herein refers to a monocyclic 3- to 10 membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclo hexyl, cycloheptyl, cyclooctyl and cyclodecyl, where some or all of the hydrogen atoms 20 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. 25 With respect to the use according to the invention of the compounds of formula 1, par ticular 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 1, wherein 30 Ar is a cyclic radical selected from phenyl, naphthyl, a 5- or 6-membered heterocyc lic radical with 1 to 3 heteroatoms which are selected, independently of one an other, from 0, 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 sub stituted as defined above, i.e. by 1, 2, 3, 4 or 5 of the above mentioned radicals 35 R". Particular preference is given to the use of compounds of formula 1, wherein Ar is a cyclic radical selected from phenyl, triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, 40 thiadiazolyl, oxadiazolyl, isothiazolyl, isoxazolyl, naphthyl, quinolinyl, isoquino linyl, indolyl, indazolyl, benzofuryl, benzthienyl, benzthiazolyl, benzoxazolyl, ben zimidazolyl, chromenyl, chromenonyl, dibenzopyranyl or fluorenyl and where the cyclic radical is unsubstituted or substituted as defined above.
WO 2004/105488 PCT/EP2004/005681 9 Furthermore, particular preference is given to the use of compounds of formula 1, wherein Ar is a cyclic radical selected from thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, tria zolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, phenyl, 5 pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, naphthyl, dibenzopyranyl, indolyl, ben zimidazolyl, 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. 10 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 R". 15 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 20 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, isoxazoyl or 25 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 option ally substituted phenyl are also highly preferred. Preferably, the cyclic radical mentioned for Ar is unsubstituted or carries 1, 2, 3 or 4 30 substituents R, in particular 1, 2 or 3 and more preferably 1 or 2 substituents R". Preferred substituents R" are selected, independently of one another, from halogen, cyano, nitro, CrC 1 o-alkyl, C-C 1 o-haloalkyl, Ca-C 10 -cylcoalkyl, C 3
-C
1 o-halocycloalkyl, C
C
10 -alkoxy, C-C 1 o-haloalkoxy, C-C 10 -alkylthio, C-C 1 o-haloalkylthio, C-C 1 o 35 alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, phenyl, phenoxy, NR 5
R
6 , C 1
C
10 alkoxycarbonyl, C-C 1 o-haloalkoxycarbonyl, C-C 10 -alkylcarbonyl, C-C 1 o haloalkylcarbonyl and NR 5 R-CO-. Particularly preferred substituents Ra are selected, independently of one another, from 40 halogen, hydroxy, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-Crhaloalkoxy, phenyl, which is unsubstituted or substituted by by I to 3 substituents Rb which are in particular selected, independently of one another, from halogen, C-C 4 -alkyl, C-Crhaloalkyl and C-Cralkoxy, especially by halogen, and phenoxy which is unsubstituted or substituted by 1 to 3 substituents Rb which are in particular selected, independently of one another, WO 2004/105488 PCT/EP2004/005681 10 from halogen, C-C 4 -alkyl, CrC 4 -haloalkyl and C-C 4 -alkoxy, especially by C-C 4 haloalkyl. More preferred substituents Ra are selected, independently of one another, from halo 5 gen, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy and C-C 4 -haloalkoxy. Especially preferred substituents Ra are selected, independently of one another, from fluorine, chlorine, bromine, CrC 4 -alkyl, C-C 4 -alkoxy, in particular methoxy, C-C 4 haloalkoxy, in particular difluoromethoxy or trifluoromethoxy and CF 3 . 10 Preference is given to the use of compounds of formula I, wherein R' is H, C-C 4 -alkyl or C-C 4 -haloalkyl. Particular preference is given to the use of compounds of formula I, wherein 15 R' is H or methyl, most preferably H. Preference is given to the use of compounds of formula I, wherein
R
2 is H, C-C 1 O-alkyl, C-C 1 o-haloalkyl, halogen, phenyl or cyano. 20 Particular preference is given to the use of compounds of formula I, wherein
R
2 is H, C-C 1 o-alkyl, , in particular C-C 4 -alkyl, halogen, phenyl or cyano. Furthermore, particular preference is given to the use of compounds of formula 1, wherein 25 R 2 is H, C-C 1 o-alkyl, in particular C-C 4 -alkyl or halogen, e.g. methyl, ethyl, isopro pyl, fluorine, chlorine or bromine. Most preferably R 2 is C-C 4 -alkyl, in particular methyl or ethyl. Preference is given to the use of compounds of formula I, wherein 30 R 3 is H, C-C 4 -alkyl, C-C 4 -haloalkyl, halogen or phenyl. Particular preference is given to the use of compounds of formula 1, wherein
R
3 is H, C-C 4 -alkyl, halogen or phenyl, especially H or halogen. 35 Preference is given to the use of compounds of formula I, wherein
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 Rc. 40 Particular preference is given to the use of compounds of formula I, wherein
R
4 is phenyl where phenyl is unsubstituted or substituted as defined above. 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 Rc. 45 WO 2004/105488 PCT/EP2004/005681 11 Preferred substituents RC are selected, independently of one another, from hydroxy, halogen, cyano, nitro, C-C 1 o-alkyl, C-C 1 o-haloalkyl, C 3 -Coo-cylcoalkyl, C 3
-C
10 halocycloalkyl, C-C 10 -alkoxy, C-C 1 o-haloalkoxy, C-C 1 o-alkylthio, C-C 1 o-haloalkylthio,
C-C
1 o-alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, NR 5
R
6 , C-C 10 -alkoxycarbonyl, C-C 10 5 haloalkoxycarbonyl, R 5
R
6 N-CO- and phenoxy which may be substituted by G 1
-C
4 haloalkyl. Particularly preferred substituents R* are selected, independently of one another, from halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-C 4 -haloalkoxy, C-C 4 -alkylthio, 10 C-C 4 -haloalkylthio, cyano, nitro, NRR 6 and phenoxy which may be substituted by C Crhaloalkyl. More preferred substituents Rc are selected, independently of one another, from halo gen, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-C 4 -haloalkoxy and C-C 4 15 haloalkylthio, e.g. from fluorine, chlorine, methyl, ethyl, propyl, isopropyl, butyl, fluoro methyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy and trifluoromethylthio. Especially preferred substituents Rare selected, independently of one another, from 20 halogen, C-Cralkyl and C-C 4 -haloalkyl. If R 4 is phenyl, which carries 1, 2 or 3 of the aforementioned substituents R", then at least one of the substituents is preferably located in the 2, 4 and/or 6-postion. Exam ples of paricularly preferred substituted phenyl are those mentioned in tables 2 and 3 25 as radicals R 4 . Alternatively, preference is given to the use of compounds of formula I, wherein
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, 30 independently of one another, from 0, N and S, where the 5- or 6-membered hetero cyclic 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 aforemen tioned substituents R*. Preferably, the substituents R* are selected, independently of one another, from halogen, C-C 4 -alkyl, C-Crhaloalkyl, C-Cralkoxy, C-C 4 35 haloalkoxy, C-C 4 -alkylthio, C-C 4 -haloalkylthio, cyano, nitro, phenyl, which is unsubsti tuted or is substituted by 1, 2 or 3 substituents Rf which are selected, independently of one another, from C-C 4 -alkyl, C-Crhaloalklyl C-C 4 -alkoxy and halogen, and phenoxy which is unsubstituted or substituted by 1 to 3 substituents which are selected, inde pendently of one another, from C-C 4 -alkyl, Cl-C 4 -haloalklyl, C-C 4 -alkoxy and halogen, 40 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 R 2 and R 4 together with the carbon atoms to which they are bound form a 45 phenyl, benzofuranyl, benzothienyl, indolyl, chromenyl, chromenonyl, pyrazolyl or fu- WO 2004/105488 PCT/EP2004/005681 12 ranyl moiety, and where the moiety may carry 1, 2, 3 or 4 substituents of the aforemen tioned substiuents R". Furthermore, particular preference is given to the use of compounds of formula 1, 5 wherein R 2 and R 4 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 o3 3 substituents Re. Even more preference is given to the use of compounds of formula 1, wherein R 2 and 10 R 4 together with the carbon atoms to which they are bound form a benzofuranyl or benzothienyl moiety. In this alternative, 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. 15 In particular substituents R* are selected, independently of one another, from halogen,
C-C
4 -alkyl, C-C 4 -haloalkyl, C-C 4 -haloalkoxy, C-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 C-C 4 -haloalklyl and halogen, and phenoxy which is 20 unsubstituted or substituted by C-C 4 -haloalklyl. Preferably, the substituents R* are selected, independently of one another, from halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, C
C
4 -alkoxy, C-C 4 -haloalkoxy, C-C 4 -haloalkylthio, cyano and nitro. More preferably sub stituents R* are selected, independently of one another, from C-C 4 -alkyl, C-C 4 haloalkyl and halogen. 25 Particularly preferred radicals Rb, Rd and Rf are selected from halogen, C-C 4 -alkyl, C
C
4 -haloalkyl, Cr-C 4 -haloalkoxy, C-C 4 -haloalkylthio, cyano and nitro, especially from halogen, C-C 4 -alkyl, C-C 4 -alkoxy, Cl-C 4 -haloalkyl, C-C 4 -haloalkoxy. 30 A very preferred embodiment of the invention relates to the use of pyridyl compounds of the general formula la 0 R1 N-N- R3 (Ra)m H - (la) R a R4a 35 wherein R", R 1 and R 3 are as defined herein, m is 0, 1, 2 or 3,
R
2 ' is H or C-C 4 alkyl and 40
R
4 3 is phenyl, which may carry 1, 2, 3 or 4 substituents R4 as defined herein, WO 2004/105488 PCT/EP2004/005681 13 In case R 2 a 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 5 ii) R 4 " carries at least one substituent Rc being different from hydrogen iii) or R' is different from hydrogen, iv) or R 2 " is different from methyl. In formula la preference is given to compounds wherein m is 0, 1 or 2. 10 Preferably Ra in formula la has one of the meanings which are indicated as being pre ferred, more preferred, particularly preferred or especially preferred. Most preferably R" is Halogen, in particular F, Cl or Br, C-C 4 -alkyl, in particular methyl or ethyl, phenyl, difluoromethyl, trifluoromethyl or C-C 4 -alkoxy, in particular methoxy. 15 Amongst the compounds of the formula la those are preferred wherein R 1 and Ra have, independently of each other, one of the meanings which are indicated as being pre ferred, more preferred, particularly preferred or especially preferred. Most preferred are compounds la, wherein R 1 and R 3 are hydrogen. 20 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, Cl, methoxy or methyl. In particular substituted phenyl is selected from one of the meanings given for R 4 in tables 3 or 4, in particular from 2 25 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 30 trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-difluoromethoxyphenyl, 3 difluoromethoxyphenyl, 4-difluormethoxyphenyl. However, compounds la, wherein R 4 ' is unsubstituted phenyl, are also highly preferred. In formula la R 2 a is most preferably methyl or ethyl. 35 Another very preferred embodiment of the invention relates to the use of isoxazol com pounds of the general formula lb
R
1 Ar(H)-X-N-N- R3 (IH - b) R R4 WO 2004/105488 PCT/EP2004/005681 14 wherein 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 as defined herein. 5 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 pre sent invention. 10 Amongst the compounds of the formula lb those are preferred wherein n, X, Ra, 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. In particular the variables R1, R 2 , R 3 and R" have the meanings outlined below: 15 R' is H,
R
2 is H or C1-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 Rc as defined herein, 20 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, Cl, methoxy or methyl. In particular 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 25 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 30 difluoromethoxyphenyl, 4-difluormethoxyphenyl. However, compounds la, wherein R 4 is unsubstituted phenyl, are also highly preferred. In formula lb X is preferably C=O and n is preferably 0. 35 Another very preferred embodiment of the invention relates to the use of pyrazol com pounds of the general formula Ic Ri Ar-(CH 2 )n X-N-N R3 H - (Ic) R R WO 2004/105488 PCT/EP2004/005681 15 wherein n, X, R', R 2 , Ra and R 4 are as defined in claim 1, Ar is pyrazolyl which carries a substituent Ra 2 on the pyrazol nitrogen atom, and which may additionally carry 1 or 2 substituents R" as defined in claim 1, wherein 5 Ra 2 is selected from C-C 1 o-alkyl, C-C 1 o-haloalkyl, C 3
-C
1 o-cylcoalkyl, C 3
-C
1 o halocycloalkyl, C 2
-C
10 -alkenyl, C 2
-C
1 o-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 Rb as defined in claim 1 10 The compounds of the formula Ic are new and thus are also part of the present inven tion. Amongst the compounds of the formula Ic those are preferred wherein n, X, Ra, Rb, R 1 ,
R
2 , R 3 and R 4 have, independently of each other, one of the meanings which are indi 15 cated as being preferred, more preferred, particularly preferred or especially preferred. Ro 2 is preferably selected from C-CB-alkyl, C 3 -C6-cycloalkyl or phenyl. In a particularly preferred embodiment Ra 2 is C-C 4 -alkyl. 20 In particular the variables R 1 , R 2 , R 3 and R 4 have the meanings outlined below: R' is H,
R
2 is H or CrC 4 alkyl most preferably methyl or ethyl,
R
3 is H, and 25 R 4 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 R is selected from F, Cl, methoxy or methyl. In particular substituted phenyl 30 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-trifluoromethoxyphenyl, 3 35 trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2-trifluoromethylphenyl, 3 trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-difluoromethoxyphenyl, 3 difluoromethoxyphenyl, 4-difluormethoxyphenyl. However, compounds la, wherein R 4 is unsubstituted phenyl, are also highly preferred. 40 In formula lc X is preferably C=O and n is preferably 0.
WO 2004/105488 PCT/EP2004/005681 16 A very preferred embodiment of the invention relates to the use of phenyl compounds of the general formula Id 0 Ri N-N~ R3 (Ram H -- (Id) Rd R4d 5 wherein Ra, R' and R are as defined herein, m is 1, 2 or 3, 10 R 2 d is H or CrC 4 alkyl and
R
4 d is phenyl, which may carry 1, 2, 3 or 4 substituents Rc as defined herein, In formula Id preference is given to compounds wherein m is 1 or 2. 15 Preferably R in formula Id has one of the meanings which are indicated as being pre ferred, more preferred, particularly preferred or especially preferred. Most preferably R" is Halogen, in particular F, Cl or Br, C-C 4 -alkyl, in particular methyl or ethyl, phenyl, difluoromethyl, trifluoromethyl or CrC 4 -alkoxy, in particular methoxy. Most preferably at 20 least one radical R" is halogen, especially fluorine. Amongst the compounds of the formula Id those are preferred wherein R' and Ra have, independently of each other, one of the meanings which are indicated as being pre ferred, more preferred, particularly preferred or especially preferred. Most preferred are 25 compounds la, wherein R' and R 3 are hydrogen. Preferably, the substituent R4, 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, Cl, methoxy or methyl. In particular substituted phenyl 30 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-chloropheny, 3 fluoro-4-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 2-trifluoromethoxyphenyl, 3 35 trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2-trifluoromethylphenyl, 3 trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-difluoromethoxyphenyl, 3 difluoromethoxyphenyl, 4-difluormethoxyphenyl.
WO 2004/105488 PCT/EP2004/005681 17 In formula Id R 2 d 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 5 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 R 2 and R 4 are bound cis to each other. Preference is also given to mixtures of the cis/trans isomers, 10 referring to the position of R 2 and R 4 towards each other, wherein the cis isomer is pre.
dominating. The compounds of the formula I may be readily synthesized using techniques generally known by synthetic organic chemists. Exemplary synthesis methods are described for 15 example in WO 87/06133. For instance, suitable acyl hydrazides can be reacted with aldehydes or ketones to form acyl hydrazones: R1C Ra R1 20 Ar-(CH 2 )h-CO-NH-NH 2 + R2 R43 : Ar-(CH 2 )1CO-NH-N= C / R R2 RR Cinnamic aldehydes and analogous ketones can be obtained according to a literature 25 procedure (Organikum, Johann Ambrosius Barth Verlag, Heidelberg, 1996, pp. 493 495) from benzaldehydes and aliphatic ketones or aldehydes. The sulfonyl hydrazones (X = SO 2 ) can be obtained in an analogous way starting from the corresponding sulfonic acid hydrazides (e.g. Munshi, Shah, Trivedi,lndian J. Chem. 30 1963, 1, 318-320): R0C \ Ra R/ Ar-(CH 2
),-SO
2
-NH-NH
2 + R2 R4 Ar-(CH 2
),SO
2 -NH-N=C R 3 R2>=< R4R2> R4 If not commercially available, the starting materials (acyl hydrazides) can be prepared according to literature procedures (e.g. Khan, Siddiqui, Bhatt, Oriental Journal of 35 Chemistry 2002, 18, 163-164) e.g. from carboxylic acid esters (Ar-(CH 2 )n-COOR") or other acid derivatives such as Ar-(CH 2 )r-COY (Y = halogen) which are reacted with hydrazine to form the corresponding acyl hydrazides. Alternatively, carboxylic acids (Ar-(CH 2 )n-COOH) can be reacted with protected hydrazine in the presence of a cou pling reagent such as DCC or DIC (according to Guan, Green, Bergstrom, J. Comb. 40 Chem. 2000, 2, 297-300), and subsequent removal of the protecting group (Messina, WO 2004/105488 PCT/EP2004/005681 18 Botta, Corelli, Paladino, Tetrahedron Asymm. 2000, 11, 4895-4901; Greene, Wuts, Protective Groups in Organic Synthesis, 2nd edition, 1991, pp. 309): Ar-(CH 2 )n-COORa + NH 2
-NH
2 > Ar-(CH 2 )n-CO-NH-NH 2 5 Ar-(CH 2 )n-COOH + NH 2 NHP*-- Ar-(CH2)n-CO-NH-NHP* : Ar-(CH 2 )n-CO-NH-NH 2 * P = protective group; R' = C 1
-C
10 -alkyl 10 The sulfonyl hydrazides (X = SO 2 ) can be obtained in an analogous way starting from the corresponding sulfonic acid derivatives, e.g. from the corresponding sulfonic acid (Ar-(CH 2 )n-SO 2 OH) or another derivative such as the sulfonic acid halogenide (Ar
(CH
2 )n-SO 2 Y; Y = halogen): (e.g. EI-Maghrabi, Mohamed, J. Chem. Tech. Biotechnol. 1983, 33A, 25-32) 15 Ar-(CH 2 )n-SO 2 OH + NH 2 -NHP* Ar-(CH 2 )n-SO 2 -NH-NHP* : Ar-(CH 2 )n-SO 2
-NH-NH
2 * P = protective group; Ra = C 1
-C
1 o-alkyl 20 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 25 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 30 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, 35 Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo 40 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 45 dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma WO 2004/105488 PCT/EP2004/005681 19 saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrela, Pieris bras sicae, Plathypena scabra, Pluteila xylostella, Pseudoplusia includens, Rhyacionia frus trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera eridania, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumato 5 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 10 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, 15 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 20 lineatus and Sitophilus granaria, dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi nivorax, Chrysomya macelaria, Contarinia sorghicola, Cordylobia anthropophaga, 25 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 trifoli, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destruc tor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinela frit, Pegomya hyso 30 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 35 tabaci, hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So lenopsis geminata and Solenopsis invicta, 40 heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus (eucopterus, 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, 45 WO 2004/105488 PCT/EP2004/005681 20 homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturti, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypfi, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifoli, Brachycaudus cardui, Brachycaudus helichrysi, Brachy 5 caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypi, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus Iactu cae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rose, Megoura 10 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 mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maids, Rhopalosi phum padi, Rhopalosiphum insettum, Sappaphis mala, Sappaphis mali, Schizaphis 15 graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiland, and Viteus vitifoli. termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis, 20 orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Giyllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melano plus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri 25 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 30 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. 35 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 40 Lepidoptera, Thysanoptera, Homoptera and Acarina and more preferably for controlling insects of the orders Lepidoptera and Homoptera. The compounds of formula (1) 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 45 cidally effective amount of compounds of formula (1). The term "crop" refers both to WO 2004/105488 PCT/EP2004/005681 21 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 5 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). 10 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 (1). As such, the application may be carried out before or after the infection of the locus, grow ing crops, or harvested crops by the pest. 15 "Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environ ment 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 20 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 25 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, 30 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 in vention. The formulations are prepared in a known manner, e.g. by extending the active ingre 35 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 frac tions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. 40 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. poly oxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose. 45 WO 2004/105488 PCT/EP2004/005681 22 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 5 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 10 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 15 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, par affin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexa 20 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. 25 Granules, e.g. coated granules, compacted granules, impregnated granules and ho mogeneous granules, can be prepared by binding the active ingredients to solid carri ers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, less, clay, dolomite, diatomaceous 30 earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materi als, 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. 35 Such formulations or compositions of the present invention include a formula I com pound 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. 40 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). 45 The following are exemplary formulations: WO 2004/105488 PCT/EP2004/005681 23 1. 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. 5 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 ac tive ingredient with good adhesion properties (comprises 23% by weight of active in 10 gredient). 1i1. 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 ethyl ene oxide and I mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium 15 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 20 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 25 weight of sodium diisobutyinaphthalene-alpha-sulfonate, 10 parts by weight of the so dium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pul verulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient). 30 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 35 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. Pour ing 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. 40 VIII.20 parts by weight of a compound of formula I are mixed thoroughly with 3 parts by weight of sodium diisobutyinaphthalene-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 pulveru lent silica gel, and the mixture is ground in, a hammer mill. Finely distributing the mix- WO 2004/105488 PCT/EP2004/005681 24 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 5 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 10 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 15 be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alter natively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concen trates are suitable for dilution with water. 20 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 25 (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 30 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 35 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 40 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: 45 WO 2004/105488 PCT/EP2004/005681 25 Organophosphates: Acephate, Azinphos-methyl, Chlorpyrifos, Chlorfenvinphos, Diazi non, Dichiorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, 5 Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Triazophos, Trichiorfon; Carbamates: Alanycarb, Benfuracarb, Carbaryl, Carbosulfan, Fenoxycarb, Furathio carb, Indoxacarb, Methiocarb, Methomyl, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, 10 Triazamate; Pyrethroids: Bifenthrin, Cyfluthrin, Cypermethrin, Deltamethrin, Esfenvalerate, Ethofen prox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda-Cyhalothrin, Permethrin, Si lafluofen, Tau-Fluvalinate, Tefluthrin, Tralomethrin, Zeta-Cypermethrin; 15 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; 20 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 25 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. 30 1. Synthesis Examples 1.1 Preparation of the starting materials 35 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. 40 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 45 mmol) Boc-protected hydrazine and 518 mg (1 mmol) N-cyclohexyl-N'-methyl- WO 2004/105488 PCT/EP2004/005681 26 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) = 5 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]*). 10 1.2 Preparation of the final hydrazones of formula 1 1.2.1 Preparation of furan-2-carboxylic acid [(benzofuran-2-yl)methylene] hydrazide 15 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 1 H NMR.> 20 'H NMR (d 6 -DMSO; 400 MHz); 6.8 (s, 1H), 7.3 (m, IH), 7.4 (m, IH), 7.45 (m, 1H), 7.6 (d, 1H), 7.7 (d, 1H), 8.0 (s, 1H), 8.5 (s, IH), 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 25 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.
WO 2004/105488 PCT/EP2004/005681 27 CC C: o c) - O ; V- ) 0~~~ 0 0) -V -j ob 4) r .- _ A_ 3;CC CC c La c'L :3 2a La-LC 0 a ~E z -cq11 1 11 2 0j - - - - - - A! S?1 AAAA?= I 6S 00 00 q- 0,+ -2C - 0 0000- - - 0 o A m o o 6 L6 A 4 rto U)
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d. LO E L 0 0 0 >,a _1 > --- ow 0 20 a -C~~ -C= 2 ( = 0.0 a oL0C 0 000 L 0 00a C .2 -0- - - I ceC C C6) 0) 0 - ) 0 0)0) 0) 0) ) CC 0CC LDL( CO C4 C-4l O CO D* )i . D N > 0i a) a r C C D 0 oOO 0) 0)))00 ,))) 0 ,0 0 a) a ) a - Ew WO 2004/105488 PCT/EP2004/005681 35 + I 0 00 0 0 00 0 ) m 0) 0 I c; 4 6o oE co 4- ob 6 oZCL 0 _N CW- 04 - C C oN EE a) OLa) 0a) a 22 2N r I I I o I f~~* "W MT ,cq 3I- T- M m c Z L) o 04 C) 0~ C) CL) - C E ~ c a c .- = I I II..5 C M C? CC? a) a ) 0I (D a) a) . a) 2C.NN A -0. -0 0 0 .0C 0 cc a)U i a .a CY) y. co mV CO) L. 6 (6 C6o6 65 ~C i L6 C6 -:CO 0) EO 0 000 C) CD CD CV -T - T MU Z T* - V- - V- .- WO 2004/105488 PCT/EP2004/005681 36 ++ + + + r_+ a+ c+ c+ r+ co _ + :+ c + 22 E N M N No M N C) N N Nt N N E E E E 2 E E E E C a) C: C > > .C-) . C ) C= C C a) C C: r_ 2- 9I c a 0. CL C C 0) 2I U 0 56 22 0 0 a) o~ 0. 0.- LU) C 4 o cq c o co C C9 C Il I: a: I 00 42 E L L L6 LO co r.- Lo L. L. 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C CL' CL' CL CL C LC 0) CD aI CD 0. 0. 0 C CL CL I r00 E ~ E:E E E E C6) E ' r ' 0 0 co 00 00 cc Go o cc x WO 2004/105488 PCT/EP2004/005681 41 + - + + + + + + + + a: a: M x M m X ~ o o N N N- N N - NZ N N E E E E E E E E E E E E E 2 0 D a) 2 ) 2 1 e ~ C D~ A--C 0 0. 0. 0- a) 0 13 CD- 0L 0) 00 0 -~ . .C c -~.c=3 0 m0 x 0. m.. . . ' 0 C C: C ) m 0- a) a) CL CL 0 CL CL C C 0 0C CL C 0 0 0 0 0 0 0 0 0 0 0 0 0 C4 c'Jq C'~j C'.j cq C'4 C\J Y 0..0 6j 4 C C6 r L 6 6 E 0 cO 0) 0) 0) 0D 0) 0) 0) 0) 0) 0) 0 mU Z . ~ ' - C'1 x WO 2004/105488 PCT/EP2004/005681 42 m: X: 3 : m: M: 3 3 0 N N! N N N N N N N Ei E E 2 E E 2 2 E E C a~ ) C:~c~ c a) () aI - ) a) a) U) (D 4) (D 0. 0. 0. CL 0a 0 0 0. 0. 22 2 0 2 2 2 2 2 00 2 0 0 0 r-. 0 0 0 0 0 0o 3: Mi 2 cm M Eo m 4o MA 4 c 0 Cy) I C: a) a) a) a) a) a) C ' I 2 2 2 2 ~ 2 2i 2 2 A- II c 2 0 0 0 0 0 0 0 0 0L 000 ~~ ti Z 04 I 2 : I - C C Cq C C a (q C6 C !E ~ - 0U) C ) C) U) U) U) U) U) v-T w N.q C .. .C .CM N C .Cl -q Cl q C~ 0.x . 0 . 0 i 2 2 2 Z dc WO 2004/105488 PCT/EP2004/005681 43 d. E Eocl -E y cm E- E cE Ej t EE 35; 3 ; 3 33; 3;; 71 7; 3; 3; a) ) ) a a a) a) a) a) a) a) .C . C . c .Z C- -- I- 0. 0. 0 0- 0- 0. CL 0- 0. 0L. 0. o 0 0 0 0 0 0 0 0 0 0 UF cli C6 C1 C6 C6 C6 C6 a C4) C6 co co co co mo m co Co C) mo m o 0 0 0 U U 0 0 U 0 * I I' 6 c C c c r_ C N LD o) (1) CI) >rI 5; e ='; Z; 3; 2'4- I 4 a) 0 aC) U)D C 'a E E E~ E E C' C) C C; C') C) S to CC r- 06 oi o5 IV. C ~ cf ) E' 0' NT- V - - T N CA N Nl m Z C~l q C~l N Nq N* ~ ~l Cl x wU WO 2004/105488 PCT/EP2004/005681 44 + f+ + +±c + ~+ ~+ + + ~+ 0 N N N N N N N _N NZ N SE E E E E E E E E E E E a) a) CD 4 2 2 0 2 2 U) 0 2 i o0 - 0 0 0 0 0 ~ 0 co~ o o 00 0 Ic 3I a: I I cI C ~cl CY) 0 a) 5, a) a x 0 0 w, 2 ON ON O 0 0 E E m 00 x .2 x ~<XXi 2 ~ 2 o.OC =. o E y~ E - * w c. in 0 U C . L.6 (6 l'- c6 0) 6i c'i C6~~ E 0 N Nq N N cr) m~ m) mo V N Z NqC4 C N N~ N* N~ N N~ NM x wU WO 2004/105488 PCT/EP2004/005681 45 +-+ + z: ~~- 3:, m: -c Z a.0 "t 2 0 (0 e ( O 0 f 0(0 0 to5.CC M N , LO C4LO Co LO C e) Ce C I)C CfJ V ( )L) I , C o 0 Ci 1 COi Co Co C 11 1 C 1 Co 1 Coi Ci C6 N N4 N N JN N N U) C a) (D a) a) C-U( 3% oL c- 0m ~ ~ -C U) U . U) c CL CL) CL 2 5 0.CED 0C 0.C 0.L - 5*C 2 2 2 2 2 2 2 > > 0 0 0 0 0 0 0 .2 = L( o C, tOo (Yn CE C') m4: m m m o-0t 0d 0 o6 oi 0 0 ~ '~. 3: m3 : :c a : 3 IwL - L L - WO 2004/105488 PCT/EP2004/005681 46 + + ++ + + + + IL E2LE E E E E E E m ~ (o w ; . L C6 C'i C! Cl) C6 11Cl)i 11 C 0 N E -E E E E c E E E E .c a) 0(D ~a CL~ ct CL1 0 0 0 2~l 2 2 0: E: E z 0 0 0 a)I I : I : 2 2 a) a) 2 I I I co N I I I I CJ ~ J CM C'.J (N cqNI ( N ( -1 -cc-oc~ . 0 - V V (N ( J (N C', CN (CJ (N (N (N x6 wL CL C WO 2004/105488 PCT/EP2004/005681 47 C E E 2 E E E E 2 E , M N , 3, "T a L c m 0 N w co m 0I 0)i CD C (D c CD a) 0 . a ) . L. o R 0 2 2. 0 0 0 a S 0 0 0 0~ . EV N N~ N ce) LO CY) LO ItO 0 L) 7, 7, 7,3,3 N N N N N N > >1 >1 >1 >1 C C C C C C 3, 3 , L a L a. a a a 0.~-.' a) ) a) '& .6 r-.: 06 oi 6 V- c'. c L6 (6 E 0 L to) LO LO (0 co (0 ( C t CD CD AsZ N N~ N~ C1 N1 N4 N N NA N N4 x wL WO 2004/105488 PCT/EP2004/005681 48 +' N0t, N O N N N N N dLE E E E E E E E E E E C: C: C: a a a a) a) C CD _ 2 2 2 m CL2 2 C :0 0 0 02 2 2 o2 0o . 0 0 li Li 1;4 i Y I r I I i C~ C) m ~ 'm C'm o C.) 0 0 0 0 0 0 0 0 C 4 C i C I Cq. U CI CI N I I I I CJ C CLI C' " 3;3 ;0 0 0 0 0 0 SE E E E 0 0 a) al) a) a) 2 2 2 2 a : E 0 (0 - t- r-- f- r-- I- N mN zN 04J NN 04J (NJ (NJ~lCl ~ Cj x wm WO 2004/105488 PCT/EP2004/005681 49
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0 N N N N N N E E E E E E E E E E E m CL C: C CL C CL flW 2 2 (D 2 2 2 (D 2 2 a) 0 0 0 0.0 go 0 0 0 0 co) N~ co N CY) C 2 C ) C C C)C E I E I E N E 64 E 2o 0 ,r 0 0 0 0- 0 C N c6 ii 6 11:r l 4 L E~ 0 - 0' 00 0 ' O0 0 0 00'O (aZ.qN C4 .Cl 04 .C Cl CM -j 04 ( o ' xI I . 0. 0 . i WO 2004/105488 PCT/EP2004/005681 50 +. ++ + ~+ + ~+ I 11 6 116 1 1 U 6 11 C611 Ci11 16 '11611 * E E E E E E E E E E E (D) a ) a) a) Q. c . C. 2 a- 2 2 2 2 0 0( 0 0 0 0 0 0 o 0 0 0 _ 4r IT 7 7? 7 C*J C) C~f C6 i C4) I6 o 0 0) 0 0 0 0 0 0 0 -7, -5 -1 5 , ) (D ( 0) a) r, 2L 2 2 m. 2 2~ 2. 2~ -6 0 0 0 0 0 C: o 0 -~ 0 CL a- 0_ 04 0 C6) C6 C6) CL c oi 5 r- c'J C6 'i L6 (6 t x wi WO 2004/105488 PCT/EP2004/005681 U51 IJ 0 00 0 0 0 0c o- -- V- N -oW M L 1 I q C C co co .7 ICT Y3 D c Ci 1 - r- C(C6 ) C Ci 0 0N . ~ .~ a) r~ -o = wV W CL ~ CL CL a 2L a ~3 2(- 2 2 CL CL 0000000 0 0 02 0 0 E~j C ~~~~ ~ ~ ~ 64 co C l 4 ( Ll c z t c CYI *o -qc) Y =111 0V 0. 0. X IM 7* '5 2 2 ~E 6 a -0~> >~ -0 00 0o - - a DE EO1O 0 0 0 0 0 0 E0m m 0 0 c a C) C)C)CD 0' T-) T- C x w WO 2004/105488 PCT/EP2004/005681 52 + + + + + + + + + + + Co LcO L oO 0.) LO (j)M 0 0 N- N WN N, N .- N N N N: N N E E E E E E E E E E E 3 5 5 5 -5 -3 -5 c c c c a C a CD) 0 (D aI ) a ) CD) a) X- _c_ C- _C0 . ~ 0 2 0 a) 2 2 0 2 2 2 I 0 0 0 0 0 o 0 I0 0 0 C0 mI CI4 CL) m ) C 0. 0. 35 -D 0 ~~.C 0 - L 0 1--C C 0- (N WO 2004/105488 PCT/EP2004/005681 53 + :+c+C +++ + + 1 C N II C O(Y ) II 't 0 4 II Nt 0 ) (% . i C N II 0 4 .) II ) W~ N Nt N N N N N N N -N E E E E E E E E E E E (D c c~ 5. c Cc --. a) a) a) (D a) a) C a. C CL0. CL c 0. CL 0 0 _r_ 0 0 a) 0 0 w qF E qF q_ 4 E co C'J o C~ CO 3: co co V) mO m 00C a) a) a) a) a) aI) a) a) a) a) a) -C .C I-- .C .C -a .C .C am C. a. 0. C. 0- 0. 0- 0l. CL O I~ -L -L -1 -L -L3 0 0 C- C r E E aI) a) aI ) a) aI) U) 2 E E E E E -9 -9 c; Ct 6 At Ct 6 4t 4 4 4~. CL. cvi L~ 6 (6 1,- co 6) C C'~l co E\ 0' C~J (C4 N C%4 c\J mt mt co) m w O ce) 0t ce) co) Ct) co o m)o c x wj WO 2004/105488 PCT/EP2004/005681 54 a. co M f, C Z ) ; U) M . r U)) E Ut) _% M ) oo UO ) - *e) -O CO) , o 0 N 4 E ItL~ a' ) a) r' ')C) o o0 0 0 CL 0 0 a- 0 0 0 a) CD)a) a) L C a) CD ) a) CL 0. 1. a). 0 L0 0 0 0 a ~- CL D I~ L. -0 CL L 2 002 2 0 2~ 2 2 0 p *E 0 0 0 0 y -y 0. 2 y Y I? m fl C'J C~Jl CV) co w ) LO C14 N~ 04J c'i cV) iC L C6 r_ 6 C6 6 V- C'~i cli x uJ WO 2004/105488 PCT/EP2004/005681 55 +) ++ + + + ~+ ~+c+ 00 C Z 111C' Cl v 1i 61 I C6116Cin11 6 6 o0 . N N N N4 N N N jE E E E E E E E E 2 E CD C C (D~~~~* -5 5 5 5 , c c c c c0 CL a) (DU 0 ) ()X 2 . CL a- C0 00 .0 0 Ao T Cfo "- C) Co) LO a:4 X- T- a : : 3 o 00 0co U)~~a a) a)U a)U U C C C c: 2 2 2 2 2 2U)UU)t) 000 m M 0 0 0 0 -E5 :E5 E5 -5 4I C; I - 3 I I I I co Co) 0o Lr 'I r - LO LO LO co mo m CV) C6 (Nq (NI ( LL c6 iCo r-: 6 6 T-: C~ 6y li L6
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6 0 d t I lr It t O L O m z m m m m m m co c WO 2004/105488 PCT/EP2004/005681 56 + + + + + + CO co CO ~ q 9 c E0 N N N NoC tC E E E E2 E E 2 E E E E C CD (D (D) a) c a) (D) CD) a CI c CL a ~ a- CL .C 0 2 i a) 0 0 00 0 0 C 0 0- =. = c . 2 2 2 ,m 0L LC 0 0 0 0 0 4 4 4 4 co c o c C~C: CC : 02 0 0 0 0 0 0- + Cl Cl Cq ~ ~ ~ 06) ) ci C C6 C C6 ( o 0 ) m L ( 0 -D .D (D co c w ~ I z. co0 0. 0. co 0o 0. m0.c c 0 0 L. .
WO 2004/105488 PCT/EP2004/005681 57 00 C4 , LO LO M'N ) C) c ~Lo 0 ) ULO 0 Y)L N0 N N _N N 2 E E E E E E E E E ai) a ) - c) (D a) _ r. : c c: CL. a CL 0. 0. 2 a) 0l 0I a)0 2 0 0 2a2 = , 0 a- 0. 00 C 0 3 0 0 9: C; Cr 4' N 0 co IT co0 lowO 3 0 a: 3: 3:a'~ a) 3: 3: ~ io m) a) co m_ 3_ 3- 7 a)M a)-. 0-. 0. C C E E) 0 : I 0w 0% WO 2004/105488 PCT/EP2004/005681 58 00 N I' W0 o N N N N . N N Nf ~~~C EE , CV) C~ aC - ) a) a) a) (D a) "51 a) a) a) 00 0 0 0 2 0.-C . a. a 0 0 0 0 0 a It C)cf)C) C) Cl'r o 0 o m mc 3, a, c5 *5 -- '51 ' S a) a) a) U) U)U a) a) a. 0- aC.C 4~ a. 0 0 0 .2 0 2 0 0 Z' o E c -E 0 2 2. 2 a) a O6 sr Vr & -a) &~ ~ I "; Li Iq * o .Co It -C E Cf) co Cf) IC CL 06 oi 6 - C Ci 4 L6 (6 r_: 06 Eo 0 1- 1- (0 (0 00 (o00 00 0c) 00 co x WO 2004/105488 PCT/EP2004/005681 59 ~~++ + +++ + *1-M2!5 2: + + + m 0 _ r- LO) M 0) LO r- rt r N NNN N J JN N oo E E E 22 E 2 E E E E C'5 EI E6 iiH HEi i 0 N JN N N *E E E EE EE EE E EE EE LO CO04 - 0 0 0 00Lo CM E [1- 0 r-_ 0 m o 0) (D0V o U c! U o c 0 0 a0 0000C000)0 )0 0 0 0 200 0 2~ .0 0 o=o=oL o o CM N C 3: Z: 3 N c4iCNN Z 3 z CL 0. 0- . L- L- L L r- c.= I L:) ~ ~ 5;5 0 0 0 0 0 0> ,> 7,~ 52 5,== 0 0 0 0 E a La) a a) .. & E E- 5rci c--. EO 0 c 0) 0) 0)0) 0)0) 0 0)0))00c x WO 2004/105488 PCT/EP2004/005681 60 £0 ++ + CD )LO 0) ' CY)O f)LO LO I] 111 1111 'n i~~ V- V T- - N! N N N NN -NC ~ ~ c6 I 4I 10)VILo ~ ~CjU O U. O9) l E- E E EE E E 0 C\JLLO )0)- LO 00 CLC'O T.- Q) ) [I- )O 0 N \C, 0000Q0C000010000000 x 0000600000 00000 C j C) CD 0 - - 00 00 0- -0 00 D-c 2 a a ,: =C:C 2~ ~ ~~i c: C a L- -C ~ 2 -9 x w WO 2004/105488 PCT/EP2004/005681 61 4-+ + + ++ + + + + I+ + o + + + + + .+.+..+.+ + + [I- V--LU') 0) D N o0 O C\ C-0 0) Lo 0C0 vf) o 0 cq J(\NJ N" " ~CJ'cC' N N 0 CO)C4J II _I N~I N111 N Z4C\Jc0JcON N-N N -N N N N N C4J 4 E E 6E E E c EE EE E E E E E E E E E EE E EE E E 0[1- cc (o -- 1- 0) 'IT m NLo oC LO0V. C) (0 1- N0) t0C) qC)0 m 0 Eo co N cq oc Nc oc N ooooooooooooowooooo x00000000000000000000000 7; LDLD - L -fL C -a 04 30N N CL 1 C _C I N -, - - " :2 > c,4 ci m ' I a) a) :E. a -6 > E '0 42 4: >>>I.>0c N N 04-4 a) a) a Ccl' ROC 2~ 2 S -0 C 0 0 ce Ej I . x Lu WO 2004/105488 PCT/EP2004/005681 62 CIO + + + + + + + 1 L.MmMmm r7 0 + + + o)JCN ' CY) ODJ 0' C) + +f. c +~ c + + c + c N N N N N N .-. iz vZI Z I I 11 ci Iv 11 cj e ei N QO O IO O O ' Cl) Cl) Clo CO m LooLo E E E) LO N 0 0- 0) 0 0I N0000000000 0 0 , 0 0w x 00000000 0 0 0 0 0 0 UQO000 L) L >C >I >I> 0 0 0 C )ClC (D C O O~ 0) r > 0D a) CD > 0 0 CL a) 0 0~ 0 5 a)) a) 2t 2 2_ Lh Rc c; C L6) 04~I - 0 . 6i 6 0 6 6 C6 r- o6 ci 6= E 6 ";r r t m mo 0 6 LO LO LO) to U) C0 x wU WO 2004/105488 PCT/EP2004/005681 63 F F: F F* T ~E-E-~ XE F: F F- X m~E* p N Nd N " N N N N N No N 0 E E E E E E E E E E E N U) U) co cn co) co C/) U) CO (1 x 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0) 0 0 o _ 0 0 0 0> 0 0 0 0 0 .r- a)) 0 >1 CL -- C ~ 0a) "51- - U 20 0 .~ 0 =3 I U)~~~ LO ~ 0 E C\ 0 I CY ? m0 cr) CNI C- C6~ c 4 L6 ci r- C6i i 63 E o c o (D co (D to to co r x WO 2004/105488 PCT/EP2004/005681 64 £0 N r N Nr N N N N N N N N 0 E E E E E E E E E E CL N0 0 0 0 0 0 0 0 0 0 0 x 0 0 0 0 0 0 0 0 0 0 0 o0 0 0 ) 0 00 0 0 0 0 c C) 0 0 0 CD 0 0 0 0) 0) 0 0. C: - : c ~ (1 a m~ (D) a)a.)0C ( - C-- - C C) 9~ - ~ 0. L C- 0 0o .D 0\ 00 a).r a 0 -0 y-5 - 4 4 CN4 tO a CLC\J C6 4 L6 (0 r-: 06 a; o 0 I - P- I- rl- r- P- r- rl- co co w WO 2004/105488 PCT/EP2004/005681 65 £0 + + + + + + + + + + + + + + + + + + o, ) ')F- 1)0) c )c - c ) c 'IT 0) 0 0 NIN N JN N N N N 0 E E E E E E E E a) N 0 0 0 0 0 0 0 0 2 z x 0 0 0 0 0 0 0 0 0 o 0 0 0 0 0) 0 0 0) o_ oC 0 0 0 0 0 0 C0 CL > 0 - 6 CL "5; a) a) 0. Ic. C) 0. 2 2 R 2~~ 0 0 (D > E) 0 0 =3 0 a) 2 =3 :34 .0 23 Cf co LO 0 0 0 c'! C*'J C6) CV) C\J E 0.. C' ci 4t L6 c6 fr- c6 o 6 E 6 co 00 co 00 co co 00 co C0) .0 x U wl WO 2004/105488 PCT/EP2004/005681 2. Examples of action against pests The action of the compounds of formula I against pests was demonstrated by the fol lowing experiments. 5 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 10 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 15 pillars. At 5 days, observations are made of mortality, reduced feeding, or any interfer ence 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% 20 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* 25 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 30 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, 35 447, 450 and 451 at 300 ppm showed over 75% mortality in comparison with untreated controls. 2.3 Green Peach Aphid (Myzus persicae) 40 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 45 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.
WO 2004/105488 PCT/EP2004/005681 67 Test plants were maintained under fluorescent light (24 hour photoperiod) at about 250C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days. 5 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) 10 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 (variety 'Mixed Jewle') 15 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 250C with continuous fluorescent light. 20 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. 25 2.5 Silverleaf whitefly (bemisia argentifolit) The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic* surfactant. 30 Selected cotton plants were grown to the cotyledon state (one plant per pot). The coty ledons 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. 35 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 re usable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test 40 plants were maintained in the holding room at about 25 0C and 20-40% relative humidity for 3 days avoiding direct exposure to the fluores cent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.
WO 2004/105488 PCT/EP2004/005681 68 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) 5 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 10 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 15 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. 20 2.7 Orchid thrips (dichromothrips corbetti) Dichromothrips corbetti adults used for bioassay were obtained from a colony main tained continuously under laboratory conditions. For testing purposes, the test com 25 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 tech nique. Plastic petri dishes were used as test arenas. All petals of individual, intact or 30 chid flowers were dipped into treatment solution for approximately 3 seconds and al lowed 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 0 C for duration of the assay. After 4 days, the numbers of live thrips were counted on each flower, and along 35 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. 40
Claims (21)
1. A method for combating insects or arachnids which comprises contacting the insects or the arachnids, their habitat, breeding ground, food supply, plant, seed, 5 soil, area, material or environment in which the insects or the arachnids are grow ing 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 10 R1 Ar-(CH 2 )n-X-NH-N==C R 3 () R R4 15 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, independ ently of one another, from 0, N and S, where the 5- or 6-membered hetero cyclic radical may be fused to 1 or 2 phenyl rings, and where the cyclic 20 radical may have 1, 2, 3, 4 or 5 substituents R" which are selected, inde pendently of one another, from halogen, cyano, nitro, C-C 1 o-alkyl, Ci-C1a haloalkyl, C 3 -C 1 o-cylcoalkyl, C 3 -C 1 o-halocycloalkyl, C 2 -C 1 o-alkenyl, C 2 -C 1 o haloalkenyl, C 2 -Clo-alkynyl, C 3 -C 10 -haloalkynyl, C-C 1 o-alkoxy, C-C 1 o haloalkoxy, C 2 -C 1 o-alkenyloxy, C 2 -C 1 o-haloalkenyloxy, C 2 -C 1 o-alkynyloxy, 25 C 3 -C 1 o-haloalkynyloxy, C-C 10 -alkylthio, C-C 1 o-haloalkylthio, C-C1 0 alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C-C 1 o haloalkylsulfonyl, hydroxy, NR 5 R 6 , C-C 10 -alkoxycarbonyl, CrClo haloalkoxycarbonyl, C 2 -C 10 -alkenyloxycarbony, C 2 C 1 o haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl, 30 R 5 R 6 N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be substituted by 1, 2, 3, 4 or 5 substituents Rb which are se lected, independently of one another, from halogen, cyano, nitro, C-C 10 alkyl, C-C 1 o-haloalkyl, Ca-C 10 -cylcoalkyl, C 3 -C 1 o-halocycloalkyl, C 2 -Clo alkenyl, C 2 -C 1 o-haloalkeny, C 2 -C 10 -alkynyl, C 3 -C 1 o-haloalkynyl, C-C 1 o 35 alkoxy, C-C 1 o-haloalkoxy, C 2 -Clo-alkenyloxy, C 2 -C 1 o-haloalkenyloxy, C 2 C 1 0 -alkynyloxy, C 3 -C 1 o-haloalkynyloxy, C-C 1 o-alkylthio, C-C 1 o-haloalkylthio, C-C 10 -alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o-alkylsulfony, C-C 1 o haloalkylsulfonyl, hydroxy, NRR 6 , C-C 10 -alkoxycarbonyl, C-C 1 0 haloalkoxycarbonyl, C 2 -C 1 o-alkenyloxycarbonyl, C 2 -C 1 O 40 haloalkenyloxycarbonyl, C-C 10 -alkylcarbonyl, C-C 1 o-haloalkylcarbonyl and R 5 R 6 N-CO-; X is CO or SO 2 ; 45 R' is H, C-C 1 o-alkyl, C-C 10 -haloalkyl, C3-C 10 -cycloalkyl, C 3 -C 1 o-halocycloalkyl, C 2 -C 1 o-alkenyl, C 2 -C 1 o-haloalkenyl, C 2 -C 1 o-alkynyl, C 2 -C 1 o-haloalkynyl or WO 2004/105488 PCT/EP2004/005681 70 phenyl which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, C-Clo-alkyl, C .C 1 o-haloalkyl, C 3 -C 10 -cylcoalkyl, Ca-C 1 o-halocycloalkyl, C 2 -C 10 -alkenyl, C2 C 1 o-haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 1 o-haloalkynyl, C-C 10 -alkoxy, C-C10 5 haloalkoxy, C 2 -C 1 o-alkenyloxy, C 2 -C 1 o-haloalkenyloxy, C 2 -C 1 o-alkynyloxy, C 3 -C 1 o-haloalkynyloxy, C-C 10 -alkylthio, C-C 1 o-haloalkylthio, C-C 1 o alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C1-C1o haloalkylsulfonyl, hydroxy, NRR 6 , C-C 1 o-alkoxycarbonyl, Cr-C10 haloalkoxycarbonyl, C 2 -C 1 o-alkenyloxycarbonyl, C-C10 10 haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl and R 5 R 6 N-CO-; R 2 and R 3 are independently of one another H, halogen, cyano, C-C 1 o-alkyl, C C 1 o-haloalkyl, C3-C 1 o-cylcoalkyl, C 3 -C 1 o-halocycloalkyl, C 2 -C 1 o-alkenyl, C 2 15 C 1 o-haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 1 o-haloalkynyl, C-C 1 o-alkoxy, C-C 1 o haloalkoxy, C 2 -C 1 o-alkenyloxy, C 2 -C 1 o-haloalkenyloxy, C 2 -C 1 o-alkynyloxy, C 3 -C 1 o-haloalkynyloxy, C-Clo-alkylthio, C-C 1 o-haloalkylthio, hydroxy-C C 10 -alkyl, C-C 1 o-alkoxy- C-C 1 o-alkyl, halo-C 1 -0o-alkoxy-C-C 10 -alkyl, C C 1 o-alkoxycarbonyl-C-C 1 o-alkyl, halo-C-C 1 o-alkoxycarbonyl-C-C 1 o-alky or 20 phenyl which may be substituted by 1 to 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, C-C 1 o-alkyl, C 1 C 1 o-haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 1 o-halocycloalkyl, C 2 -Clo-alkenyl, C2 C 10 -haloalkenyl, C 2 -C 1 o-alkynyl, C 3 -C 1 o-haloalkynyl, C-C 10 -alkoxy, C1rC1o haloalkoxy, C 2 -C 1 o-alkenyloxy, C 2 -C 1 o-haloalkenyloxy, C 2 -C 1 o-alkynyloxy, 25 C 3 -C 1 o-haloalkynyloxy, C-C 10 -alkylthio, C-C 1 o-haloalkylthio, C-C1 alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C1-01o haloalkylsulfonyl, hydroxy, NR 5 R, C-C 1 o-alkoxycarbonyl, C-C10 haloalkoxycarbonyl, C 2 -C 1 o-alkenyloxycarbonyl, C 2 -C 1 o-haloalkenyl oxycarbonyl, C-C 1 -alkylcarbonyl, C 1 -0o-haloalkylcarbonyl and R 5 RON-CO; 30 R 4 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, C C 10 -alkyl, C-C 1 o-haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 1 o-halocycloalkyl, C2C1o 35 alkenyl, C 2 -C 1 o-haloalkenyl, C 2 -C 1 o-alkynyl, C 3 -C 1 o-haloalkynyl, Cr-C1o alkoxy, C-C 1 o-haloalkoxy, C 2 C 10 -alkenyloxy, C 2 -C 1 o-haloalkenyloxy, C 2 C 10 -alkynyloxy, C 3 -C 1 o-haloalkynyloxy, C-C 1 o-alkylthio, C-C 1 o-haloalkylthio, C-C 1 o-alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C-Clo haloalkylsulfonyl, hydroxy, NR 5 R 6 , C-C 1 o-alkoxycarbonyl, CrClo-. 40 haloalkoxycarbonyl, C 2 -C 1 o-alkenyloxycarbonyl, C2Co haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl, R 5 R 6 N-CO- and phenoxy which may be substituted by I to 5 substituents which are selected, independently of one another, from halogen, cyano, ni tro, C-C 1 o-alkyl, C-C 1 o-haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 1 -halocycloalkyl, WO 2004/105488 PCT/EP2004/005681 71 C 2 -C 10 -alkenyl, C 2 -C 1 o-haloalkenyl, C 2 -C 1 o-alkynyl, C 3 -C 1 o-haloalkynyl, C C 10 -alkoxy, C-C 1 o-haloalkoxy, C 2 -C 1 o-alkenyloxy, C 2 C 1 o-haloalkenyloxy, C 2 -C 1 o-alkynyloxy, Ca-C 1 o-haloalkynyloxy, C-C 1 o-alkylthio, C-C 10 haloalkylthio, C-C 1 o-alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 10 5 alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, NR 5 R 6 , Cr-C 10 alkoxycarbonyl, C 1 -C 1 o-haloalkoxycarbonyl, C 2 -C 1 o-alkenyloxycarbonyl, C 2 C 1 O-haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl and R 5 R 6 N-CO; or 10 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 0, 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 15 cyclic ring and/or the phenyl ring to which they are fused may carry 1, 2, 3 or 4 substituents R* which are selected, independently of one another, from halogen, cyano, nitro, C-C 1 o-alkyl, C-C 1 o-haloalkyl, C 3 -C 10 -cyicoalkyl, C 3 -C 1 o-halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 1 o-haloalkenyl, C 2 -C 10 -alkynyl, C 2 -Clo-haloalkynyl, C-C 1 o-alkoxy, C-C 1 o-haloalkoxy, C 2 -C 1 o-alkenyloxy, 20 C 2 -C 1 o-haloalkenyloxy, C 2 -C 1 o-alkynyloxy, C 2 -C 1 o-haloalkynyloxy, C-C 1 o alkylthio, C-C 1 o-haloalkylthio, C-C 1 o-alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o-alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, NR 5 R 6 , C-C 10 alkoxycarbonyl, C-C 1 o-haloalkoxycarbonyl, C2-C1-alkenyloxycarbonyl, C2 C 1 O-haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl, 25 R5R 6 N-CO and phenoxy which may be substituted by 1, 2, 3, 4 or 5 sub stituents R' which are selected, independently of one another, from halo gen, cyano, nitro, C-C 1 o-alkyl, C-C 1 o-haloalkyl, C3-C1 0 -cylcoalkyl, C3rC1o halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 1 o-haloalkenyl, C 2 -C 1 o-alkynyl, C 3 C 10 haloalkynyl, C-C 1 a-alkoxy, C-C 1 o-haloalkoxy, C 2 -C 1 o-alkenyloxy, C 2 -C 1 o 30 haloalkenyloxy, C-C 10 -alkynyloxy, C 3 -C 1 o-haloalkynyloxy, C-C 1 o-alkylthio, C-C 1 o-haloalkylthio, C-C 1 o-alkylsulfinyl, C-C 1 o-haloalkylsulfinyl, C-C 1 o alkylsulfonyl, C-C 1 o-haloalkylsulfonyl, hydroxy, NR 5 R 6 , C 1 -C 10 alkoxycarbonyl, C-C 1 o-haloalkoxycarbonyl, C 2 -C 1 o-alkenyloxycarbonyl, C2r C1 0 -haloalkenyloxycarbonyl, C-C 1 o-alkylcarbonyl, C-C 1 o-haloalkylcarbonyl 35 and R 5 R 6 N-CO, and where the 5- or 6-membered heterocyclic ring may contain 1 carbonyl group as a ring member; R 5 and R independently of one another are H or C-C 1 o-alkyl; and 40 n is 0 or 1.
2. The method as claimed in claim 1, where WO 2004/105488 PCT/EP2004/005681 72 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, independ ently of one another, from 0, N and S, where the 5- or 6-membered hetero cyclic radical may be fused to 1 or 2 phenyl rings, and where the cyclic 5 radical may have 1, 2, 3 or 4 substituents Ra which are selected, independ ently of one another, from halogen, hydroxy, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-C 4 -haloalkoxy, C-C 4 -alkylthio, C-C 4 -haloalkylthio, phenyl, which is unsubstituted or substituted by 1, 2 or 3 substituents Rb which are selected, independently of one another, from halogen, C-C 4 -alkyl, C-C 4 10 haloalkyl and C-C 4 -alkoxy, and phenoxy which is unsubstituted or substi tuted by 1, 2 or 3 substituents Rb which are selected, independently of one another, from halogen, C-C 4 -alkyl, C-C 4 -haloalkyl and C-C 4 -alkoxy.
3. The method as claimed in claim 2, where 15 Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxa zolyl, thiazolyl, thiadiazolyl, phenyl, pyridyl, pyrazinyl, naphthyl, diben zopyranyl, indolyl or benzothienyl, and where the cyclic radical may be substituted by 1, 2 or 3 substuituents R" which are selected, independently 20 of one another, from halogen, hydroxy, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 alkoxy, C-C 4 -haloalkoxy, phenyl, which is unsubstituted or substituted by 1, 2 or 3 substituents Rb which -are selected, independently of one another, from halogen, C-C 4 -alkyl, C 1 -C 4 -haloalkyl and C-C 4 -alkoxy, and phenoxy which is unsubstituted or substituted by 1, 2 or 3 substituents Rb which are 25 selected, independently of one another, from halogen, C-C 4 -alkyl, C-C 4 alkoxy and C-C 4 -haloalkyl.
4. The method as claimed in claim 3 where 30 Ar is a cyclic radical selected from thienyl, furyl, pyrazolyl, imidazolyl, isoxa zolyl, phenyl, pyridyl, pyrazinyl, naphthyl, indolyl or benzothienyl, and where the cyclic radical may be substituted by 1 or 2 substituents Ra which are se lected, independently of one another, from halogen, hydroxy, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy and C-C 4 -haloalkoxy. 35
5. The method as claimed in any one of the preceding claims, where R 1 is H, C-C 4 -alkyl or Cr-C 4 -haloalkyl. 40
6. The method as claimed in claim 5, where R' is H or methyl.
7. The method as claimed in one of the preceding claims, where WO 2004/105488 PCT/EP2004/005681 73 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 0, N and S, where the 5 or 6-membered heterocyclic ring may be fused to a phenyl ring, and where 5 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 R* which are selected, independ ently of one another, from halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, Cl-C 4 alkoxy, C-C 4 -haloalkoxy, C-C 4 -haloalkylthio, cyano, nitro, phenyl, which is unsubstituted or is substituted by 1, 2 or 3 substituents which are selected, 10 independently of one another, from C-C 4 -alkyl, C-C 4 -haloalklyi, Cl-C 4 alkoxy and halogen; and phenoxy which is unsubstituted or substituted by 1, 2 or 3 substituents R which are selected, independently of one another, from C-C 4 -alkyl, C-C 4 -haloalklyl, C-C 4 -alkoxy and halogen, and where the 5- or 6-membered heterocyclic ring may contain 1 carbonyl group as a ring 15 member.
8. The method as claimed in claim 7, where R 2 and R 4 together with the carbon atoms to which they are bound form a phenyl, 20 benzofuranyl, benzothienyl, indolyl, chromenyl, chromenonyl, pyrazolyl or furanyl moiety, and where the moiety may carry 1, 2, 3 or 4 substituents R" which are selected, independently of one another, from halogen, C-C 4 alkyl, C-C 4 -haloalkyl, C-C 4 -haloalkoxy, C-C 4 -haloalkylthio, cyano and ni tro. 25
9. The method as claimed in claim 8, where R 2 and R 4 together with the carbon atoms to which they are bound form a phenyl, benzofuranyl, benzothienyl or chromenyl moiety, and where the moiety may 30 be substituted by 1, 2 or 3 substituents R* which are selected, independ ently of one another, from C-C 4 -alkyl, C-C 4 -haloalkyl and halogen.
10. The method as claimed in one of claims I to 6, where 35 R 2 is H, C-C 1 o-alkyl, C-C 1 o-haloalkyl, halogen, phenyl or cyano.
11. The method as claimed in one of claims 1 to 6 or 10, where Ra is H, C-C 4 -alkyl, halogen or phenyl. 40
12. The method as claimed in one of claims I to 6, 10 or 11, where R 4 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 WO 2004/105488 PCT/EP2004/005681 74 which are selected, independently of one another, from hydroxy, halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-C 4 -haloalkoxy, C-C 4 alkylthio, C-C 4 -haloalkylthio, cyano, nitro, NRR and phenoxy which may be substituted by C-C 4 -haloalkyl; and 5 RI and R are defined as in claim 1.
13. The method as claimed in claim 12, where 10 R 4 is phenyl which may 1, 2, 3, 4 or 5 substituents R4 which are selected, inde pendently of one another, from hydroxy, halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-C 4 -haloalkoxy, C-C 4 -alkylthio, C-C 4 -haloalkylthio, cyano, nitro, NR 5 R 6 and phenoxy which may be substituted by C-C 4 -haloalkyl. 15
14. The method as claimed in one of claims 1 to 6 or 10 to 12, where R 2 is H, C-C 1 o-alkyl, C-C 1 o-haloalkyl, halogen, phenyl or cyano; R' is H, C-C 4 -alkyl, halogen or phenyl; and 20 R 4 is an aromatic radical selected from phenyl, pyridyl, pyrimidyl, furyl, or thienyl, where the aromatic radical may carry 1, 2, 3 or 4 substituents R* which are selected, independently of one another, from hydroxy, halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-C 4 -haloalkoxy, C-C 4 25 alkylthio, C-C 4 -haloalkylthio, cyano, nitro, NR 5 RS and phenoxy which may be substituted by C-C 4 -haloalkyl; and R and R are defined as in claim 1. 30
15. The method as claimed in claim 14, where R 4 is phenyl, which may carry 1, 2, 3 or 4 substituents Rc which are selected, independently of one another, from halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy, C-C 4 -haloalkoxy, C-C 4 -alkylthio, CrC 4 -haloalkylthio, cyano, 35 nitro, NR 5 R and phenoxy which may be substituted with C-C 4 -haloalkyl.
16. The method as claimed in one of claims 14 or 15, where R 2 is H, C-C 1 o-alkyl or halogen; 40 R 3 is H or halogen; and R 4 is phenyl which may carry 1,2 or 3 substituents Rc which are selected, in dependently of one another, from halogen, C-C 4 -alkyl, C-C 4 -haloalkyl, C- WO 2004/105488 PCT/EP2004/005681 75 C 4 -alkoxy, CrC 4 -haloalkoxy, C-C 4 -alkylthio C-C 4 -haloalkylthio, cyano and nitro.
17. A method for protecting crops from attack or infestation by insects or arachnids 5 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 ap plied at a rate of from 0.1 g/ha to 4000 g/ha. 10
19. A pryridyl compound of the general formula la 0 R1 N-N R3 (Ra)m H - (la) Ra R 4 a 15 wherein R, R' and R 3 are as defined in claim 1, m is0,1,2or3, R 2 ' is C-C 4 alkyl and 20 R 4 a 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 25 ii) R 4 a carries at least one substituent R4 being different from hydrogen iii) or R' is different from hydrogen, iv) or R2a is different from methyl.
20. An isoxazolyl compound of the formula lb 30 R 1 Ar-(CH 2 )n~X-N-N R 3 H (Ib) RR4 wherein n, X, R 1 , R 2 , R 3 and R 4 are as defined in claim 1, 35 Ar is isoxazolyl, which may carry 1 or 2 substituents R' as defined in claim 1, WO 2004/105488 PCT/EP2004/005681 76 provided that Ar does not carry an optionally substituted phenyl group if Ar is substituted 4-isoxazolyl.
21 A pyrazolyl compound of the formula Ic 5 R1 Ar-(CH 2 )n-X-N-N- R 3 H - (Ic) R R wherein n, X, R 1 , R 2 , R 3 and R 4 are as defined in claim 1, 10 Ar is pyrazolyl which carries a substituent Ra 2 on the pyrazol nitrogen atom, and which may carry 1 or 2 substituents R" as defined in claim 1, wherein R 2 is selected from C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C 3 -C 1 o-cylcoalkyl, C 3 C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 1 o-haloalkenyl, C 2 -C 10 -alkynyl, C3 C 1 o-haloalkynyl, phenyl and benzyl, wherein phenyl and benzyl may be un 15 substituted or substituted by 1, 2, 3, 4 or 5 substituents Rb as defined in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47314103P | 2003-05-27 | 2003-05-27 | |
| US60/473,141 | 2003-05-27 | ||
| PCT/EP2004/005681 WO2004105488A1 (en) | 2003-05-27 | 2004-05-26 | Hydrazone derivatives for combatting harmful insects and arachnids |
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| AU2004243492A1 true AU2004243492A1 (en) | 2004-12-09 |
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| AU2004243492A Abandoned AU2004243492A1 (en) | 2003-05-27 | 2004-05-26 | Hydrazone derivatives for combatting harmful insects and arachnids |
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| EP (1) | EP1631143A1 (en) |
| JP (1) | JP2006528955A (en) |
| KR (1) | KR20060019558A (en) |
| CN (1) | CN1842272A (en) |
| AR (1) | AR045688A1 (en) |
| AU (1) | AU2004243492A1 (en) |
| BR (1) | BRPI0410626A (en) |
| CL (1) | CL2004001296A1 (en) |
| MX (1) | MXPA05012226A (en) |
| WO (1) | WO2004105488A1 (en) |
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| MX2009008243A (en) | 2007-02-02 | 2009-08-12 | Redpoint Bio Corp | Use of a trpm5 inhibitor to regulate insulin and glp-1 release. |
| WO2012051708A1 (en) * | 2010-10-21 | 2012-04-26 | The University Of British Columbia | Anti-bacterial pyruvate kinase modulator compounds, compositions, uses, and methods |
| KR101565430B1 (en) | 2012-09-07 | 2015-11-03 | 한국생명공학연구원 | Composition for prevention or treatment of cancer comprising N-methylenenaphtho[2,1-b]furan-2-carbohydrazide derivatives as an active ingredient |
| CN103641782B (en) * | 2013-12-26 | 2015-01-28 | 青岛科技大学 | Pyrazol acylhydrazone compounds and application thereof |
| EP3418271A4 (en) * | 2016-02-19 | 2019-10-30 | Korea Research Institute of Bioscience and Biotechnology | Novel indole derivative and anti-cancer composition containing same |
| CN110627692B (en) * | 2019-10-14 | 2021-09-24 | 河南科技大学 | Paeonol benzenesulfonylhydrazone and derivative thereof, preparation method of paeonol benzenesulfonylhydrazone and derivative thereof, botanical insecticide and application of botanical insecticide |
| AR126670A1 (en) * | 2021-08-02 | 2023-11-01 | Eurofarma Laboratorios S A | N-ACYLYDRAZONIC COMPOUNDS INHIBITORS OF Nav 1.7 AND/OR Nav 1.8, THEIR OBTAINING PROCESSES, COMPOSITIONS, USES, TREATMENT METHODS OF THESE AND KITS |
| AR126669A1 (en) * | 2021-08-02 | 2023-11-01 | Eurofarma Laboratorios S A | N-ACYLYDRAZONIC COMPOUNDS INHIBITORS OF Nav 1.7 AND/OR Nav 1.8, THEIR OBTAINING PROCESSES, COMPOSITIONS, USES, TREATMENT METHODS OF THESE AND KITS |
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| JP2000169461A (en) * | 1998-09-28 | 2000-06-20 | Nippon Nohyaku Co Ltd | Insecticide and microbicide composition and its production |
| JP2004149413A (en) * | 2000-06-30 | 2004-05-27 | Agro Kanesho Co Ltd | Hydrazone derivative or its salt effective in controlling pest |
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2004
- 2004-05-26 BR BRPI0410626-1A patent/BRPI0410626A/en not_active IP Right Cessation
- 2004-05-26 KR KR1020057022609A patent/KR20060019558A/en not_active Application Discontinuation
- 2004-05-26 AU AU2004243492A patent/AU2004243492A1/en not_active Abandoned
- 2004-05-26 EP EP04734834A patent/EP1631143A1/en not_active Withdrawn
- 2004-05-26 WO PCT/EP2004/005681 patent/WO2004105488A1/en active Search and Examination
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| WO2004105488A1 (en) | 2004-12-09 |
| AR045688A1 (en) | 2005-11-09 |
| MXPA05012226A (en) | 2006-02-10 |
| BRPI0410626A (en) | 2006-06-20 |
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| JP2006528955A (en) | 2006-12-28 |
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