WO2005085234A2 - Bycyclic anthranilamide derivatives useful as insecticides - Google Patents

Bycyclic anthranilamide derivatives useful as insecticides Download PDF

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WO2005085234A2
WO2005085234A2 PCT/EP2005/002204 EP2005002204W WO2005085234A2 WO 2005085234 A2 WO2005085234 A2 WO 2005085234A2 EP 2005002204 W EP2005002204 W EP 2005002204W WO 2005085234 A2 WO2005085234 A2 WO 2005085234A2
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formula
group
compounds
atom
spp
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PCT/EP2005/002204
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French (fr)
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WO2005085234A3 (en
Inventor
Dave Hughes
James Edward Peace
Suzanna Riley
Sally Russell
Joe Swanborough
Roger Graham Hall
André Jeanguenat
Olivier Loiseleur
Peter Renold
Stephan Trah
Jean Wenger
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Syngenta Participations Ag
Syngenta Limited
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Priority claimed from GB0404801A external-priority patent/GB0404801D0/en
Priority claimed from GB0425453A external-priority patent/GB0425453D0/en
Priority to US10/598,041 priority Critical patent/US7812170B2/en
Priority to KR1020067017852A priority patent/KR101086627B1/en
Priority to NZ549166A priority patent/NZ549166A/en
Priority to JP2007501212A priority patent/JP4865695B2/en
Priority to CA002556387A priority patent/CA2556387A1/en
Priority to BRPI0508401-6A priority patent/BRPI0508401A/en
Priority to AU2005219545A priority patent/AU2005219545B2/en
Priority to EP05715671A priority patent/EP1737844B1/en
Application filed by Syngenta Participations Ag, Syngenta Limited filed Critical Syngenta Participations Ag
Priority to RU2006134629/04A priority patent/RU2369603C2/en
Priority to AT05715671T priority patent/ATE478862T1/en
Priority to DE602005023140T priority patent/DE602005023140D1/en
Priority to CN2005800067570A priority patent/CN1926129B/en
Publication of WO2005085234A2 publication Critical patent/WO2005085234A2/en
Publication of WO2005085234A3 publication Critical patent/WO2005085234A3/en
Priority to IL177345A priority patent/IL177345A/en
Priority to EGNA2006000810 priority patent/EG25775A/en
Priority to HK07107116.7A priority patent/HK1101304A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—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 three or more hetero rings
    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the present invention relates to bicyclic bisamide derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling insects or representatives of the order Acarina.
  • Bisamide derivatives with insecticidal action are known and described, for example, in US 2003/0229050.
  • Z-i is an oxygen atom; or a sulfur atom
  • Z 2 is an oxygen atom; or a sulfur atom
  • Ri is an aryl or heteroaryl group, which is unsubstituted or substituted
  • R 2 is hydrogen; or an organic substituent
  • R 3 is hydrogen; or an organic substituent
  • R 4 is hydrogen; or an organic substituent; or R 3 and R 4 , taken together, form, together with the nitrogen atom, to which they are attached, a ring, which is unsubstituted or substituted
  • R 5 is hydrogen; or an unsubstituted or substituted alkyl group; or forms, taken together with R 8 or with a monovalent substituent attached to that atom of R 6 , via which atom R 6 is directly connected with the carbon atom, shown in the formula I, which carries R 5 , one additional bond
  • R 6 and R 7 taken together, form, together with the two carbon atoms, shown in the formula I, to which atoms they are attached, a bi
  • the compounds of formula I can exist as tautomers.
  • the compounds of formula I hereinabove and hereinbelow are to be understood as including such tautomers, where appropriate, even though the latter are not mentioned specifically in each individual case.
  • Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C ⁇ -C 4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C C alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by
  • Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • the corresponding internal salts can furthermore be formed.
  • agrochemically advantageous salts Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds of formula I or agrochemically utilizable salts thereof.
  • the free compounds of formula I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds of formula I.
  • the free form is preferred in each case.
  • the invention relates (2) to a compound according to (1) of formula I, in which Z is an oxygen atom; or a sulfur atom; Z 2 is an oxygen atom; or a sulfur atom; R-i is a phenyl or naphthyl group, which is substituted independently by 1 or 2 substituents R a and optionally further substituted independently by 1 to 3 substituents R ; R a is cyano; nitro; halogen; CrC 6 alkyl; halo-CrC ⁇ alkyl; CrC 6 alkoxy-C ⁇ -C 6 alkyl; C 2 - C 6 alkenyl; halo-C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; halo-C 2 -C 6 alkynyl; C 3 -C 6 cycloalkyl; halo-C 3 - C 6 cycloalkyl; hydroxy; CrC 6 alkoxy; halo-
  • -C 6 alkoxy in
  • R g . n is a substituent R c ;
  • R g - n is cyano; nitro; d-C 6 alkyl; halo-d-C 6 alkyl; d-C 6 alkoxy-C- ⁇ -C 6 alkyl; C 2 -C 6 alkenyl; halo-C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; halo-C -C 6 alkynyl; C 3 -C 6 cycloalkyl; halo-C 3 -C 6 cycloalkyl; d- C 6 alkoxy; halo-d-C 6 alkoxy; C 3 -C 6 cycloalkoxy; d-C 6 alkylthio; halo-C ⁇ -C 6 alkylthio; d- C 6 alkylthio; halo-C ⁇ -C 6 alkylthio; d- C 6 alkylthio;
  • R j . c is a substituent R c
  • R j . n is a substituent R g . n
  • R k is either attached to a carbon atom and then selected from the group, consisting of the substituents R k . c ; or attached to a nitrogen atom and then selected from the group, consisting of the substituents R k .
  • R k substituents R k , the first of which is attached to the atom G 6 and is represented by R 62 , if G 6 is a nitrogen atom, and by R 6 ⁇ or R 62 , if G 6 is a carbon atom, and the second of which is attached to the atom G 9 and is represented by R 92 , if G 9 is a nitrogen atom, and by R 91 or R 92 , if G 9 is a carbon atom, taken together, are -CH 2 -; or -O-; R k .
  • R c is a substituent R c ;
  • R k - n is a substituent R g - n ;
  • R 8 is hydrogen; d-C 6 alkyl; or halo-d-C 6 alkyl; or has one of the meanings defined hereinbefore or hereinafter; or R 5 and R 8 , taken together, are a bond; with the proviso, that (i) a ring oxygen atom, if present, is not directly connected with a further ring oxygen atom, if any; (ii) a ring carbon atom, selected from the group, consisting of G-i, G 2 , G 3 , G 4 , G 5 , G 6 , G 7 , G 8 , G 9 and G 10 , is, if present, not directly connected with any other atom by a triple bond or with any other 2 different atoms by 2 double bonds; (iii) not more than 6 of the variables Gi, G 2 , G 3 , G 4
  • Halogen - as a group per se and as a structural element of other groups and compounds, such as haloalkyl - is, for example, fluorine, chlorine, bromine or iodine, in particular flluorine, chlorine or bromine, but especially chlorine or bromine.
  • carbon-containing groups and compounds comprise for example in each case 1 up to and including 15, preferably 1 up to and including 10, especially 1 up to and including 8, in particular 1 up to and including 5, especially 1 or 2, carbon atom(s).
  • Cycloalkyl - as a group per se and as a structural element of other groups and compounds, such as halocycloalkyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Alkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain, for example methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec- butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Alkenyl - as a group per se and as a structural element of other groups and compounds, such as haloalkenyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon double bond(s), the double bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, allyl, propen-2-yl, methallyl, but-2-en-1-yl, but-3-en-1 -yl or pent-4-en-1 -yl.
  • Alkynyl - as a group per se and as a structural element of other groups and compounds, such as haloalkynyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon triple bond(s), the triple bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, propargyl, but-2-ynyl or but-3-yn-2-yl.
  • Aryl is, for example, naphthyl or, preferably, phenyl.
  • Heteroaryl has, for example, an aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur, and is, for example, pyridyl, thienyl, pyrazolyl, thiazolyl, thiadiazolyl, furyl, oxadiazolyl, indolizinyl, pyrimidyl, quinolyl or pteridinyl.
  • Non-aromatic heterocyclyl has, for example, a non-aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur and is, for example, piperidyl, pyrrolinyl, tetrahydrofuryl or chromanyl.
  • Halogen-substituted carbon-containing groups and compounds, such as haloalkyl, can be partially halogenated or perhalogenated, where, in the case of polyhalogenation, the halogen substituents can be identical or different.
  • the following are further preferred embodiments within the scope of the invention:
  • R-i is a phenyl, pyridyi or pyrazolyl group, which is unsubstituted or preferably substituted; especially a phenyl, pyridyi or pyrazolyl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, d-C 6 alkyl.
  • a pyrid-2-yl group which group is substituted independently by 1 or 2 substituents, selected from the group, consisting of halogen; especially a pyrazol-5-yl group, which is substituted in the 3-position by halogen, halo-d-
  • a further preferred subgroup of the compounds of formula I is represented by the compounds of formulae Vila and Vllb
  • R 0 ⁇ is hydrogen; amino or nitro; R 02 is hydrogen or d-C alkyl;
  • R 03 is d-C alkyl, d-C 4 alkyl mono- or disubstituted by cyano, COOH, nitro, d-C alkoxy or cyclopropyl;
  • CrC 6 alkylthio-CrC 4 alkyl C 2 -C 6 alkenylthio-C C 4 alkyl, C 3 -C 6 alkinylthio-CrC 4 alkyl, dioxolan-2- yl-d-C 4 aIkyl, (CrC 4 alkyl-dioxolan-2-yl)-CrC 4 alkyl, triazolyl-d-C 4 alkyl, thienyl-d-C 4 alkyI, morpholinyl-CrC 4 alkyl, CrC 4 alkylthio-d-C 4 alkyl, 2,3-dihydro-1 H-isoindolyl, halo-substituted- thiazolyl-d-C 4 alkyl, CrC alkylsulfonyl-d-C 4 alkyl or quinolyIthio-d-C 4 alkyl, wherein the quinoline group may be substituted by
  • Ro 4 is d-C haloalkyl
  • R05 is halogen; each of R 06 and R 0 ⁇ o, which may be the same or different, represents hydrogen, d-C 6 alkyl,
  • R 07 is hydrogen, nitro or halogen
  • Y 01 is C(Ros), sulfur, nitrogen or a chemical bond
  • R 08 is hydrogen, halogen, d-C 4 alkyl or nitro
  • Y 02 is C(R og ), a chemical bond, or is nitrogen or sulfur; and R 09 is hydrogen, phenyl, phenyl substituted by halogen, or halogen.
  • Preferred compounds of the formula Vila are those, wherein
  • R 01 is hydrogen;
  • R 02 is hydrogen;
  • R 03 is d-C 4 alkyl, preferably methyl;
  • R 0 is C 1 -C 4 fluoroalkyl, preferably trifluoromethyl;
  • R 05 is chloro;
  • R 06 is halogen, preferably chloro;
  • R 07 is hydrogen;
  • R 01 0 is hydrogen; Y 01 is C(R 08 ); Ros is halogen, preferably chloro; Y 02 is C(R 09 ), and R 09 is hydrogen.
  • each of the compounds T2.1 , T22.3, T75.1 , T75.3, T76.1 , T76.3, T78.1 , T79.1 and T81.1 is individually preferred within the scope of the invention.
  • Compounds of formula A wherein Z and Z ⁇ are oxygen and Ri is hydrogen, may be made from the ring opening of a benzoxazinone of formula B with an amine of formula NHR 3 R 4 .
  • Such amines are either known or they may be made analogously to known processes.
  • Benzoxazinones of formula B may be made from amino acids of formula C by treatment with a carboxylic acid of formula RrCOOH and a dehydrating reagent such as methanesulfonyl chloride (optionally in the presence of a base such as pyridine or triethylamine).
  • benzoxazinones of formula B may be obtained by the treatment of amino acids of formula C with an acid chloride of formula RrCOCI under basic conditions (for example in pyridine), followed if necessary by a second cyclisation step (which may be achieved using a dehydrating agent for example acetic anhydride).
  • Acid chlorides of formula RrCOCI may be made from carboxylic acids of formula RrCOOH under standard conditions (for example by treatment with thionyl chloride or oxalyl chloride).
  • Carboxylic acids of formula RrCOOH are either known compounds or they may be made analogously to known processes.
  • Compounds of formula A, wherein Zi and Z are sulfur may be made from compounds of formula A, wherein Z ⁇ and Z 2 are oxygen, by treatment with a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide.
  • a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide.
  • compounds of formula A, wherein Zi and Z-i are oxygen may be made by treatment of compounds of formula D, wherein Z ⁇ is oxygen and R is OH, C C 4 alkoxy or CI, with an amine of formula NHR 3 R 4 .
  • Acid chlorides of formula D wherein Z ⁇ is oxygen and R is CI, may be made from carboxylic acids of formula D, wherein Z 1 is oxygen and R is OH, under standard conditions (such as treatment with thionyl chloride or oxalyl chloride).
  • Carboxylic acids of formula D, wherein Z is oxygen and R is OH may be formed from esters of formula D, wherein Z is oxygen and R is d-C alkoxy. It is well known for a person skilled in the art that there are many methods for the hydrolysis of such esters depending on the nature of the alkoxy group.
  • One widely used method to achieve such a transformation is the treatment of the ester with an alkali such as sodium hydroxide in a solvent such as ethanol.
  • Esters of formula D, wherein Z 1 is oxygen and R is d-C alkoxy may be made by treatment of compounds of formula E, wherein R is d-C alkoxy, by acylation with compounds of formula
  • RrCOOH or R COCI under standard conditions as previously described.
  • Compounds of formula E, wherein R is C C 4 alkoxy may be made from compounds of formula C by sequential treatment with an alcohol under acidic conditions and then formation of the N-R 2 bond. It is known to a person skilled in the art that there are many reported methods for the formation of this bond depending on the nature of the substituent R 2 .
  • reductive amination may be achieved by treatment of the amine with an aldehyde or ketone and a reducing agent such as sodium cyanoborohydride.
  • alkylation may be achieved by treating the amine with an alkylating agent such as an alkyl halide, optionally in the presence of a base.
  • arylation may be achieved by treatment of the amine with an aryl halide or sulfonate in the presence of a suitable catalyst ligand system, often a palladium (0) complex.
  • compounds of formula E wherein R is d-C alkoxy
  • compounds of formula E may be made from a compound of formula F, wherein R is C C 4 alkoxy and LG is a leaving group such as fluoro, chloro or sulfonate, via nucleophilic displacement of the leaving group by an amine of formula R 2 -NH 2 .
  • LG is a leaving group such as fluoro, chloro or sulfonate
  • Compounds of formula A, wherein Zi is sulfur and Z 2 is oxygen can be made from compounds of formula D, wherein Z 1 is oxygen and R is OH or d-C alkoxy, by treatment with a thio-transfer reagent such as Lawessen's reagent or phosphorus pentasulfide prior to coupling with the amine of formula NHR 3 R 4 .
  • a thio-transfer reagent such as Lawessen's reagent or phosphorus pentasulfide
  • compounds of formula D wherein R is OH and Z 1 is oxygen, may be dehydrated to benzoxazinones of formula B by treatment with a dehydrating agent such as acetic anhydride.
  • compounds of formula A, wherein Z and Z 2 are oxygen may be made by the treatment of compounds of formula G, wherein Z 2 is oxygen, with a carboxylic acid of formula RrCOOH or an acid chloride of formula RrCOCI as previously described.
  • Compounds of formula G, wherein Z 2 is oxygen may be formed from compounds of formula H, wherein P is a suitable protecting group and R is OH, CI or d-C 4 alkoxy, by amide bond formation with an amine of formula NHR 2 R 3 as previously described for compounds of formula D, followed by removal of the protecting group P under standard conditions.
  • Compounds of formula H, wherein R is OH or d-C alkoxy may be made by the protection of the amine functionality in compounds of formula E, wherein R is OH or d-C 4 alkoxy.
  • Suitable protecting groups include carbamates (such as t-butyloxycarbonyl, allyloxycarbonyl and benzyloxycarbonyl), trialkylsilyl groups (such as t-butydimethylsilyl) and acyl groups (such as acetyl). The formation and removal of such groups is widely reported in the literature and is well known to a person skilled in the art.
  • esters may be hydrolysed to the acids (wherein R is OH) by treatment with an alkali such as sodium hydroxide in a solvent such as ethanol.
  • the acids may be converted to the acid chlorides (wherein R is CI) by treatment with thionyl chloride or oxalyl chloride as previously described for compounds of formula D.
  • compounds of formula G wherein Z 2 is oxygen
  • compounds of formula JK wherein Z 2 is oxygen and LG is a leaving group such as fluoro, chloro or sulfonate, by displacement of the leaving group with a compound of formula R 2 NH 2 .
  • Such reactions are usually performed under basic conditions.
  • Such compounds of formula JK may be made from compounds of formula J, wherein R is CI or OH and LG is a leaving group as previously described, via amide bond formation under standard conditions as previously described.
  • Such compounds of formula J and formula E are either known compounds or may be made by known methods by someone skilled in the art.
  • Compounds of formula A, wherein Z is oxygen and Z 2 is sulfur may be made by treatment of compounds of formula JK, wherein Z 2 is oxygen and LG is a leaving group, or compounds of formula G, wherein Z 2 2 is oxygen, with a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide prior to elaborating to compounds of formula A, wherein Z is oxygen and Z 2 is sulfur, as previously described for compounds of formula A, wherein Z 1 is oxygen and Z 2 is oxygen).
  • a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide
  • amino acids of formula C may be formed by hydrolysis of isatoic anhydrides of formula K.
  • isatoic anhydrides of formula K may be reacted with amines of formula NHR 3 R to give compounds of formula G, wherein R-i is H, directly.
  • Isatoic anhydrides of formula K are either known compounds or may be made by known methods obvious to those skilled in the art, for instance they made be derived from treatment of amino acids of formula C with phosgene or a synthetic equivalent of phosgene (for example carbonyl diimidazole).
  • compounds of formula C may be derived from the treatment of an isatin of formula L with hydrogen peroxide under basic conditions.
  • Isatins of formula L are either known or may be made by methods known to persons skilled in the art, for example they may be derived from amino compounds of formula M, wherein R 5 and R 8 taken together form an additional bond between the carbon atoms bearing substituents R 6 and R 7 , by treatment for example with oxalyl chloride (optionally in the presence of a Lewis acid catalyst) or chloral hydrate under various conditions.
  • Amino compounds of formula M are either known compounds or may be made by known methods obvious to those skilled in the art.
  • compounds of formula C may be derived from the treatment of an isoxazole of formula N with aqueous base.
  • Isoxazoles of formula N may be derived from nitroaldehydes of formula O by treatment with a reducing agent such as zinc in acetic acid.
  • Nitroaldehydes of formula O are either known or may be made by methods known to persons skilled in the art, for instance they may be derived from nitro compounds of formula P by treatment with chloroform under basic conditions followed by treatment with strong aqueous acid.
  • nitroaldehydes of formula O may be derived from oxidation of 1 -nitro-2-methyl aromatic compounds of formula Q.
  • a particularly convenient method of achieving such an oxidation involves treating the compound Q with dimethylformamide dimethylacetal under basic conditions followed by treatment with sodium periodate.
  • Compounds of formula P and Q are either known or may be made by methods known to those skilled in the art, for instance compounds of formula Q may be synthesised from compounds of formula R by nitration (e.g. with a mixture of nitric acid and sulphuric acid).
  • the reactants can preferably be reacted in the presence of a base.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • DBU ,8-diazabicyclo[5.4.0]undec-7-ene
  • the reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between room temperature and approximately +80°C.
  • salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds of formula I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereose- lective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the invention relates to all those embodiments of the process by which, starting from a compound obtainable at any level of the process as starting material or intermediate, all or some of the missing steps are carried out or a starting material is used in the form of a derivative and/or salt and/or racemates or antipodes thereof or, in particular, is formed under the reaction conditions.
  • the invention relates to the preparation processes described in the Examples P1 to P11 .
  • the compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e.
  • Examples of the abovementioned animal pests are: from the order Acarina, for example,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
  • Curculio spp. Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp.,
  • Aedes spp. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp.,
  • Cimex spp. Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.; from the order Homoptera, for example,
  • Aleurothrixus floccosus Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspi- diotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,
  • Myzus spp. Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Planococ- cus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica,
  • Quadraspidiotus spp. Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; from the order Hymenoptera, for example,
  • Vespa spp. from the order Isoptera, for example,
  • Reticulitermes spp. from the order Lepidoptera, for example,
  • Ostrinia nubilalis Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypi- ela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scir- pophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp.,
  • Thaumetopoea spp. Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Mallophaga, for example,
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Psocoptera, for example,
  • Liposcelis spp. from the order Siphonaptera, for example,
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on or- gans, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • crops is to be understood as including also crops that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (giutamine synthetase) inhibitors as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • ALS inhibitors for example primisulfuron, prosulfuron and trifloxysulfuron
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors
  • GS giutamine synthetase inhibitors as a result of conventional methods of breeding or genetic engineering.
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
  • the term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry ⁇ c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popliae
  • Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A
  • VIP vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D-recognition sequence is inserted into a CrylllA toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin);
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bl) toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur BioWhen und Nachhaltmaschine, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a. selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A- 0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins for example the viral KP1 , KP4 or KP6 toxins
  • stilbene synthases such as the viral K
  • the invention therefore also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
  • pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
  • the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C 8 to C 12 of alkylbenzenes, such as xylene mixtures, al- kylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as
  • Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silicas or highly disperse absorbtive polymers are also possible to add highly disperse silicas or highly disperse absorbtive polymers.
  • Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand.
  • a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.
  • the surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
  • Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols.
  • water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups.
  • the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit.
  • nonylphenoxypolyethoxyethanol examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol.
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are, especially, quartemary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzy!bis(2-chloroethyl)ethyl- ammonium bromide.
  • Suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds.
  • suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates.
  • synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.
  • the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate.
  • suitable phosphates such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.
  • the compositions comprise from 0.0001 to 99.9999 %, in particular 0.1 to 95 %, of active ingredient, and 0.0001 to 99.9999 %, in particular 5 to 99.9 %, of - at least - one solid or liquid auxiliary, it being possible, as a rule, for 0 to 25 %, in particular 0.1 to 20 %, of the compositions to be surfactants (% in each case is per cent by weight). While concentrated compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions which have considerably lower concentrations of active ingredient.
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally or acaricidally active ingredients.
  • Suitable additions to active ingredients are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • Examples of especially suitable mixing partners include compounds selected from the following group M:
  • Group M especially suitable mixing partners for the compounds of formula I: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a compound obtainable from the Bacillus thuringiensis strain GC91 or from strain NCTC11821 ; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau-fluvalinate; thiocyclam; thiometon; aldicarb; azin
  • M means one member selected from the group M.
  • compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing.
  • the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • the Table A discloses 338 meanings of the variables Z 17 Z 2 , Ri, R 2 , R 3 and R 4 in a compound of the formula I.
  • Table 1 This table discloses the 338 compounds T1.1 to T1.338 of the formula
  • each of the variables Z , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • the specific compound T1.23 is the compound of the formula T1 , in which each of the variables Z ⁇ Z 2 , Ri, Ra, R 3 and R 4 has the specific meaning given in the line A.23 of the Table A. According to the same system, also all of the other 337 specific compounds disclosed in the Table 1 as well as all of the specific compounds disclosed in the Tables 2 to 85 are specified analogously.
  • Table 2 This table discloses the 338 compounds T2.1 to T2.338 of the formula
  • each of the variables Z ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 3 This table discloses the 338 compounds T3.1 to T3.338 of the formula
  • each of the variables Z-i, Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 4 This table discloses the 338 compounds T4.1 to T4.338 of the formula
  • each of the variables Z ⁇ , Z 2 , R-i, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 5 This table discloses the 338 compounds T5.1 to T5.338 of the formula
  • each of the variables Zi, Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 6 This table discloses the 338 compounds T6.1 to T6.338 of the formula
  • each of the variables Z Z 2 , R 1 f R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 7 This table discloses the 338 compounds T7.1 to T7.338 of the formula
  • each of the variables Z , Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 8 This table discloses the 338 compounds T8.1 to T8.338 of the formula
  • each of the variables Zi, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 9 discloses the 338 compounds T9.1 to T9.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , R 1 ; R 2) R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 10 This table discloses the 338 compounds T10.1 to T10.338 of the formula
  • each of the variables Z 1 t Z 2 , R ⁇ R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 11 This table discloses the 338 compounds T11.1 to T11.338 of the formula
  • each of the variables Z-,, Z 2 , R 1 ? R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 12 This table discloses the 338 compounds T12.1 to T12.338 of the formula in which, for each of these 338 specific compounds, each of the variables Zi, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 13 This table discloses the 338 compounds T13.1 to T13.338 of the formula
  • each of the variables Z-i, Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 14 This table discloses the 338 compounds T14.1 to T14.338 of the formula
  • each of the variables Zi, Z 2 , R-i, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 15 This table discloses the 338 compounds T15.1 to T15.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z 1; Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 16 This table discloses the 338 compounds T16.1 to T16.338 of the formula
  • each of the variables Z ⁇ Z 2 , R 1 ( R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 17 This table discloses the 338 compounds T17.1 to T17.338 of the formula
  • each of the variables Z , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 18 discloses the 338 compounds T18.1 to T18.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ; Z 2 , R ⁇ R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 19 This table discloses the 338 compounds T19.1 to T19.338 of the formula
  • each of the variables Zi, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 20 This table discloses the 338 compounds T20.1 to T20.338 of the formula
  • each of the variables Z 1 ; Z 2 , R-i, R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 21 discloses the 338 compounds T21.1 to T21.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 22 This table discloses the 338 compounds T22.1 to T22.338 of the formula
  • each of the variables Z-i, Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 23 This table discloses the 338 compounds T23.1 to T23.338 of the formula
  • each of the variables Z ⁇ , Z 2 , R 1 ? R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 24 discloses the 338 compounds T24.1 to T24.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z , Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 25 This table discloses the 338 compounds T25.1 to T25.338 of the formula
  • each of the variables Z Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 26 This table discloses the 338 compounds T26.1 to T26.338 of the formula
  • each of the variables Z-,, Z 2 , R 1 f R 2) R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 27 This table discloses the 338 compounds T27.1 to T27.338 of the formula
  • each of the variables Z , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 28 This table discloses the 338 compounds T28.1 to T28.338 of the formula
  • each of the variables Z-i, Z 2 , R-i, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 29 This table discloses the 338 compounds T29.1 to T29.338 of the formula
  • each of the variables Z Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 30 discloses the 338 compounds T30.1 to T30.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z 1 ; Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 31 discloses the 338 compounds T31.1 to T31.338 of the formula
  • each of the variables Z-i, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 32 This table discloses the 338 compounds T32.1 to T32.338 of the formula
  • each of the variables Z-,, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 33 discloses the 338 compounds T33.1 to T33.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z , Z 2 , R ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 34 This table discloses the 338 compounds T34.1 to T34.338 of the formula
  • each of the variables Z ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 35 This table discloses the 338 compounds T35.1 to T35.338 of the formula
  • each of the variables Z , Z 2 , R-i, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 36 This table discloses the 338 compounds T36.1 to T36.338 of the formula
  • each of the variables Z 1 ; Z 2 , Ri, R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 37 This table discloses the 338 compounds T37.1 to T37.338 of the formula
  • each of the variables Z ⁇ , Z 2 , R , R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 38 This table discloses the 338 compounds T38.1 to T38.338 of the formula
  • each of the variables Z Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 39 discloses the 338 compounds T39.1 to T39.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 40 This table discloses the 338 compounds T40.1 to T40.338 of the formula
  • each of the variables Z , Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 41 discloses the 338 compounds T41.1 to T41.338 of the formula
  • each of the variables Z , Z 2 , R 1 f R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 42 discloses the 338 compounds T42.1 to T42.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 43 This table discloses the 338 compounds T43.1 to T43.338 of the formula
  • each of the variables Z 1 ; Z 2 , Ri, R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 44 This table discloses the 338 compounds T44.1 to T44.338 of the formula
  • each of the variables Z- ⁇ , Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 45 discloses the 338 compounds T45.1 to T45.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z 1 ( Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 46 This table discloses the 338 compounds T46.1 to T46.338 of the formula Z. R ⁇
  • Table 47 This table discloses the 338 compounds T47.1 to T47.338 of the formula
  • each of the variables Z ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 48 This table discloses the 338 compounds T48.1 to T48.338 of the formula
  • each of the variables Z ⁇ Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 49 This table discloses the 338 compounds T49.1 to T49.338 of the formula
  • each of the variables Zi, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 50 This table discloses the 338 compounds T50.1 to T50.338 of the formula
  • each of the variables Z , Z 2 , R 1 ; R 2) R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 51 This table discloses the 338 compounds T51.1 to T51.338 of the formula
  • each of the variables Z Z 2 , R 1 ( R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 52 This table discloses the 338 compounds T52.1 to T52.338 of the formula
  • each of the variables Z 1 ; Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 53 This table discloses the 338 compounds T53.1 to T53.338 of the formula
  • each of the variables Z- ⁇ , Z 2 , R 1 ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 54 discloses the 338 compounds T54.1 to T54.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 55 This table discloses the 338 compounds T55.1 to T55.338 of the formula
  • each of the variables Z 1 ; Z 2 , R 1 ; R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 56 This table discloses the 338 compounds T56.1 to T56.338 of the formula
  • each of the variables Z ⁇ , Z 2) R 1 ; R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 57 discloses the 338 compounds T57.1 to T57.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 58 This table discloses the 338 compounds T58.1 to T58.338 of the formula
  • each of the variables Z-i, Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 59 This table discloses the 338 compounds T59.1 to T59.338 of the formula
  • each of the variables Z , Z , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 60 discloses the 338 compounds T60.1 to T60.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 61 This table discloses the 338 compounds T61.1 to T61.338 of the formula
  • each of the variables Z-i, Z 2 , Ri, Ra, R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 62 This table discloses the 338 compounds T62.1 to T62.338 of the formula
  • each of the variables Z , Z 2) Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 63 discloses the 338 compounds T63.1 to T63.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z Z 2 , R-i, R 2) R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 64 This table discloses the 338 compounds T64.1 to T64.338 of the formula
  • each of the variables Z-i, Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 65 This table discloses the 338 compounds T65.1 to T65.338 of the formula
  • each of the variables Z- ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 66 This table discloses the 338 compounds T66.1 to T66.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ( Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 67 This table discloses the 338 compounds T67.1 to T67.338 of the formula
  • each of the variables Z , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 68 This table discloses the 338 compounds T68.1 to T68.338 of the formula
  • each of the variables Z-i, Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 69 discloses the 338 compounds T69.1 to T69.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z 1 ; Z 2 , R-i, R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 70 This table discloses the 338 compounds T70.1 to T70.338 of the formula
  • each of the variables Z , Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 71 This table discloses the 338 compounds T71.1 to T71.338 of the formula
  • each of the variables Zi, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 72 This table discloses the 338 compounds T72.1 to T72.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z-i, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 73 This table discloses the 338 compounds T73.1 to T73.338 of the formula
  • each of the variables Z-i, Z 2 , R-,, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 74 This table discloses the 338 compounds T74.1 to T74.338 of the formula
  • each of the variables Z 1 ; Z 2) R 1 ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 75 discloses the 338 compounds T75.1 to T75.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 76 This table discloses the 338 compounds T76.1 to T76.338 of the formula
  • each of the variables Z ⁇ , Z 2 , R 1 ( R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 77 This table discloses the 338 compounds T77.1 to T77.338 of the formula
  • each of the variables Z 1 ( Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 78 discloses the 338 compounds T78.1 to T78.338 of the formula in which, for each of these 338 specific compounds, each of the variables Zi, Z 2 , Ri, R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 79 This table discloses the 338 compounds T79.1 to T79.338 of the formula
  • each of the variables Z ⁇ Z 2 , Ri, R 2 , R 3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 80 This table discloses the 338 compounds T80.1 to T80.338 of the formula
  • each of the variables Z 1 f Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 81 discloses the 338 compounds T81.1 to T81.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 82 This table discloses the 338 compounds T82.1 to T82.338 of the formula
  • each of the variables Zi, Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 83 This table discloses the 338 compounds T83.1 to T83.338 of the formula
  • each of the variables Z , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 84 This table discloses the 338 compounds T84.1 to T84.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z 1 ( Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 85 This table discloses the 338 compounds T85.1 to T85.338 of the formula
  • each of the variables Z ⁇ Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 86 This table discloses the 338 compounds T86.1 to T86.338 of the formula
  • each of the variables Z 1 ( Z 2 , R , R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 87 This table discloses the 338 compounds T87.1 to T87.338 of the formula (T87), in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 88 This table discloses the 338 compounds T88.1 to T88.338 of the formula
  • each of the variables Z , Z 2 , Ri, R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 89 This table discloses the 338 compounds T89.1 to T89.338 of the formula
  • each of the variables Z 1 ; Z 2 , R 1 ; R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 90 discloses the 338 compounds T90.1 to T90.338 of the formula in which, for each of these 338 specific compounds, each of the variables Z ⁇ , Z 2 , R R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Table 91 This table discloses the 338 compounds T91.1 to T91.338 of the formula
  • each of the variables Z 1 t Z 2 , R ⁇ R 2 , R 3 and R 4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
  • Example F1 Emulsion concentrates a) b) c)
  • Tributylphenoxypolyethylene glycol ether (30 mol of EO) - 12 % 4 %
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Example F2 Solutions a) b) c) d)
  • Petroleum ether (boiling range: 160-190°) - - 94 %
  • the solutions are suitable for use in the form of microdrops.
  • Example F3 Granules a) b) c) d)
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.
  • Example F4 Dusts a) b)
  • Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.
  • Example F5 Wettable powders a) b) c)
  • the active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.
  • Example F6 Extruder granules
  • the active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
  • Example F7 Coated granules
  • the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.
  • Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
  • Silicone oil (75 % aqueous emulsion) 0.8 %
  • Example B1 Activity against Aphis craccivora
  • Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
  • Maize seedlings are sprayed with an aqueous emulsion spray, mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 larvae (2nd instar) of Diabrotica balteata and introduced into a plastic container. 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead larvae between the treated and untreated plants.
  • Example B3 Activity against Heliothis virescens (foliar application)
  • Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Heliothis virescens and introduced into a plastic container. 6 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
  • T8.1 , T5.1 , T5.3, T20.1 , T20.3, T9.1 , T9.3 and T9.2 have an activity of over 80 %.
  • Example B4 Activity against Heliothis virescens (application to eggs)
  • Heliothis virescens eggs which have been deposited on cotton, are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars (% activity) are evaluated in comparison with untreated control batches.
  • Pea seedlings are infected with Myzus persicae, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
  • Example B6 Activity against Myzus persicae (systemic application)
  • Pea seedlings are infected with Myzus persicae, and their roots are subsequently placed into a spray mixture comprising 400 ppm of active ingredient. The seedlings are then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
  • Example B7 Activity against Plutelia xylostella
  • Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising
  • Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Spodoptera littoralis and introduced into a plastic container. 3 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
  • T20.1 , T20.3, T9.1 , T9.3 and T9.2 have an activity of over 80 %.

Abstract

Compounds of the formula (I), according to claim 1 and, where appropriate, tautomers thereof, in each case in free form or in salt form, can be used as agrochemical active ingredients and can be prepared in a manner known per se.

Description

Novel Insecticides
The present invention relates to bicyclic bisamide derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling insects or representatives of the order Acarina.
Bisamide derivatives with insecticidal action are known and described, for example, in US 2003/0229050.
There have now been found novel bicyclic bisamide derivatives with pesticidal properties. The present invention accordingly relates to compounds of formula I
Figure imgf000003_0001
in which Z-i is an oxygen atom; or a sulfur atom; Z2 is an oxygen atom; or a sulfur atom; Ri is an aryl or heteroaryl group, which is unsubstituted or substituted; R2 is hydrogen; or an organic substituent; R3 is hydrogen; or an organic substituent; R4 is hydrogen; or an organic substituent; or R3 and R4, taken together, form, together with the nitrogen atom, to which they are attached, a ring, which is unsubstituted or substituted; R5 is hydrogen; or an unsubstituted or substituted alkyl group; or forms, taken together with R8 or with a monovalent substituent attached to that atom of R6, via which atom R6 is directly connected with the carbon atom, shown in the formula I, which carries R5, one additional bond; R6 and R7, taken together, form, together with the two carbon atoms, shown in the formula I, to which atoms they are attached, a bicyclic ring system, which ring system is carbocyclic or heterocyclic, which ring system is substituted, in the manner shown in the formula I, by the four substituents -N(R2)-C(=Z1)-R1, -C(=Z2)-N(R3)-R4, R5 and R8, and which ring system is optionally further substituted; and R8 is hydrogen; or an unsubstituted or substituted alkyl group; or forms, taken together with R5 or with a monovalent substituent attached to that atom of R7, via which atom R7 is directly connected with the carbon atom, shown in the formula I, which carries R8, one additional bond, in free form or in salt form, where appropriate to tautomers, in free form or in salt form, of these compounds, to a process for the preparation and to the use of these compounds and tautomers, to pesticidal compositions whose active ingredient is selected from amongst these compounds and tautomers, in each case in free form or in agrochemically utilizable salt form, to a process for the preparation and to the use of these compositions, to plant propagation material treated with these compositions, to a method of controlling pests with these active ingredients and compositions, to intermediates, in free form or in salt form, for the preparation of these compounds, where appropriate to tautomers, in free form or in salt form, of these intermediates, and to a process for the preparation and to the use of these intermediates.
In some cases, the compounds of formula I can exist as tautomers. For example, if in the compounds of formula I the substituent -N(R2)-C(=Z1)-R1 is -N(R2)-C(=O)-R1 and R2 is hydrogen, corresponding compounds of formula I, i. e. those in which -N(R2)-C(=Z1)-Rι is - N(H)-C(=O)-R1, can be in equilibrium with the respective tautomers, in which the respective substituent has the tautomeric structure -N=C(OH)-R1. Accordingly, the compounds of formula I hereinabove and hereinbelow are to be understood as including such tautomers, where appropriate, even though the latter are not mentioned specifically in each individual case.
Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Cι-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C C alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p- toluenesulfonic acid. Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. Where appropriate, the corresponding internal salts can furthermore be formed. Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds of formula I or agrochemically utilizable salts thereof. Owing to the close relationship between the compounds of formula I in free form and in the form of their salts, for the purposes of the invention the free compounds of formula I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds of formula I. The same applies analogously to tautomers of compounds of formula I and salts thereof. In general, the free form is preferred in each case.
Preferably the invention relates (2) to a compound according to (1) of formula I, in which Z is an oxygen atom; or a sulfur atom; Z2 is an oxygen atom; or a sulfur atom; R-i is a phenyl or naphthyl group, which is substituted independently by 1 or 2 substituents Ra and optionally further substituted independently by 1 to 3 substituents R ; Ra is cyano; nitro; halogen; CrC6alkyl; halo-CrCβalkyl; CrC6alkoxy-Cι-C6alkyl; C2- C6alkenyl; halo-C2-C6alkenyl; C2-C6alkynyl; halo-C2-C6alkynyl; C3-C6cycloalkyl; halo-C3- C6cycloalkyl; hydroxy; CrC6alkoxy; halo- |-C6alkoxy; C3-C6cycloalkoxy; mercapto; d- C6alkylthio; halo-Cι-C6alkylthio;
Figure imgf000005_0001
halo-CrC6alkylsulfinyl; CrC6alkylsulfonyl; halo-C C6alkyIsulfonyl; amino; Cι-C6alkylamino; halo-Cι-C6alkylamino; di-CrC6alkylamino, in which the two alkyl groups are the same or different or, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, C C alkyl and d-C4alkoxy; di- (halo-CrCealky -amino, in which the two haloalkyl groups are the same or different; C3- C6cycloalkyIamino; N-(C1-C6alkyl)-N-(C3-C6cycloalkyl)-amino; carboxy; C-ι-C6alkoxycarbonyl; halo-CrC6alkoxycarbonyl; aminocarbonyl; d-Cβalkylaminocarbonyl; halo-d- C6alkylaminocarbonyl; di-d-C-ealkylaminocarbonyl, in which the two alkyl groups are the same or different or, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C4alkyl and Cι-C4alkoxy; di-(halo-d-C6alkyl)-aminocarbonyl, in which the two haloalkyl groups are the same or different; d-C6alkyIcarbonyl; halo-d- C6alkylcarbonyl; or tri-d-C6alkylsilyl, in which the three alkyl groups are the same or different; or 2 substituents Ra, which are attached to adjacent carbon atoms, taken together, are -(CH2-)3; -(CH2-)4; -(CH2-)5; -(CH=CH-)2; -OCH2O-; -O-(CH2-)2O-; -OCF2O-; -(CF2-)2O-; -O-(CF2-)2; or -O-(CF2-)2O-; Rb is halogen; d-C6alkyl; C2-C6alkenyl; C2-C6alkynyl; C3-C6cycloalkyl; d-C6alkoxy; d- C6alkoxycarbonyl; or a phenyl, benzyl, phenoxy or monocyclic or bicyclic heteroaryl group, which group is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of the substituents Ra; or R-i is a monocyclic or bicyclic heteroaryl group, which is unsubstituted or substituted independently by 1 to 4 substituents Rc; Rc is a substituent Ra; or a phenyl, benzyl, benzoyl, phenoxy or monocyclic or bicyclic heteroaryl group, which group is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of the substituents Ra; R2 is hydrogen; a d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycIoalkyl group, which group is unsubstituted or substituted independently by one or more substituents, selected from the group, consisting of the substituents Ra; a group C(=O)Rd; or a group C(=S)Rd; Rd is a substituent R-,; C C6alkyl; halo-Cι-C6alkyl; CrC6alkoxy-Cι-C6alkyl; a group CH2Rι; a group CH2ORι; a group CHaSR^ a group CH2NHRL which group is optionally further substituted at the nitrogen atom by d-C6alkyl or halo-d-C6alkyl; C2-C6alkenyl; halo- C2-C6alkenyl; C2-C6alkynyl; halo-C2-C6alkynyl; C3-C6cycloalkyl; halo-C3-C6cycloalkyl; C C6aIkoxy; halo-d-C6alkoxy; C3-C6cycloalkoxy; a group OR1; Cι-C6alkylthio; halo-C C6alkylthio; a group SRi; CrCealkylamino; halo-d-C6alkylamino; di-d-C6alkylamino, in which the two alkyl groups are the same or different or, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C4alkyl and d-C4alkoxy; di- (halo-d-C6alkyI)-amino, in which the two haloalkyl groups are the same or different; C3- C6cycloalkylamino; N-(d-C6alkyl)-N-(C3-C6cycIoalkyl)-amino; or a group NHR-i, which group is optionally further substituted at the nitrogen atom by d-C6alkyl or halo-d-C6alkyl; R3 is hydrogen; a C C6aIkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl group, which group is unsubstituted or substituted independently by one or more substituents, selected from the group, consisting of the substituents Ra; d-C6alkoxy; halo-d-C6alkoxy; C3-C6cycloalkoxy; d-C6alkylthio; halo-d-C6alkylthio; d-C6alkylamino; halo-d-C6alkylamino; di-Cι-C6alkylamino, in which the two alkyl groups are the same or different or, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C4alkyl and d-C4alkoxy; di-(halo-d-C6alkyl)-amino, in which the two haloalkyl groups are the same or different; C3-C6cycloalkylamino; N-(d-C6alkyl)-N-(C3-C6cycloalkyl)- amino; d-C6alkoxycarbonyl; halo-d-C6alkoxycarbonyl; d-C6alkylcarbonyl or halo-d- C6alkylcarbonyl; R4 is hydrogen; a substituent R-i; a substituent RΘ; a d-C6alkyl- C2-C6alkenyl, C2- C6alkynyl or C3-C6cycloalkyl group, which group is unsubstituted or substituted independently by one or more substituents, selected from the group, consisting of the substituents Ra, the substituents Re and a phenyl, benzoyl, phenoxy or monocyclic or bicyclic heteroaryl group, which group is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of the substituents Rc; a group CF^OR^ a group CH2SRι; a group CH2NHR-1, which group is optionally further substituted at the nitrogen atom by d-C6alkyl or halo-d-C6alkyl; d-C6alkoxy; halo-d-C6aIkoxy; C3-C6cycloalkoxy; a group OR^ d- C6alkylthio; halo-d-C6alkylthio; a group SR^ d-C6alkylsuIfinyl; halo-d-C6alkylsulfinyl; C C6alkylsulfonyl; halo-d-C6alkylsulfonyl; d-C6alkylamino; halo-CrCβalkylamino; di-C C6alkylamino, in which the two alkyl groups are the same or different or, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C4alkyl and d- C4alkoxy; di-(halo-d-C6alkyl)-amino, in which the two haloalkyl groups are the same or different; C3-C6cycloalkylamino; N-(C1-C6alkyl)-N-(C3-C6cycloalkyl)-amino; a group NHR^ which group is optionally further substituted at the nitrogen atom by d-C6alkyl or halo-d- C6alkyl; a group C(=O)Rd; a group C(=O)Re; a group C(=S)Rd; or a group C(=S)Re; Re is a carbocyclyl or heterocyciyl group, which group is monocyclic or bicyclic and is non-aromatic, in which group 1 or 2 of the ring members are optionally selected from the group, consisting of the groups C(=O), S(=O) and S(=O)2, and which group is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C alkyl and d-C alkoxy; or R3 and R4, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 6 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C4alkyl and Cι-C4alkoxy; R5 is hydrogen; C C6alkyl; or halo-d-C6alkyl; or has one of the meanings defined hereinafter; R6 and R7, taken together, are either a group of the formula
Figure imgf000008_0001
(R12)f (R22)α (R32)h (R42)i (R52. j in which Gi is attached to the carbon atom, shown in the formula I, that carries R5; and in which G5 is attached to the carbon atom, shown in the formula I, that carries R8; or are a group of the formula (R1l)a (R2l)b (R3l)c (R4l)d
Figure imgf000009_0001
(R12)f (R22)g (R32)h (R42)i in which G1 is attached to the carbon atom, shown in the formula I, that carries R5; and in which G4 is attached to the carbon atom, shown in the formula I, that carries R8; or are a group of the formula
Figure imgf000009_0002
(R12)f (R22)g (R32)h in which Gi is attached to the carbon atom, shown in the formula I, that carries R5; and in which G3 is attached to the carbon atom, shown in the formula I, that carries R8; in which formulae la, lb and Ic either a is 0; f is 0; and Gi is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or a is 0; f is 1 ; and Gi is a nitrogen atom; or a is 1 ; f is 1 ; and G-i is a carbon atom; either b is 0; g is 0; and G2 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or b is 0; g is 1 ; and G2 is a nitrogen atom; or b is 1 ; g is 1 ; and G2 is a carbon atom; and either c is 0; h is 0; and G3 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or c is 0; h is 1 ; and G3 is a nitrogen atom; or c is 1 ; h is 1 ; and G3 is a carbon atom; in which formulae la and lb either d is 0; i is 0; and G4 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or d is 0; i is 1 ; and G4 is a nitrogen atom; or d is 1 ; i is 1 ; and G4 is a carbon atom; in which formula la either e is 0; j is 0; and G5 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or e is 0; j is 1 ; and G5 is a nitrogen atom; or e is 1 ; j is 1 ; and G5 is a carbon atom; in which formula la either f is 1 ; g is 1 ; and R12 and R22, taken together, are either a group of the formula
Figure imgf000010_0001
( 62)p (R72- q ( 82)r (R92)s (R102)t in which G6 is attached to G^ and in which Gι0 is attached to G2; or are a group of the formula ( 6l)k (R7l)| (R8l)m (R9l)n
Figure imgf000010_0002
( 62)p (R72)q (R82)r ( 92)s in which G6 is attached to G^ and in which G9 is attached to G2; or are a group of the formula
Figure imgf000010_0003
in which G6 is attached to G^ and in which G8 is attached to G2; or g is 1 ; h is 1 ; and R22 and R32, taken together, are either a group of the formula Id, in which G6 is attached to G2; and in which Gι0 is attached to G3; or are a group of the formula le, in which G6 is attached to G2; and in which G9 is attached to G3; or are a group of the formula If, in which G6 is attached to G2; and in which G8 is attached to G3; or h is 1 ; i is 1 ; and R32 and R42, taken together, are either a group of the formula Id, in which G6 is attached to G3; and in which Gι0 is attached to G4; or are a group of the formula le, in which G6 is attached to G3; and in which G9 is attached to G ; or are a group of the formula If, in which G6 is attached to G3; and in which G8 is attached to G ; or i is 1 ; j is 1 ; and R4 and R52, taken together, are either a group of the formula Id, in which G6 is attached to G4; and in which Gι0 is attached to G5; or are a group of the formula le, in which G6 is attached to G4; and in which G9 is attached to G5; or are a group of the formula If, in which G6 is attached to G4; and in which G8 is attached to G5; in which formula lb either f is 1 ; g is 1 ; and Rι2 and R 2, taken together, are either a group of the formula Id, in which G6 is attached to Gi; and in which G 0 is attached to G2; or are a group of the formula le, in which G6 is attached to G^ and in which G9 is attached to G2; or are a group of the formula If, in which G6 is attached to Gi; and in which G8 is attached to G2; or g is 1 ; h is 1 ; and R22 and R32, taken together, are either a group of the formula Id, in which G6 is attached to G2; and in which G10 is attached to G3; or are a group of the formula le, in which G6 is attached to G2; and in which G9 is attached to G3; or are a group of the formula If, in which G6 is attached to G2; and in which G8 is attached to G3; or h is 1 ; i is 1 ; and R32 and R 2, taken together, are either a group of the formula Id, in which G6 is attached to G3; and in which G10 is attached to G4; or are a group of the formula le, in which G6 is attached to G3; and in which G9 is attached to G4; or are a group of the formula If, in which G6 is attached to G3; and in which G8 is attached to G4; in which formula Ic either f is 1 ; g is 1 ; and Rι2 and R22, taken together, are either a group of the formula Id, in which G6 is attached to Gi; and in which Gι0 is attached to G2; or are a group of the formula le, in which G6 is attached to Gi; and in which G9 is attached to G2; or are a group of the formula If, in which G6 is attached to G^ and in which G8 is attached to G2; or g is 1 ; h is 1 ; and R22 and R32, taken together, are either a group of the formula Id, in which G6 is attached to G2; and in which G10 is attached to G3; or are a group of the formula le, in which G6 is attached to G2; and in which G9 is attached to G3; or are a group of the formula If, in which G6 is attached to G2; and in which G8 is attached to G3; in which formulae la, lb and Ic the atoms G and G2 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R12, if G is a nitrogen atom, and which is R-n or R12, if G is a carbon atom, and a second substituent, which is R22, if G2 is a nitrogen atom, and which is R2 or R22, if G2 is a carbon atom, taken together; in which formulae la, lb and Ic the atoms G2 and G3 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R22, if G2 is a nitrogen atom, and which is R21 or R22, if G2 is a carbon atom, and a second substituent, which is R32, if G3 is a nitrogen atom, and which is R3 or R32, if G3 is a carbon atom, taken together; in which formulae la and lb the atoms G3 and G4 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R32, if G3 is a nitrogen atom, and which is R3ι or R32, if G3 is a carbon atom, and a second substituent, which is R 2, if G is a nitrogen atom, and which is R4ι or R42, if G4 is a carbon atom, taken together; in which formula la the atoms G and G5 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R42, if G4 is a nitrogen atom, and which is R41 or R42, if G4 is a carbon atom, and a second substituent, which is R52, if G5 is a nitrogen atom, and which is R51 or R52, if G5 is a carbon atom, taken together; in which formulae la, lb and Ic the atom G can be connected with the carbon atom, shown in the formula I, that carries R5, by one additional bond, which bond, if present, is represented by a first substituent, which is R12, if Gi is a nitrogen atom, and which is Rn or R12, if Gi is a carbon atom, and a second substituent, which is R5, taken together; in which formula la the atom G5 can be connected with the carbon atom, shown in the formula I, that carries R8, by one additional bond, which bond, if present, is represented by a first substituent, which is R52, if G5 is a nitrogen atom, and which is R51 or R52, if G5 is a carbon atom, and a second substituent, which is R8, taken together; in which formula lb the atom G can be connected with the carbon atom, shown in the formula I, that carries R8, by one additional bond, which bond, if present, is represented by a first substituent, which is R42, if G4 is a nitrogen atom, and which is R41 or R 2, if G4 is a carbon atom, and a second substituent, which is R8, taken together; in which formula Ic the atom G3 can be connected with the carbon atom, shown in the formula I, that carries R8> by one additional bond, which bond, if present, is represented by a first substituent, which is R3 , if G3 is a nitrogen atom, and which is R31 or R32, if G3 is a carbon atom, and a second substituent, which is R8, taken together; in which formula la each of those substituents, selected from the group, consisting of the substituents Rn, R12) R21, R22, R31, R32, R4ι, R42, R51 and R52, which are different from the two substituents, which, taken together, form the group of the formula Id, le or If, and different from any first substituent, if present, as defined hereinbefore for the formula la, and from any second substituent, if present, as defined hereinbefore for the formula la, is independently selected from the group, consisting of the substituents Rf; in which formula lb each of those substituents, selected from the group, consisting of the substituents Rn, R12, R2ι, R22, R31, R32, R4ι and R42, which are different from the two substituents, which, taken together, form the group of the formula Id, le or If, and different from any first substituent, if present, as defined hereinbefore for the formula lb, and from any second substituent, if present, as defined hereinbefore for the formula lb, is independently selected from the group, consisting of the substituents R ; in which formula Ic each of those substituents, selected from the group, consisting of the substituents Rn, R12, R21, R22, R31 and R32, which are different from the two substituents, which, taken together, form the group of the formula Id, le or If, and different from any first substituent, if present, as defined hereinbefore for the formula Ic, and from any second substituent, if present, as defined hereinbefore for the formula Ic, is independently selected from the group, consisting of the substituents Rf; Rf is hydrogen; or a substituent Rg; the total number of the substituents Rg, if present, having an upper limit of 5 for a group of the formula la; of 4 for a group of the formula lb; and of 3 for a group of the formula Ic; which total number can, however, be limited for a specific group of the formula la, lb or Ic to a value lower than the upper limit mentioned hereinbefore, which value is then equal to the number of the positions available for the substitution by a substituent Rg in this specific group; Rg is either attached to a carbon atom and then selected from the group, consisting of the substituents Rg.c; or attached to a nitrogen atom and then selected from the group, consisting of the substituents Rg.n; Rg-C is a substituent Rc; Rg-n is cyano; nitro; d-C6alkyl; halo-d-C6alkyl; d-C6alkoxy-C-ι-C6alkyl; C2-C6alkenyl; halo-C2-C6alkenyl; C2-C6alkynyl; halo-C -C6alkynyl; C3-C6cycloalkyl; halo-C3-C6cycloalkyl; d- C6alkoxy; halo-d-C6alkoxy; C3-C6cycloalkoxy; d-C6alkylthio; halo-Cι-C6alkylthio; d- C6alkylsulfinyl; halo-Cι-C6alkylsulfinyl; d-C6alkylsulfonyl; halo-d-C6alkylsulfonyl; amino; C C6alkylamino; halo-d-C6alkylamino; di-d-C6alkylamino, in which the two alkyl groups are the same or different or, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C4alkyl and d-C4alkoxy; di-(halo-Cι-C6alkyl)-amino, in which the two haloalkyl groups are the same or different; C3-C6cycloaIkylamino; N-(Cr C6alkyl)-N-(C3-C6cycloalkyl)-amino; d-C6alkoxycarbonyl; halo-d-C6alkoxycarbonyl; aminocarbonyl; C C6alkylaminocarbonyl; halo-d-C6alkylaminocarbonyl; di-C C6alkylaminocarbonyl, in which the two alkyl groups are the same or different or, taken together, form, together with the nitrogen atom, to which they are attached, a ring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms and optionally 1 further ring hetero atom, which then replaces 1 ring carbon atom and is selected from the group, consisting of an oxygen, a sulfur and a nitrogen atom, which ring is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of cyano, nitro, halogen, d-C4alkyl and Cι-C alkoxy; di-(halo-C1-C6alkyl)-aminocarbonyl, in which the two haloalkyl groups are the same or different; d-C6alkylcarbonyl; halo-d-C6alkylcarbonyl; tri- d-C6alkylsilyl, in which the three alkyl groups are the same or different; or a phenyl, benzyl, benzoyl, phenoxy or monocyclic or bicyclic heteroaryl group, which group is unsubstituted or substituted independently by 1 to 4 substituents, selected from the group, consisting of the substituents Ra; in which formulae Id, le and If either k is 0; p is 0; and G6 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or k is 0; p is 1 ; and G6 is a nitrogen atom; or k is 1 ; p is 1 ; and G6 is a carbon atom; either I is 0; q is 0; and G7 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or I is 0; q is 1 ; and G7 is a nitrogen atom; or I is 1 ; q is 1 ; and G7 is a carbon atom; and either m is 0; r is 0; and G8 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or m is 0; r is 1 ; and G8 is a nitrogen atom; or m is 1 ; r is 1 ; and G8 is a carbon atom; in which formulae Id and le either n is 0; s is 0; and G9 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or n is 0; s is 1 ; and G9 is a nitrogen atom; or n is 1 ; s is 1 ; and G9 is a carbon atom; in which formula Id either o is 0; t is 0; and G10 is a group C(=O); a group C(=S); an oxygen atom; a sulfur atom; a group S(=O); or a group S(=O)2; or o is 0; t is 1 ; and G10 is a nitrogen atom; or o is 1 ; t is 1 ; and Gι0 is a carbon atom; in which formulae Id, le and If the atoms G6 and G7 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R62, if G6 is a nitrogen atom, and which is R6ι or R62, if G6 is a carbon atom, and a second substituent, which is R72, if G7 is a nitrogen atom, and which is R71 or R72, if G7 is a carbon atom, taken together; in which formulae Id, le and If the atoms G7 and G8 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R72, if G is a nitrogen atom, and which is R71 or R72, if G7 is a carbon atom, and a second substituent, which is R8 , if G8 is a nitrogen atom, and which is R81 or R82, if G8 is a carbon atom, taken together; in which formulae Id and le the atoms G8 and G9 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R82, if G8 is a nitrogen atom, and which is R8ι or R82, if G8 is a carbon atom, and a second substituent, which is R92, if G9 is a nitrogen atom, and which is R91 or R92, if G9 is a carbon atom, taken together; in which formula Id the atoms G9 and G10 can be connected by one additional bond, which bond, if present, is represented by a first substituent, which is R92, if G9 is a nitrogen atom, and which is R9 or R92, if G9 is a carbon atom, and a second substituent, which is R-102, if G10 is a nitrogen atom, and which is R10ι or R102, if G10 is a carbon atom, taken together; in which formulae Id, le and If the atom G6 can be connected either with the atom G^ shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R62, if G6 is a nitrogen atom, and which is R61 or R62, if G6 is a carbon atom, and a second substituent, which is R12, if Gi is a nitrogen atom, and which is Rn or R12, if Gi is a carbon atom, taken together; or with the atom G2, shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R62, if G6 is a nitrogen atom, and which is R6ι or R62, if G6 is a carbon atom, and a second substituent, which is R22, if G2 is a nitrogen atom, and which is R21 or R22, if G2 is a carbon atom, taken together; or with the atom G3, shown in the formulae la and lb, by one additional bond, which bond, if present, is represented by a first substituent, which is R62, if G6 is a nitrogen atom, and which is R6ι or R62, if G6 is a carbon atom, and a second substituent, which is R32, if G3 is a nitrogen atom, and which is R3ι or R32, if G3 is a carbon atom, taken together; or with the atom G4, shown in the formula la, by one additional bond, which bond, if present, is represented by a first substituent, which is R62, if G6 is a nitrogen atom, and which is R6ι or R62, if G6 is a carbon atom, and a second substituent, which is R42, if G4 is a nitrogen atom, and which is R41 or R42, if G4 is a carbon atom, taken together; in which formula Id the atom G10 can be connected either with the atom G2, shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R102, if G10 is a nitrogen atom, and which is R10ι or R102, if G10 is a carbon atom, and a second substituent, which is R22, if G2 is a nitrogen atom, and which is R21 or R22, if G2 is a carbon atom, taken together; or with the atom G3, shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R102, if G10 is a nitrogen atom, and which is R1OT or R102, if G10 is a carbon atom, and a second substituent, which is R32, if G3 is a nitrogen atom, and which is R31 or R32, if G3 is a carbon atom, taken together; or with the atom G4, shown in the formulae la and lb, by one additional bond, which bond, if present, is represented by a first substituent, which is R102, if G10 is a nitrogen atom, and which is R10ι or R102, if G10 is a carbon atom, and a second substituent, which is R42, if G4 is a nitrogen atom, and which is R 1 or R 2, if G is a carbon atom, taken together; or with the atom G5, shown in the formula la, by one additional bond, which bond, if present, is represented by a first substituent, which is R102, if G10 is a nitrogen atom, and which is R10ι or R102, if G10 is a carbon atom, and a second substituent, which is R52, if G5 is a nitrogen atom, and which is R5 or R52, if G5 is a carbon atom, taken together; in which formula le the atom G9 can be connected either with the atom G2, shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R92, if G9 is a nitrogen atom, and which is R91 or R92, if G9 is a carbon atom, and a second substituent, which is R22, if G2 is a nitrogen atom, and which is R21 or R22, if G2 is a carbon atom, taken together; or with the atom G3, shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R92, if G9 is a nitrogen atom, and which is R91 or R92, if G9 is a carbon atom, and a second substituent, which is R32, if G3 is a nitrogen atom, and which is R31 or R32, if G3 is a carbon atom, taken together; or with the atom G4, shown in the formulae la and lb, by one additional bond, which bond, if present, is represented by a first substituent, which is R92, if G9 is a nitrogen atom, and which is R9ι or R92, if G9 is a carbon atom, and a second substituent, which is R42, if G4 is a nitrogen atom, and which is R41 or R42, if G4 is a carbon atom, taken together; or with the atom G5, shown in the formula la, by one additional bond, which bond, if present, is represented by a first substituent, which is R92, if G9 is a nitrogen atom, and which is R9 or R92, if G9 is a carbon atom, and a second substituent, which is R52, if G5 is a nitrogen atom, and which is R51 or R52, if G5 is a carbon atom, taken together; in which formula If the atom G8 can be connected either with the atom G2, shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R82, if G8 is a nitrogen atom, and which is R81 or R82, if G8 is a carbon atom, and a second substituent, which is R22, if G2 is a nitrogen atom, and which is R21 or R22, if G2 is a carbon atom, taken together; or with the atom G3, shown in the formulae la, lb and Ic, by one additional bond, which bond, if present, is represented by a first substituent, which is R82, if G8 is a nitrogen atom, and which is R8ι or R82, if G8 is a carbon atom, and a second substituent, which is R32, if G3 is a nitrogen atom, and which is R31 or R32, if G3 is a carbon atom, taken together; or with the atom G4, shown in the formulae la and lb, by one additional bond, which bond, if present, is represented by a first substituent, which is R82, if G8 is a nitrogen atom, and which is R8ι or R82, if G8 is a carbon atom, and a second substituent, which is R 2, if G4 is a nitrogen atom, and which is R41 or R 2, if G4 is a carbon atom, taken together; or with the atom G5, shown in the formula la, by one additional bond, which bond, if present, is represented by a first substituent, which is R82, if G8 is a nitrogen atom, and which is R81 or R82, if G8 is a carbon atom, and a second substituent, which is R52, if G5 is a nitrogen atom, and which is R51 or R5 , if G5 is a carbon atom, taken together; in which formula Id each of those substituents, selected from the group, consisting of the substituents R6ι, R62, R ι, R72, Rβi, β2, R91, R92, R101 and R 02, which are different from any first substituent, if present, as defined hereinbefore for the formula Id, and from any second substituent, if present, as defined hereinbefore for the formula Id, is independently selected from the group, consisting of the substituents Rr,; in which formula le each of those substituents, selected from the group, consisting of the substituents R6ι, Rβ2, R71, R72, Rβi, s2, R91 and R92, which are different from any first substituent, if present, as defined hereinbefore for the formula le, and from any second substituent, if present, as defined hereinbefore for the formula le, is independently selected from the group, consisting of the substituents RJ; in which formula If each of those substituents, selected from the group, consisting of the substituents R6ι, R62, R71, R72, Rsi and R82, which are different from any first substituent, if present, as defined hereinbefore for the formula If, and from any second substituent, if present, as defined hereinbefore for the formula If, is independently selected from the group, consisting of the substituents Rh; Rh is hydrogen; or a substituent RJ; the total number of the substituents Rj, if present, having an upper limit of 6 for a group of the formula Id; and of 4 for a group of the formula If; which total number can, however, be limited for a specific group of the formula Id or If to a value lower than the upper limit mentioned hereinbefore, which value is then equal to the number of the positions available for the substitution by a substituent Rj in this specific group; Ri is hydrogen; or a substituent Rk; the total number of the substituents Rk, if present, having an upper limit of 5; which total number can, however, be limited for a specific group of the formula le to a value lower than the upper limit mentioned hereinbefore, which value is then equal to the number of the positions available for the substitution by a substituent Rk in this specific group; Rj is either attached to a carbon atom and then selected from the group, consisting of the substituents Rj.c; or attached to a nitrogen atom and then selected from the group, consisting of the substituents R,--n; Rj.c is a substituent Rc; Rj.n is a substituent Rg.n; Rk is either attached to a carbon atom and then selected from the group, consisting of the substituents Rk.c; or attached to a nitrogen atom and then selected from the group, consisting of the substituents Rk.n; or 2 substituents Rk, the first of which is attached to the atom G6 and is represented by R62, if G6 is a nitrogen atom, and by R6ι or R62, if G6 is a carbon atom, and the second of which is attached to the atom G9 and is represented by R92, if G9 is a nitrogen atom, and by R91 or R92, if G9 is a carbon atom, taken together, are -CH2-; or -O-; Rk.c is a substituent Rc; Rk-n is a substituent Rg-n; R8 is hydrogen; d-C6alkyl; or halo-d-C6alkyl; or has one of the meanings defined hereinbefore or hereinafter; or R5 and R8, taken together, are a bond; with the proviso, that (i) a ring oxygen atom, if present, is not directly connected with a further ring oxygen atom, if any; (ii) a ring carbon atom, selected from the group, consisting of G-i, G2, G3, G4, G5, G6, G7, G8, G9 and G10, is, if present, not directly connected with any other atom by a triple bond or with any other 2 different atoms by 2 double bonds; (iii) not more than 6 of the variables Gi, G2, G3, G4, G5, G6, G7, G8, G9 and G 0 can, if present, be selected from the group, consisting of an oxygen atom, a sulfur atom, a group S(=O), a group S(=O)2 and a nitrogen atom, each of the remaining of these variables, if any, being selected from the group, consisting of a carbon atom, a group C(=O) and a group C(=S), and not more than 3 of the said 6 variables can be selected from the group, consisting of an oxygen atom, a sulfur atom, a group S(=O) and a group S(=O)2; and (iv) unless otherwise defined hereinbefore, the meaning of a variable at a certain occurrence can be selected independently from the meaning of the same variable at any other occurrence, if any.
Unless otherwise defined, the general terms used hereinabove and hereinbelow have the meanings which follow.
Halogen - as a group per se and as a structural element of other groups and compounds, such as haloalkyl - is, for example, fluorine, chlorine, bromine or iodine, in particular flluorine, chlorine or bromine, but especially chlorine or bromine.
Unless otherwise defined, carbon-containing groups and compounds comprise for example in each case 1 up to and including 15, preferably 1 up to and including 10, especially 1 up to and including 8, in particular 1 up to and including 5, especially 1 or 2, carbon atom(s).
Cycloalkyl - as a group per se and as a structural element of other groups and compounds, such as halocycloalkyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain, for example methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec- butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl - as a group per se and as a structural element of other groups and compounds, such as haloalkenyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon double bond(s), the double bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, allyl, propen-2-yl, methallyl, but-2-en-1-yl, but-3-en-1 -yl or pent-4-en-1 -yl.
Alkynyl - as a group per se and as a structural element of other groups and compounds, such as haloalkynyl - is, in each case with due consideration of the number of carbon atoms contained in each case in the relevant group or compound, either straight-chain or branched and comprises in each case 2 or more than 2 or preferably 1 carbon-carbon triple bond(s), the triple bonds of these substituents being separated from the remaining moiety of the compound I by preferably at least one saturated carbon atom, and is, for example, propargyl, but-2-ynyl or but-3-yn-2-yl.
Aryl is, for example, naphthyl or, preferably, phenyl.
Heteroaryl has, for example, an aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur, and is, for example, pyridyl, thienyl, pyrazolyl, thiazolyl, thiadiazolyl, furyl, oxadiazolyl, indolizinyl, pyrimidyl, quinolyl or pteridinyl.
Non-aromatic heterocyclyl has, for example, a non-aromatic ring skeleton composed of a ring having 5 or 6 ring members or of a combination of at least two rings having in each case independently of one another 5 or 6 ring members, where for example 1 up to and including 4 of the ring members is (are) (a) heteroatom(s) selected from the group consisting of nitrogen, oxygen and sulfur and is, for example, piperidyl, pyrrolinyl, tetrahydrofuryl or chromanyl.
Halogen-substituted carbon-containing groups and compounds, such as haloalkyl, can be partially halogenated or perhalogenated, where, in the case of polyhalogenation, the halogen substituents can be identical or different. The following are further preferred embodiments within the scope of the invention:
(3) A compound according to (1 ) or (2) of the formula I, in which Z1 is an oxygen atom;
(4) A compound according to any one of (1) to (3) of the formula I, in which Z2 is an oxygen atom;
(5) A compound according to any one of (1) to (4) of the formula I, in which R-i is a phenyl, pyridyi or pyrazolyl group, which is unsubstituted or preferably substituted; especially a phenyl, pyridyi or pyrazolyl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, d-C6alkyl. halo-CrC6aIkyl, d- C6alkoxy, halo-CrC6alkoxy and a phenyl or pyridyi group, which group is unsubstituted or preferably substituted; more especially a phenyl, pyridyi or pyrazolyl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, CrC6alkyl, halo-CrC6alkyl, halo-d-C6alkoxy and a phenyl or pyridyi group, which group is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen and d-C6alkyl; preferably a phenyl or pyridyi group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of d-C6alkyl and halo-CrC6alkyl; or a pyrazolyl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, d-C6alkyl, halo-CrC6alkyl, halo-d-C6alkoxy and a phenyl or pyridyi group, which group is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen and CrC6alkyl; more preferably a pyrazolyl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, d-C6alkyl, halo-d-C-ealkyl, halo-d-C6alkoxy and a phenyl or pyridyi group, which group is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen and CrC6alkyl; especially a pyrazol-3-yl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, CrC6alkyl, halo-d-C6alkyl, halo-d-C6alkoxy and a phenyl or pyridyi group, which group is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen and CrC6alkyl; more especially a pyrazol-3-yl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, halo-d-C6aIkyl, halo-d- C6alkoxy and a phenyl or pyridyi group, which group is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen and CrCealkyl; preferably a pyrazol-3-yl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, halo-d-C6alkyl, halo-CrC6alkoxy and a pyridyi group, which group is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen; more preferably a pyrazol-3-yl group, which is substituted independently by 1 to 3 substituents, selected from the group, consisting of halogen, halo-CrCβaikyl, halo-d-
C6alkoxy and a pyrid-2-yl group, which group is substituted independently by 1 or 2 substituents, selected from the group, consisting of halogen; especially a pyrazol-5-yl group, which is substituted in the 3-position by halogen, halo-d-
C6alkyl or halo-d-C6alkoxy and in the 1 -position by a pyrid-2-yl group, which group is substituted independently by 1 or 2 substituents, selected from the group, consisting of halogen; more especially a pyrazol-5-yl group, which is substituted in the 3-position by halogen, halo- d-C6alkyl or halo-d-C6alkoxy and in the 1 -position by a pyrid-2-yl group, which group is substituted in the 3-position by halogen; preferably a pyrazol-5-yl group, which is substituted in the 3-position by halogen, halo-d-
C6alkyl or halo-CrC6alkoxy and in the 1 -position by a pyrid-2-yl group, which group is substituted in the 3-position by chlorine or bromine; more preferably a pyrazol-5-yl group, which is substituted in the 3-position by halo-d-C6alkyl and in the 1 -position by a pyrid-2-yl group, which group is substituted in the 3-position by chlorine or bromine; most preferably a pyrazol-5-yl group, which is substituted in the 3-position by trifluoromethyl and in the 1 -position by a pyrid-2-yl group, which group is substituted in the 3-position by chlorine or bromine;
(6) A compound according to any one of (1 ) to (5) of the formula I, in which R2 is hydrogen or CrC6alkyl; preferably hydrogen;
(7) A compound according to any one of (1) to (6) of the formula I, in which R3 is hydrogen or CrC6alkyl; preferably hydrogen; (8) A compound according to any one of (1 ) to (7) of the formula I, in which R4 is d-C6alkyl; preferably methyl or isopropyl;
(9) A compound according to any one of (1) to (8) of the formula I, in which R5 and R8, taken together, are a bond;
(10) A compound according to any one of (1) to (9) of the formula I, in which R6 and R7, taken together, are a group of the formula lb or a group of the formula Ic;
(11) A compound according to any one of (1) to (10) of the formula I, in which the two carbon atoms, shown in the formula I, to which atoms R6 and R7 are attached, are two ring members of an aromatic ring;
(12) A compound according to any one of (1) to (11) of the formula I, in which R6 and R7, taken together, form, together with the two carbon atoms, shown in the formula I, to which atoms they are attached, and together with R5 and with R8, one of the bicyclic ring systems shown in the formulae T1 to T85, or shown in the formulae T1 to T71 , each of which ring systems is substituted by the two substituents -N(R2)-C(=Z1)-R1 and -C(=Z2)-N(R3)-R4; preferably taken together, form, together with the two carbon atoms, shown in the formula I, to which atoms they are attached, and together with R5 and with R8, one of the bicyclic ring systems shown in the formulae T1 , T6, T7, T21 , T37 and T38, each of which ring systems is substituted by the two substituents -N(R2)-C(=Z1)-R1 and -C(=Z2)-N(R3)-R4; more preferably taken together, form, together with the two carbon atoms, shown in the formula I, to which atoms they are attached, and together with R5 and with R8, one of the bicyclic ring systems shown in the formulae T1 and T7, or shown in the formulae T2, T22, T75, T76, T78, T79 and T81 , each of which ring systems is substituted by the two substituents -N(R2)-C(=Z1)-R1 and -C(=Z2)-N(R3)-R4.
A further preferred subgroup of the compounds of formula I is represented by the compounds of formulae Vila and Vllb
Figure imgf000024_0001
wherein
R0ι is hydrogen; amino or nitro; R02 is hydrogen or d-C alkyl;
R03 is d-C alkyl, d-C4alkyl mono- or disubstituted by cyano, COOH, nitro, d-C alkoxy or cyclopropyl;
C2-C8alkenyl, C2-C8alkenyl substituted by halogen; d-C4alkoxy, C3-C6-alkinyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl substituted by d-C4alkyl, pyridyi, phenyl-C2-C6alkenyl or cyclopropyl; cyclobutyl substituted by d-C alkyl; cyclopentylthio-d-C4alkyl, benzyloxy, benzyloxy substituted by halogen; benzylthio-Crdalkyl, wherein the benzyl group may itself be substituted by d-C4alkyl; thiophenyl substituted by halophenyl; phenoxy-Crdalkyl, wherein the phenyl group may be mono- or disubstituted by halogen; phenyl-Crdalkyl, wherein the phenyl group may itself be mono- or disubstituted by substituents selected from halogen, nitro, benzothiazol-2-yloxy, d-C4haloalkyl, d-C4alkoxy and d-C4alkyI; 3,4-dihydro-2H-benzo[b][1 ,4]dioxepinyl, 1 ,2,3,4-tetrahydro-naphthalenyl substituted by d- C4alkoxy;
C2-C6alkenyloxy, isoxazolyl substituted by d-C alkyl; thiazolyl, d-C4alkoxycarbonyl-CrC4alkyl, phenyl substituted by hydroxy, halophenyloxy, d- C4alkyl-silyl(d-C4-alkyl)3 or C2-C6alkinyl; pyridyi substituted by d-C4alkoxy;
CrC6alkylthio-CrC4alkyl, C2-C6alkenylthio-C C4alkyl, C3-C6alkinylthio-CrC4alkyl, dioxolan-2- yl-d-C4aIkyl, (CrC4alkyl-dioxolan-2-yl)-CrC4alkyl, triazolyl-d-C4alkyl, thienyl-d-C4alkyI, morpholinyl-CrC4alkyl, CrC4alkylthio-d-C4alkyl, 2,3-dihydro-1 H-isoindolyl, halo-substituted- thiazolyl-d-C4alkyl, CrC alkylsulfonyl-d-C4alkyl or quinolyIthio-d-C4alkyl, wherein the quinoline group may be substituted by d-C4haloalkyl;
Ro4 is d-C haloalkyl;
R05 is halogen; each of R06 and R0ιo, which may be the same or different, represents hydrogen, d-C6alkyl,
CrC6alkoxycarbonyloxy, CrC6alkyIcarbonylamino, hydroxy, cyano, halogen or d-C6lkoxy;
R07 is hydrogen, nitro or halogen;
Y01 is C(Ros), sulfur, nitrogen or a chemical bond;
R08 is hydrogen, halogen, d-C4alkyl or nitro;
Y02 is C(Rog), a chemical bond, or is nitrogen or sulfur; and R09 is hydrogen, phenyl, phenyl substituted by halogen, or halogen.
Preferred compounds of the formula Vila are those, wherein
R01 is hydrogen; R02 is hydrogen; R03 is d-C4alkyl, preferably methyl; R0 is C1-C4fluoroalkyl, preferably trifluoromethyl; R05 is chloro; R06 is halogen, preferably chloro; R07 is hydrogen;
R010 is hydrogen; Y01 is C(R08); Ros is halogen, preferably chloro; Y02 is C(R09), and R09 is hydrogen.
Especially preferred within the scope of the invention are the compounds of the formula I mentioned in the Examples P3, P6 and P9 to P11.
Individually preferred within the scope of the invention is each of the compounds T1.1 , T1.3, T6.1 , T6.3, T7.1 , T7.3, T21.3, T37.3 and T38.3.
Also individually preferred within the scope of the invention is each of the compounds T2.1 , T22.3, T75.1 , T75.3, T76.1 , T76.3, T78.1 , T79.1 and T81.1.
The process according to the invention for preparing compounds of the formula I is carried out analogously to known processes. In the section that follows, the substituents R^ R2, R3, R4, R5, Re, R7, Re, ! and Z2 are as defined under formula I in claim 1 unless otherwise stated.
Figure imgf000026_0001
B A
Compounds of formula A, wherein Z and ZΛ are oxygen and Ri is hydrogen, may be made from the ring opening of a benzoxazinone of formula B with an amine of formula NHR3R4. Such amines are either known or they may be made analogously to known processes. Benzoxazinones of formula B may be made from amino acids of formula C by treatment with a carboxylic acid of formula RrCOOH and a dehydrating reagent such as methanesulfonyl chloride (optionally in the presence of a base such as pyridine or triethylamine). Alternatively benzoxazinones of formula B may be obtained by the treatment of amino acids of formula C with an acid chloride of formula RrCOCI under basic conditions (for example in pyridine), followed if necessary by a second cyclisation step (which may be achieved using a dehydrating agent for example acetic anhydride). Acid chlorides of formula RrCOCI may be made from carboxylic acids of formula RrCOOH under standard conditions (for example by treatment with thionyl chloride or oxalyl chloride). Carboxylic acids of formula RrCOOH are either known compounds or they may be made analogously to known processes.
Compounds of formula A, wherein Zi and Z are sulfur, may be made from compounds of formula A, wherein Z^ and Z2 are oxygen, by treatment with a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide.
Figure imgf000027_0001
Figure imgf000027_0002
Alternatively, compounds of formula A, wherein Zi and Z-i are oxygen, may be made by treatment of compounds of formula D, wherein ZΛ is oxygen and R is OH, C C4alkoxy or CI, with an amine of formula NHR3R4. The standard conditions for such acylation reactions are as follows: when R is OH such reactions are usually carried out in the presence of a coupling reagent such as DCC (N,N'-dicyclohexylcarbodiimide) or EDC (1 -Ethyl-3-[3-dimethylamino- propyljcarbodiimide hydrochloride) optionally in the presence of a nucleophilic catalyst such as hydroxybenzotriazole or 4-(dimethylamino)-pyridine. When R is CI, such reactions are usually carried out under basic conditions (for example in the presence of pyridine or triethylamine), again optionally in the presence of a nucleophilic catalyst. It may be possible to convert esters (wherein R is d-C4alkoxy) directly to amides by heating the ester and amine together in a thermal process.
Acid chlorides of formula D, wherein Z^ is oxygen and R is CI, may be made from carboxylic acids of formula D, wherein Z1 is oxygen and R is OH, under standard conditions (such as treatment with thionyl chloride or oxalyl chloride). Carboxylic acids of formula D, wherein Z is oxygen and R is OH, may be formed from esters of formula D, wherein Z is oxygen and R is d-C alkoxy. It is well known for a person skilled in the art that there are many methods for the hydrolysis of such esters depending on the nature of the alkoxy group. One widely used method to achieve such a transformation is the treatment of the ester with an alkali such as sodium hydroxide in a solvent such as ethanol. Esters of formula D, wherein Z1 is oxygen and R is d-C alkoxy, may be made by treatment of compounds of formula E, wherein R is d-C alkoxy, by acylation with compounds of formula
RrCOOH or R COCI under standard conditions as previously described. Compounds of formula E, wherein R is C C4alkoxy, may be made from compounds of formula C by sequential treatment with an alcohol under acidic conditions and then formation of the N-R2 bond. It is known to a person skilled in the art that there are many reported methods for the formation of this bond depending on the nature of the substituent R2. For example, reductive amination may be achieved by treatment of the amine with an aldehyde or ketone and a reducing agent such as sodium cyanoborohydride. Alternatively alkylation may be achieved by treating the amine with an alkylating agent such as an alkyl halide, optionally in the presence of a base. Alternatively arylation may be achieved by treatment of the amine with an aryl halide or sulfonate in the presence of a suitable catalyst ligand system, often a palladium (0) complex.
Alternatively, compounds of formula E, wherein R is d-C alkoxy, may be made from a compound of formula F, wherein R is C C4alkoxy and LG is a leaving group such as fluoro, chloro or sulfonate, via nucleophilic displacement of the leaving group by an amine of formula R2-NH2. Such compounds of formula F and amines of formula R2-NH2 are either known compounds or can be made by known methods obvious to someone skilled in the art.
Compounds of formula A, wherein Zi is sulfur and Z2 is oxygen, can be made from compounds of formula D, wherein Z1 is oxygen and R is OH or d-C alkoxy, by treatment with a thio-transfer reagent such as Lawessen's reagent or phosphorus pentasulfide prior to coupling with the amine of formula NHR3R4.
Alternatively, compounds of formula D, wherein R is OH and Z1 is oxygen, may be dehydrated to benzoxazinones of formula B by treatment with a dehydrating agent such as acetic anhydride.
Figure imgf000029_0001
Figure imgf000029_0002
J JK
Alternatively, compounds of formula A, wherein Z and Z2 are oxygen, may be made by the treatment of compounds of formula G, wherein Z2 is oxygen, with a carboxylic acid of formula RrCOOH or an acid chloride of formula RrCOCI as previously described. Compounds of formula G, wherein Z2 is oxygen, may be formed from compounds of formula H, wherein P is a suitable protecting group and R is OH, CI or d-C4alkoxy, by amide bond formation with an amine of formula NHR2R3 as previously described for compounds of formula D, followed by removal of the protecting group P under standard conditions. Compounds of formula H, wherein R is OH or d-C alkoxy, may be made by the protection of the amine functionality in compounds of formula E, wherein R is OH or d-C4alkoxy. Suitable protecting groups include carbamates (such as t-butyloxycarbonyl, allyloxycarbonyl and benzyloxycarbonyl), trialkylsilyl groups (such as t-butydimethylsilyl) and acyl groups (such as acetyl). The formation and removal of such groups is widely reported in the literature and is well known to a person skilled in the art.
For compounds of formula H and compounds of formula E, the esters (wherein R is d- C4alkoxy) may be hydrolysed to the acids (wherein R is OH) by treatment with an alkali such as sodium hydroxide in a solvent such as ethanol. The acids (wherein R is OH) may be converted to the acid chlorides (wherein R is CI) by treatment with thionyl chloride or oxalyl chloride as previously described for compounds of formula D.
Alternatively, it may be possible to convert compounds of formula E, wherein R is OH, CI or C C alkoxy, directly to compounds of formula G by amide bond formation with an amine of formula NHR3R4 under standard conditions (as previously described for compounds of formula D).
Alternatively, compounds of formula G, wherein Z2 is oxygen, may be made from compounds of formula JK, wherein Z2 is oxygen and LG is a leaving group such as fluoro, chloro or sulfonate, by displacement of the leaving group with a compound of formula R2NH2. Such reactions are usually performed under basic conditions. Such compounds of formula JK may be made from compounds of formula J, wherein R is CI or OH and LG is a leaving group as previously described, via amide bond formation under standard conditions as previously described. Such compounds of formula J and formula E are either known compounds or may be made by known methods by someone skilled in the art.
Compounds of formula A, wherein Z is oxygen and Z2 is sulfur, may be made by treatment of compounds of formula JK, wherein Z2 is oxygen and LG is a leaving group, or compounds of formula G, wherein Z22 is oxygen, with a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide prior to elaborating to compounds of formula A, wherein Z is oxygen and Z2 is sulfur, as previously described for compounds of formula A, wherein Z1 is oxygen and Z2 is oxygen).
Figure imgf000030_0001
K
Compounds of formula C are either known or may be made by methods known to a person skilled in the art. For instance, amino acids of formula C may be formed by hydrolysis of isatoic anhydrides of formula K. Alternatively, isatoic anhydrides of formula K may be reacted with amines of formula NHR3R to give compounds of formula G, wherein R-i is H, directly. Isatoic anhydrides of formula K are either known compounds or may be made by known methods obvious to those skilled in the art, for instance they made be derived from treatment of amino acids of formula C with phosgene or a synthetic equivalent of phosgene (for example carbonyl diimidazole).
Figure imgf000031_0001
M
Alternatively, compounds of formula C may be derived from the treatment of an isatin of formula L with hydrogen peroxide under basic conditions. Isatins of formula L are either known or may be made by methods known to persons skilled in the art, for example they may be derived from amino compounds of formula M, wherein R5 and R8 taken together form an additional bond between the carbon atoms bearing substituents R6 and R7, by treatment for example with oxalyl chloride (optionally in the presence of a Lewis acid catalyst) or chloral hydrate under various conditions. Amino compounds of formula M are either known compounds or may be made by known methods obvious to those skilled in the art.
Figure imgf000031_0002
Figure imgf000031_0003
Q
Alternatively, compounds of formula C, wherein R5 and R8 taken together form an additional bond between the carbon atoms bearing substituents R6 and R7, may be derived from the treatment of an isoxazole of formula N with aqueous base. Isoxazoles of formula N may be derived from nitroaldehydes of formula O by treatment with a reducing agent such as zinc in acetic acid. Nitroaldehydes of formula O are either known or may be made by methods known to persons skilled in the art, for instance they may be derived from nitro compounds of formula P by treatment with chloroform under basic conditions followed by treatment with strong aqueous acid. Alternatively, nitroaldehydes of formula O may be derived from oxidation of 1 -nitro-2-methyl aromatic compounds of formula Q. A particularly convenient method of achieving such an oxidation involves treating the compound Q with dimethylformamide dimethylacetal under basic conditions followed by treatment with sodium periodate. Compounds of formula P and Q are either known or may be made by methods known to those skilled in the art, for instance compounds of formula Q may be synthesised from compounds of formula R by nitration (e.g. with a mixture of nitric acid and sulphuric acid).
Figure imgf000032_0001
T
An alternative synthesis of compounds of formula G, wherein R2 is hydrogen, may be achieved by the reduction of nitro compounds of formula S. There are numerous methods for achieving such a transformation reported in the literature such as treatment with tin or iron under acidic conditions, or hydrogenation catalysed by a noble metal such as palladium on carbon. Compounds of formula S may be derived from compounds of formula T, wherein R is OH, CI, or d-C4alkoxy, via acylation with an amine of formula NHR3R4 under the standard conditions already described for a compound of formula D. Similarly conversion of esters of formula T, wherein R is d-C4alkoxy, to acids of formula T, wherein R is OH, to acid chlorides of formula T, wherein R is CI, is also described for compounds of formula D. Compounds of formula T are either known or may be made by methods known to persons skilled in the art.
It must be recognised that some reagents and reaction conditions may not be compatible with certain functionalities that may be present in the molecules described. In such cases it may be necessary to employ standard protection/deprotection protocols comprehensively reported in the literature and well known to a person skilled in the art.
Also in some cases it may be necessary to perform further routine synthetic steps not described herein to complete the synthesis of the desired compounds. An artisan will also recognise that it may be possible to achieve the synthesis of the desired compounds by performing some of the steps in these synthetic routes in a different order to that described.
A person skilled in the art will also recognise that it may be possible to perform standard functional group interconversions or substitution reactions on the compounds described herein to introduce or modify existing substituents.
The reactants can preferably be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between room temperature and approximately +80°C.
The compounds of formula B, D and of formula A, wherein Z2 is sulfur (compounds of formula AA) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, are novel and are also subjects of the invention. Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
Salts of compounds of formula I can be converted in the customary manner into the free compounds of formula I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
Depending on the procedure or the reaction conditions, the compounds of formula I, which have salt-forming properties can be obtained in free form or in the form of salts.
The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.
Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereose- lective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
The invention relates to all those embodiments of the process by which, starting from a compound obtainable at any level of the process as starting material or intermediate, all or some of the missing steps are carried out or a starting material is used in the form of a derivative and/or salt and/or racemates or antipodes thereof or, in particular, is formed under the reaction conditions.
Those starting materials and intermediates, in each case in free form or in salt form, which lead to the compounds of formula I or salts thereof which have been described at the outset as being particularly valuable are preferably used in the process of the present invention.
In particular, the invention relates to the preparation processes described in the Examples P1 to P11 .
Starting materials and intermediates, in each case in free form or salt form, which are used in accordance with the invention for the preparation of the compounds of formula I or salts thereof and which are novel, a process for their preparation, and their use as starting materials and intermediates for the preparation of the compounds of formula I are also a subject of the invention; in particular, this applies to the compounds of formula II, IV and V.
The compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.
Examples of the abovementioned animal pests are: from the order Acarina, for example,
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophi- lus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Derma- nyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Oly- gonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polypha- gotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; from the order Anoplura, for example,
Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp.,
Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp.,
Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order Diptera, for example,
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp.,
Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp.,
Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit,
Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp.,
Tabanus spp., Tannia spp. and Tipula spp.; from the order Heteroptera, for example,
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.; from the order Homoptera, for example,
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspi- diotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,
Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp.,
Myzus spp., Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Planococ- cus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica,
Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; from the order Hymenoptera, for example,
Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and
Vespa spp.; from the order Isoptera, for example,
Reticulitermes spp.; from the order Lepidoptera, for example,
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambi- guella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Gra- pholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Ly- onetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,
Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypi- ela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scir- pophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp.,
Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Mallophaga, for example,
Damalinea spp. and Trichodectes spp.; from the order Orthoptera, for example,
Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Psocoptera, for example,
Liposcelis spp.; from the order Siphonaptera, for example,
Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; from the order Thysanoptera, for example,
Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii, Taeniothrips spp., Thrips palmi and Thrips tabaci; and from the order Thysanura, for example,
Lepisma saccharina.
The active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on or- gans, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family, latex plants and ornamentals.
The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
The term "crops" is to be understood as including also crops that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (giutamine synthetase) inhibitors as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®. The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cryθc, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In the context of the present invention there are to be understood by δ-endotoxins, for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D-recognition sequence is inserted into a CrylllA toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® and Protecta®.
Further examples of such transgenic crops are:
1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylA(b) toxin.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bl) toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL 00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).
The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a. selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A- 0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
Other fields of application of the active ingredients according to the invention are the protection of stored products and stores and of material, such as wood, textiles, floor coverings or buildings, and, in the hygiene sector, particularly the protection of humans, domestic animals and productive livestock against pests of the abovementioned type.
The invention therefore also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances. ln these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C8 to C12 of alkylbenzenes, such as xylene mixtures, al- kylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.
Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
The cationic surfactants are, especially, quartemary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzy!bis(2-chloroethyl)ethyl- ammonium bromide.
Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.
As a rule, the compositions comprise from 0.0001 to 99.9999 %, in particular 0.1 to 95 %, of active ingredient, and 0.0001 to 99.9999 %, in particular 5 to 99.9 %, of - at least - one solid or liquid auxiliary, it being possible, as a rule, for 0 to 25 %, in particular 0.1 to 20 %, of the compositions to be surfactants (% in each case is per cent by weight). While concentrated compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions which have considerably lower concentrations of active ingredient.
The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally or acaricidally active ingredients. Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
Examples of especially suitable mixing partners include compounds selected from the following group M:
Group M: especially suitable mixing partners for the compounds of formula I: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a compound obtainable from the Bacillus thuringiensis strain GC91 or from strain NCTC11821 ; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau-fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cyhalothrin; alpha-cypermethrin; zeta- cypermethrin; deltamethrin; diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb; fenvalerate; formothion; methiocarb; heptenophos; imidacloprid; thiamethoxam; clothianidin; isoprocarb; methamidophos; methomyl; mevinphos; parathion; parathion- methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; acetamiprid; emamectin; emamectin-benzoate; spinosad; a plant extract that is active against insects; a preparation that comprises nematodes and is active against insects; a preparation obtainable from Bacillus subtilis; a preparation that comprises fungi and is active against insects; a preparation that comprises viruses and is active against insects; chlorfenapyr; acephate; acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541 ; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap; beta-cyfluthrin; BPMC; brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben; cadusafos; carbaryl; carbophenothion; chloethocarb; chlorethoxyfos; chlor- mephos; cis-resmethrin; clocythrin; clofentezine; cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoate; dimethylvinphos; dioxathion; edifenphos; esfenvalerate; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion; ivermectin; malathion; mecarbam; mesulfenphos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoate; oxamyl; oxydemethon M; oxydeprofos; permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M; pirimiphos E; promecarb; propaphos; prothiofos; prothoate; pyrachlophos; pyradaphenthion; pyresmethrin; pyrethrum; tebufenozide; salithion; sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; teme- phos; terbam; tetrachlorvinphos; thiacloprid; thiafenox; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarathene; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; Yl 5301/5302; zetamethrin; DPX-MP062 — indoxacarb; methoxyfenozide; bifenazate; XMC (3,5-xylyl methylcarbamate); or the fungus pathogen Metarhizium anisopliae.
The following mixtures of the compounds of formula I with one member of the group M are preferred ( in the following listing, "M" means one member selected from the group M. ) T1.1 + M; T38.3 + M; T37.3 + M; T20.1 + M; T1.3 + M; T1.121 + M; T2.1 + M; T2.3 + M; T6.1 + M; T6.3 + M; T7.1 + M; T7.3 + M; T21.3 + M; T22.3 + M; T46.1 + M; T46.3 + M; T50.1 + M; T50.3 + M; T51.1 + M; T51.3 + M; T52.1 + M; T52.3 + M; T53.1 + M; T53.3 + M; T72.1 + M; T72.3 + M; T72.207 + M; T72.273 + M; T73.1 + M; T73.3 + M; T73.207 + M; T73.273 + M; T74.1 + M; T74.3 + M; T75.1 + M; T75.3 + M; T76.1 + M; T76.3 + M; T77.1 + M; T77.3 + M; T78.1 + M; T78.3 + M; T79.1 + M; T80.3 + M; T81.1 + M; T81.3 + M; T82.1 + M; T83.3 + M; T84.3 + M and T85.3 + M; P2.001 + M; P2.002 + M; P2.003 + M; P2.004 + M;
P2.005 + M P2.006 + M P2.007 + M P2.008 + M P2.009 + M P2.010 + M P2.011 + M P2.012 + M P2.013 + M P2.014 + M P2.015 + M P2.016 + M P2.017 + M P2.018 + M P2.019 + M P2.020 + M P2.021 + M P2.022 + M P2.023 + M P2.024 + M P2.025 + M P2.026 + M P2.027 + M P2.028 + M P2.029 + M P2.030 + M P2.031 + M P2.032 + M P2.033 + M P2.034 + M P2.035 + M P2.036 + M P2.037 + M P2.038 + M P2.039 + M P2.040 + M P2.041 + M P2.042 + M P2.043 + M P2.044 + M P2.045 + M P2.046 + M P2.047 + M P2.048 + M P2.049 + M P2.050 + M P2.051 + M P2.052 + M P2.053 + M P2.054 + M P2.055 + M P2.056 + M P2.057 + M P2.058 + M P2.059 + M P2.060 + M P2.061 + M P2.062 + M P2.063 + M P2.064 + M P2.065 + M P2.066 + M P2.067 + M P2.068 + M P2.069 + M P2.070 + M P2.071 + M P2.072 + M P2.073 + M P2.074 + M P2.075 + M P2.076 + M P2.077 + M P2.078 + M P2.079 + M P2.080 + M P2.081 + M P2.082 + M P2.083 + M P2.084 + M P2.085 + M P2.086 + M P2.087 + M P2.088 + M P2.089 + M P2.090 + M P2.091 + M P2.092 + M P2.093 + M P2.094 + M P2.095 + M P2.096 + M P2.097 + M P2.098 + M P2.099 + M P2.100 + M P2.101 + M P2.102 + M P2.103 + M P2.104 + M P2.105 + M P2.106 + M P2.107 + M P2.108 + M P2.109 + M P2.110 + M P2.111 + M P2.112 + M P2.113 + M P2.114 + M P2.115 + M P2.116 + M P2.117 + M P2.118 + M P2.119 + M P2.120 + M P2.121 + M P2.122 + M P2.123 + M P2.124 + M P2.125 + M P2.126 + M P2.127 + M P2.128 + M P2.129 + M P2.130 + M P2.131 + M P2.132 + M P2.133 + M P2.134 + M P2.135 + M P2.136 + M P2.137 + M P2.138 + M P2.139 + M P2.140 + M P2.141 + M P2.142 + M P2.143 + M P2.144 + M P2.145 + M P2.146 + M P2.147 + M P2.148 + M P2.149 + M P2.150 + M P2.151 + M P2.152 + M P2.153 + M P2.154 + M P2.155 + M P2.156 + M P2.157 + M P2.158 + M P2.159 + M P2.160 + M P2.161 + M P2.162 + M P2.163 + M P2.164 + M and P2.165 + M.
The compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds of formula I for the preparation of these compositions are also a subject of the invention.
The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
The compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing. Alternatively, the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
The examples which follow are intended to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius. The abbreviation "M. P." means "melting point" .
Preparation Examples
Example P1
Figure imgf000050_0001
1.9 g (14.7 mmol) of N-chlorosuccinimide and 10 mg of 2,2'-azoisobutyric nitrile are added to a suspension of 2.5 g (13.3 mmol) of 2-amino-3-carboxy-naphthaIene in 100 ml of tetrachloromethane. The reaction mixture is stirred for 18 hours at room temperature, treated with 250 ml of aqueous sodium chloride solution and extracted with ethyl acetate (3 x 250 ml)-. The combined organic layers are dried over magnesium sulfate and filtered, and the filtrate is concentrated in vacuo. This gives the title compound in the form of a brown solid [1H-NMR (CDCI3): 8.53 (s, 1 H), 7.98 (d, 1 H), 7.73 (d, 1 H), 7.55 (t, 1 H), 7.25 (t, 1 H)].
Example P2
Figure imgf000050_0002
In a nitrogen atmosphere 0.5 ml (5.75 mmol) of oxalyl chloride are added dropwise at room temperature with stirring to a suspension of 295 mg (1.0 mmol) of 5-carboxy-1 -(3- chIoropyrid-2-yl)-3-trifluoromethyl-pyrazole in 2 ml of dichloromethane. The reaction mixture is stirred for 1 hour and then added dropwise to a solution of 0.25 g (1 mmol) of the title compound of Example P1 in a mixture of 20 ml of dichloromethane and 0.38 ml of triethylamine. The reaction mixture is subsequently stirred for 3 hours. Further 0.7 ml of triethylamine are added, followed by the addition of a single portion of 0.22 ml (2.8 mmol) of methane sulfonic acid chloride. The reaction mixture is then stirred for 18 hours and concentrated in vacuo, and the residue is purified by column chromatography [silica gel; hexane/ethyl acetate (3:1)], which gives the title compound [1H-NMR (CDCI3): 8.78 (s, 1 H), 8.61 (m, 1 H), 8.30 (m, 2H), 8.03 (dd, 1 H), 7.78 (m, 1 H), 7.67 (m, 1 H), 7.56 (m, 2H); MS (electrospray): 477, 479, 481 ((M+H)+)].
Example P3
Figure imgf000051_0001
In a nitrogen atmosphere 1 ml of a solution (2.0 M) of methylamine in anhydrous tetrahydrofuran is added with stirring to a solution of 0.07 g (0.15 mmol) of the title compound of Example P2 in 5 ml of anhydrous tetrahydrofuran. The reaction mixture is heated to 50° for 1 hour, allowed to cool to room temperature and concentrated in vacuo, and the residue is purified by column chromatography [silica gel; hexane, followed by hexane/ethyl acetate (3:1)], which gives the title compound T1.1 [1H-NMR (DMSO-d6): 10.80 (s, 1 H), 8.53 (d, 1 H), 8.45 (br s, 1 H), 8.21 (m, 2H), 8.08 (m, 2H), 7.87 (s, 1 H), 7.78 (t, 1 H), 7.70 (t, 1 H), 7.64 (dd, 1 H), 2.70 (d, 3H); MS (electrospray): 508, 510, 512 ((M+H)+)].
Example P4
Figure imgf000051_0002
0.91 ml (8.46 mmol) of methyl acetoacetate and 1.98 ml (16.9 mmol) of tin tetrachloride are added to a solution of 1 g (8.46 mmol) of 1 -amino-2-cyano-benzene in 20 ml of toluene. The reaction mixture is heated to reflux for 2 hours, allowed to cool to room temperature and concentrated in vacuo. The residue is suspended in 250 ml of aqueous sodium carbonate solution, and the suspension is stirred for 30 minutes, allowed to stand overnight and then extracted with ethyl acetate (3 x 250 ml). The combined organic layers are dried over magnesium sulfate and filtered, the filtrate is concentrated in vacuo, and the yellow solid residue is triturated with diethyl ether. This gives the title compound in the form of a yellow powder [1H-NMR (CDCI3): 7.88 (d, 1 H), 7.77 (d, 1 H), 7.68 (m, 1 H), 7.43 (m, 1 H), 7.06 (br s, 2H), 3.96 (s, 3H). 2.82 (s, 3H); MS (electrospray): 217 ((M+H)+)].
Example P5
Figure imgf000052_0001
In a nitrogen atmosphere 4 drops of N,N-dimethyIformamide and then 0.08 ml (0.93 mmol) of oxalyl chloride are added dropwise at room temperature with stirring to a suspension of 250 mg (0.86 mmol) of 5-carboxy-1-(3-chloropyrid-2-yl)-3-trifluoromethyl-pyrazole in 10 ml of dichloromethane. The reaction mixture is stirred for 1 hour, the solvent is removed in vacuo, and the residue is co-evaporated three times with toluene and then suspended in 3 ml of toluene to give the suspension "A". 105 mg (0.858 mmol) of 4-dimethylaminopyridine are added to a suspension of 185 mg (0.858 mmol) of the title compound of Example P4 in 3 ml of toluene to give the suspension "B". The suspension "A" is added to the suspension "B", for a complete transfer of the suspension "A" into the reaction flask the vessel containing the suspension "A" being rinsed out with a small amount of a mixture of toluene and a few drops of N,N-dimethylformamide. The reaction mixture is heated to reflux for 3 hours and then allowed to cool to room temperature. The yellow precipitate is filtered off and washed with diethyl ether. The filtrate is washed with 10 ml of water, and the water is back-extracted with ethyl acetate (2 x 50 ml). The combined organic layers are dried over magnesium sulfate and filtered, the filtrate is concentrated in vacuo, and the residue is purified by column chromatography [silica gel; hexane/ethyl acetate (1 :2)], which gives the title compound [1H- NMR (CDCI3): 8.66 (d, 1 H), 8.09 (d, 1 H), 8.03 (d, 1 H), 7.86 (t, 1 H), 7.67 (s, 1 H), 7.67 (d, 1 H), 7.45 (m, 1 H), 7.40 (dd, 1 H), 3.09 (s, 3H); MS (electrospray): 458 ((M+H)+)].
Example P6
Figure imgf000053_0001
0.022 ml (0.262 mmol) of isopropylamine are added with stirring to a suspension of 40 mg (0.087 mmol) of the title compound of Example P5 in 1 ml of anhydrous tetrahydrofuran. The reaction mixture is heated to 60° for 90 minutes, allowed to cool to room temperature and concentrated in vacuo, and the residue is purified by column chromatography [silica gel; methanol/dichloromethane (1 :9)], which gives the title compound T38.3 [1H-NMR (CDCI3): 11.17 (s, 1 H), 8.42 (d, 1 H), 8.09 (s, 1 H), 7.81 (d, 1 H), 7.71 (t, 1 H), 7.70 (d, 1 H), 7.60 (d, 1 H), 7.48 (t, 1 H), 7.36 (m, 1 H), 6.31 (d, 1 H), 4.23 (m, 1 H), 2.30 (s, 3H), 1.16 (d, 6H); MS (electrospray): 517 ((M+H)+)].
Example P7
Figure imgf000053_0002
Starting from 1 -amino-2-cyano-cyclopent-1 -ene, the title compound can be prepared in a manner analogous to the procedure described in Example P4 [ H-NMR (CDCI3): 5.77 (br s, 2H), 3.90 (s, 3H), 2.97 (m, 2H), 2.70 (m, 2H), 2.15 (m, 2H); MS (electrospray): 207 ((M+H)+)].
Example P8
Figure imgf000054_0001
ln a nitrogen atmosphere 4 drops of N,N-dimethylformamide and then 0.16 ml (1.86 mmol) of oxalyl chloride are added dropwise at room temperature with stirring to a suspension of 0.5 g (1.72 mmol) of 5-carboxy-1-(3-chloropyrid-2-yl)-3-trifluoromethyl-pyrazole in 20 ml of dichloromethane. The reaction mixture is stirred for 90 minutes, the solvent is removed in vacuo, and the residue is co-evaporated three times with toluene and then dissolved in 10 ml of tetrahydrofuran to give the solution "A". 0.24 ml (1.72 mmol) of triethylamine are added to a suspension of 195 mg (0.95 mmol) of the title compound of Example P7 in 10 ml of tetrahydrofuran to give the suspension "B". 5 ml of the solution "A" are added in portions over a period of 30 minutes to the suspension "B". The reaction mixture is stirred for 2.5 hours, treated with 10 ml of aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate (2 x 40 ml). The combined organic layers are dried over magnesium sulfate and filtered, the filtrate is concentrated in vacuo, and the residue is purified by column chromatography (silica gel; ethyl acetate), which gives the title compound [1H-NMR (CDCI3): 10.15 (s, 1 H), 8.49 (d, 1 H), 7.92 (d, 1 H), 7.45 (m, 1 H), 7.22 (s, 1 H), 3.96 (s, 3H), 2.99 (m, 2H), 2.75 (m, 2H), 2.67 (s, 3H), 2.06 (m, 2H); MS (electrospray): 480 ((M+H)+)].
Example P9
Figure imgf000054_0002
0.04 ml (0.47 mmol) of isopropylamine are added at room temperature with stirring to a mixture of 0.24 ml of a solution (2.0 M) of trimethylaluminium in hexane and 3 ml of dichloromethane. The reaction mixture is stirred for 40 minutes. A solution of 110 mg (0.22 mmol) of the title compound of Example P8 in 3 ml of dichloromethane is added, and the reaction mixture is heated to reflux for 6 hours, allowed to cool to room temperature and to stand overnight and then poured into 20 ml of water. The mixture is extracted with dichloromethane (2 x 30 ml). The combined organic layers are dried over magnesium sulfate and filtered, the filtrate is concentrated in vacuo, and the residue is purified by column chromatography [silica gel; ethyl acetate/hexane (2:1), followed by neat ethyl acetate], which gives the title compound T37.3 [ H-NMR (CDCI3): 10.69 (s, 1 H), 8.49 (d, 1 H), 7.88 (d, 1 H), 7.70 (s, 1 H), 7.42 (m, 1 H), 5.89 (d, 1H), 4.24 (m, 1H), 2.87 (t, 2H), 2.57 (t, 2H), 2.49 (s, 3H), 2.02 (m, 2H), 1.19 (d, 6H); MS (electrospray): 507 ((M+H)+)].
Example P10
The compounds listed in the Table P1 and P2 can be prepared in a manner analogous to the procedures described in the Examples P1 to P9. Melting points are given in °C. In the following structures, tertiary hydrogen atoms attached to carbon atoms are not drawn, e.g. the group
Figure imgf000055_0001
Table P1 :
Figure imgf000055_0002
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Table P2:
Figure imgf000073_0002
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Example P11
The other compounds listed in the Tables 1 to 85 can also be prepared in a manner analogous to the procedures described in the Examples P1 to P10.
The Table A discloses 338 meanings of the variables Z17 Z2, Ri, R2, R3 and R4 in a compound of the formula I.
Table A
Figure imgf000126_0001
Figure imgf000126_0002
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000129_0002
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000143_0002
Figure imgf000144_0001
Figure imgf000144_0002
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000147_0001
Figure imgf000147_0002
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0001
Figure imgf000158_0001
Figure imgf000158_0002
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000163_0003
Table 1 : This table discloses the 338 compounds T1.1 to T1.338 of the formula
Figure imgf000163_0001
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
For example, the specific compound T1.23 is the compound of the formula T1 , in which each of the variables Z^ Z2, Ri, Ra, R3 and R4 has the specific meaning given in the line A.23 of the Table A. According to the same system, also all of the other 337 specific compounds disclosed in the Table 1 as well as all of the specific compounds disclosed in the Tables 2 to 85 are specified analogously.
Table 2: This table discloses the 338 compounds T2.1 to T2.338 of the formula
Figure imgf000163_0002
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 3: This table discloses the 338 compounds T3.1 to T3.338 of the formula
Figure imgf000164_0001
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 4: This table discloses the 338 compounds T4.1 to T4.338 of the formula
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R-i, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 5: This table discloses the 338 compounds T5.1 to T5.338 of the formula
Figure imgf000164_0003
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A. Table 6: This table discloses the 338 compounds T6.1 to T6.338 of the formula
Figure imgf000165_0001
(T6), in which, for each of these 338 specific compounds, each of the variables Z Z2, R1 f R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 7: This table discloses the 338 compounds T7.1 to T7.338 of the formula
Figure imgf000165_0002
(T7), in which, for each of these 338 specific compounds, each of the variables Z , Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 8: This table discloses the 338 compounds T8.1 to T8.338 of the formula
Figure imgf000165_0003
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 9: This table discloses the 338 compounds T9.1 to T9.338 of the formula
Figure imgf000166_0001
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R1 ; R2) R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 10: This table discloses the 338 compounds T10.1 to T10.338 of the formula
Figure imgf000166_0002
in which, for each of these 338 specific compounds, each of the variables Z1 t Z2, R^ R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 11 : This table discloses the 338 compounds T11.1 to T11.338 of the formula
Figure imgf000166_0003
in which, for each of these 338 specific compounds, each of the variables Z-,, Z2, R1 ? R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 12: This table discloses the 338 compounds T12.1 to T12.338 of the formula
Figure imgf000167_0001
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 13: This table discloses the 338 compounds T13.1 to T13.338 of the formula
Figure imgf000167_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 14: This table discloses the 338 compounds T14.1 to T14.338 of the formula
Figure imgf000167_0003
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, R-i, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 15: This table discloses the 338 compounds T15.1 to T15.338 of the formula
Figure imgf000168_0001
in which, for each of these 338 specific compounds, each of the variables Z1; Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 16: This table discloses the 338 compounds T16.1 to T16.338 of the formula
Figure imgf000168_0002
in which, for each of these 338 specific compounds, each of the variables Z^ Z2, R1 ( R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 17: This table discloses the 338 compounds T17.1 to T17.338 of the formula
Figure imgf000168_0003
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 18: This table discloses the 338 compounds T18.1 to T18.338 of the formula
Figure imgf000169_0001
in which, for each of these 338 specific compounds, each of the variables Z ; Z2, R^ R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 19: This table discloses the 338 compounds T19.1 to T19.338 of the formula
Figure imgf000169_0002
(T19), in which, for each of these 338 specific compounds, each of the variables Zi, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 20: This table discloses the 338 compounds T20.1 to T20.338 of the formula
Figure imgf000169_0003
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, R-i, R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 21 : This table discloses the 338 compounds T21.1 to T21.338 of the formula
Figure imgf000170_0001
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 22: This table discloses the 338 compounds T22.1 to T22.338 of the formula
Figure imgf000170_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 23: This table discloses the 338 compounds T23.1 to T23.338 of the formula
Figure imgf000170_0003
in which, for each of these 338 specific compounds, each of the variables Z^, Z2, R1 ? R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 24: This table discloses the 338 compounds T24.1 to T24.338 of the formula
Figure imgf000171_0001
in which, for each of these 338 specific compounds, each of the variables Z , Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 25: This table discloses the 338 compounds T25.1 to T25.338 of the formula
Figure imgf000171_0002
in which, for each of these 338 specific compounds, each of the variables Z Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 26: This table discloses the 338 compounds T26.1 to T26.338 of the formula
Figure imgf000171_0003
(T26), in which, for each of these 338 specific compounds, each of the variables Z-,, Z2, R1 f R2) R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 27: This table discloses the 338 compounds T27.1 to T27.338 of the formula
Figure imgf000172_0001
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 28: This table discloses the 338 compounds T28.1 to T28.338 of the formula
Figure imgf000172_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, R-i, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 29: This table discloses the 338 compounds T29.1 to T29.338 of the formula
Figure imgf000172_0003
(T29), in which, for each of these 338 specific compounds, each of the variables Z Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 30: This table discloses the 338 compounds T30.1 to T30.338 of the formula
Figure imgf000173_0001
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 31 : This table discloses the 338 compounds T31.1 to T31.338 of the formula
Figure imgf000173_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 32: This table discloses the 338 compounds T32.1 to T32.338 of the formula
Figure imgf000173_0003
in which, for each of these 338 specific compounds, each of the variables Z-,, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 33: This table discloses the 338 compounds T33.1 to T33.338 of the formula
Figure imgf000174_0001
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 34: This table discloses the 338 compounds T34.1 to T34.338 of the formula
Figure imgf000174_0002
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 35: This table discloses the 338 compounds T35.1 to T35.338 of the formula
Figure imgf000174_0003
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R-i, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 36: This table discloses the 338 compounds T36.1 to T36.338 of the formula
Figure imgf000175_0001
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, Ri, R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 37: This table discloses the 338 compounds T37.1 to T37.338 of the formula
Figure imgf000175_0002
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R , R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 38: This table discloses the 338 compounds T38.1 to T38.338 of the formula
Figure imgf000175_0003
in which, for each of these 338 specific compounds, each of the variables Z Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 39: This table discloses the 338 compounds T39.1 to T39.338 of the formula
Figure imgf000176_0001
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z , Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 40: This table discloses the 338 compounds T40.1 to T40.338 of the formula
Figure imgf000176_0002
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 41 : This table discloses the 338 compounds T41.1 to T41.338 of the formula
Figure imgf000176_0003
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R1 f R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 42: This table discloses the 338 compounds T42.1 to T42.338 of the formula
Figure imgf000177_0001
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 43: This table discloses the 338 compounds T43.1 to T43.338 of the formula
Figure imgf000177_0002
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, Ri, R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 44: This table discloses the 338 compounds T44.1 to T44.338 of the formula
Figure imgf000177_0003
in which, for each of these 338 specific compounds, each of the variables Z-\, Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 45: This table discloses the 338 compounds T45.1 to T45.338 of the formula
Figure imgf000178_0001
in which, for each of these 338 specific compounds, each of the variables Z1 ( Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 46: This table discloses the 338 compounds T46.1 to T46.338 of the formula Z. Rι
R/ ^R "4 "3 (T46), in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R1 ( R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 47: This table discloses the 338 compounds T47.1 to T47.338 of the formula
Figure imgf000178_0002
in which, for each of these 338 specific compounds, each of the variables Z^, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 48: This table discloses the 338 compounds T48.1 to T48.338 of the formula
Figure imgf000179_0001
in which, for each of these 338 specific compounds, each of the variables Z^ Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 49: This table discloses the 338 compounds T49.1 to T49.338 of the formula
Figure imgf000179_0002
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 50: This table discloses the 338 compounds T50.1 to T50.338 of the formula
Figure imgf000179_0003
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R1 ; R2) R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 51 : This table discloses the 338 compounds T51.1 to T51.338 of the formula
Figure imgf000180_0001
in which, for each of these 338 specific compounds, each of the variables Z Z2, R1 ( R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 52: This table discloses the 338 compounds T52.1 to T52.338 of the formula
Figure imgf000180_0002
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 53: This table discloses the 338 compounds T53.1 to T53.338 of the formula
Figure imgf000180_0003
in which, for each of these 338 specific compounds, each of the variables Z-\, Z2, R1 } R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 54: This table discloses the 338 compounds T54.1 to T54.338 of the formula
Figure imgf000181_0001
in which, for each of these 338 specific compounds, each of the variables Z< , Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 55: This table discloses the 338 compounds T55.1 to T55.338 of the formula
Figure imgf000181_0002
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, R1 ; R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 56: This table discloses the 338 compounds T56.1 to T56.338 of the formula
Figure imgf000181_0003
in which, for each of these 338 specific compounds, each of the variables Zλ, Z2) R1 ; R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 57: This table discloses the 338 compounds T57.1 to T57.338 of the formula
Figure imgf000182_0001
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 58: This table discloses the 338 compounds T58.1 to T58.338 of the formula
Figure imgf000182_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 59: This table discloses the 338 compounds T59.1 to T59.338 of the formula
Figure imgf000182_0003
in which, for each of these 338 specific compounds, each of the variables Z , Z , Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 60: This table discloses the 338 compounds T60.1 to T60.338 of the formula
Figure imgf000183_0001
in which, for each of these 338 specific compounds, each of the variables Z Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 61 : This table discloses the 338 compounds T61.1 to T61.338 of the formula
Figure imgf000183_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, Ri, Ra, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 62: This table discloses the 338 compounds T62.1 to T62.338 of the formula
Figure imgf000183_0003
in which, for each of these 338 specific compounds, each of the variables Z , Z2) Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 63: This table discloses the 338 compounds T63.1 to T63.338 of the formula
Figure imgf000184_0001
in which, for each of these 338 specific compounds, each of the variables Z Z2, R-i, R2) R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 64: This table discloses the 338 compounds T64.1 to T64.338 of the formula
Figure imgf000184_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 65: This table discloses the 338 compounds T65.1 to T65.338 of the formula
Figure imgf000184_0003
in which, for each of these 338 specific compounds, each of the variables Z-\, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 66: This table discloses the 338 compounds T66.1 to T66.338 of the formula
Figure imgf000185_0001
in which, for each of these 338 specific compounds, each of the variables Z ( Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 67: This table discloses the 338 compounds T67.1 to T67.338 of the formula
Figure imgf000185_0002
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 68: This table discloses the 338 compounds T68.1 to T68.338 of the formula
Figure imgf000185_0003
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 69: This table discloses the 338 compounds T69.1 to T69.338 of the formula
Figure imgf000186_0001
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, R-i, R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 70: This table discloses the 338 compounds T70.1 to T70.338 of the formula
Figure imgf000186_0002
in which, for each of these 338 specific compounds, each of the variables Z , Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 71 : This table discloses the 338 compounds T71.1 to T71.338 of the formula
Figure imgf000186_0003
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 72: This table discloses the 338 compounds T72.1 to T72.338 of the formula
Figure imgf000187_0001
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 73: This table discloses the 338 compounds T73.1 to T73.338 of the formula
Figure imgf000187_0002
in which, for each of these 338 specific compounds, each of the variables Z-i, Z2, R-,, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 74: This table discloses the 338 compounds T74.1 to T74.338 of the formula
Figure imgf000187_0003
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2) R1 } R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 75: This table discloses the 338 compounds T75.1 to T75.338 of the formula
Figure imgf000188_0001
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 76: This table discloses the 338 compounds T76.1 to T76.338 of the formula
Figure imgf000188_0002
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R1 ( R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 77: This table discloses the 338 compounds T77.1 to T77.338 of the formula
Figure imgf000188_0003
in which, for each of these 338 specific compounds, each of the variables Z1 ( Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 78: This table discloses the 338 compounds T78.1 to T78.338 of the formula
Figure imgf000189_0001
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, Ri, R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 79: This table discloses the 338 compounds T79.1 to T79.338 of the formula
Figure imgf000189_0002
in which, for each of these 338 specific compounds, each of the variables Z^ Z2, Ri, R2, R3 and R has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 80: This table discloses the 338 compounds T80.1 to T80.338 of the formula
Figure imgf000189_0003
(T80), in which, for each of these 338 specific compounds, each of the variables Z1 f Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 81 : This table discloses the 338 compounds T81.1 to T81.338 of the formula
Figure imgf000190_0001
in which, for each of these 338 specific compounds, each of the variables Z^ Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 82: This table discloses the 338 compounds T82.1 to T82.338 of the formula
Figure imgf000190_0002
in which, for each of these 338 specific compounds, each of the variables Zi, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 83: This table discloses the 338 compounds T83.1 to T83.338 of the formula
Figure imgf000190_0003
in which, for each of these 338 specific compounds, each of the variables Z , Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 84: This table discloses the 338 compounds T84.1 to T84.338 of the formula
Figure imgf000191_0001
in which, for each of these 338 specific compounds, each of the variables Z1 ( Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 85: This table discloses the 338 compounds T85.1 to T85.338 of the formula
Figure imgf000191_0002
in which, for each of these 338 specific compounds, each of the variables Z^ Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 86: This table discloses the 338 compounds T86.1 to T86.338 of the formula
Figure imgf000191_0003
in which, for each of these 338 specific compounds, each of the variables Z1 ( Z2, R , R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 87: This table discloses the 338 compounds T87.1 to T87.338 of the formula
Figure imgf000192_0001
(T87), in which, for each of these 338 specific compounds, each of the variables Z^, Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 88: This table discloses the 338 compounds T88.1 to T88.338 of the formula
Figure imgf000192_0002
in which, for each of these 338 specific compounds, each of the variables Z , Z2, Ri, R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 89: This table discloses the 338 compounds T89.1 to T89.338 of the formula
Figure imgf000192_0003
in which, for each of these 338 specific compounds, each of the variables Z1 ; Z2, R1 ; R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 90: This table discloses the 338 compounds T90.1 to T90.338 of the formula
Figure imgf000193_0001
in which, for each of these 338 specific compounds, each of the variables ZΛ, Z2, R R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Table 91 : This table discloses the 338 compounds T91.1 to T91.338 of the formula
Figure imgf000193_0002
in which, for each of these 338 specific compounds, each of the variables Z1 t Z2, R^ R2, R3 and R4 has the specific meaning given in the corresponding line, appropriately selected from the 338 lines A.1 to A.338, of the Table A.
Formulation Examples (% = per cent by weight)
Example F1 : Emulsion concentrates a) b) c)
Active ingredient 25 % 40 % 50 %
Calcium dodecylbenzenesulfonate 5 % 8 % 6 %
Castor oil polyethylene glycol ether (36 mol of EO) 5 % - -
Tributylphenoxypolyethylene glycol ether (30 mol of EO) - 12 % 4 %
Cyclohexanone - 15 % 20 %
Xylene mixture 65 % 25 % 20 %
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. Example F2: Solutions a) b) c) d)
Active ingredient 80 % 10 % 5 % 95 %
Ethylene glycol monomethyl ether 20 % -
Polyethylene glycol MW 400 - 70 % -
N-Methylpyrrolid-2-one - 20 %
Epoxidized coconut oil - - 1 % 5 %
Petroleum ether (boiling range: 160-190°) - - 94 %
The solutions are suitable for use in the form of microdrops.
Example F3: Granules a) b) c) d)
Active ingredient 5 % 10 % 8 % 21 %
Kaolin 94 % - 79 % 54 %
Highly disperse silica 1 % - 13 % 7 %
Attapulgite - 90 % - 18 %
The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.
Example F4: Dusts a) b)
Active ingredient 2 % 5 %
Highly disperse silica 1 % 5 %
Talc 97 % -
Kaolin - 90 %
Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.
Example F5: Wettable powders a) b) c)
Active ingredient 25 % 50 % 75 %
Sodium lignosulfonate 5 % 5 %
Sodium lauryl sulfate 3 % - 5 %
Sodium diisobutylnaphthalenesulf onate - 6 % 10 %
Octylphenoxypolyethylene glycol ether (7-8 mol of EO) - 2 % - Highly disperse silica 5 % 10 % 10 %
Kaolin 62 % 27 % -
The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.
Example F6: Extruder granules
Active ingredient 10 %
Sodium lignosulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 87 %
The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
Example F7: Coated granules
Active ingredient 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %
In a mixer, the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.
Example F8: Suspension concentrate
Active ingredient 40 %
Ethylene glycol 10 % Ό
Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
Sodium lignosulfonate 10 % o
Carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
Silicone oil (75 % aqueous emulsion) 0.8 %
Water 32 % The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.
Biological Examples (% = per cent by weight, unless otherwise specified)
Example B1 : Activity against Aphis craccivora
Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
In this test, compounds listed in the Tables 1 to 85 show good activity.
Example B2: Activity against Diabrotica balteata
Maize seedlings are sprayed with an aqueous emulsion spray, mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 larvae (2nd instar) of Diabrotica balteata and introduced into a plastic container. 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead larvae between the treated and untreated plants.
In this test, compounds listed in the Tables 1 to 85 show good activity. In particular, the compounds T1.1 , T1.3, T7.1 and T7.3 have an activity of over 80 %.
Example B3: Activity against Heliothis virescens (foliar application)
Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Heliothis virescens and introduced into a plastic container. 6 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
In this test, compounds listed in the Tables 1 to 85 show good activity. In particular, the compounds T1.1 , T1.3, T2.1 , T7.1 , T7.3, T75.1 , T75.3, T76.1 , T76.3, T79.1 , T81.1 , T2.2,
T8.1 , T5.1 , T5.3, T20.1 , T20.3, T9.1 , T9.3 and T9.2 have an activity of over 80 %.
Example B4: Activity against Heliothis virescens (application to eggs) Heliothis virescens eggs, which have been deposited on cotton, are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars (% activity) are evaluated in comparison with untreated control batches.
In this test, compounds listed in the Tables 1 to 85 show good activity. In particular, the compounds T1.1 , T1.3, T2.1 , T7.1 , T7.3, T75.1 , T75.3, T76.1 , T76.3, T79.1 ,T81.1 , T2.2, T8.1 , T5.1 , T5.3, T20.1 , T20.3, T9.1 , T9.3 and T9.2 have an activity of over 80 %.
Example B5: Activity against Myzus persicae (foliar application)
Pea seedlings are infected with Myzus persicae, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
In this test, compounds listed in the Tables 1 to 85 show good activity. In particular, the compounds T1.1 and T7.1 have an activity of over 80 %.
Example B6: Activity against Myzus persicae (systemic application)
Pea seedlings are infected with Myzus persicae, and their roots are subsequently placed into a spray mixture comprising 400 ppm of active ingredient. The seedlings are then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
In this test, compounds listed in the Tables 1 to 85 show good activity.
Example B7: Activity against Plutelia xylostella
Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising
400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (3rd instar) of Plutelia xylostella and introduced into a plastic container. 3 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
In this test, compounds listed in the Tables 1 to 85 show good activity. In particular, the compounds T1.1 , T1.3, T2.1 , T7.1 , T7.3, T22.3, T75.1 , T75.3, T76.1 , T76.3, T78.1 , T79.1 , T81.1 , T2.2, T8.1 , T5.1 , T5.3, T20.1 , T20.3, T9.1 , T9.3 and T9.2 have an activity of over 80
Example B8: Activity against Spodoptera littoralis
Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Spodoptera littoralis and introduced into a plastic container. 3 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
In this test, compounds listed in the Tables 1 to 85 show good activity. In particular, the compounds T1.1 , T1.3, T2.1 , T7.1 , T7.3, T75.1 , T75.3, T76.1 , T76.3, T2.2, T8.1 , T5.1 , T5.3,
T20.1 , T20.3, T9.1 , T9.3 and T9.2 have an activity of over 80 %.

Claims

What is claimed is:
1. A compound of the formula
Figure imgf000199_0001
in which Z is an oxygen atom; or a sulfur atom; Z2 is an oxygen atom; or a sulfur atom; R-i is an aryl or heteroaryl group, which is unsubstituted or substituted; R2 is hydrogen; or an organic substituent; R3 is hydrogen; or an organic substituent; R4 is hydrogen; or an organic substituent; or R3 and R , taken together, form, together with the nitrogen atom, to which they are attached, a ring, which is unsubstituted or substituted; R5 is hydrogen; or an unsubstituted or substituted alkyl group; or forms, taken together with R8 or with a monovalent substituent attached to that atom of R6, via which atom R6 is directly connected with the carbon atom, shown in the formula I, which carries R5, one additional bond; R6 and R7, taken together, form, together with the two carbon atoms, shown in the formula I, to which atoms they are attached, a bicyclic ring system, which ring system is carbocyclic or heterocyclic, which ring system is substituted, in the manner shown in the formula I, by the four substituents -N(R2)-C(=Z1)-R1, -C(=Z2)-N(R3)-R4) R5 and R8, and which ring system is optionally further substituted; and R8 is hydrogen; or an unsubstituted or substituted alkyl group; or forms, taken together with R5 or with a monovalent substituent attached to that atom of R7, via which atom R7 is directly connected with the carbon atom, shown in the formula I, which carries R8, one additional bond, or, where appropriate, a tautomer thereof, in each case in free form or in salt form.
2. A compound according to claim 1 of the formula I, in which Z1 is an oxygen atom, or, where appropriate, a tautomer thereof.
3. A compound according to claim 1 of the formula I, in which Z2 is an oxygen atom, or, where appropriate, a tautomer thereof.
4. A compound according to claim 1 of the formula I, in which Ri is a phenyl, pyridyi or pyrazolyl group, which is unsubstituted or substituted, or, where appropriate, a tautomer thereof.
5. A compound according to claim 4 of the formula I, in which R<ι is a pyrazol-5-yl group, which is substituted in the 3-position by halogen, halo-C Cealkyl or halo-C C6alkoxy and in the 1 -position by a pyrid-2-yl group, which group is substituted in the 3-position by chlorine or bromine, or, where appropriate, a tautomer thereof.
6. A compound according to claim 1 of the formula I, in which R2 is hydrogen or C Cealkyl, or, where appropriate, a tautomer thereof.
7. A compound according to claim 1 of the formula I, in which R3 is hydrogen or CrC6alkyl, or, where appropriate, a tautomer thereof.
8. A compound according to claim 1 of the formula I, in which R4 is CrC6alkyl, or, where appropriate, a tautomer thereof.
9. A compound according to claim 1 of the formula I, in which R5 and R8, taken together, are a bond, or, where appropriate, a tautomer thereof.
10. A compound according to claim 1 of the formula I, in which the two carbon atoms, shown in the formula I, to which atoms R6 and R7 are attached, are two ring members of an aromatic ring, or, where appropriate, a tautomer thereof.
11. A pesticidal composition, which comprises at least one compound according to claim 1 of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary.
1 . A composition according to claim 11 for controlling insects or representatives of the order Acarina.
13. A method for controlling pests, which comprises applying a composition according to claim 11 to the pests or their environment.
14. A method according to claim 13 for controlling insects or representatives of the order Acarina.
15. A method according to claim 13 for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted.
16. Plant propagation material treated in accordance with the method described in claim 15.
17. A compound of the formula B
Figure imgf000201_0001
in which R1 t R5, R6, R and R8 have the meanings given in claim 1 for the formula I, or, where appropriate, a tautomer thereof, in each case in free form or in salt form.
18. A compound of the formula D
Figure imgf000201_0002
in which Zi, R^ R2, R5, R6, R7 and R8 have the meanings given in claim 1 for the formula I; and R is OH, C C4alkoxy or Cl, or, where appropriate, a tautomer thereof, in each case in free form or in salt form.
19. A compound of the formula AA
in which R2, R3, R4, R5, R6, R and R8 have the meanings given in claim 1 for the formula I, or, where appropriate, a tautomer thereof, in each case in free form or in salt form.
PCT/EP2005/002204 2004-03-03 2005-03-02 Bycyclic anthranilamide derivatives useful as insecticides WO2005085234A2 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
DE602005023140T DE602005023140D1 (en) 2004-03-03 2005-03-02 BICYCLIC ANTHRANILAMIDE DERIVATIVES SUITABLE AS INSECTICIDES
CN2005800067570A CN1926129B (en) 2004-03-03 2005-03-02 Double amide insecticides
RU2006134629/04A RU2369603C2 (en) 2004-03-03 2005-03-02 New insecticides
NZ549166A NZ549166A (en) 2004-03-03 2005-03-02 Bicyclic anthranilamide derivatives useful as insecticides
JP2007501212A JP4865695B2 (en) 2004-03-03 2005-03-02 New insecticide
CA002556387A CA2556387A1 (en) 2004-03-03 2005-03-02 Bicyclic anthranilamide derivatives useful as insecticides
BRPI0508401-6A BRPI0508401A (en) 2004-03-03 2005-03-02 insecticides
AU2005219545A AU2005219545B2 (en) 2004-03-03 2005-03-02 Novel insecticides
EP05715671A EP1737844B1 (en) 2004-03-03 2005-03-02 Bicyclic anthranilamide derivatives useful as insecticides
US10/598,041 US7812170B2 (en) 2004-03-03 2005-03-02 Insecticides
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IL177345A IL177345A (en) 2004-03-03 2006-08-07 Bicyclic bisamide derivatives and pesticidal compositions comprising them
EGNA2006000810 EG25775A (en) 2004-03-03 2006-08-31 Novel insecticides
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Cited By (46)

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Publication number Priority date Publication date Assignee Title
WO2006063178A2 (en) * 2004-12-07 2006-06-15 Abbott Laboratories Thienopyridyl compounds that inhibit vanilloid receptor subtype 1 (vr1) and uses thereof
WO2006080311A1 (en) * 2005-01-25 2006-08-03 Ishihara Sangyo Kaisha, Ltd. Anthranilamide compound, method for producing same and pest control agent containing same
WO2006111341A1 (en) * 2005-04-20 2006-10-26 Syngenta Participations Ag Cyano anthranilamide insecticides
WO2007009661A2 (en) * 2005-07-15 2007-01-25 Syngenta Participations Ag Pesticidal mixtures containing bicyclic anthranilamides
WO2007020050A2 (en) * 2005-08-15 2007-02-22 Syngenta Participations Ag Bicyclic bisamide derivatives and use thereof as insecticides
WO2007093402A1 (en) * 2006-02-16 2007-08-23 Syngenta Participations Ag Pesticides containing a bicyclic bisamide structure
WO2007144100A1 (en) 2006-06-13 2007-12-21 Bayer Cropscience Ag Anthranilic acid diamide derivative with hetero-aromatic and hetero-cyclic substituents
EP1900730A1 (en) * 2006-09-11 2008-03-19 Syngeta Participations AG Process for the preparation of anthranilamide derivatives
WO2009010260A2 (en) 2007-07-16 2009-01-22 Syngenta Participations Ag Condensed anthranilamide insecticides
WO2009021717A2 (en) * 2007-08-14 2009-02-19 Syngenta Participations Ag Pesticidal formulation
WO2009024341A3 (en) * 2007-08-22 2009-08-13 Syngenta Participations Ag Condensed anthran i lami de derivatives as insectisides
US7867949B2 (en) 2005-10-14 2011-01-11 Sumitomo Chemical Company, Limited Hydrazide compound and pesticidal use of the same
WO2011095461A1 (en) 2010-02-04 2011-08-11 Syngenta Participations Ag Pyridazine derivatives, processes for their preparation and their use as fungicides
WO2011098408A2 (en) 2010-02-09 2011-08-18 Bayer Cropscience Ag Hydrazine-substituted anthranilic acid derivatives
WO2011104183A1 (en) 2010-02-24 2011-09-01 Syngenta Participations Ag Novel microbicides
WO2011128329A1 (en) 2010-04-16 2011-10-20 Bayer Cropscience Ag Triazole-substituted anthranilic acid amides as pesticides
WO2011157654A1 (en) 2010-06-15 2011-12-22 Bayer Cropscience Ag Anthranilic acid diamide derivatives
WO2011157653A1 (en) 2010-06-15 2011-12-22 Bayer Cropscience Ag Anthranilic acid derivatives
WO2011157663A1 (en) 2010-06-15 2011-12-22 Bayer Cropscience Ag Novel ortho-substituted aryl amide derivatives
WO2011157651A1 (en) 2010-06-15 2011-12-22 Bayer Cropscience Ag Anthranilic acid diamide derivatives with cyclical side chains
WO2012001040A1 (en) 2010-07-02 2012-01-05 Syngenta Participations Ag Novel microbiocidal dioxime ether derivatives
WO2012004208A1 (en) 2010-07-09 2012-01-12 Bayer Cropscience Ag Anthranilic acid diamide derivative as a pesticide
WO2012013754A1 (en) 2010-07-29 2012-02-02 Syngenta Participations Ag Novel microbiocidal dioxime ether derivatives
WO2012066122A1 (en) 2010-11-18 2012-05-24 Syngenta Participations Ag 2 - (pyridin- 2 -yl) -quinazoline derivatives and their use as microbicides
WO2012069652A2 (en) 2010-11-26 2012-05-31 Syngenta Participations Ag Fungicide mixtures
CN101184747B (en) * 2005-04-20 2012-08-08 先正达参股股份有限公司 Cyano anthranilamide insecticides
EP2484676A2 (en) 2008-12-18 2012-08-08 Bayer CropScience AG Tetrazol-substituted anthranilic acid amides as pesticides
WO2013011010A1 (en) 2011-07-19 2013-01-24 Syngenta Participations Ag Fungizide mixtures
WO2013024006A1 (en) 2011-08-12 2013-02-21 Basf Se Anthranilamide compounds and their use as pesticides
WO2013024005A1 (en) 2011-08-12 2013-02-21 Basf Se Anthranilamide compounds and their use as pesticides
WO2013026866A2 (en) 2011-08-23 2013-02-28 Syngenta Participations Ag Novel microbiocides
US8415333B2 (en) 2009-02-24 2013-04-09 Respiratorious Ab Bronchodilating diazaheteroaryls
US20130129677A1 (en) * 2009-02-27 2013-05-23 Siga Technologies, Inc. Thienopyridine Derivatives for the Treatment and Prevention of Dengue Virus Infections
EP2606732A1 (en) 2011-12-19 2013-06-26 Bayer CropScience AG Use of an anthranilic diamide derivatives with heteroaromatic and heterocyclic substituents in combination with a biological control agent
WO2013092519A1 (en) 2011-12-19 2013-06-27 Bayer Cropscience Ag Use of anthranilic acid diamide derivatives for pest control in transgenic crops
US9044016B2 (en) 2011-08-12 2015-06-02 Basf Se N-thio-anthranilamide compounds and their use as pesticides
US9056853B2 (en) 2005-07-07 2015-06-16 Basf Se N-Thio-anthranilamid compounds and their use as pesticides
US20150175624A1 (en) * 2006-10-16 2015-06-25 Thesan Pharmaceuticals, Inc. Therapeutic pyrazolyl thienopyridines
US9314022B2 (en) 2007-04-25 2016-04-19 Syngenta Crop Protection, Llc Fungicidal compositions
US9533968B2 (en) 2012-05-24 2017-01-03 Basf Se N-thio-anthranilamide compounds and their use as pesticides
US9609868B2 (en) 2013-03-06 2017-04-04 Bayer Cropscience Ag Alkoximino-substituted anthranilic acid diamides as pesticides
WO2019123195A1 (en) 2017-12-20 2019-06-27 Pi Industries Ltd. Pyrazolopyridine-diamides, their use as insecticide and processes for preparing the same.
WO2019123194A1 (en) 2017-12-20 2019-06-27 Pi Industries Ltd. Anthranilamides, their use as insecticide and processes for preparing the same.
WO2019150220A1 (en) 2018-01-30 2019-08-08 Pi Industries Ltd. Novel anthranilamides, their use as insecticide and processes for preparing the same.
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5887345B2 (en) 2010-08-27 2016-03-16 グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Substituted 2-amino-quinoline-3-carboxamides as KCNQ2 / 3 modulators
PL2609086T3 (en) 2010-08-27 2015-07-31 Gruenenthal Gmbh Substituted 2-oxo- and 2-thioxo-dihydroquinoline-3-carboxamides as kcnq2/3 modulators
RU2595894C2 (en) 2010-08-27 2016-08-27 Грюненталь Гмбх Substituted 2-oxy-quinoline-3-carboxamides as kcnq2/3 modulators
AR082813A1 (en) 2010-09-01 2013-01-09 Gruenenthal Gmbh 1-OXO-DIHYDROISOQUINOLIN-3-CARBOXAMIDS REPLACED AS MODULATORS OF KCNQ2 / 3
WO2014089378A1 (en) * 2012-12-07 2014-06-12 Siga Technologies, Inc. Thienopyridine derivatives for the treatment and prevention of dengue virus infections

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0353191A2 (en) 1988-07-29 1990-01-31 Ciba-Geigy Ag DNA sequences encoding polypeptides having beta-1,3-glucanase activity
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0392225A2 (en) 1989-03-24 1990-10-17 Ciba-Geigy Ag Disease-resistant transgenic plants
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995033818A2 (en) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes for the synthesis of antipathogenic substances
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003000906A2 (en) 2001-06-22 2003-01-03 Syngenta Participations Ag Plant disease resistance genes
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL9202078A (en) * 1992-11-30 1994-06-16 Rijkslandbouwhogeschool Novel N-acyl-anthranilic acid compounds, and use of N- acyl-anthranilic acid compounds in insect control
GB9424379D0 (en) * 1994-12-02 1995-01-18 Agrevo Uk Ltd Fungicides
GB9717576D0 (en) 1997-08-19 1997-10-22 Xenova Ltd Pharmaceutical compounds
AU3665199A (en) * 1998-04-29 1999-11-16 Vertex Pharmaceuticals Incorporated Inhibitors of impdh enzyme
MY138097A (en) * 2000-03-22 2009-04-30 Du Pont Insecticidal anthranilamides
CA2437840A1 (en) * 2001-03-05 2002-09-12 E.I. Du Pont De Nemours Heterocyclic diamide invertebrate pest control agents
AR035884A1 (en) * 2001-05-18 2004-07-21 Nihon Nohyaku Co Ltd DERIVED FROM AROMATIC AMIDA REPLACED, DERIVED FROM AROMATIC AMINA REPLACED WITH A USEFUL FLUOROALKYL GROUP AS AN INTERMEDIARY TO OBTAIN THE SAME, INSECTICIATED FOR AGROHORTICULTURE THAT CONTAINS AND METHOD TO USE THIS LAST
AU2002305669B2 (en) * 2001-05-21 2008-09-11 E.I. Du Pont De Nemours And Company Diamide invertebrate pest control agents containing a non-aromatic heterocyclic ring
JP2004051614A (en) * 2001-08-01 2004-02-19 Nissan Chem Ind Ltd Substituted amide compound and vermin-controlling agent
TWI325302B (en) 2001-08-13 2010-06-01 Du Pont Benzoxazinone compounds
AR036872A1 (en) 2001-08-13 2004-10-13 Du Pont ANTRANILAMIDE COMPOSITE, COMPOSITION THAT INCLUDES IT AND METHOD FOR CONTROLLING AN INVERTEBRATE PEST
TWI327566B (en) * 2001-08-13 2010-07-21 Du Pont Novel substituted ihydro 3-halo-1h-pyrazole-5-carboxylates,their preparation and use
CN100453532C (en) 2001-08-16 2009-01-21 纳幕尔杜邦公司 Substituted anthranilamides for controlling invertebrate pests
TWI283164B (en) * 2001-09-21 2007-07-01 Du Pont Anthranilamide arthropodicide treatment
JP2003212834A (en) * 2002-01-24 2003-07-30 Nissan Chem Ind Ltd Acylanthranylic acid amide compound and pest controlling agent
EP1546089A2 (en) * 2002-08-09 2005-06-29 TransTech Pharma Inc. Aryl and heteroaryl compounds and methods to modulate coagulation
WO2004099127A1 (en) 2003-05-07 2004-11-18 Novo Nordisk A/S Novel compounds as kinase inhibitors
JP4543043B2 (en) * 2003-06-12 2010-09-15 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Process for producing condensed oxazinone

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0353191A2 (en) 1988-07-29 1990-01-31 Ciba-Geigy Ag DNA sequences encoding polypeptides having beta-1,3-glucanase activity
EP0367474A1 (en) 1988-11-01 1990-05-09 Mycogen Corporation Novel bacillus thuringiensis isolate denoted b.t. ps81gg, active against lepidopteran pests, and a gene encoding a lepidopteran-active toxin
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0392225A2 (en) 1989-03-24 1990-10-17 Ciba-Geigy Ag Disease-resistant transgenic plants
WO1990013651A1 (en) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Bacterial genes
EP0401979A2 (en) 1989-05-18 1990-12-12 Mycogen Corporation Novel bacillus thuringiensis isolates active against lepidopteran pests, and genes encoding novel lepidopteran-active toxins
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995033818A2 (en) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes for the synthesis of antipathogenic substances
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO2002015701A2 (en) 2000-08-25 2002-02-28 Syngenta Participations Ag Bacillus thuringiensis crystal protein hybrids
WO2003000906A2 (en) 2001-06-22 2003-01-03 Syngenta Participations Ag Plant disease resistance genes
WO2003018810A2 (en) 2001-08-31 2003-03-06 Syngenta Participations Ag Modified cry3a toxins and nucleic acid sequences coding therefor
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event

Cited By (89)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7875627B2 (en) 2004-12-07 2011-01-25 Abbott Laboratories Thienopyridyl compounds that inhibit vanilloid receptor subtype 1 (VR1) and uses thereof
WO2006063178A3 (en) * 2004-12-07 2006-08-24 Abbott Lab Thienopyridyl compounds that inhibit vanilloid receptor subtype 1 (vr1) and uses thereof
WO2006063178A2 (en) * 2004-12-07 2006-06-15 Abbott Laboratories Thienopyridyl compounds that inhibit vanilloid receptor subtype 1 (vr1) and uses thereof
US8501769B2 (en) 2004-12-07 2013-08-06 Abbvie Inc. Thienopyridyl compounds that inhibit vanilloid receptor subtype 1 (VR1) and uses thereof
WO2006080311A1 (en) * 2005-01-25 2006-08-03 Ishihara Sangyo Kaisha, Ltd. Anthranilamide compound, method for producing same and pest control agent containing same
WO2006111341A1 (en) * 2005-04-20 2006-10-26 Syngenta Participations Ag Cyano anthranilamide insecticides
CN101184747B (en) * 2005-04-20 2012-08-08 先正达参股股份有限公司 Cyano anthranilamide insecticides
JP2008536885A (en) * 2005-04-20 2008-09-11 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Cyanoanthranilamide insecticide
US7601743B2 (en) 2005-04-20 2009-10-13 Syngenta Crop Protection, Inc. Cyano anthranilamide insecticides
US9056853B2 (en) 2005-07-07 2015-06-16 Basf Se N-Thio-anthranilamid compounds and their use as pesticides
US9365543B2 (en) 2005-07-07 2016-06-14 Basf Se N-Thio-anthranilamid compounds and their use as pesticides
WO2007009661A3 (en) * 2005-07-15 2007-03-29 Syngenta Participations Ag Pesticidal mixtures containing bicyclic anthranilamides
WO2007009661A2 (en) * 2005-07-15 2007-01-25 Syngenta Participations Ag Pesticidal mixtures containing bicyclic anthranilamides
WO2007020050A3 (en) * 2005-08-15 2007-04-19 Syngenta Participations Ag Bicyclic bisamide derivatives and use thereof as insecticides
JP2009507779A (en) * 2005-08-15 2009-02-26 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト New insecticide
WO2007020050A2 (en) * 2005-08-15 2007-02-22 Syngenta Participations Ag Bicyclic bisamide derivatives and use thereof as insecticides
US8580785B2 (en) 2005-08-15 2013-11-12 Syngenta Crop Protection Llc Insecticides
US7968573B2 (en) 2005-10-14 2011-06-28 Sumitomo Chemical Company, Limited Hydrazide compound and pesticidal use of the same
US7867949B2 (en) 2005-10-14 2011-01-11 Sumitomo Chemical Company, Limited Hydrazide compound and pesticidal use of the same
CN101426779B (en) * 2006-02-16 2013-08-21 先正达参股股份有限公司 Pesticides containing a bicyclic bisamide structure
JP2009526798A (en) * 2006-02-16 2009-07-23 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Insecticides containing a bicyclic bisamide structure
AU2007214661B2 (en) * 2006-02-16 2012-05-17 Syngenta Limited Pesticides containing a bicyclic bisamide structure
US8658801B2 (en) 2006-02-16 2014-02-25 Syngenta Crop Protection, Llc Pesticides containing a bicyclic bisamide structure
WO2007093402A1 (en) * 2006-02-16 2007-08-23 Syngenta Participations Ag Pesticides containing a bicyclic bisamide structure
JP2009539902A (en) * 2006-06-13 2009-11-19 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト Anthranilic acid diamide derivatives with heteroaromatic and heterocyclic substituents
US8536092B2 (en) 2006-06-13 2013-09-17 Bayer Cropscience Ag Anthranilic acid diamide derivative with hetero-aromatic and hetero-cyclic substituents
US8101550B2 (en) 2006-06-13 2012-01-24 Bayer Cropscience Ag Anthranilic acid diamide derivative with hetero-aromatic and hetero-cyclic substituents
WO2007144100A1 (en) 2006-06-13 2007-12-21 Bayer Cropscience Ag Anthranilic acid diamide derivative with hetero-aromatic and hetero-cyclic substituents
US8946236B2 (en) 2006-06-13 2015-02-03 Bayer Cropscience Ag Anthranilic acid diamide derivative with hetero-aromatic and hetero-cyclic substituents
WO2008031549A1 (en) * 2006-09-11 2008-03-20 Syngenta Participations Ag Process for the preparation of anthranilamide derivatives
EP1900730A1 (en) * 2006-09-11 2008-03-19 Syngeta Participations AG Process for the preparation of anthranilamide derivatives
US9260450B2 (en) * 2006-10-16 2016-02-16 Thesan Pharmaceuticals, Inc. Therapeutic pyrazolyl thienopyridines
US20150175624A1 (en) * 2006-10-16 2015-06-25 Thesan Pharmaceuticals, Inc. Therapeutic pyrazolyl thienopyridines
US9642365B2 (en) 2007-04-25 2017-05-09 Syngenta Crop Protection, Llc Fungicidal compositions
US10143201B2 (en) 2007-04-25 2018-12-04 Syngenta Crop Protection, Llc Fungicidal compositions
US11647749B2 (en) 2007-04-25 2023-05-16 Syngenta Participations Ag Fungicidal compositions
US9314022B2 (en) 2007-04-25 2016-04-19 Syngenta Crop Protection, Llc Fungicidal compositions
WO2009010260A3 (en) * 2007-07-16 2009-05-22 Syngenta Participations Ag Condensed anthranilamide insecticides
US8399490B2 (en) 2007-07-16 2013-03-19 Syngenta Crop Protection Llc Insecticides
WO2009010260A2 (en) 2007-07-16 2009-01-22 Syngenta Participations Ag Condensed anthranilamide insecticides
JP2010533662A (en) * 2007-07-16 2010-10-28 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト New insecticide
WO2009021717A2 (en) * 2007-08-14 2009-02-19 Syngenta Participations Ag Pesticidal formulation
WO2009021717A3 (en) * 2007-08-14 2010-04-29 Syngenta Participations Ag Pesticidal formulation
JP2010536814A (en) * 2007-08-22 2010-12-02 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト New insecticide
WO2009024341A3 (en) * 2007-08-22 2009-08-13 Syngenta Participations Ag Condensed anthran i lami de derivatives as insectisides
CN101827837A (en) * 2007-08-22 2010-09-08 先正达参股股份有限公司 The condensed anthranilamide derivatives as insectisides
US8598078B2 (en) 2007-08-22 2013-12-03 Syngenta Crop Protection, Llc Condensed anthran I lami de derivatives as insecticides
EP2484676A2 (en) 2008-12-18 2012-08-08 Bayer CropScience AG Tetrazol-substituted anthranilic acid amides as pesticides
US8324390B2 (en) 2008-12-18 2012-12-04 Bayer Cropscience Ag Tetrazole-substituted anthranilamides as pesticides
US8415333B2 (en) 2009-02-24 2013-04-09 Respiratorious Ab Bronchodilating diazaheteroaryls
US20130129677A1 (en) * 2009-02-27 2013-05-23 Siga Technologies, Inc. Thienopyridine Derivatives for the Treatment and Prevention of Dengue Virus Infections
WO2011095461A1 (en) 2010-02-04 2011-08-11 Syngenta Participations Ag Pyridazine derivatives, processes for their preparation and their use as fungicides
WO2011098408A2 (en) 2010-02-09 2011-08-18 Bayer Cropscience Ag Hydrazine-substituted anthranilic acid derivatives
US8410106B2 (en) 2010-02-09 2013-04-02 Bayer Cropscience Ag Hydrazine-substituted anthranilic acid derivatives
WO2011104183A1 (en) 2010-02-24 2011-09-01 Syngenta Participations Ag Novel microbicides
WO2011128329A1 (en) 2010-04-16 2011-10-20 Bayer Cropscience Ag Triazole-substituted anthranilic acid amides as pesticides
US8536202B2 (en) 2010-04-16 2013-09-17 Bayer Cropscience Ag Triazole-substituted anthranilamides as pesticides
US8980886B2 (en) 2010-06-15 2015-03-17 Bayer Cropscience Ag Anthranilic acid derivatives
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WO2012066122A1 (en) 2010-11-18 2012-05-24 Syngenta Participations Ag 2 - (pyridin- 2 -yl) -quinazoline derivatives and their use as microbicides
WO2012069652A2 (en) 2010-11-26 2012-05-31 Syngenta Participations Ag Fungicide mixtures
WO2013011010A1 (en) 2011-07-19 2013-01-24 Syngenta Participations Ag Fungizide mixtures
WO2013024005A1 (en) 2011-08-12 2013-02-21 Basf Se Anthranilamide compounds and their use as pesticides
US9044016B2 (en) 2011-08-12 2015-06-02 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2013024006A1 (en) 2011-08-12 2013-02-21 Basf Se Anthranilamide compounds and their use as pesticides
WO2013026866A2 (en) 2011-08-23 2013-02-28 Syngenta Participations Ag Novel microbiocides
US9572342B2 (en) 2011-12-19 2017-02-21 Bayer Intellectual Property Gmbh Use of an anthranilic diamide derivatives with heteroaromatic and heterocyclic substituents in combination with a biologicalcontrol agent
EP2606732A1 (en) 2011-12-19 2013-06-26 Bayer CropScience AG Use of an anthranilic diamide derivatives with heteroaromatic and heterocyclic substituents in combination with a biological control agent
US9414595B2 (en) 2011-12-19 2016-08-16 Bayer Cropscience Ag Use of anthranilic acid diamide derivatives for pest control in transgenic crops
US9854802B2 (en) 2011-12-19 2018-01-02 Bayer Intellectual Property Gmbh Use of an anthranilic diamide derivatives with heteroaromatic and heterocyclic substituents in combination with a biological control agent
WO2013092516A1 (en) 2011-12-19 2013-06-27 Bayer Intellectual Property Gmbh Use of an anthranilic diamide derivatives with heteroaromatic and heterocyclic substituents in combination with a biological control agent
WO2013092519A1 (en) 2011-12-19 2013-06-27 Bayer Cropscience Ag Use of anthranilic acid diamide derivatives for pest control in transgenic crops
US9533968B2 (en) 2012-05-24 2017-01-03 Basf Se N-thio-anthranilamide compounds and their use as pesticides
US9609868B2 (en) 2013-03-06 2017-04-04 Bayer Cropscience Ag Alkoximino-substituted anthranilic acid diamides as pesticides
WO2019123195A1 (en) 2017-12-20 2019-06-27 Pi Industries Ltd. Pyrazolopyridine-diamides, their use as insecticide and processes for preparing the same.
WO2019123194A1 (en) 2017-12-20 2019-06-27 Pi Industries Ltd. Anthranilamides, their use as insecticide and processes for preparing the same.
WO2019150220A1 (en) 2018-01-30 2019-08-08 Pi Industries Ltd. Novel anthranilamides, their use as insecticide and processes for preparing the same.
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor

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AR048669A1 (en) 2006-05-17
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JP2007526271A (en) 2007-09-13
US7812170B2 (en) 2010-10-12
BRPI0508401A (en) 2007-07-17
NZ549166A (en) 2009-12-24
MA28453B1 (en) 2007-03-01
ATE478862T1 (en) 2010-09-15
DE602005023140D1 (en) 2010-10-07
AU2005219545B2 (en) 2011-09-01
KR20060126584A (en) 2006-12-07
EP1737844A2 (en) 2007-01-03
RU2369603C2 (en) 2009-10-10
EG25775A (en) 2012-07-11
CN1926129B (en) 2011-06-15
JP4865695B2 (en) 2012-02-01
IL177345A (en) 2012-10-31
CA2556387A1 (en) 2005-09-15
RU2006134629A (en) 2008-04-10
AU2005219545A1 (en) 2005-09-15
CN1926129A (en) 2007-03-07
HK1101304A1 (en) 2007-10-12
US20070281930A1 (en) 2007-12-06
IL177345A0 (en) 2006-12-10

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