WO2007009661A2 - Melanges pesticides - Google Patents

Melanges pesticides Download PDF

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Publication number
WO2007009661A2
WO2007009661A2 PCT/EP2006/006866 EP2006006866W WO2007009661A2 WO 2007009661 A2 WO2007009661 A2 WO 2007009661A2 EP 2006006866 W EP2006006866 W EP 2006006866W WO 2007009661 A2 WO2007009661 A2 WO 2007009661A2
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WIPO (PCT)
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group
formula
ccn
alternative name
spp
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PCT/EP2006/006866
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English (en)
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WO2007009661A3 (fr
Inventor
David John Hughes
James Edward Peace
Suzanna Riley
Sally Russell
Joseph John Swanborough
André Jeanguenat
Peter Renold
Roger Graham Hall
Olivier Loiseleur
Stephan Trah
Jean Wenger
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Syngenta Participations Ag
Syngenta Limited
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Publication of WO2007009661A2 publication Critical patent/WO2007009661A2/fr
Publication of WO2007009661A3 publication Critical patent/WO2007009661A3/fr

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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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the invention relates to a pesticidal composition comprising as active ingredient a mixture consisting of at least two substances, to the use of such a composition, to a method of controlling pests using such a composition and to plant propagation material treated with such a composition.
  • the invention accordingly relates to a pesticidal composition
  • a pesticidal composition comprising as active ingredient a mixture consisting of at least two substances, namely a compound (A) as mentioned hereinbelow and one or more than one compound (B) as mentioned hereinbelow.
  • a preferred embodiment of the subject-matter of the invention is a pesticidal composition
  • a pesticidal composition comprising a mixture consisting of at least two substances, namely one compound (A) and at least one compound (B), as active ingredient and at least one auxiliary, wherein the compound (A) is the compound of formula (I)
  • Z 1 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
  • 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;
  • megidis (alternative name) (433), Hippodamia convergens (alternative name) (442), Leptomastix dactylopii (alternative name) (488), Macrolophus caliginosus (alternative name) (491 ), Mamestra brassicae NPV (alternative name) (494), Metaphycus helvolus (alternative name) (522), Metarhizium anisopliae var. acridum (scientific name) (523), Metarhizium anisopliae var. anisopliae (scientific name) (523), Neodiprion sertifer NPV and N.
  • lecontei NPV (alternative name) (575), Orius spp. (alternative name) (596), Paecilomyces fumosoroseus (alternative name) (613), Phytoseiulus persimilis (alternative name) (644), Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741 ), Steinernema bibionis (alternative name) (742), Steinernema carpocapsae (alternative name) (742), Steinernema feltiae (alternative name) (742), Steinernema glaseri (alternative name) (742), Steinernema riobrave (alternative name) (742), Steinernema riobravis (alternative name) (742), Steinernema scapterisci (alternative name) (742), Steinernema spp.
  • Ra 5 is trifluoromethyl or difluoromethyl (WO2004/058723); the compound of formula F-2
  • Ra 6 is trifluoromethyl or difluoromethyl (WO2004/058723); the racemic compound of formula F-3 (syn)
  • Ra 7 is trifluoromethyl or difluoromethyl (W 02004/035589) ;the compound of formula F-5
  • Ra 8 is trifluoromethyl or difluoromethyl (WO2004/035589); the racemic compound of formula F-7 (trans) wherein Ra g is trifluoromethyl or difluoromethyl (WO03/074491); the racemic compound of formula F-8 (cis)
  • Ra 9 is trifluoromethyl or difluoromethyl (WO03/074491 ); the compound of formula F-9
  • R 11 is trifluoromethyl or difluoromethyl (WO03/074491); the racemic compound of formula F-12 (cis)
  • R 11 is trifluoromethyl or difluoromethyl (WO03/074491 ); the compound of formula F- 13 which is a racemic mixture of the formulae F- 11 (trans) and F-12 (cis), and wherein Rn is trifluoromethyl or difluoromethyl (WO 03/074491 );and the compound of formula F-14
  • 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.
  • compositions comprising a compound of formula I, in which
  • Z 1 is an oxygen atom; or a sulfur atom
  • Z 2 is an oxygen atom; or a sulfur atom
  • R 1 is a phenyl or naphthyl group, which is substituted independently by 1 or 2 substituents R 3 and optionally further substituted independently by 1 to 3 substituents R b ;
  • R 3 is cyano; nitro; halogen; CrC 6 alkyl; halo-CVC ⁇ alkyl; d-Cealkoxy-CrC ⁇ 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; d-C ⁇ alkoxy; halo-CrC 6 alkoxy; C 3 -C 6 cycloalkoxy; mercapto; C 1 - C 6 alkylthio; halo-d-C ⁇ alkylthio; d-C ⁇ alkylsulfinyl; halo-CVC ⁇ alkylsulfinyl; CrC 6 alkylsulfonyl; halo-CVC ⁇ al
  • R b is halogen; d-C 6 alkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; C 3 -C 6 cycloalkyl; CrC 6 alkoxy; C 1 - C 6 alkoxycarbonyl; 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 R a ; or R 1 is a monocyclic or bicyclic heteroaryl group, which is unsubstituted or substituted independently by 1 to 4 substituents R c ;
  • R c is a substituent R a ; 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 R a ;
  • R d is a substituent R 1 ; d-C 6 alkyl; halo-d-C 6 alkyl; Ci-C 6 alkoxy-Ci-C 6 alkyl; a group CH 2 R 1 ; a group CH 2 OR 1 ; a group CH 2 SR 1 ; a group CH 2 NHR 1 , which group is optionally further substituted at the nitrogen atom by d-C 6 alkyl or halo-d-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; C 1 - C 6 alkoxy; halo-d-C 6 alkoxy; C 3 -C 6 cycloalkoxy; a group OR 1 ; d-C 6
  • R 4 is hydrogen; a substituent R 1 ; a substituent R e ; a d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl or C 3 -C 6 cycloalkyl group, which group is unsubstituted or substituted independently by one or more substituents, selected from the group, consisting of the substituents R 3 , the substituents R e 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 R c ; a group CH 2 OR 1 ; a group CH 2 SR 1 ; a group CH 2 NHR 1 , which group is optionally further substituted at the nitrogen atom by d-C 6 alkyl or halo-d-C 6 alkyl; d-C 6 alkoxy;
  • R 5 is hydrogen; d-C 6 alkyl; or halo-d-C 6 alkyl; or has one of the meanings defined hereinafter;
  • R 6 and R 7 taken together, are either a group of the formula
  • G 6 is attached to G 3 ; and in which G 10 is attached to G 4 ; or are a group of the formula Ie, in which G 6 is attached to G 3 ; and in which G 9 is attached to G 4 ; or are a group of the formula
  • G 6 is attached to G 4 ; and in which G 10 is attached to G 5 ; or are a group of the formula Ie, in which G 6 is attached to G 4 ; and in which G 9 is attached to G 5 ; or are a group of the formula
  • R( is hydrogen; or a substituent R 9 ; the total number of the substituents R 9 , if present, having an upper limit of 5 for a group of the formula Ia; of 4 for a group of the formula Ib; and of 3 for a group of the formula Ic; which total number can, however, be limited for a specific group of the formula Ia, Ib 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 R 9 in this specific group;
  • R 9 is either attached to a carbon atom and then selected from the group, consisting of the substituents R g . c ; or attached to a nitrogen atom and then selected from the group, consisting of the substituents R g . n ;
  • R 9 - C is a substituent R c ;
  • R g . n is cyano; nitro; d-C 6 alkyl; halo-C r C 6 alkyl; d-Cealkoxy-d-Cealkyl; 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; C 1 - C 6 alkoxy; halo-Ci-C 6 alkoxy; C 3 -C 6 cycloalkoxy; CrC 6 alkylthio; halo-Ci-C 6 alkylthio; C 1 - C 6 alkylsulfinyl; halo-d-C 6 alkylsulfinyl; d-C 6 alkylsulfonyl; halo-CrC
  • R ⁇ i, R ⁇ 2, R91 and R 92 which are different from any first substituent, if present, as defined hereinbefore for the formula Ie, and from any second substituent, if present, as defined hereinbefore for the formula Ie, is independently selected from the group, consisting of the substituents R,; in which formula If each of those substituents, selected from the group, consisting of the substituents R 61 , R 62 , R 71 , R 72 , R 81 and R 82 , 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 R h ;
  • Rn is hydrogen; or a substituent R 1 ; the total number of the substituents R,, 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 R, in this specific group;
  • R 1 is hydrogen; or a substituent R k ; the total number of the substituents R k , if present, having an upper limit of 5; which total number can, however, be limited for a specific group of the formula Ie 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 R k in this specific group; R, is either attached to a carbon atom and then selected from the group, consisting of the substituents R ⁇ ; or attached to a nitrogen atom and then selected from the group, consisting of the substituents R,. n ;
  • R j-0 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 . n ; or 2 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 i 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 . 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-CrC ⁇ 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
  • a ring carbon atom selected from the group, consisting of Gi, G 2 , G 3 , G 4 , G 5 , G 6 , G 7 , G 8 , G 9 and Gi 0 , 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;
  • 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), th ⁇ 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.
  • composition comprising a compound of formula I, in which R 2 is hydrogen or C 1 - C 6 alkyl; preferably hydrogen;
  • composition comprising a compound of formula I, in which R 3 is hydrogen or C 1 - C 6 alkyl; preferably hydrogen;
  • composition comprising a compound of formula I, in which R 4 is CVCealkyl; preferably methyl or isopropyl;
  • composition comprising a compound of formula I, in which R 5 and R 8 , taken together, are a bond;
  • composition comprising a compound of formula I, in which R 6 and R 7 , taken together, are a group of the formula Ib or a group of the formula Ic;
  • composition comprising a compound of formula I, in which the two carbon atoms, shown in the formula I, to which atoms R 6 and R 7 are attached, are two ring members of an aromatic ring;
  • compositions according to the present invention comprises compounds of formula I wherein said compounds are represented by the compounds of formulae Vila and VIIb
  • Roi is hydrogen; amino or nitro
  • Ro 2 is hydrogen or CrC 4 alkyl
  • Ro 3 is Ci-C 4 alkyl, d-C 4 alkyl mono- or disubstituted by cyano, COOH, nitro, Ci-C 4 alkoxy or cyclopropyl;
  • Yo 2 is C(R 09 ), a chemical bond, or is nitrogen or sulfur; and R 09 is hydrogen, phenyl, phenyl substituted by halogen, or halogen.
  • compositions comprising a compound of the formula Vila are those, wherein
  • R 01 is hydrogen;
  • R 02 is hydrogen;
  • R 03 is d-dalkyl, preferably methyl;
  • R 04 is CrC 4 fluoroalkyl, preferably trifluoromethyl;
  • R 05 is chloro;
  • R 06 is halogen, preferably chloro;
  • R 07 is hydrogen;
  • R ⁇ io is hydrogen; Y 01 is C(R 08 ); R 08 is halogen, preferably chloro; Y 02 is C(R 09 ), and R 09 is hydrogen.
  • compositions comprising a compounds of the formula I mentioned in the Examples P3, P6 and P9 to P11.
  • Compounds of formula A1 wherein Z 1 and Z 1 are oxygen and R 1 is hydrogen, may be made from the ring opening of a benzoxazinone of formula B1 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 B1 may be made from amino acids of formula C1 by treatment with a carboxylic acid of formula R 1 -COOH and a dehydrating reagent such as methanesulfonyl chloride (optionally in the presence of a base such as pyridine or triethylamine).
  • benzoxazinones of formula B1 may be obtained by the treatment of amino acids of formula C1 with an acid chloride of formula R 1 -COCI 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 R 1 -COCI may be made from carboxylic acids of formula R 1 -COOH under standard conditions (for example by treatment with thionyl chloride or oxalyl chloride).
  • Carboxylic acids of formula R 1 -COOH are either known compounds or they may be made analogously to known processes.
  • Compounds of formula A1 wherein Z 1 and Z 1 are sulfur, may be made from compounds of formula A1 , wherein Z 1 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 A1 wherein Z 1 and Z 1 are oxygen, may be made by treatment of compounds of formula D, wherein Z 1 is oxygen and R is OH, d-C 4 alkoxy or Cl, with an amine of formula NHR 3 R 4 .
  • Acid chlorides of formula D, wherein Z 1 is oxygen and R is Cl 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 1 is oxygen and R is OH may be formed from esters of formula D, wherein Z 1 is oxygen and R is C 1 -C ⁇ IkOXy. 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 C 1 -C 4 BIkOXy may be made by treatment of compounds of formula E, wherein R is by acylation with compounds of formula
  • R 1 -COOH or R 1 -COCI under standard conditions as previously described.
  • Compounds of formula E, wherein R is C T ⁇ 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 C 1 -C ⁇ IkOXy, may be made from a compound of formula F, wherein R is CrC 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 A1 wherein Z 1 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 ⁇ lkoxy, 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 B1 by treatment with a dehydrating agent such as acetic anhydride.
  • compounds of formula A, wherein Z 1 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 R 1 -COOH or an acid chloride of formula R 1 -COCI 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, Cl or C 1 -C 4 BIkOXy, 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 C 1 -C 4 BIkOXy 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 Cl) 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 Cl 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 1 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 1 wherein Z 1 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 4 to give compounds of formula G, wherein R 1 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
  • lsatins 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 0 C to approximately +140 0 C, preferably from approximately -30 0 C to approximately +100 0 C, in many cases in the range between room temperature and approximately +80 0 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 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".
  • the Table A discloses 338 meanings of the variables Z 1 , Z 2 , R 1 , 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 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.
  • the specific compound T1.23 is the compound of the formula T1 , in which each of the variables Z 1 , Z 2 , R 1 , R 2 , 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 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 3 This table discloses the 338 compounds T3.1 to T3.338 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 4 This table discloses the 338 compounds T4.1 to T4.338 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 5 This table discloses the 338 compounds T5.1 to T5.338 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 6 This table discloses the 338 compounds T6.1 to T6.338 of the formula
  • 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 7 This table discloses the 338 compounds T7.1 to T7.338 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 8 This table discloses the 338 compounds T8.1 to T8.338 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 9 This table discloses the 338 compounds T9.1 to T9.338 of the formula
  • 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 10 This table discloses the 338 compounds T10.1 to T10.338 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 11 This table discloses the 338 compounds T11.1 to T11.338 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 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 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 13 This table discloses the 338 compounds T13.1 to T13.338 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 14 This table discloses the 338 compounds T14.1 to T14.338 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 15 This table discloses the 338 compounds T15.1 to T15.338 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 16 This table discloses the 338 compounds T16.1 to T16.338 of the formula
  • 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 17 This table discloses the 338 compounds T17.1 to T17.338 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 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 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 19 This table discloses the 338 compounds T19.1 to T19.338 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 20 This table discloses the 338 compounds T20.1 to T20.338 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 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 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 22 This table discloses the 338 compounds T22.1 to T22.338 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 23 This table discloses the 338 compounds T23.1 to T23.338 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 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 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 25 This table discloses the 338 compounds T25.1 to T25.338 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 26 This table discloses the 338 compounds T26.1 to T26.338 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 27 This table discloses the 338 compounds T27.1 to T27.338 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 28 This table discloses the 338 compounds T28.1 to T28.338 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 29 This table discloses the 338 compounds T29.1 to T29.338 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 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 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 32 This table discloses the 338 compounds T32.1 to T32.338 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 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 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 34 This table discloses the 338 compounds T34.1 to T34.338 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 35 This table discloses the 338 compounds T35.1 to T35.338 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 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 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 37 This table discloses the 338 compounds T37.1 to T37.338 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 38 This table discloses the 338 compounds T38.1 to T38.338 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 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 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 40 This table discloses the 338 compounds T40.1 to T40.338 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 41 discloses the 338 compounds T41.1 to T41.338 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 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 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 43 This table discloses the 338 compounds T43.1 to T43.338 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 44 This table discloses the 338 compounds T44.1 to T44.338 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 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 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 46 This table discloses the 338 compounds T46.1 to T46.338 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 47 This table discloses the 338 compounds T47.1 to T47.338 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 48 discloses the 338 compounds T48.1 to T48.338 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 49 This table discloses the 338 compounds T49.1 to T49.338 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 50 This table discloses the 338 compounds T50.1 to T50.338 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 51 discloses the 338 compounds T51 .1 to T51.338 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 52 This table discloses the 338 compounds T52.1 to T52.338 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 53 This table discloses the 338 compounds T53.1 to T53.338 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 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 1 , Z 2 , R 1 , R 2 , R3 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 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 56 This table discloses the 338 compounds T56.1 to T56.338 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 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 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 58 This table discloses the 338 compounds T58.1 to T58.338 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 59 This table discloses the 338 compounds T59.1 to T59.338 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 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 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 61 This table discloses the 338 compounds T61.1 to T61.338 of the formula
  • 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 62 This table discloses the 338 compounds T62.1 to T62.338 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 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 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 64 This table discloses the 338 compounds T64.1 to T64.338 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 65 This table discloses the 338 compounds T65.1 to T65.338 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 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 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 67 This table discloses the 338 compounds T67.1 to T67.338 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 68 This table discloses the 338 compounds T68.1 to T68.338 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 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 , 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 70 This table discloses the 338 compounds T70.1 to T70.338 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 71 This table discloses the 338 compounds T71.1 to T71.338 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 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 1 , Z 2 , Ri, R 2 , R3 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 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 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 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 76 This table discloses the 338 compounds T76.1 to T76.338 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 77 This table discloses the 338 compounds T77.1 to T77.338 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 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 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 79 This table discloses the 338 compounds T79.1 to T79.338 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 80 This table discloses the 338 compounds T80.1 to T80.338 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 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 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 82 This table discloses the 338 compounds T82.1 to T82.338 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 83 This table discloses the 338 compounds T83.1 to T83.338 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 84 This table discloses the 338 compounds T84.1 to T84.338 of the formula (T84), 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 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 86 This table discloses the 338 compounds T86.1 to T86.338 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 87 This table discloses the 338 compounds T87.1 to T87.338 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 88 This table discloses the 338 compounds T88.1 to T88.338 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 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 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 91 This table discloses the 338 compounds T91.1 to T91.338 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.
  • the compounds (B) are known. Where the compounds (B) are included in "The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound (B); for example, the compound “abamectin” is described under entry number (1 ). Where “[CCN]” is added hereinabove to the particular compound (B), the compound (B) in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names. Copyright ⁇ 1995-2004]; for example, the compound "acetoprole” is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
  • Compounds (A) or compounds (B) having at least one basic centre are capable of forming, for example, acid addition salts, e.g. with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted substituted, e.g. halo-substituted, C 1 -C 4 alkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g.
  • strong inorganic acids such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid
  • strong organic carboxylic acids such as unsubstituted substituted, e.g. halo-substituted, C 1 -C
  • oxalic, malonic, succinic, maleic, fumaric and phthalic acid hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric and citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo-substituted, C 1 -C 4 alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid.
  • Compounds (A) or compounds (B) having at least one acid group are capable of forming, for example, salts with bases, e.g.
  • metal salts such as alkali metal or alkaline earth metal salts, e.g. 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, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine.
  • corresponding internal salts may optionally be formed. In the context of the invention, preference is is given to agrochemically advantageous salts.
  • any reference to the free compounds (A) or free compounds (B) or to their salts should be understood as including also the corresponding salts or the free compounds (A) or free compounds (B), respectively, where appropriate and expedient.
  • the equivalent also applies to tautomers of compounds (A) or compounds (B) and to their salts.
  • the active ingredient mixture according to the invention [in the preferred case, where only at least one compound (B) is included in the mixture] comprises the compound (A) and the compound (B) preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1
  • the active ingredient mixture according to the invention not only brings about the additive enhancement of the spectrum of action with respect to the pests to be controlled that was in principle to be expected but achieves a synergistic effect which extends the range of action of the compound (A) and of the compound (B) in two ways. Firstly, the rates of application of the compound (A) and of the compound (B) are lowered whilst the action remains equally good. Secondly, the active ingredient mixture still achieves a high degree of pest control even where the two individual compounds have become totally ineffective in such a low application rate range. This allows, on the one hand, a substantial broadening of the spectrum of pests that can be controlled and, on the other hand, increased safety in use.
  • the pesticidal compositions according to the invention also have further surprising advantages which can also be described, in a wider sense, as synergistic activity.
  • pests or fungi can be controlled which cannot be controlled, or cannot be controlled with sufficient effectiveness, using an individual compound (A) or an individual compound (B).
  • the active ingredient mixture according to the invention is also better tolerated by plants, that is to say, for example, it exhibits reduced phytotoxicity, compared to the individual compounds (A) and (B).
  • insects can be controlled in their different development stages, which is not the case with some of the individual compounds (A) and (B), because those individual compounds can be used, for example, only as adulticides or only as larvicides against highly specific larval stages.
  • the pesticidal compositions according to the invention in some cases exhibit better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • compositions according to the invention exhibit, in the area of pest control, valuable preventive and/or curative activity with a very advantageous biocidal spectrum, even at low rates of concentration, while being well tolerated by warm-blooded organisms, fish and plants.
  • the compositions according to the invention are effective especially against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the compositions according to the invention may manifest itself directly, i.e.
  • the compound (B) in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • good activity corresponding to a mortality of at least 50 to 60 %.
  • the compound (B) it is also possible to achieve in addition, for example, an algicidal, anthelmintic, avicidal, bactericidal, molluscicidal, nematicidal, plant-activating, rodenticidal or virucidal action of the compositions according to the invention.
  • the mentioned animal pests include, for example: of the order Acarina, for example,
  • Boophilus spp. Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp.,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; of 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.,
  • Leptocorisa spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
  • Aleurothrixus floccosus Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,
  • Aspidiotus spp. Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma lanigerum, Erythroneura spp.,
  • Myzus spp. Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp.,
  • Planococcus spp. Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp.,
  • Hoplocampa spp. Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order Isoptera, for example,
  • Reticulitermes spp. of the order Lepidoptera, for example,
  • Euxoa spp. Grapholita spp., Hedya nubiferana, Heliothis spp., HeIIuIa undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta,
  • Operophtera spp. Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,
  • Liposcelis spp. of the order Siphonaptera, for example,
  • Nematicidal action can be exhibited, for example, with respect to the following pests of the class Nematoda: root knot nematodes, cyst-forming nematodes, stem nematodes or leaf nematodes; pests of the families Filariidae or Setariidae; or pests of the genera Ancylostoma, especially Ancylostoma caninum, Anguina, Aphelenchoides, Ascaridia, Ascaris, Bunostumum, Capillaria, Chabertia, Cooperia, Dictyocaulus, Dirofilaria, especially Dirofilaria immitis, Ditylenchus, Globodera, especially Globodera rostochiensis, Haemonchus, Heterakis, Heterodera, especially Heterodera avenae, Heterodera glycines, Heterodera schachtii or Heterodera trifolii, Longidorus, Meloidogyne
  • compositions according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.
  • Target crops are especially cereals, e.g. wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g.
  • strawberries, raspberries and blackberries leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
  • the target crops may be crops of conventional plants or crops of genetically modified plants ("GM plants” or "GMOs").
  • compositions according to the invention are therefore also suitable for use in herbicide- resistant, pest-resistant and/or fungus-resistant transgenic crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops (e.g. citrus fruits, coffee, bananas), rape, maize and rice.
  • herbicide- resistant, pest-resistant and/or fungus-resistant transgenic crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops (e.g. citrus fruits, coffee, bananas), rape, maize and rice.
  • Herbicide-resistant crops are to be understood as including those that have been made tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD- inhibitors) by means of conventional breeding or genetic engineering methods.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO- and HPPD- inhibitors
  • An example of a crop that has been made tolerant by conventional breeding methods to, for example, imidazolinones such as imazamox is Clearfield® summer rape (canola).
  • crops made tolerant to herbicides by genetic engineering methods are maize varieties resistant to, for example, glyphosate or glufosinate, which are commercially available under the trade names RoundupReady® and LibertyLink®, respectively.
  • pest-resistant and/or fungus-resistant transgenic useful plants are expressely understood to include those useful plants which, in addition to having the pest resistance and/or fungus resistance, also have herbicide tolerance.
  • group of herbicide-tolerant useful plants preference is given, in accordance with the invention, to useful plants having tolerance with respect to glyphosate, glufosinate- ammonium, ALS (acetolactate synthase) inhibitors, such as sulfonylureas, e.g. primisulforon, prosulfuron and trifloxysulfuron, or bromoxynil, such as, for example, Bt1 1 maize or Herculex I® maize.
  • Pest-resistant transgenic crop plants are to be understood in the context of the present invention as being 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, e.g. 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(bi ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria that colonise nematodes, for example Photorhabdus spp.
  • insecticidal proteins e.g. insecticidal proteins from Bacillus cereus or Bacillus popliae
  • Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c
  • 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 trypsin 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, ec
  • ⁇ -endotoxins for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) 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 ).
  • a truncated toxin is a truncated CrylA(b), which is expressed in Bt1 1 maize of Syngenta Seeds SAS, as described hereinbelow.
  • modified toxins one or more amino acids of the naturally occurring toxin is/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-O 374 753, WO 93/07278, WO 95/34656, EP-A-O 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-O 367 474, EP-A-O 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants provides the plants with tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Diabrotica virgifera virgifera western corn rootworm
  • 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(bi ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bi ) 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) tox
  • 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(bi ) toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1 150 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, including the European corn borer.
  • fungus-resistant transgenic crop plants are to be understood as being those 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-O 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-O 392 225, WO 95/33818 and EP-A-O 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-O 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 stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called
  • compositions according to the invention are the protection of stored goods and storerooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp., Call
  • Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and
  • the pesticidal compositions according to the invention are, for example, emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, powders for application in sprays, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising one of the active ingredient mixtures according to the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • composition stands for the various mixtures or combinations of components (A) and (B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix”, and also in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the components (A) and (B) is not essential for working the present invention.
  • the active ingredient mixture is used in those compositions in pure form, a solid active ingredient mixture, for example, in a specific particle size, or preferably together with - at least - one of the auxiliaries customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • extenders for example solvents or solid carriers, or surface-active compounds (surfactants).
  • Suitable solvents are, for example: optionally partially hydrogenated aromatic hydrocarbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated 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 or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methyl- pyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, vegetable oils or epoxidised vegetable oils, such as rapeseed oil,
  • the solid carriers used are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand.
  • suitable nonsorbent carriers are calcite or sand.
  • a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • the surfactants listed below are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.
  • Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids or alkylphenols, said derivatives containing about 3 to about 30 glycol ether groups and about 8 to about 20 carbon atoms in the (cyclo)aliphatic hydrocarbon moiety and about 6 to about 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to about 10 carbon atoms in the alkyl chain, which adducts contain about 20 to about 250 ethylene glycol ether groups and about 10 to about 100 propylene glycol ether groups. These compounds usually contain 1 to about 5 ethylene glycol units per propylene glycol unit.
  • non-ionic surfactants are nonylphenol polyethoxyethanol, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which generally contain, as substituent, at least one C 8 -C 22 alkyl radical and, as further substituents, (unsubstituted or halogenated) lower alkyl or hydroxy-lower alkyl or benzyl radicals.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethyl- ammonium chloride and benzyl bis(2-chloroethyl)ethylammonium bromide.
  • Suitable anionic surfactants are, for example, water-soluble soaps and water-soluble synthetic surface-active compounds.
  • Suitable soaps are, for example, the alkali metal salts, alkaline earth metal salts or (unsubstituted or substituted) ammonium salts of fatty acids containing about 10 to about 22 carbon atoms, e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil; mention may also be made of fatty acid methyltaurin salts.
  • fatty sulfonates especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates and fatty sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or (unsubstituted or substituted) ammonium salts and generally contain an alkyl radical containing about 8 to about 22 carbon atoms, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salts of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
  • These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing about 8 to about 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzene- sulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
  • compositions according to the invention usually comprise 0.1 to 99 %, especially 0.1 to 95 %, of an active ingredient mixture according to the invention and 1 to 99.9 %, especially 5 to 99.9 %, of - at least - one solid or liquid auxiliary, it generally being possible for 0 to 25 %, preferably 0.1 to 20 %, of the composition to be surfactants (in each case percentages are by weight).
  • surfactants in each case percentages are by weight.
  • the end user will normally employ dilute formulations, which have considerably lower active ingredient concentrations.
  • Emulsifiable concentrates active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % solvent: 5 to 98 %, preferably 70 to 85 %
  • active ingredient mixture 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 99 %, preferably 15 to 98 %
  • Granules active ingredient mixture: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers or fertilisers.
  • auxiliaries such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers or fertilisers.
  • compositions according to the invention are prepared in a manner known per S ⁇ , in the absence of auxiliaries, for example by grinding, sieving and/or compressing a solid active ingredient mixture, and in the presence of at least one auxiliary, for example by intimately mixing and/or grinding the active ingredient mixture with the auxiliary/auxiliaries.
  • auxiliaries for example by grinding, sieving and/or compressing a solid active ingredient mixture
  • at least one auxiliary for example by intimately mixing and/or grinding the active ingredient mixture with the auxiliary/auxiliaries.
  • the invention relates also to those processes for the preparation of the compositions and to the use of the compounds (A) and compounds (B) in the preparation of those compositions.
  • the invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type.
  • Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient mixture.
  • the rates of application per hectare are generally from 1 to 2000 g of active ingredient mixture per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • the rate of application may vary within wide limits and depends on the nature of the soil, the method of application (foliar application; seed dressing; application to the seed furrow), the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a preferred method of application in the area of crop protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question.
  • the active ingredient mixture can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient mixture is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
  • compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruit, tubers or grains, or plant seedlings, from pests of the mentioned type.
  • the propagation material can be treated with the compositions before planting: seed material, for example, can be dressed before being sown.
  • the compositions can also be applied to seed grains (coating), either by impregnating the grains with a liquid composition or by coating them with a solid composition.
  • the compositions can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.
  • TX means "one compound selected from the group consisting of the compounds specifically described in tables P1 , P2 and T1 to T91 of the present invention":
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • N-methylpyrrolid-2-one 20 % - epoxidised coconut oil - - - - 1 1 % % 5 % benzine (boiling range: 160-190°) _ 94 %
  • the solutions are suitable for application in the form of micro-drops.
  • Example F3 Granules a) b) c) d) active ingredient mixture
  • the active ingredient mixture is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
  • the active ingredient mixture is mixed with the additives and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • the active ingredient mixture is mixed with the additives, and the mixture is ground, moistened with water, extruded and granulated and the granules are dried in a stream of air.
  • the finely ground active ingredient mixture is intimately mixed with the additives, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • Y percentage mortality on treatment with the compound (B) at a rate of application of q kg per hectare, compared with the untreated control.
  • Example B1 Action against Aphis craccivora
  • Pea seedlings are infested with Aphis craccivora, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient mixture and then incubated at 20°. Evaluation is made 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants. Active ingredient mixtures according to the invention exhibit good activity in this test.
  • Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient mixture. After the spray-coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae (in the second stage) and then placed in a plastics container. The evaluation is made 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.
  • Active ingredient mixtures according to the invention exhibit good activity in this test.
  • Example B3 Action against Heliothis virescens (foliar application) Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient mixture. After the spray-coating has dried, the plants are populated with 10 Heliothis virescens caterpillars (in the first stage) and then placed in a plastics container. Evaluation is made 6 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the treated plants and untreated plants in respect of the number of dead caterpillars and the feeding damage.
  • Active ingredient mixtures according to the invention exhibit good activity in this test.
  • Example B4 Action against Heliothis virescens (application to eggs)
  • Heliothis virescens eggs deposited on cotton are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient mixture. After 8 days, the percentage hatching rate from the eggs and the survival rate of the caterpillars are evaluated (% reduction in population) by comparison with untreated control batches.
  • Active ingredient mixtures according to the invention exhibit good activity in this test.
  • Example B5 Action against Mvzus persicae (foliar application)
  • Pea seedlings are infested with Myzus persicae, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient mixture and then incubated at 20°. Evaluation is made 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants. Active ingredient mixtures according to the invention exhibit good activity in this test.
  • Example B6 Action against Mvzus persicae (systemic application)
  • Pea seedlings are infested with Myzus persicae; the roots are subsequently placed in a spray mixture comprising 400 ppm of active ingredient mixture and the seedlings are then incubated at 20°. Evaluation is made 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.
  • Active ingredient mixtures according to the invention exhibit good activity in this test.
  • Example B7 Action against Plutella xylostella caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient mixture. After the spray-coating has dried, the plants are populated with 10 Plutella xylostella caterpillars (in the third stage) and then placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the treated plants and untreated plants in respect of the number of dead caterpillars and the feeding damage. Active ingredient mixtures according to the invention exhibit good activity in this test. •
  • Example B8 Action against Spodoptera littoralis caterpillars
  • the plants are populated with 10 Spodoptera littoralis caterpillars (in the third stage) and then placed in a plastics container. Evaluation is made 3 days later.
  • the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the treated plants and untreated plants in respect of the number of dead caterpillars and the feeding damage.
  • Active ingredient mixtures according to the invention exhibit good activity in this test.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une composition pesticide comprenant comme principe actif un mélange comprenant un composé (A) tel que défini dans les revendications du brevet et au moins un composé (B) tel que défini dans les revendications du brevet, l'utilisation d'une telle composition, un procédé de lutte contre les ravageurs mettant en oeuvre une telle composition et un matériau de propagation des végétaux traité au moyen d'une telle composition.
PCT/EP2006/006866 2005-07-15 2006-07-13 Melanges pesticides WO2007009661A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0514652.7 2005-07-15
GBGB0514652.7A GB0514652D0 (en) 2005-07-15 2005-07-15 Pesticidal mixtures

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WO2007009661A2 true WO2007009661A2 (fr) 2007-01-25
WO2007009661A3 WO2007009661A3 (fr) 2007-03-29

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100130578A1 (en) * 2006-07-18 2010-05-27 Bayer Cropscience Ag Active ingredient combinations having insecticide and acaricide properties
WO2011136269A1 (fr) 2010-04-28 2011-11-03 アステラス製薬株式会社 Composé de tétrahydrobenzothiophène
WO2013079026A1 (fr) * 2011-12-03 2013-06-06 深圳诺普信农化股份有限公司 Composition bactéricide contenant du fluazinam
US8551912B2 (en) 2007-04-25 2013-10-08 Syngenta Crop Protection Llc Fungicidal compositions
WO2013168967A1 (fr) * 2012-05-07 2013-11-14 주식회사경농 Dérivés de diamine-aryle substitués par carbamate, et composition pesticide contenant ces dérivés
EA018993B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
CN103601718A (zh) * 2013-12-05 2014-02-26 江西天人生态股份有限公司 一类基于鱼泥丁受体的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途
WO2014073623A1 (fr) * 2012-11-09 2014-05-15 住友化学株式会社 Procédé pour promouvoir la croissance des plantes
WO2014073622A1 (fr) * 2012-11-09 2014-05-15 住友化学株式会社 Procédé permettant de favoriser la croissance des plantes
WO2014073626A1 (fr) * 2012-11-09 2014-05-15 住友化学株式会社 Procédé permettant de favoriser la croissance des plantes
WO2014128136A1 (fr) 2013-02-20 2014-08-28 Basf Se Composés d'anthranilamide et leur utilisation comme pesticides
CN105669643A (zh) * 2013-12-05 2016-06-15 江西天人生态股份有限公司 一类基于鱼泥丁受体的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途
CN105777713A (zh) * 2016-04-06 2016-07-20 武汉工程大学 N-(2-吡啶基)-2-(2,4-二甲基吡唑甲酰胺基)苯甲酰胺及其制备和用途
WO2019123194A1 (fr) 2017-12-20 2019-06-27 Pi Industries Ltd. Anthranilamides, leur utilisation en tant qu'insecticides et leurs procédés de préparation
WO2019150220A1 (fr) 2018-01-30 2019-08-08 Pi Industries Ltd. Nouveaux anthranilamides, leur utilisation en tant qu'insecticides et leurs procédés de préparation
CN110810438A (zh) * 2019-09-29 2020-02-21 西南大学 烟草疫霉菌纳米氧化铜抗菌剂及其制备方法
CN111116578A (zh) * 2019-12-26 2020-05-08 深圳市老年医学研究所 去亚甲基小檗碱的制备方法及其应用
CN111164076A (zh) * 2017-09-13 2020-05-15 先正达参股股份有限公司 杀微生物的喹啉(硫代)甲酰胺衍生物
WO2021083936A1 (fr) * 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Composés hétéroaromatiques bicycliques fusionnés à action pesticide
WO2021114313A1 (fr) * 2019-12-14 2021-06-17 Shanghai East Hospital Antagonistes/bloqueurs des canaux ioniques et leurs utilisations
WO2023021020A1 (fr) * 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Procédé de lutte contre des nuisibles résistants au diamide et composés associés
WO2023114823A1 (fr) * 2021-12-15 2023-06-22 Bristol-Myers Squibb Company Dérivés de benzothiophène utilisés en tant qu'agonistes de rxfp1
CN116965413A (zh) * 2023-09-25 2023-10-31 云南省农业科学院农业环境资源研究所 一种含尼古丁与天然柠檬烯的植物性杀虫组合物及其应用
US12054486B2 (en) 2021-09-24 2024-08-06 Xenon Pharmaceuticals Inc. Pyridine derivatives and their use as sodium channel activators

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003015518A1 (fr) * 2001-08-13 2003-02-27 E.I. Du Pont De Nemours And Company Procede permettant de lutter contre des insectes nuisibles particuliers par application de composes d'anthranilamide
WO2005048713A1 (fr) * 2003-11-14 2005-06-02 Bayer Cropscience Aktiengesellschaft Combinaisons d'agents a proprietes insecticides
DE102004021565A1 (de) * 2003-12-04 2005-06-30 Bayer Cropscience Ag Wirkstoffkombinationen mit insektiziden Eigenschaften
WO2005085234A2 (fr) * 2004-03-03 2005-09-15 Syngenta Participations Ag Nouveaux insecticides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003015518A1 (fr) * 2001-08-13 2003-02-27 E.I. Du Pont De Nemours And Company Procede permettant de lutter contre des insectes nuisibles particuliers par application de composes d'anthranilamide
WO2005048713A1 (fr) * 2003-11-14 2005-06-02 Bayer Cropscience Aktiengesellschaft Combinaisons d'agents a proprietes insecticides
DE102004021565A1 (de) * 2003-12-04 2005-06-30 Bayer Cropscience Ag Wirkstoffkombinationen mit insektiziden Eigenschaften
WO2005085234A2 (fr) * 2004-03-03 2005-09-15 Syngenta Participations Ag Nouveaux insecticides

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100130578A1 (en) * 2006-07-18 2010-05-27 Bayer Cropscience Ag Active ingredient combinations having insecticide and acaricide properties
US8816097B2 (en) * 2006-07-18 2014-08-26 Bayer Cropscience Ag Active ingredient combinations having insecticide and acaricide properties
US9642365B2 (en) 2007-04-25 2017-05-09 Syngenta Crop Protection, Llc Fungicidal compositions
EA018821B1 (ru) * 2007-04-25 2013-10-30 Синджента Партисипейшнс Аг Фунгицидная композиция
EA019042B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Способ борьбы с заболеваниями полезных растений
EA018992B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
EA019005B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
EA019018B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
EA019006B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
EA018993B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
EA019004B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
EA019007B1 (ru) * 2007-04-25 2013-12-30 Синджента Партисипейшнс Аг Фунгицидная композиция
US9314022B2 (en) 2007-04-25 2016-04-19 Syngenta Crop Protection, Llc Fungicidal compositions
US8551912B2 (en) 2007-04-25 2013-10-08 Syngenta Crop Protection Llc Fungicidal compositions
US11647749B2 (en) 2007-04-25 2023-05-16 Syngenta Participations Ag Fungicidal compositions
EA018805B1 (ru) * 2007-04-25 2013-10-30 Синджента Партисипейшнс Аг Фунгицидная композиция
US10143201B2 (en) 2007-04-25 2018-12-04 Syngenta Crop Protection, Llc Fungicidal compositions
US8729068B2 (en) 2010-04-28 2014-05-20 Astellas Pharma Inc. Tetrahydrobenzothiophene compound
US9284295B2 (en) 2010-04-28 2016-03-15 Astellas Pharma Inc. Tetrahydrobenzothiophene compound
KR20130073908A (ko) 2010-04-28 2013-07-03 아스텔라스세이야쿠 가부시키가이샤 테트라하이드로벤조티오펜 화합물
WO2011136269A1 (fr) 2010-04-28 2011-11-03 アステラス製薬株式会社 Composé de tétrahydrobenzothiophène
WO2013079026A1 (fr) * 2011-12-03 2013-06-06 深圳诺普信农化股份有限公司 Composition bactéricide contenant du fluazinam
WO2013168967A1 (fr) * 2012-05-07 2013-11-14 주식회사경농 Dérivés de diamine-aryle substitués par carbamate, et composition pesticide contenant ces dérivés
CN104271562B (zh) * 2012-05-07 2017-03-15 株式会社经农 经氨基甲酸酯取代的二氨基芳基衍生物及包含所述衍生物的杀虫组合物
CN104271562A (zh) * 2012-05-07 2015-01-07 株式会社经农 经氨基甲酸酯取代的二氨基芳基衍生物及包含所述衍生物的杀虫组合物
US9018233B2 (en) 2012-05-07 2015-04-28 Kyung Nong Corporation Diaminoaryl derivatives substituted by carbamate and pesticidal composition containing same
CN104902752A (zh) * 2012-11-09 2015-09-09 住友化学株式会社 促进植物生长的方法
US9955689B2 (en) 2012-11-09 2018-05-01 Sumitomo Chemical Company, Limited Method for promoting plant growth
CN104902750A (zh) * 2012-11-09 2015-09-09 住友化学株式会社 促进植物生长的方法
CN104902749A (zh) * 2012-11-09 2015-09-09 住友化学株式会社 促进植物生长的方法
WO2014073623A1 (fr) * 2012-11-09 2014-05-15 住友化学株式会社 Procédé pour promouvoir la croissance des plantes
US9894901B2 (en) 2012-11-09 2018-02-20 Sumitomo Chemical Company, Limited Method for promoting plant growth
WO2014073626A1 (fr) * 2012-11-09 2014-05-15 住友化学株式会社 Procédé permettant de favoriser la croissance des plantes
WO2014073622A1 (fr) * 2012-11-09 2014-05-15 住友化学株式会社 Procédé permettant de favoriser la croissance des plantes
US9872493B2 (en) 2012-11-09 2018-01-23 Sumitomo Chemical Company, Limited Method for promoting plant growth
WO2014128136A1 (fr) 2013-02-20 2014-08-28 Basf Se Composés d'anthranilamide et leur utilisation comme pesticides
CN105669643A (zh) * 2013-12-05 2016-06-15 江西天人生态股份有限公司 一类基于鱼泥丁受体的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途
CN103601718A (zh) * 2013-12-05 2014-02-26 江西天人生态股份有限公司 一类基于鱼泥丁受体的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途
CN105777713A (zh) * 2016-04-06 2016-07-20 武汉工程大学 N-(2-吡啶基)-2-(2,4-二甲基吡唑甲酰胺基)苯甲酰胺及其制备和用途
CN111164076A (zh) * 2017-09-13 2020-05-15 先正达参股股份有限公司 杀微生物的喹啉(硫代)甲酰胺衍生物
WO2019123194A1 (fr) 2017-12-20 2019-06-27 Pi Industries Ltd. Anthranilamides, leur utilisation en tant qu'insecticides et leurs procédés de préparation
WO2019150220A1 (fr) 2018-01-30 2019-08-08 Pi Industries Ltd. Nouveaux anthranilamides, leur utilisation en tant qu'insecticides et leurs procédés de préparation
CN110810438A (zh) * 2019-09-29 2020-02-21 西南大学 烟草疫霉菌纳米氧化铜抗菌剂及其制备方法
WO2021083936A1 (fr) * 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Composés hétéroaromatiques bicycliques fusionnés à action pesticide
CN114630825A (zh) * 2019-11-01 2022-06-14 先正达农作物保护股份公司 杀有害生物活性的稠合二环杂芳香族化合物
WO2021114313A1 (fr) * 2019-12-14 2021-06-17 Shanghai East Hospital Antagonistes/bloqueurs des canaux ioniques et leurs utilisations
CN114401935A (zh) * 2019-12-14 2022-04-26 上海市东方医院（同济大学附属东方医院） 离子通道拮抗剂/阻断剂及其用途
CN114401935B (zh) * 2019-12-14 2024-04-05 上海市东方医院（同济大学附属东方医院） 离子通道拮抗剂/阻断剂及其用途
CN111116578A (zh) * 2019-12-26 2020-05-08 深圳市老年医学研究所 去亚甲基小檗碱的制备方法及其应用
WO2023021020A1 (fr) * 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Procédé de lutte contre des nuisibles résistants au diamide et composés associés
US12054486B2 (en) 2021-09-24 2024-08-06 Xenon Pharmaceuticals Inc. Pyridine derivatives and their use as sodium channel activators
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CN116965413B (zh) * 2023-09-25 2023-12-05 云南省农业科学院农业环境资源研究所 一种含尼古丁与天然柠檬烯的植物性杀虫组合物及其应用

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