Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/28—Two oxygen or sulfur atoms
  • C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
  • C07D231/32—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems

Definitions

• the present invention relates to novel, pesticidally active 4-aryl- and 4-heteroaryl-5-oxo-pyrazoline derivatives, to a process for their preparation, to compositions which comprise these compounds as active substances, and to their use as pesticides, especially as insecticides, acaricides or herbicides.
• 4-Aryl-5-oxo-pyrazolines and 4-aryl- and 4-heteroarylpyrazolidine-3,5-diones having insecticidal, acaricidal and herbicidal action arc already known and are described, for example, in EP-A-0508 126 and WO-92 16510.
• Ri is the group the substituents R 4 independently of one another are halogen, nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyI, Cj-C 10 alkoxy, C r C 4 haloalkoxy, C3-C 6 alkenyloxy, C r C 4 alkoxy-C 2 -C 4 alkoxy, C 3 -C 6 alkynyloxy, C r C 4 alkylcarbonyl, ⁇ alkoxycarbonyl, C C alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, amino, C ⁇ -C 4 aIkyl__mino or di(Cj -C 4 alkyl)amino;
• R 5 is the group n is O, 1, 2, 3 or 4; m is 0 or 1, and the sum of m and n is 0, 1, 2, 3 or 4; q is O, 1, 2 or 3;
• Xj is oxygen, sulfur, -CH 2 - or -N(R 7 )-; the substituents R 6 independently of one another are halogen, C 1 -C 4 haloalkyl,
• R 7 is hydrogen, C ⁇ -C 4 alkyl, formyl or C ⁇ -C alkylca ⁇ bonyl;
• R 2 and R 3 independently of one another are hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl,
• R 2 and R 3 together form the bivalent radical of a saturated or unsaturated, unsubstituted or substituted, mono-, bi-, tri- or polycyclic system, which system can optionally contain, in positions not adjacent to the nitrogen atoms shown in formula I, one or more ring hetero atoms;
• G is the group -CO-A (a) or -SO 2 -B (b);
• A is C r C 8 alkyl substituted by nitro, cyano, Si(C ⁇ -C 4 alkyl) 3 , amino, Cj-C alkylamino, di(C 1 -C 4 alkyl)amino, substituted or unsubstituted benzyloxy or a group ⁇ CH_ N Ros ⁇ ,
• COORo j o or A is C 3 -C 8 cycloalkyl which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C ⁇ -C 4 alkyl, C C 4 alkoxy, C ⁇ -C alkylthio,
• C 3 -C 8 cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by Cj-C 4 alkyl, or A is adamantyl, naphthyl, naphthyl substituted by halogen, C 1 -C alkyl, C r C haloalkyl or C ⁇ -C 4 alkoxy, or A is a group
• Ros, Rr ⁇ and R Q IQ independendy of one another are hydrogen or C ⁇ -C 6 alkyl
• R 8 and R 9 independently of one another arc hydrogen, C C 6 alkyl or phenyl
• R 10 is hydrogen, C 1 -C ⁇ 0 alkyl, Cj-Cjoalkyl substituted by halogen, C r C 4 alkoxy, C r C alkylthio, C 3 -C 1 2cycloalkyl, cyano, aryl or aryloxy,
• Y and Z independently of one another are oxygen or NR 12 ; p is 1 to 10;
• RJI is C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted by halogen or ⁇ alkyl, aryloxy, aryloxy substituted by halogen, C ⁇ -C 4 alkyl, C C 4 haloalkyl, C ⁇ -C 4 alkoxy,
• R 12 is hydrogen, C r C 4 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 10 alkenyl or C 3 -C 10 alkynyl;
• R j3 is C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted by halogen or -Qalkyl, or cyano-C r C 6 alkyl;
• B is C r C 10 alkyl substituted by C r C alkoxy, C,-C 6 alkoxy-C r C 4 alkoxy, C r C 4 haloalkoxy, C r C alkylthio, C r C 4 haloalkylthio, C,-C alkylsulfinyl, C r C 4 alkylsulfonyl, C 1 -C 4 alkylsulfonyloxy, C r C alkylcarbonyl, C C 4 alkoxycarbonyl, C r C 4 alkylcarbonyloxy, di(C ⁇ -C 4 alkyl)amino, C 3 -C 8 cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl, it being possible for the aryl and pyr
• R 2 ⁇ is C 1 -C 4 haloalkoxy, C r C alkylthio, C r C 4 haloalkylthio, C ⁇ -C alkylsulfinyl, C r C 4 alkylsulfonyl, C 1 -C 4 alkylsulfonyloxy, C ⁇ -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, Cj-C 4 alkylcarbonyloxy, di(C ⁇ -C 4 alkyl)amino, C 3 -C 8 cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl, it being possible for the aryl and pyridyl groups if desired to be substituted by halogen, Ci-C-jalkyl, Cj-
• halogen refers to iodine and preferably to fluorine, chlorine and bromine.
• the alkyl, alkenyl and alkynyl groups preferably have 1 or, respectively, 2 to 8 carbon atoms and can be straight-chain or branched, specifications which also apply to the alkyl, alkenyl and alkynyl moieties of alkylsilanes, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, alkenyloxy, alkynyloxy, alkylcarbonyl, alkoxycarbonyl, alkylthio, alkenylthio, alkynylthio, alkylthioalkyl, alkylsulfinyl, alkylsulfonyl, alkylamino and dialkylamino groups.
• alkyl groups occurring in the definitions of the substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and die isomeric pentyls, hexyls, heptyls and octyls.
• the alkyl groups occurring as or in the substituents preferably have 1-8 carbon atoms.
• Alkenyl refers for example to allyl, methallyl, 1-methylvinyl or but-2-en-l-yl.
• Preferred alkenyl radicals are those having a chain length of 2 to 8 carbon atoms.
• the alkenyl radicals are preferably attached to a heteroatom via a saturated carbon atom.
• alkynyl examples include propargyl, but-2-yn-l-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl and pent-4-yn-l-yl.
• Preferred alkynyl radicals are those having a chain length of 2 to 8 carbon atoms.
• the alkynyl radicals are preferably attached to a heteroatom via a saturated carbon atom.
• Haloalkyl radicals preferably have a chain length of 1 to 8 carbon atoms.
• Haloalkyl is for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preference is given to trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
• Suitable haloalkenyl groups are alkenyl groups substituted one or more times by halogen, in whic context halogen is bromine, iodine and, in particular, fluorine and chlorine, examples being 2,2-difluoro-l -methyl vinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-l-yl.
• halogen is bromine, iodine and, in particular, fluorine and chlorine, examples being 2,2-difluoro-l -methyl vinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-l-yl.
• Suitable haloalkynyl groups are, for example, alkynyl groups which are mono- or polysubstituted by halogen, where halogen is bromine, iodine and, in particular, fluorine and chlorine, examples being 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluorobut-2-yn-l-yl.
• halogen is bromine, iodine and, in particular, fluorine and chlorine
• examples being 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluorobut-2-yn-l-yl.
• alkynyl radicals substituted one or more times by halogen preference is given to those having a chain length of 3 to 5 carbon atom
• Alkoxy radicals preferably have a chain length of 1 to 6 carbon atoms.
• Alkoxy is for example methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and the isomers of pentyloxy and hexyloxy; methoxy and ethoxy arc preferred.
• Alkylcarbonyl is especially acetyl and propionyl.
• Alkoxycarbonyl is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl; methoxycarbonyl and ethoxycarbonyl are preferred.
• Haloalkoxy radicals preferably have a chain length of 1 to 8 carbon atoms.
• Haloalkoxy is for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; difluoromethoxy, 2-chloroethoxy and trifluoromethoxy are preferred.
• Alkylthio radicals preferably have a chain length of 1 to 8 carbon atoms.
• Alkyl thio is for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio; methylthio and ethylthio are preferred.
• Alkylsulfinyl is methylsulf ⁇ nyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; methylsulfinyl and ethylsulfinyl arc preferred.
• Alkylsulfonyl is methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl; methylsulfonyl and ethylsulfonyl are preferred.
• Alkoxyalkoxy radicals preferably have a chain length of 1 to 8 carbon atoms. Examples of alkoxyalkoxy are methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy and butoxybutoxy.
• Alkylamino is for example methylamino, ethylamino, n-propylamino, isopropylamino and die isomeric butylamines.
• Dialkylamino is for example dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino radicals having a chain length of 1 to 4 carbon atoms.
• Alkoxyalkyl radicals preferably have 1 to 8 carbon atoms.
• Alkoxyalkyl is for example methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl and isopropoxyethyl.
• Alkylthioalkyl radicals preferably have 1 to 8 carbon atoms.
• Alkylthioalkyl is for example methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.
• the cycloalkyl radicals preferably have 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. These cycloalkyl radicals can if desired be interrupted by heteroatoms such as, for example, oxygen atoms and/or sulfur atoms and/or nitrogen atoms. Similar comments apply to the cycloalkyloxy radicals.
• Phenyl on its own or as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyi, phenylthio, phenylalkyl or phenoxyalkyl, can in general be unsubstituted or substituted. In the latter case the substituents can be in an ortho, meta and/or para position. Preferred substituent positions are the ortho and para positions relative to the ring linking site.
• Preferred substituents are halogen, nitro, cyano, C ⁇ -C 4 alkoxy, C Q-jhaloalkoxy, C r C 4 alkylthio, C r C 4 haloalkylthio, C r C 4 alkyl and C r C haloalkyl.
• Aryl in the definition of die radicals R 2 , R 3 and R 10 is ⁇ - or ⁇ -naphthyl, especially phenyl, which aromatic ring systems can carry one or more identical or different substituents, examples being halogen, nitro, cyano, C 1 -C 4 alkoxy, C r C 4 haloalkylthio, C r C 4 alkyl and Cj-C 4 haloalkyl.
• Examples of the unsubstituted or mono- to trisubstituted, nonaromatic, mono- or bicyclic heterocyclic rings which the substituents R 2 ⁇ and R 2 2, together with the nitrogen atom to which they are attached, are able to form are, for example, 1-pyrrolidinyl, 1-piperidyl, 2,6-dimeu ⁇ yl-l-piperidyl, 4-morpholinyl, 4-methylpiperazin-l-yl, 4-phenylpiperazin-l-yl, 4-benzylpiperazin- 1 -yl, 4-(3,4-dichlorophenyl)piperazin- 1 -yl, 4-thiomorpholinyl, 2,6-dimed ⁇ yl-4-morpholinyl, 2,6-dimethylthio-4-mo ⁇ pholinyl, 1 ,2,3,4-tetrahydro- quinolin-1-yl orindolin-1-yl.
• ring systems can be substituted by halogen, C C ⁇ alkyl, C r C 16 haloalkyl, C 2 -C ⁇ 6 alkenyl, C r C 16 alkoxy-C 2 -C 6 alkyl, C r C 6 polyalkoxy-C 2 -C 6 alkyl or by phenyl or benzyl each of which is unsubstituted or substituted by halogen, nitro, C ⁇ -C 4 alkyl, ⁇ alkoxy or C Cshaloalkyl; and R 14 is halogen or unsubstituted or halo-substituted C or C ⁇ alkoxy.
• acids are inter alia hydrochloric acid, hydrobromic acid, nitric acid, various phosphorus acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid.
• COORQJO which R Q10 is hydrogen can also be alkali metal salts, for example sodium salts and potassium salts; alkaline earth metal salts, for example calcium salts and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or polysubstituted ammonium salts, and salts with other organic nitrogen bases.
• alkali metal salts for example sodium salts and potassium salts
• alkaline earth metal salts for example calcium salts and magnesium salts
• ammonium salts i.e. unsubstituted ammonium salts and mono- or polysubstituted ammonium salts, and salts with other organic nitrogen bases.
• suitable salt formers are alkali metal hydroxides and alkaline earth metal hydroxides, especially the hydroxides of litfiium, sodium, potassium, magnesium or calcium, with particular importance being attached to those of sodium or potassium.
• Examples of amines suitable for forming ammonium salts include not only ammonia but also primary, secondary and tertiary C ⁇ -C ⁇ 8 alkylamines, C ⁇ -C 4 hydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine,
• R 09 and RQIQ are hydrogen.
• the asymmetrically substituted compounds of die formula I are generally - unless chiral precursors are used - obtained as racemates.
• the stereoisomers can then be separated on die basis of physicochemical properties by known methods, for instance fractional crystallization after die formation of salts with optically pure bases, acids or metal complexes, or else by chromatographic methods such as, for example, high-performance liquid chromatography (HPLC) on acetylcellulose.
• Preferred compounds of die formula I are those in which Rj is the group
• R 4 is fluorine, chlorine or Cj-C 4 alkyl; n is 1, 2 or 3; and m is 0. Of these compounds, very particular prcference is given to those in which R 4 is fluorine, chlorine or methyl; and n is 2 or 3.
• R 2 and R 3 are C r C 6 alkyl; or R 2 and R 3 togedier form a substituted or unsubstituted alkylene chain -(CH ⁇ s--- -(CH 2 ) 4 - or -(CH 2 ) 3 -.
• G is the group -CO-A (a).
• A is a group -(CR 8 R 9 ) p -(Y) o -CO-(Z) r -R 10 , -(CRsR ⁇ p -Ru or -N(R, 0 )R 13 , or substituted or unsubstituted naphd yl.
• R 8 and R independently of one anod er are hydrogen or metiiyl; and p is 1 or 2.
• RJQ is C j -C 8 -alkyl, preferably Cj-Q-alkyl, C 3 -C 6 cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl;
• R ! j is C 3 -Cgcycloalkyl, benzyloxy, benzyloxy substituted by halogen, C C 4 haloalkyl or phenoxy, or is naphthyloxy; and
• R 13 is C 3 -C 7 cycloalkyl or cyano-C r C 6 alkyl.
• Y and Z are NR 12 .
• R ⁇ 2 is hydrogen or C r C 4 alkyl.
• R 8 and R 9 independendy of one another are hydrogen or methyl; p is 1 or 2; R l0 is C j -Qalkyl, C 3 -C 6 cycloalkyl, phenyl, phenyl substituted by halogen, or is naphthyl; R u is C 3 -C 6 cycloalkyl, benzyloxy, benzyloxy substituted by halogen, C 1 -C 4 haloalkyl or phenoxy, or is naphthyloxy; Y and Z are NR 12 ; R 1 2 is hydrogen or ⁇ alkyl; and R 13 is C 3 -C 8 cycloalkyl orcyano-C r C 6 alkyl.
• Preferred compounds are those in which Rj is the group & is fluorine, chlorine or C r C alkyl; n is 1, 2 or 3; m is 0; R 2 and R 3 are C C 6 alkyl; or R 2 and R 3 togedier form a substituted or unsubstituted alkylene chain -(CH 2 ) 5 -, -(CH 2 ) 4 - or -(CH ⁇ ) 3 -; G is the group -CO-A (a); A is a group -(CR 8 R 9 ) p -(Y) o -CO-(Z) r -R 10 , -(CRgR ⁇ p -R j , or -N(R ⁇ 0 )R 13 , or is unsubstituted or substituted naphdiyl; R 8 and R 9 independently of one another arc hydrogen or metiiyl; p is 1 or 2; R 10 is C ⁇ -C 4 alkyl, C 3 -
• prefe ⁇ ed compounds of die formula I are those
• R 1 is the group ⁇ d m is 0-
• R 4 is - or C 2 alkyl
• n is 1, 2 or 3.
• R 4 is C j - or C ⁇ alkyl in positions 2, 4 and 6 relative to the phenyl hnkage site; and ⁇ is 3.
• R 4 is Cj- or C ⁇ alkyl; n is 1, 2 or 3; R 2 and R 3 are C ⁇ -C 6 alkyl; or R 2 and R 3 togedier form a substituted or unsubstituted alkylene chain -(CH 2 ) 5 -, -(CH ⁇ 4 - or -(CH 2 ) 3 -.
• G is a group -CO-A (a); and A is Cj-C 8 alkyl substituted by nitro, cyano, Si(C r C 4 alkyl) 3 , amino, Cj ⁇ alkylamino, di(C ⁇ -C 4 alkyl)amino, substituted or unsubstituted benzyloxy or a group ⁇ CH— NR 08Ro9 ,
• COOR 010 or A is C 3 -C 8 cycloalkyl, which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C ⁇ -C 4 alkyl, C r C 4 alkoxy, C ⁇ -C alkylthio, C ] -C 4 alkylsulfonyl or substituted or unsubstituted phenyl, or A is C 3 -C 8 cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by Ci-Qalkyl, or A is a group -(CR 8 R 9 ) p -(Y) o -CO-(Z) r -R 10 or -(CR 8 R 9 ) p -R 1 j .
• Rj is the group or C 2 alkyl; n is 1, 2 or 3; m is 0; R 2 and R 3 are C r C 6 alkyl; or R 2 and R 3 togedier form a substituted or unsubstituted alkylene chain -(CH 2 )5-, -(CH ⁇ - or -(CH ) 3 -; G is the group -CO-A (a); and A is C r C 8 alkyl substituted by nitro, cyano, Si(C r C 4 alkyl) 3 , amino, C 1 -C 4 alkylamino, di(C 1 -C 4 alkyl)amino, substituted or unsubstituted benzyloxy or a group -CH- NR r ⁇ Rr ⁇ t or A is C 3 -C 8 cycloalkyl which can if desired contain as heteroatom
• Rj is 2,4,6-trimethylphenyl
• Rj is 2,4,6-trimethylphenyl
• Rj is 2,6-dichlorophenyl
• the process according to die invention for die preparation of compounds of the formula I is carried out in analogy to known processes and comprises a) for the preparation of the 4-aryl- and 4-heteroaryl-5-oxopyrazoline derivatives of the formula
• A is as defined and E j is a leaving group, preferably halogen and especially chlorine;
• R R 2 and R 3 are as defined under formula I
• G is the group -CO-A (a)
• A is -N(Rj 0 )Ri 3 , where RJO and Rj3 are as defined under formula I with the exception of R j0 as hydrogen, reacting a compound of the formula
• R 10 and R !3 are as defined and Ej is a leaving group, preferably halogen and especially chlorine; or
• Rj, R 2 and R 3 are as defined under formula I
• G is die group -SO 2 -B (b)
• B is as defined under foi ⁇ iula I
• R 1? R and R 3 are as defined under formula I, with a compound of die formula in which B is as defined and E l is a leaving group such as halogen, especially chlorine, if desired in a solvent and in die presence or absence of a base.
• the reactions according to process variants (a), (b) and (c) can be carried out in analogy to known processes, advantageously in a reaction-inert, hydroxyl-free solvent in the presence of an organic base such as, for example, pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamines, N,N-dialkylaniline, or bicyclic nonnucleophilic bases such as, for example, l,4-diazabicyclo[2.2.2]octane (DABOO), l,5-diazabicyclo[4.3.0]non-5-ene (DBN) or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• an organic base such as, for example, pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamines, N,N-dialkylaniline, or bicyclic nonnucleophilic bases such as, for
• the reaction is generally carried out at temperatures of from 0 to 120°C, preferably from 20 to 90°C, advantageously in the presence of a reaction-inert solvent or solvent mixture.
• a reaction-inert solvent or solvent mixture examples include aliphatic and aromatic hydrocarbons such as benzene, toluene, petroleum ether or hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; ethers and ether-like compounds, such as dialkyl etiiers, for example dietiiyl ether, diisopropyl ether and tert-butyl methyl ether, and also anisole, dioxane and tetrahydrofuran; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate, propyl acetate and butyl acetate
• the reaction of die compound of die formula II widi the reactive sulfonic acid derivative of the formula VI takes place advantageously in equimolar quantities at temperatures of from 0 to 150°C, preferably from 20 to 70°C.
• Suitable solvents are the customary reaction-inert, polar, organic solvents, such as etiiers, amides, nitriles, alcohols, sulfones or sulfoxides, especially dimetiiyl sulfoxide, tetrahydrofuran or N,N-dimed ⁇ ylformamide.
• Suitable binding agents for die acid formed are the known inorganic and organic bases such as sodium hydroxide, sodium carbonate, potassium carbonate or pyridines.
• the reaction can take place under elevated pressure or, in particular, at atmospheric pressure. If desired it is also possible to operate under phase transfer conditions, in which case from 0.3 to 1.5 mol of reactive sulfonic acid derivative of the formula VI are employed per mole of die compound of die formula II at from 0 to 150°C, preferably from 20 to 70°C.
• Phase transfer catalysts which can be used are the customary quaternary ammonium salts, such as tetraoctylammonium bromide or benzyltriethylammonium chloride.
• suitable organic solvents are all inert apolar solvents, such as benzene or toluene.
• the compounds of the formulae III, IV, V and VI required for the preparation processes are ei ⁇ ier commercial products or can be prepared in analogy to known standard processes.
• the end products of the formula I can be isolated in a customary manner by concentration and/or evaporation of the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, alkanes, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of chromatography over a silica gel column.
• Salts of compounds of the formula I can be prepared in a manner known per se.
• acid addition salts of compounds of die formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases by treatment with a suitable base or a suitable ion exchanger reagent
• Salts of compounds of the formula I can be convened into die free compounds of the formula I in a customary manner; acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchanger reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchanger reagent.
• Salts of compounds of die formula I can be converted into other salts of compounds of die formula I in a manner known per se; acid addition salts, for example, can be converted into other acid addition salts, for example, by treating a salt of an inorganic acid, such as a hydrochloride, with an appropriate metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which die inorganic salt which forms, for example silver chloride, is insoluble and therefore separates out of the reaction mixture.
• an inorganic acid such as a hydrochloride
• an appropriate metal salt such as a sodium, barium or silver salt
• d e compounds of the formula I with salt-forming properties can be obtained in free form or in the form of salts.
• the product can be obtained as a mixture of two or more isomers.
• the isomers can be separated by methods known per se.
• compositions comprising the compounds of the formula I
• the preferences which apply are the same as those for the compounds of die formula I.
• the present invention also relates to a selective-herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in crops of maize and cereal, which composition comprises a herbicide and a safener (counteracting agent, antidote) and which protects the useful plants but not the weeds against the phytotoxic action of the herbicide, and to die use of this composition for weed control in crops of useful plants.
• a herbicide and a safener (counteracting agent, antidote) and which protects the useful plants but not the weeds against the phytotoxic action of the herbicide
• safeners which are capable of antagonizing die damaging effect of the herbicide on die crop plant, in other words of protecting the crop plant from said effect, while causing virtually no impairment of the herbicidal action on the weeds to be controlled.
• tiiat die proposed safeners often have a very specific action with respect to the crop plants and wid respect to the herbicide and, in some cases, in dependence on die mode of application; in otiier words, a certain safener is often suitable only for one specific crop plant and one specific class of herbicide or a specific herbicide.
• EP-A-0094 349 discloses quinoline derivatives which protect crop plants against the phytotoxic effect of herbicides of particular classes, for example chloroacetanilides, phenoxypropionates, ureas, triazines, carbamates or diphenyl ethers.
• EP-A-0558 448 describes l,5-diphenylpyrazole-3-carboxylic acid derivatives for protecting against the phytotoxic effect of sulfonylureas.
• tiiat safener compounds selected from the classes of the quinoline, pyrazole or triazole derivatives are suitable for protecting crop plants against the phytotoxic effect of 4-aryl- and 4-heteroaryl-5-oxopyrazoline derivatives of the formula I.
• a selective-herbicidal composition which comprises, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, an active substance comprising a mixture of a) a herbicidally effective quantity of a herbicide compound of the formula I as defined hereinbefore and b) a herbicide-antagonistically effective quantity of either a quinoline derivative of die formula in which
• R 15 is hydrogen, Cj-C 8 alkyl or Cj-C 8 alkyl which is substituted by Cj- alkoxy or
• X 2 is hydrogen or chlorine; or of a l-phenylazole-3-carboxylic acid derivative of die formula
• E is nitrogen or methine
• R 16 is -CCI 3 or unsubstituted or halo-substituted phenyl
• R 17 and R 18 independently of one another are hydrogen or halogen
• R 19 is C j -C 4 alkyl.
• Preferred compounds of the formula I in the composition according to the invention arc
• Rj is the group '- ⁇ d m s 0-
• R 4 is Cj- or C ⁇ alkyl
• n is 1, 2 or 3.
• compositions according to d e invention in which, in die compounds of the formula I, R j is the group m is 0; R is Cj- or
• n 1, 2 or 3;
• R 2 and R 3 are C j -C 6 alkyl; or R and R 3 together form a substituted or unsubstituted alkylene chain -(CH 2 ) 5 -, -(CH ⁇ - or -(CH ⁇ -.
• COORQJO or A is C 3 -C 8 cycloalkyl which if desired can contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C j ⁇ alkyl, Cj-C 4 alkoxy, Cj-C alkylthio, Cj-C alkylsulfinyl, C j -C 4 alkylsulfonyl or substituted or unsubstituted phenyl, or A is C 3 -C 8 cycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by or A is a group -(CR 8 R 9 ) p -(Y) o -CO-(Z) r -R 10 or
• R 4 is Cj- or C 2 alkyl; n is 1, 2 or 3; m is 0; R 2 and R 3 are Cj-C 6 alkyl; or
• R 2 and R 3 together form a substituted or unsubstituted alkylene chain -(CH 2 ) 5 -, -(CH ⁇ - or -(CH 2 ) 3 -;
• G is the group -CO-A (a); and
• A is Cj-Cgalkyl substituted by nitro, cyano, Si(Cj-C 4 alkyl) 3 , amino, Cj ⁇ alkylamino, di(Cj-C 4 alkyl)amino, unsubstituted or substituted benzyloxy or a group ⁇ ⁇ " ⁇ t ⁇ t 08 ⁇ 09 , or
• A is C 3 -C 8 cycloalkyl which can if
• COORQIO desired contain as heteroatom oxygen, sulfur or nitrogen and is substituted by C j -C alkyl, Cj-C 4 alkoxy, C j -C alkylthio, Cj-C 4 alkylsulfinyl, Cj-C 4 alkylsulfonyl or substituted or unsubstituted phenyl, or A is C 3 -Cgcycloalkyloxy which can if desired contain as heteroatom oxygen, sulfur or nitrogen and is unsubstituted or substituted by C j -C 4 alkyl, or A is a group -(CR 8 R 9 ) p -(Y) o -CO-(Z) r -R, 0 or -(CR 8 R 9 ) p -R ⁇ .
• compositions which comprise a safener of the formula
• the compounds of die formula I according to die invention used even at low concentrations, are active substances having preventive and/or curative value, a very favourable biocidal spectrum and favourable tolerance by warm-blooded animals, fish and plants.
• the active substances according to die invention are effective against all or individual development stages of normally sensitive, but also of resistant, animal pests, such as insects or members of the order Acarina.
• the insecticidal or acaricidal action of the active substances according to the invention can become apparent direcdy, i.e.
• the favourable action corresponding to a rate of destruction (mortality) of at least 50 to 60 %.
• the animal pests mentioned include, for example: from the order Lepidoptera, for example
• Euxoa spp. Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula 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,
• Synand edon spp. Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Coleoptera, for example
• Otiorhynchus spp. Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,
• Trogoderma spp. from the order Orthoptera, for example
• Periplaneta spp. and Schistocerca spp. from the order Isoptera, for example,
• Reticulitermes spp. from the order Psocoptera, for example
• Liposcelis spp. from the order Anoplura, for example
• Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Mallophaga, for example
• Scirtothrips aurantii from the order Heteroptera, for example
• Leptocorisa spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
• Scotinophara spp. and Triatoma spp. from the order Homoptera, for example
• Aleurothrixus floccosus Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,
• Aspidiotus spp. Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
• Erythroneura spp. Gascardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp.,
• Macrosiphus spp. Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,
• Pemphigus spp. Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,
• Hoplocampa spp. Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; from the order Diptera, for example
• Aedes spp. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chiysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,
• Ceratophyllus spp. and Xenopsylla cheopis from the order Thysanura, for example
• Lepisma saccharina and from the order Acarina for example
• active substances according to die invention it is possible to control pests of the type mentioned which occur on plants, especially on useful and ornamental plants in agriculture, gardening and forestry, or on parts of such plants, such as fruits, flowers, foliage, stems, tubers or roots, control in this context meaning restrict or destroy, while in some cases also providing protection against these pests to parts of plants which grow subsequently.
• Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar and fodder beet; fruit, for example pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; pulses, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor, cacao or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell pepper, the laurel family, such as avocado, cinnamon or camphor, and also tobacco, nuts, coffee, eggplants, sugar can
• die active substances according to die invention are the protection of stocks, warehouses and material and in the hygiene sector, especially the protection of domestic and productive animals against pests of the type mentioned.
• the invention therefore also relates to pesticides which are forms, to be chosen in accordance with the intended aims and prevailing conditions, such as emulsifiable concentrates, suspension concentrates, direcdy sprayable or dilutable solutions, brushable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, dusts, granules or encapsulations in polymeric substances, and which comprise - at least - one of the active substances according to the invention.
• pesticides which are forms, to be chosen in accordance with the intended aims and prevailing conditions, such as emulsifiable concentrates, suspension concentrates, direcdy sprayable or dilutable solutions, brushable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, dusts, granules or encapsulations in polymeric substances, and which comprise - at least - one of the active substances according to the invention.
• the active substance is employed in tiiese compositions in pure form, a solid active substance, for example, in a specific particle size, or, preferably, together with - at least - one of the auxiliaries which are customary in die art of formulation, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
• auxiliaries which are customary in die art of formulation, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
• suitable solvents are unmodified or partially hydrogenated aromatic hydrocarbons, preferably the C to Cj 2 fractions of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphdialene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and ed ers and esters tiiereof, such as propylene glycol, dipropylene glycol ether, ediylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-med ⁇ ylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unmodified or epoxidized vegetable oils, such
• solid carriers for example for dusts and dispersible powders, use is generally made of ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite.
• ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
• highly disperse silicas or highly disperse absorbent polymers Suitable granulated, adsorptive granule carriers arc porous types, such as pumice, broken brick, sepiolite or bentonite, while suitable non-sorbent carrier materials are calcite or sand.
• a large number of granulated materials of inorganic or organic type, especially dolomite or comminuted plant residues can be used.
• Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants, or surfactant mixtures having good emulsifying, dispersing and wetting properties.
• the surfactants listed below should be regarded only as examples; the relevant literature describes many other surfactants which are common in the art of formulation and are suitable in accordance with the invention.
• Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of die alkylphenols. Also suitable are water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain.
• the compounds mentioned usually contain, per propylene glycol unit, 1 to 5 ethylene glycol units.
• examples which may be mentioned are nonyl- phenolpolyetiioxyethanols, castor polyglycol ediers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxy- polyethoxyetiianol.
• fatty acid esters of polyoxyethylenesorbitan such as polyoxyethylenesorbitan trioleate.
• the cationic surfactants are primarily quaternary ammonium salts which have as substituents at least one alkyl radical having 8 to 22 carbon atoms and, additionally, lower, unmodified or halogenated, alkyl, benzyl or lower hydroxyalkyl radicals. These salts are preferably halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethyl- ammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.
• Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
• Suitable soaps are the alkali metal, alkaline earth metal and substituted or unsubstituted ammonium salts of higher fatty acids (C 10 -C2 2 ). such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut oil or tall oil; the fatty acid mediyl-taurine salts should also be mentioned. More often, however, synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
• the fatty sulfonates and fatty sulfates are generally in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and generally have an alkyl radical of 8 to 22 carbon atoms, alkyl also including d e alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. Also included are the salts of sulfuric esters and sulfonic acids of fatty alcohol-etiiylene oxide adducts.
• the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having about 8 to 22 carbon atoms.
• Alkylarylsulfonates are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphtiialenesulfonic acid-formaldehyde condensation product
• phosphates such as salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids.
• compositions generally contain from 0.1 to 99 %, in particular from 0.1 to 95 , of active substance and from 1 to 99.9 %, in particular from 5 to 99.9 % of - at least - one solid or liquid auxiliary, it being possible in general for from 0 to 25 %, in particular from 0.1 to 20 %, of the compositions to be surfactants (% denotes in each case percent by weight).
• the commercial product tends preferably to comprise concentrated compositions
• die end user generally uses dilute compositions with substantially lower concentrations of active substance.
• Emulsifiable concentrates Active substance: from 1 to 90%, preferably from 5 to 20% Surfactant: from 1 to 30%, preferably from 10 to 20% Solvent: from 5 to 98%, preferably from 70 to 85%
• Active substance from 0.1 to 10%, preferably from 0.1 to 1%
• Solid carrier from 99.9 to 90%, preferably from 99.9 to 99%
• Suspension concentrates Active substance: from 5 to 75%, preferably from 10 to 50% Water from 94 to 24%, preferably from 88 to 30%
• Surfactant from 1 to 40%, preferably from 2 to 30%
• Wettable powders Active subtance: from 0.5 to 90%, preferably from 1 to 80% Surfactant: from 0.5 to 20%, preferably from 1 to 15% Solid carrier: from 5 to 99%, preferably from 15 to 98%
• Granules Active substance: from 0.5 to 30%, preferably from 3 to 15%
• Solid carrier from 99.5 to 70%, preferably from 97 to 85%
• compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by d e addition of odier insecticidal or acaricidal active substances.
• suitable additions of insecticidal or acaricidal active substance are, for example, representatives of die following classes of active substance: organophosphorus compounds, nitrophenols and derivatives, formamidines, acylureas, carbamates, pyrethroids, nitroenamines and derivatives, pyrroles, thioureas and derivatives, chlorinated hydrocarbons and Bacillus tiiuringiensis preparations.
• compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unmodified or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and or adhesives, and also fertilizers or other active substances for obtaining specific effects, examples being bactericides, nematicides, molluscicides or selective herbicides.
• auxiliaries such as stabilizers, for example unmodified or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and or adhesives, and also fertilizers or other active substances for obtaining specific effects, examples being bactericides, nematicides, molluscicides or selective herbicides.
• compositions according to die invention are prepared in a known manner for example in the absence of auxiliaries, by grinding, sieving and/or compression of a solid active substance or active substance mixture, for example to a defined particle size, and, when at least one auxiliary is present, for example by intimate mixing and/or grinding of the active substance or active substance mixture with die auxiliary or auxiliaries.
• the invention relates furthermore to the methods of application for die compositions, i.e. die mediods of controlling pests of the type mentioned, tiiese methods being chosen in accordance with the intended aims and prevailing circumstances and comprising, for instance, spraying, fogging, dusting, brushing, dressing, broadcasting or watering, and to the use of the compositions for controlling pests of the type mentioned.
• typical application concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active substance.
• the application rates per hectare are generally from 1 to 200 g of active substance per hectare, in particular from 10 to 1000 g ha, preferably from 20 to 600 g/ha.
• a preferred method of application in the area of plant protection is application to the foliage of die plants (foliar application), the frequency and rate of application depending on the extent of infestation by the respective pest.
• die active substance can also pass into the plants via the root system (systemic action), by saturating die site of the plants with a liquid composition or incorporating the active substance in solid form into the site of die plants, for example into the soil, in die form of granules, for example (soil application).
• systemic action systemic action
• paddy rice cultures such granules can be metered out into the flooded rice field
• compositions according to the invention are also suitable for protecting vegetative propagation stock, for example seeds, such as fruits, tubers or grains, or plant seedlings, against animal pests.
• the propagation stock can be treated with the composition before being planted out; seed, for example, can be dressed before sowing.
• the active substances according to die invention can also be applied to seeds (coating) by eitiier soaking the seeds in a liquid composition or coating diem with a solid composition.
• the composition can also be applied when the propagation stock is planted out, at the planting site, for example in the seed drill in the case of sowing.
• the compounds of the formula I according to die invention arc also herbicidally active.
• Suitable application methods for d e herbicidal use, according to the invention, of the compounds of the formula I or of compositions comprising them arc all those methods which arc customary in agriculture, such as prcemergence application, postemergence application and seed dressing, and also a variety of methods and techniques such as, for example, the controlled release of active substance.
• the active substance in solution is applied to mineral granular carriers or polymerized granules (urea/formaldehyde) which are then dried. If desired, it is additionally possible to apply a coating (coated granules) which permits the release of the active substance in regulated amounts over a defined period.
• the compounds of the formula I can be employed in unaltered form, i.e. as they are obtained in die syndiesis, but are preferably processed in a conventional manner, using d e auxiliaries which are customary in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
• the mediods of application such as spraying, misting, dusting, wetting, scattering or pouring, are - like the nature of die compositions - chosen in accordance with die intended aims and d e prevailing conditions.
• compositions i.e. the compositions, preparations or combinations comprising the active substance of the formula I or at least one active substance of the formula I and, if desired, one or more solid or liquid additives
• the additives such as solvents or solid carriers, for example.
• surface-active compounds surfactants
• Suitable solvents, solid carriers and surface-active compounds are, for example, of the type described hereinbefore.
• the herbicidal formulations generally contain from 0.1 to 99 %, in particular from 0.1 to 95 %, of active substance of the formula I, from 1 to 99 % of a solid or liquid formulation auxiliary and from 0 to 25 %, in particular from 0.1 to 25 %, of a surfactant.
• compositions can also comprise further additives, such as stabilizers, for example unmodified or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, adhesives, and also fertilizers or other active substances for obtaining specific effects.
• stabilizers for example unmodified or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, adhesives, and also fertilizers or other active substances for obtaining specific effects.
• Emulsifiable concentrates Active substance: from 1 to 90%, preferably from 5 to 50% Surfactant: from 5 to 30%, preferably from 10 to 20% Solvent: from 15 to 94%, preferably from 70 to 85%
• Active substance from 0.1 to 50%, preferably from 0.1 to 1%
• Solid carrier from 99.9 to 90%, preferably from 99.9 to 99%
• Suspension concentrates Active substance: from 5 to 75%, preferably from 10 to 50% Water from 94 to 24%, preferably from 88 to 30%
• Surfactant from 1 to 40%, preferably from 2 to 30%
• Wettable powders Active subtance: from 0.5 to 90%, preferably from 1 to 80% Surfactant: from 0.5 to 20%, preferably from 1 to 15% Solid carrier: from 5 to 95%, preferably from 15 to 90%
• Granules Active substance: from 0.1 to 30%, preferably from 0.1 to 15%
• Solid carrier from 99.5 to 70%, preferably from 97 to 85%
• the active substances of the formula I are in general employed successfully at application rates of from 0.001 to 2 kg/ha, in particular from 0.005 to 1 kg/ha.
• the rate required in order to achieve the desired effect can be determined by means of trials. It is dependent on the nature of the effect, on the stage of development of die crop plant and of the weed, and on the application (site, time, method) and can, depending on tiiese parameters, vary within wide ranges.
• the compounds of die formula I are distinguished by herbicidal properties which render diem outstanding for use in crops of useful plants, especially in cereals, cotton, soya, oilseed rape, maize, rice and plantation crops. They can additionally be employed as burn-down agents, for example for potatoes, or as defoliants.
• references to cultures or crops are intended to include those which have been given tolerance to herbicides or classes of herbicide by means of conventional breeding mediods or methods of genetic manipulation.
• the invention also relates to a process for the selective control of broad-leaved weeds and grasses in crops of useful plants, which comprises treating the useful plants, their seeds or seedlings or their cultivation area, simultaneously or independently of one another, with a herbicidally effective quantity of d e herbicide of die formula I and widi a herbicide-antagonistically effective quantity of a safener of the formula X or XI.
• Crop plants which can be protected by die safeners of the formulae X and XI against the damaging effect of the abovementioned herbicides are, in particular, maize and cereals.
• the weeds to be controlled can be eidier monocotyledon or dicotyledon weeds.
• the areas regarded as cultivation areas are the soil areas on which the crop plants are already growing, or soil areas sown with the seed of tiiese crop plants, and also the areas intended for cultivation with diese crop plants.
• a safener of the formula X or XI can be used for pretreating die seed of the crop plant (dressing of die seed or of the seedlings), or placed in die soil before or after sowing. It can also, however, be applied, on its own or togedier with the herbicide, following the emergence of the plants.
• the treatment of the plants or of the seed with d e safener can therefore, in principle, take place independently of the point in time of die application of die herbicide.
• the plant treatment can also be carried out by simultaneous application of herbicide and safener (for example as a tank mix).
• the application rate of safener to herbicide to be applied depends largely on the method of application.
• the ratio of herbicide to safener is in general from 100:1 to 1:10, preferably from 20:1 to 1:1.
• the application rates of herbicide are generally between 0.001 and 2 kg ha, but preferably between 0.005 and 1 kg/ha.
• compositions according to the invention are suitable for all application methods which are customary in agriculture, for example prcemergence application, postemergence application and seed dressing.
• safener/kg of seed in die case of seed dressing, in general, from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, arc applied. If the safener is applied in liquid form shortly before sowing, accompanied by seed swelling, then it is expedient to use safener solutions which comprise the active substance in a concentration of from 1 to 10000 ppm, preferably from 100 to 1000 ppm.
• die safeners of the formula X or XI, or combinations of tiiese safeners with the herbicides of die formula I arc advantageously processed together witii the auxiliaries which are customary in the art of formulation to give particular formulations, for example emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
• the formulations are prepared in a known manner, for example by intimate mixing and/or grinding of the active substances with liquid or solid formulation auxiliaries such as, for example, solvents or solid carriers.
• surface-active compounds surfactants
• Suitable solvents, solid carriers and surface-active compounds are, for example, of the type described hereinbefore.
• the agrochemical formulations generally contain from 0.1 to 99 percent by weight, in particular from 0.1 to 95 % by weight, of safener or safener/herbicide active-substance mixture, from 1 to 99 % by weight, in particular from 5 to 99.8 % by weight, of a solid or liquid formulation auxiliary, and from 0 to 25 % by weight, in particular from 0.1 to 25 % by weight, of surfactant.
• While the preferred commercial product usually comprises concentrated compositions, the end user generally uses dilute compositions.
• compositions can also comprise further additives, such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active substances.
• Seed dressing a) The seeds are dressed by shaking them, in a vessel, together with an active substance of die formula X or XI formulated as a wettable powder until the active ingredient is distributed uniformly on the seed surface (dry seed dressing). In this case from about 1 to about 500 g of active substance of the formula X or XI (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed.
• seeds are dressed by immersing them into a liquor containing 100-1000 ppm of active substance of the formula X or XI for from 1 to 72 hours and tiien, if desired, by drying them (seed soaking).
• the dressing of die seed, and die treatment of the seedling which has begun germinating are of course the preferred mediods of application, since the treatment with the active substance is directed entirely towards die target crop.
• a liquid preparation of a mixture of antidote and herbicide (mutual quantitative ratio of between 10:1 and 1:100) is used, the application rate of herbicide being from 0.005 to 5.0 kg per hectare.
• Such tank mixes are applied before or after sowing.
• the safener is incorporated into the open seed drill, containing seed, as an emulsion concentrate, wettable powder or in the form of granules. After the seed drill has been covered over, die herbicide is applied preemergence in a customary manner.
• the active substance of the formula X or XI is applied in solution to mineral granule carriers or polymerized granules (urea/formaldehyde), which are then dried. If desired, a coating can be applied (coated granules), which enables the release of the active substance in regulated amounts over a defined period.
• the organic phase is dried with sodium sulfate and concentrated, and die residue obtained is stined witii hexane, filtered off with suction and dried to give the desired compound as a white powder witii a melting point of 151-153°.
• the crude product is dissolved in ethyl acetate, the solution is filtered over silica gel, the filtrate is concentrated and the residue is stined with hexane. Suction filtration and drying give the desired compound as a white powder with a melting point of 171-173°.
• Tables 8 and 9 list compounds which are preferred as safeners of the formulae X and XI.
• Example Fl Emulsion concentrates a) b) c)
• Example F2 Solutions a) b) c) d)
• the active substance is dissolved in dichloromediane, the solution is applied to die carrier mixture by spraying and the solvent is evaporated off in vacuo.
• Active substance and additives are mixed and die mixture is ground in a suitable mill. Wettable powders are obtained which can be diluted with water to give suspensions of desired concentration.
• Example F6 Emulsion concentrate
• Application-ready dusts are obtained by mixing active substance and carrier and grinding die mixture in a suitable mill.
• Example F8 Extruded granules Active substance according to Tab.1-7 10%
• Active substance and additives are mixed, the mixture is ground, wetted with water, extruded and granulated, and die granules are dried in a stream of air.
• Example FIO Suspension concentrate
• Emulsion concentrates a) b) c) d)
• Aromatic hydrocarbon mixture 85% 78% 55% 16%
• the solutions are suitable for use in the form of very small drops.
• the active substance is mixed thoroughly with the additives and die mixture is ground dioroughly in a suitable mill. Wettable powders are obtained which can be diluted widi water to give suspensions of any desired concentration.
• the active substance is dissolved in methylene chloride, the solution is applied to the carrier by spraying, and d e solvent is subsequently evaporated off in vacuo.
• the finely ground active substance is applied uniformly, in a mixer, to the carrier material wetted widi polyethylene glycol. In tiiis way, dust-free coated granules are obtained.
• the active substance is mixed with the additives, and the mixture is ground and wetted with water. This mixture is extruded and subsequendy dried in a stream of air.
• Application-ready dusts are obtained by mixing the active substance with the carriers and grinding die mixture on a suitable mill.
• the finely ground active substance is intimately mixed witii the additives. In this way a suspension concentrate is obtained which can be diluted with water to give suspensions of any desired concentration.
• Aromatic hydrocarbon mixture 85 % 78 % 55 % 16 %
• Aromatic hydrocarbon mixture Aromatic hydrocarbon mixture
• the solutions are suitable for use in the form of very small drops.
• Wettable powders a) b) c) d) Active substance mixture 5 % 25 % 50 % 80 % Sodium ligninsulfonate 4 % - 3 % - Sodium lauryl sulfate 2 %
• the active substance is mixed dioroughly with the additives and the mixture is ground dioroughly in a suitable mill. Wettable powders are obtained which can be diluted witii water to give suspensions of any desired concentration.
• the active substance is dissolved in methylene chloride, die solution is applied to die carrier by spraying and die solvent is subsequently evaporated off in vacuo.
• the finely ground active substance is applied uniformly, in a mixer, to the carrier material wetted with polyethylene glycol. In diis way, dust-free coated granules are obtained.
• Active substance mixture 0.1 % 3 % 5 % 15 %
• the active substance is mixed with die additives, ground and wetted witii water. This mixture is extruded and then dried in a stream of air.
• Application-ready dusts are obtained by mixing the active substance with the carriers and grinding die mixture in a suitable mill.
• the finely ground active substance is intimately mixed widi the additives. In this way, a suspension concentrate is obtained which can be diluted with water to give suspensions of any desired concentration.
• Pea seedlings are infected widi Myzus persicae, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and tiien incubated at 20°. The test is evaluated after 3 and 6 days. The percentage reduction in die population (% action) is determined by comparing die number of dead aphids on die treated plants with tiiose on untreated plants. Compounds of Tables 1 to 7 exhibit a good action in this test
• Example B2 Action against Nilaparvata lugens
• Rice plants are treated widi an aqueous emulsion spray liquor comprising 400 ppm of active ingredient and, after die spray coating has dried on, arc populated widi stage 2 and 3 cicada larvae. 21 days later, die percentage reduction in die population (% action) is determined by comparing die number of surviving cicadas on die treated plants with those on untreated plants.
• Example B3 Action against Nilaparvata lugens (systemic)
• Pots containing rice plants are placed in an aqueous emulsion solution comprising 400 ppm of active ingredient. The plants are then populated widi stage 2 and 3 larvae. 6 days later, die percentage reduction in the population (% action) is determined by comparing the number of cicadas on die treated plants with those on untreated plants. Compounds of Tables 1 to 7 exhibit a good action in this test.
• Example B5 Action against Tetranychus urticae
• Young bean plants are populated widi a mixed population of Tetranychus urticae, sprayed 1 day later with an aqueous emulsion spray liquor comprising 400 ppm of active ingredient, incubated at 25° for 6 days and subsequently evaluated.
• the percentage reduction in the population is determined by comparing the number of dead eggs, larvae and adults on the treated plants widi tiiose on untreated plants.
• Compounds of Tables 1 to 7 exhibit a good action in this test An action of more than 80% is shown, in particular, by the compounds nos.
• Monocotyledon and dicotyledon test plants are grown in standard soil in the greenhouse in plastic pots and, at die 4- to 6-leaf stage, are sprayed with an aqueous suspension of die test substances of the formula I, prepared from a 25 % wettable powder (Example F13, b)), at a rate of 2000 g of AS/ha (5001 of water/ha).
• die test plants are grown in plastic pots to the 4-leaf stage. At this stage, both the herbicide alone and die mixtures of the herbicide with die test substances to be tested as safeners are applied to die test plants. Application takes place in the form of an aqueous suspension of the test substances, prepared from a 25 % wettable powder (Example F21, b)), with 5001 of water/ha. 3 weeks after application, the phytotoxic action of die herbicide on die crop plants, for example maize and cereal, is evaluated using a percentage scale. 100 % denotes tiiat the test plant has died, while 0 % denotes no phytotoxic effect.

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