Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

• the present invention relates to new herbicidal compositions for combating weed grasses and weeds in crops of useful plants, which comprise a herbicide and a safener which preserves the useful plant but not the weed grasses and weeds against the phytotoxic action of the herbicide.
• the present invention also relates to the use of these compositions for combating weed grasses and weeds in crops of useful plants, in particular in crops of soya, cotton, rape, sugarcane, cereals, e.g. wheat and barley, rice and, in particular, maize.
• the crops plants may also be damaged.
• safeners are substances capable of protecting the crop plants from the damaging action of the herbicide, while not substantially reducing the effectiveness of the herbicide with a given herbicide.
• the interaction of herbicides and safeners is complex, and it is difficult to predict which safeners, if any, will be useful with a given herbicide.
• the compounds of the formulae S-I to S-X are suitable for protecting crop plants from the phytotoxic action of a certain class of isoxazoline herbicides which are described e.g. in WO 01/12613, WO 03/000686, WO 2004/014138 and JP (Kokai) 2004-2324.
• a herbicidal composition which is characterized in that it comprises a mixture of a) a
• Ri and R 2 are each independently of the other hydrogen, C ⁇ -C ⁇ oalkyl, C 3 -C 8 cycloalkyl or
• Ri and R 2 together with the carbon atom to which Ri and R 2 are bonded, form a C 3 -C 7 ring, R3 and R4 are each independently of the other hydrogen, Cr oalkyl, C ⁇ -C 10 haloalkyl,
• Cioalkyl Cioalkyl, Ci-C ⁇ alkoxy-Crdoalkyl or C 3 -C 8 cycloalkyl, or
• R 3 and 4 together with the carbon atom to which R 3 and t are bonded, form a C 3 -C ring, or
• m is an integer selected from 0, 1 or 2;
• R 5 and Re are each independently of the other hydrogen, cyano, C ⁇ -C ⁇ 0 alkyl or C ⁇ - Cioalkoxycarbonyl; n is an integer selected from 1, 2 or 3;
• Y is hydrogen, CrCealkoxycarbonyl, carboxyl, C 2 -C 6 alkenyl, C ⁇ -C ⁇ 0 alkyl or C Cioalkyl substituted by halogen, CrC 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C6alkynyloxy, benzyloxy, Ci- C ⁇ alkoxycarbonyl, carboxyl, hydroxyl or formyl, or Y is phenyl or phenyl substituted by halogen, -C ⁇ alkyl, -C ⁇ haloalkyl, C !
• Ci-Cealkyl hydroxy-Ci-C 6 alkyl, CrCealkylthio-d-Cealkyl, C Cealkylsulfinyl-C C 6 alkyl, Ci-C ⁇ alkylsulfonyl-CrCealkyl, CrCealkylamino-Ci-C ⁇ alkyl, di-Cr Cealkylamino-CrC ⁇ alkyl, cyano- -C ⁇ alkyl or phenoxy- -C ⁇ alkyl, or
• Y is phenyl substituted by C ⁇ -C alkoxy or Cr alkoxy substituted by halogen, Ci- C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C ⁇ alkoxycarbonyl, CrC 6 alkylcarbonyl or C 3 - C 8 cycloalkyl, or
• Y is phenyl substituted by C 2 -C 6 alkenyl, C 3 -C 8 cycloalkoxy, Ci-C 6 alkylthio or C C 6 alkylthiol substituted by halogen or C ⁇ -C 6 alkoxy, or
• Y is phenyl substituted by C ⁇ -C 6 alkylsulfinyl or C ⁇ -C 6 alkylsulfinyl substituted by halogen or -C ⁇ alkoxy, or
• Y is phenyl substituted by Ci-Cealkylsulfonyl or -C ⁇ alkylsulfonyl substituted by halogen or C ⁇ -C 6 alkoxy, or Y is phenyl substituted by benzyloxy, amino or amino substituted by C ⁇ -C 6 alkyl, C C 6 alkylsulfonyl, C ⁇ -C 6 alkylcarbonyl-C ⁇ -C 6 alkyl or C ⁇ -C 6 alkylsulfonyl-C ⁇ -C 6 alkyl, or
• Y is phenyl substituted by di-C ⁇ -C 6 alkylamino, cyano, nitro, C C 6 alkoxycarbonyl, carboxyl, C 3 -C 8 cycloalkoxycarbonyl, C 2 -C 6 alkenyloxycarbonyl, C 2 -C 6 alkynyloxy- carbonyl, benzyloxycarbonyl, phenoxycarbonyl or C ⁇ -C 6 alkylcarbonyloxy or Q- Cealkoxycarbonyl-Ci-Cealkyl, or
• Y is a 5- or 6-membered, mono- or bicyclic aromatic ring which contains one or more nitrogen, oxygen or sulfur atoms as heteroatoms, in which the heteroaromatic ring can be substituted by hydroxyl, mercapto, halogen, C ⁇ -C ⁇ oalkyl or C j -C ⁇ 0 alkyl substituted by hydroxyl, C 3 -C 8 cycloalkyl, halo-C 3 -C 8 cycloalkyl, C 1 -C 4 alkyl-C 3 -C 8 cycloalkyl-, Ci- Cioalkoxy, C ⁇ -C 10 alkylthio, CrC t oalkylsulfonyl, C ⁇ -C ⁇ 0 alkoxycarbonyl, C 2 - C 6 haloalkenyl, amino, CrCioalkylamino, Ci-C ⁇ acylamino, C ⁇ -C 4 haloalkylcarbonyl- amino,
• C 10 alkoxycarbonyl, phenyl, an aromatic heterocyclic radical, cyano, carbamoyl or Ci- Ci 0 alkylcarbam ⁇ yl, or the heteroaromatic ring can be substituted by C C ⁇ aloalkylthio, C 2 -C 6 alkenyl, C 2 - C 6 alkenyloxy, C -C 6 alkynyl, C 2 -C 6 alkynyloxy, Ci-Cioalkylsulfinyl or Crdoalkylsulfinyl substituted by C t -Cioalkoxycarbonyl, phenyl, an aromatic heterocyclic radical, cyano, carbamoyl or C ⁇ -C 10 alkylcarbamoyl, or the heteroaromatic ring can be substituted by CrCioalkylsulfonyl or Ci-Cioalkylsulfonyl substituted by CrQoalkoxycarbonyl,
• Xsi is hydrogen or halogen; and Rsi is hydrogen, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C C 8 alkyl or C ⁇ -C 8 alkyl substituted by d-C 8 alkoxy or C 3 -C 8 alkenyloxy, or
• Rsi is a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium or quaternary ammonium, sulfonium or phosphonium; or of a safener of the formula S -II
• E t is nitrogen or methine
• Xsi are each independently of the other hydrogen or halogen; and Rsi is hydrogen, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C ⁇ -C 8 alkyl or C ⁇ -C 8 alkyl substituted by C ⁇ -C 8 alkoxy or C -C 8 alkenyloxy, or Rsi is a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium or quaternary ammonium, sulfonium or phosphonium; or of a safener of the formula S-III
• Xsi are each independently of the other hydrogen or halogen; and Rsi are each independently of the other hydrogen, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 - C 8 cycloalkyl, C ⁇ -C 8 alkyl or C ⁇ -C 8 alkyl substituted by C ⁇ -C 8 alkoxy or C 3 -C 8 alkenyloxy, or Rsi are a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium or quaternary ammonium, sulfonium or phosphonium; or of a safener of the formula S-IN
• Rsi is hydrogen, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C C 8 alkyl or d-
• Rsi is a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium or quaternary ammonium, sulfonium or phosphonium; or of a safener of the formula S-N
• Rs 2 and Rs 3 together form a radical of the formula , wherein Rs 7 and Rs 8 are each independently of the other d-C 6 alkyl, or Rs 7 and Rs 8 together form -(CH 2 ) 5 -, and
• Rs 6 is hydrogen, Ci-C 6 alkyl, aryl or heteroaryl; or of a safener of the formula S-NI
• sn is 0 or 1 ;
• Rs 12 is hydrogen, d-C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or-N(-Rsj 3 Rs w ); wherein Rs ⁇ and Rs ⁇ 4 are each independently of the other hydrogen, C ⁇ -C 8 alkyl, C - C 8 cycloalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or Rs ⁇ 3 and Rs ⁇ 4 together form a C 4 -C 6 alkylene group, which can be interrupted by oxygen, sulfur, SO, SO 2 , NH or N(C r C 4 alkyl);
• Rs ⁇ 5 is hydrogen or a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium or quaternary ammonium, sulfonium or phosphonium;
• Rs ⁇ 6 is hydrogen, halogen, d-C 8 alkyl or methoxy
• Rs 17 is hydrogen, halogen, d-C 8 alkyl, trifluoromethyl or d-C 8 alkoxy; or of a safener of the formula S-LX
• Rsis is a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium or quaternary ammonium, sulfonium or phosphonium.
• alkyl radicals appearing in the substituent definitions are, for example methyl, ethyl, propyl and butyl, and also branched isomers thereof.
• Haloalkyl radicals include alkyl radicals substituted by one or more halogen, e.g. difluoromethyl or trifluoromethyl, and haloalkoxy radicals include alkoxy radicals substituted by one or more halogen, e.g.
• a herbicidal composition which is characterized in that it comprises a mixture of a) a herbicidally active amount of a herbicide of the formula I wherein
• Ri , R 2 , R 3 , R , R 5 , Re , m and n are defined as above;
• Y is hydrogen, d-C 6 alkoxycarbonyl, carboxyl, C 2 -C 6 alkenyl, d-C 10 alkyl or C ⁇ -C ⁇ 0 alkyl substituted by halogen, C ⁇ -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, benzyloxy, C ⁇ -
• Y is phenyl or phenyl substituted by halogen, Ci-C ⁇ alkyl, d-C 6 haloalkyl, C ⁇ -C 6 alkoxy- d-C 6 alkyl, hydroxy-C r C 6 alkyl, C ⁇ -C 6 alkylthio-C ⁇ -C 6 alkyl, CrCealkylsulfinyl-d- C 6 alkyl, d-C 6 alkylsulfonyl-d-C6alkyl, d-C 6 alkylamino-d-C 6 alkyl, di-Ci- C 6 alkylamino-C ⁇ -C 6 alkyl, cyano-d-C 6 alkyl or phenoxy-C ⁇ -C 6 alkyl, or
• Y is phenyl substituted by CrC 6 alkoxy or d-C 6 alkoxy substituted by halogen, d- C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 alkoxycarbonyl, d-C 6 alkylcarbonyl or C 3 - C 6 cycloalkyl, or
• Y is phenyl substituted by C 2 -C 6 alkenyl, C 3 -C 8 cycloalkoxy, d-Cealkylthio or d- C 6 alkylthiol substituted by halogen or d-C 6 alkoxy, or
• Y is phenyl substituted by C ⁇ -C 6 alkylsulfinyl or C ⁇ -C 6 alkylsulfinyl substituted by halogen or d-C 6 alkoxy, or
• Y is phenyl substituted by C ⁇ -C 6 alkylsulfonyl or C ⁇ -C alkylsulfonyl substituted by halogen or d-C 6 alkoxy, or Y is phenyl substituted by benzyloxy, amino or amino substituted by C ⁇ -C 6 alkyl, d- C 6 alkylsulfonyl, C ⁇ -C 6 alkylcarbonyl ⁇ d-C 6 alkyl or d-C ⁇ alkylsulfonyl-Ci-dalkyl, or
• Y is phenyl substituted by di-d-C 6 alkylamino, cyano, nitro, C ⁇ -C 6 alkoxycarbonyl, carboxyl, C 3 -C 8 cycloalkoxycarbonyl, C 2 -C 6 alkenyloxycarbonyl, C 2 -C 6 alkynyloxy- carbonyl, benzyloxycarbonyl, phenoxycarbonyl or C ⁇ -C 6 alkylcarbonyloxy or Ci- C 6 alkoxycarbonyl-C ⁇ -C 6 alkyl, or
• Y is a 5- or 6-membered, mono- or bicyclic aromatic ring which contains one or more nitrogen, oxygen or sulfur atoms as heteroatoms, in which the heteroaromatic ring can be substituted by hydroxyl, mercapto, halogen, d-C ⁇ 0 alkyl or d-Cioalkyl substituted by hydroxyl, C 3 -C 8 cycloalkyl, halo-C 3 -C 8 cycloalkyl, C ⁇ -C 4 alkyl-C 3 -C 8 cycloalkyl-, Cj- C 10 alkoxy, d-Cioalkylthio, C ⁇ -C 10 alkylsulfonyl, CrCioalkoxycarbonyl, C 2 - C 6 haloalkenyl, amino, C ⁇ -C ⁇ 0 alkylamino, C ⁇ -C 6 acylamino, Ci - C 4 haloalkylcarbonylamino, d-C
• Cioalkoxy, Ci-Cioalkoxycarbonyl or Ci-C ⁇ 0 alkoxy substituted by C ⁇ -C ⁇ 0 alkoxycarbonyl, phenyl, an aromatic heterocyclic radical, cyano or carbamoyl, or the heteroaromatic ring can be substituted by d-C 4 haloalkoxy, C 3 -C 8 cycloalkoxy, C 3 - C 8 cycloalkyl-Ci-C 3 alkoxy, Ci-Cioalkylthio or Ci-C ⁇ 0 alkylthio substituted by d- Cioalkoxycarbonyl, phenyl, an aromatic heterocyclic radical, cyano or carbamoyl, or the heteroaromatic ring can be substituted by C ⁇ -C 4 haloalkylthio, C 2 -C 6 alkenyl, C 2 - C ⁇ alkenyloxy, C 2 -C 6 alkynyl, C 2 -C 6 al
• Ri and R 2 are each independently of the other hydrogen, Ci-C 10 alkyl, C 3 -C 8 cycloalkyl or
• R 3 and 4 are each independently of the other hydrogen, d-Cioalkyl, d-C 10 haloalkyl,
• R and R- t together with the carbon atom to which R 3 and R 4 are bonded, form a C 3 -C 7 ring, or
• R 5 and Re are each independently of the other hydrogen, cyano, Ci-Cioalkyl or d-
• Cioalkoxycarbonyl is an integer selected from 1, 2 or 3;
• Y is hydrogen, d-C 6 alkoxycarbonyl, carboxyl, C 2 -C 6 alkenyl, C ⁇ -C ⁇ 0 alkyl or d-Cioalkyl substituted by halogen, C ⁇ -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, benzyloxy, Ci- C 6 alkoxycarbonyl, carboxyl, hydroxyl or formyl, or
• Y is phenyl or phenyl substituted by halogen, d-C 6 alkyl, C ⁇ -C 6 haloalkyl, C ⁇ -C 6 alkoxy-
• C 6 alkyl C ⁇ -C 6 alkylsulfonyl-d-C 6 alkyl, C ⁇ -C 6 alkylamino-C ⁇ -C 6 alkyl, di-Ci-
• Y is phenyl substituted by C 2 -C 6 alkenyl, C 3 -C 8 cycloalkoxy, C ⁇ -C 6 alkylthio or C C 6 alkylthiol substituted by halogen or d-C 6 alkoxy, or
• Y is phenyl substituted by C ⁇ -C 6 alkylsulfinyl or C ⁇ -C 6 alkylsulfinyl substituted by halogen or C ⁇ -C 6 alkoxy, or
• Y is phenyl substituted by C ⁇ -C 6 alkylsulfonyl or C ⁇ -C 6 alkylsulfonyl substituted by halogen or Ci-C 6 alkoxy, or Y is phenyl substituted by benzyloxy, amino or amino substituted by d-C 6 alkyl, d- Cealkylsulfonyl, d-C 6 alkylcarbonyl-C ⁇ -C 6 alkyl or Ci-C 6 alkylsulfonyl-Ci-C 6 alkyl, or
• Y is phenyl substituted by di-C ⁇ -C 6 alkylamino, cyano, nitro, Ci-C 6 alkoxycarbonyl, carboxyl, C 3 -C 8 cycloalkoxycarbonyl, C 2 -C 6 alkenyloxycarbonyl, C 2 -C 6 alkynyloxy- carbonyl, benzyloxycarbonyl, phenoxycarbonyl or C ⁇ -C 6 alkylcarbonyloxy or Ci- C 6 alkoxycarbonyl-Ci-C 6 alkyl, or
• Y is a 5- or 6-membered, mono- or bicyclic aromatic ring which contains a nitrogen, oxygen or sulfur atom as a heteroatom, in which the heteroaromatic ring can be substituted by hydroxyl, mercapto, halogen, Ci-doalkyl or C ⁇ -C 10 alkyl substituted by hydroxyl, C 3 -C 8 cycloalkyl, halo-C 3 -C 8 cycloalkyl, d-C 4 alkyl-C 3 -C 8 cycloalkyl-, Ci- Cioalkoxy, C ⁇ -C 10 alkylthio, Ci-Cioalkylsulfonyl, Ci-doalkoxycarbonyl, C 2 - C 6 haloalkenyl, amino, C ⁇ -C ⁇ 0 alkylamino, C ⁇ -C 6 acylamino, Ci - C haloalkylcarbonylamino, Ci-C ⁇ 0 alkylsulf
• C 10 alkoxy, C ⁇ -C 10 alkoxycarbonyl or d-Cioalkoxy substituted by Ci-doalkoxycarbonyl, phenyl, an aromatic heterocyclic radical, cyano or carbamoyl, or the heteroaromatic ring can be substituted by d-C 4 haloalkoxy, C 3 -C 8 cycloalkoxy, C - C 8 cycloalkyl-Ci-C 3 alkoxy, d-Cioalkylthio or C ⁇ -C ⁇ 0 alkylthio substituted by Ci- Cioalkoxycarbonyl, phenyl, an aromatic heterocyclic radical, cyano or carbamoyl, or the heteroaromatic ring can be substituted by d-C 4 haloalkylthio, C 2 -C 6 alkenyl, C 2 - C 6 alkenyloxy, C 2 -C 6 alkynyl, C 2 -C 6 alkyny
• Preferred safeners correspond to the formula S-I.l
• Rsi is hydrogen, C 3 -C 8 cycloalkyl, C ⁇ -C 8 alkyl or C ⁇ -C 8 alkyl substituted by Ci- C 8 alkoxy or C 3 -C 8 alkenyloxy, or
• Rsi is a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium, quaternary ammonium, sulfonium or phosphonium; or to the formula S-II.1 wherein Rsi is C ⁇ -C 8 alkyl or d-C 8 alkyl substituted by C 3 -C 8 alkenyloxy; or to the formula S-III.1
• Rs 2 and Rs 3 together form a radical of the formula , wherein Rs 7 and Rs 8 are each independently of the other C ⁇ -C 4 alkyl, or Rs and Rs 8 together form -(CH ) 5 -, and
• Rs 6 is hydrogen, C ⁇ -C 4 alkyl or ; or to the formula S-NI.l
• Rs ⁇ 3 and Rs ⁇ together form a C -C 6 alkylene group
• Rsi 5 is hydrogen or a cation chosen from the group consisting of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium or quaternary ammonium, sulfonium or phosphonium;
• Rsi 6 is hydrogen, C ⁇ -C 6 alkyl or methoxy
• Rs ⁇ is hydrogen, Ci-C ⁇ alkyl or C ⁇ -C 6 alkoxy; or to the formula S-IX.l
• Particularly preferred safeners of the formula S-I.l are cloquintocet-mexyl (CAS RN 99607-70-2) or a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof such as are known from WO 02/34048; of the formula S-II.l fenchlorazole-ethyl (CAS RN 103112- 35-2 and CAS RN 103112-36-3 for the corresponding acid); of the formula S-ffl.l mefenpyr-diethyl (CAS RN 135590-91-9 and CAS RN 135591-00-3 for the corresponding di-acid); of the formula S-1N.1 isoxadifen-ethyl (CAS R ⁇ 163520-33-0 and CAS R ⁇ 209866-92-2 for the corresponding acid); of the formula S-N.l furilazole (CAS R ⁇ 121776-33-8
• More particularly preferred safeners of the formula S-I.l are cloquintocet-mexyl or a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, phosphonium or sulfonium salt thereof; of the formula S-II.l fenchlorazole-ethyl and the corresponding acid; and of the formula S-III.1 mefenpyr- diethyl and the corresponding di-acid; of the formula S-V.l furilazole and the corresponding R isomer, benoxacor, dichlormid and MON4660.
• Safeners of the formula S-I.l are cloquintocet- mexyl or a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, , ammonium, quaternary ammonium, phosphonium or sulfonium salt thereof; of the formula S-II.l fenchlorazole-ethyl and the corresponding acid; and of the formula S-III.1 mefenpyr-diethyl and the corresponding di-acid; of the formula S-N.l benoxacor and MO ⁇ 4660.
• Even more particularly preferred safeners of the formula S-I.l are cloquintocet- mexyl; of the formula S-II.l fenchlorazole-ethyl; of the formula S-III.1 mefenpyr- diethyl; and of the formula S-N.l benoxacor and MO ⁇ 4660.
• particularly preferred safeners of the formula S-I.l are cloquintocet- mexyl or a lithium, sodium, potassium, calcium, magnesium, alun-unium, iron, ammonium, quaternary ammonium, phosphonium or sulfonium salt thereof such as are known from WO 02/34048; of the formula S-LT.l fenchlorazole-ethyl and the corresponding acid; of the formula S-III.1 mefenpyr-diethyl and the corresponding di- acid; of the formula S-IN.l isoxadifen-ethyl and the corresponding acid; of the formula S-N.l furilazole and the corresponding R isomer, benoxacor and dichlormid; of the formula S-NI.l oxabetrinil and cyometrinil and the corresponding (Z) isomer; of the formula S-NII.l fenclorim; of the formula S-NLII.l ⁇ -
• particularly preferred safeners of the formula S-I.l are cloquintocet- mexyl or sulfonium or phosphonium salts thereof such as are known from WO 02/34048; of the formula S-II.l fenchlorazole-ethyl and the corresponding acid); of the formula S- III.1 mefenpyr-diethyl and the corresponding di-acid; of the formula S-IN.1 isoxadifen- ethyl and the corresponding acid; of the formula S-N.l furilazole and the corresponding R isomer, benoxacor and dichlormid; of the formula S-NI.l oxabetrinil and cyometrinil and the corresponding (Z) isomer; of the formula S-NII.l fenclorim; of the formula S- NIII.1 ⁇ -cyclopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide and
• Preferred compounds of the formula I are those wherein Ri and R 2 are each independently of the other C d 0 alkyl or C 3 -C 8 cycloalkyl, or Ri and R 2 , together with the carbon atom to which Ri and R 2 are bonded, form a C 3 -C ring, more preferably Ri and R 2 are both methyl.
• Further preferred compounds of the formula I are those wherein R 3 and R 4 are each independently of the other hydrogen, Ci-Cioalkyl or C 3 -C 8 cycloalkyl, or R 3 and R 4 , together with the carbon atom to which R and P ⁇ are bonded, form a C -C 7 ring, more preferably R 3 and R 4 are both hydrogen.
• n is 1.
• Y is phenyl or phenyl substituted by Ci-C 6 alkyl, C ⁇ -C 6 haloalkyl, C ⁇ -C 6 alkoxy-C.-C 6 alkyl, C ⁇ -C 6 alkoxy, Ci- C ⁇ haloalkoxy, d-C 6 alkoxy-C ⁇ -C 6 alkoxy or halogen.
• Y is a 5- or 6- membered mono- or bicyclic aromatic ring which contains one or more nitrogen, oxygen or sulfur atoms as heteroatoms, in which the heteroaromatic ring can be substituted by Ci-Cioalkyl or Ci-Cioalkyl substituted by C ⁇ -C ⁇ 0 alkoxy, or the heteroaromatic ring can be substituted by Ci-Cioalkylsulfonyl, C ⁇ -C haloalkyl, C 3 -C 8 cycloalkyl, d-Cioalkoxy, Ci- C 4 haloalkoxy, Ci-doalkoxycarbonyl, C -C 8 cycloalkyl-C ⁇ -C 3 alkoxy, Ci-Cioalkylthio, phenyl, phenoxy, C ⁇ -C 4 haloalkylcarbonyl, cyano, nitro, halogen, carbamoyl, Ci-
• Y is a 5- or 6-membered mono- or bicyclic aromatic ring which contains a nitrogen, oxygen or sulfur atom as a heteroatom, in which the heteroaromatic ring can be substituted by Ci- doalkyl or Ci-Cioalkyl substituted by C ⁇ -C ⁇ 0 alkoxy; or the heteroaromatic ring can be substituted by Ci-doalkylsulfonyl, C ⁇ -C 4 haloalkyl, C 3 -C 8 cycloalkyl, C ⁇ -C ⁇ oalkoxy, Ci- Ciohaloalkoxy, Ci -Cioalkoxycarbonyl, C 3 -C 8 cycloalkyl-C ⁇ -C alkoxy, Ci-doalkylthio, phenyl, phenoxy, d-C 4 haloalkylcarbonyl, cyano, nitro, halogen, carbamoyl, Ci- Ci
• Y is thienyl, pyrazolyl, isoxazolyl, isothiazolyl, pyridyl or pyrimidyl.
• Y is thien-3-yl, pyrazol-4-yl, pyrazol-5-yl, isoxazol-4-yl, isothiazol-4-yl, pyridin-3-yl or pyrimidin-5-yl.
• a most preferred compound of the formula I is 3-(5-difluoromethoxy-l-methyl-3- trifluoromethyl-lH-pyrazol-4-ylmethylsulfonyl)-5,5-dimethyl-4,5-dihydroisoxazole, which is compound of the formula 1.27 in Table 1 below. Particularly suitable compounds of the formula I are summarized in the following table.
• a particularly preferred combination is the combination of compound of the formula 1.27 with benoxacor, in particular when used to safen compound of the formula 1.27 on maize, more particularly in post- emergent use.
• Further particularly preferred combinations are the combinations of compound of the formula 1.27 with cloquintocet-mexyl, compound of the formula 1.27 with MON4660, compound of the formula 1.27 with mefenpyr-diethyl, and compound of the formula 1.27 with fenchlorazole-ethyl, in particular when used to safen compound of the formula 1.27 on wheat or barley, more particularly in pre-emergent use.
• Particularly preferred combinations are the combinations of a compound of the formula 1.41 with benoxacor, compound of the formula 1.41 with dichlormid, compound of the formula 1.41 with furilazole, and compound of the formula 1.41 with N-isopropyl-4-(2-methoxy- benzoylsulfamoyl)-benzamide, in particular when used to safen compound of formula 1.41 on maize, more particularly in pre-emergent use.
• Particularly preferred combinations are the combinations of compound of the formula 1.57 with cloquintocet- mexyl, compound of the formula 1.57 with MON4660, compound of the formula 1.57 with mefenpyr-diethyl, and compound of the formula 1.57 with fenchlorazole-ethyl, in particular when used to safen compound of the formula 1.57 on wheat or barley, more particularly h pre-emergent use.
• the invention also relates to a method of combating weed grasses and weeds in crops of useful plants, which comprises treating the useful plants, seed or cuttings thereof or the growing area thereof simultaneously or at separate times with a herbicidally active amount of the herbicide of the formula I and a herbicide-antagonistically active amount of a safener of the formula S-I to S-X.
• a herbicidally active amount of the herbicide of the formula I and a herbicide-antagonistically active amount of a safener of the formula S-I to S-X.
• Possible crop plants which can be protected by the safeners of the formula S-I to S-X from the harmful action of the above mentioned herbicides are, in particular, soya, cotton, rape, sugarcane, cereals, e.g. wheat and barley, rice and, specifically, maize.
• Crops are also to be understood as meaning those which have been made tolerant towards herbicides or herbicide classes (e.g. ALS, GS, EPSPS, PPO and HPPD inhibitors) by conventional breeding or genetic engineering methods.
• herbicides or herbicide classes e.g. ALS, GS, EPSPS, PPO and HPPD inhibitors
• An example of crops which have been made tolerant e.g. towards imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer rape (Canola).
• crops which have been made tolerant towards herbicides by genetic engineering methods are e.g.
• the weeds to be combated can be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
• Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanth
• Crops are furthermore to be understood as meaning those which, by genetic engineering methods, have been made resistant to harmful insects, such as, for example, Bt maize (resistant to the corn borer), Bt cotton (resistant to the cotton-boll weevil) and also Bt potatoes (resistant to the potato beetle).
• Bt maize are the Bt-176 maize hybrids of NK® (Syngenta Seeds).
• the Bt toxin is a protein which is formed naturally by Bacillus thuringiensis soil bacteria.
• Examples of toxins and transgenic plants which can synthesize such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
• Examples of transgenic plants which contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and seed thereof can be resistant both to herbicides and at the same time to insect feeding (stacked transgenic events).
• Seed can have, for example, the ability to express an insecticidally active Cry3 protein and at the same can be tolerant towards glyphosate.
• Crops are also to be understood as meaning those which are obtained by conventional breeding or genetic engineering methods and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved taste).
• Growing areas are understood as meaning the areas of soil on which the crop plants are already growing or which are already charged with seed of these crop plants, and also soils intended for cultivation with these crop plants.
• the compounds of formula I according to the invention can also be used in combination with other herbicides.
• the following mixtures of the compound of formula I are important: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of formula I + acrolein, compound of formula I + alachlor, compound of formula I + alloxydim, compound of formula I 4- allyl alcohol, compound of formula I 4- ametryn, compound of formula I + amicarbazone, compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + amitrole, compound of formula I + ammonium sulfamate, compound of formula I + anilofos, compound of formula I + asulam, compound of formula I + atraton, compound of formula I + atrazine, compound of formula I + azimsulfuron, compound of formula I + BCPC, compound of formula I + beflubutamid, compound of formula I + benazolin, compound of
• the mixing partners of the compound of formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 12th Edition (BCPC), 2000.
• the mixing ratio of the compound of formula I to the mixing partner is preferably from l : 100 to 1000:1.
• the mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula I with the mixing partner).
• the compositions according to the invention are suitable for all the conventional methods of application in agriculture, such as e.g. pre-emergent application, post- emergent application and seed dressing.
• a safener of the formula S-I to S-X can be employed for pre-treatment of the seed of the crop plant (dressing of the seed or cuttings) or can be introduced into the soil before or after sowing. However, it can also be applied by itself or together with the herbicide before or after emergence of the plants.
• the treatment of the plants or seed with the safener can therefore in principle be carried out independently of the time of application of the herbicide. Treatment of the plants by simultaneous application of herbicide and safener (e.g. as a tank mix) is as a rule preferred.
• the application rate of safener to herbicide to be applied largely depends on the method of use.
• 0.001 to 5.0 kg of safener/ha preferably 0.001 to 0.5 kg of safener/ha, and as a rule between 0.001 to 2 kg of herbicide/ha, but preferably between 0.005 to 1 kg/ha are applied.
• seed dressing in general 0.001 to 10 g of safener/kg of seed, preferably 0.05 to 2 g of safener/kg of seed are applied. If the safener is applied in liquid form, with soaking of the seed, shortly before sowing, safener solutions which contain the active compound in a concentration of 1 to 10,000, preferably 100 to 1,000 ppm are expediently used.
• a mixture of a herbicidally active amount of the compound of the formula I and a herbicide- antagonistic amount of the compound of the formula S-I to S-X can be employed in unchanged form as a herbicidal composition.
• the compositions according to the invention are formulated in various ways using formulation auxiliaries, such as carrier substances, solvents and surface-active substances.
• the formulations can be in various physical forms, e.g.
• the dilutions can be prepared, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.
• the formulations can be prepared e.g. by mixing the active compound with formulation auxiliaries in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
• the active compounds can also be formulated with other auxiliaries, such as, for example, finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surface-active substances or combinations thereof.
• the active compounds can also be contained in very fine microcapsules made of a polymer.
• Microcapsules contain the active compounds in a porous carrier. This allows release of the active compounds into the environment in controlled amounts (e.g. slow release). Microcapsules conventionally have a diameter of 0.1 to 500 micron. They contain active compounds in an amount of approx. 25 to 95 wt.% of the capsule weight.
• the active compounds can be in the form of a monolithic solid, fine particles distributed in a solid or liquid, or a suitable solution.
• the enclosing membranes comprise, for example, natural and synthetic gums, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers which are known to the expert in this connection.
• very fine microcapsules in which the active compound is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not surrounded by a shell, can be formed.
• the formulation auxiliaries which are suitable for the preparation of the compositions according to the invention are known per se.
• Liquid carriers which can be used are: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2- butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamme, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate
• Water is in general the carrier of choice for dilution of the concentrates.
• suitable solid carriers are e.g. talc, titanium dioxide, pyrophyllite alumina, silica, attapulgite alumina, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton-seed husks, wheat flour, soya flour, pumice, wood flour, ground walnut shells, lignin and similar substances such as are described, for example, in CFR 180.1001.
• a large number of surface-active substances can advantageously be used both in solid and in liquid formulations, in particular in those which can be diluted with a carrier before use.
• Surface-active substances can be anionic, cationic, nonionic or polymeric, and they can be employed as emulsifying, wetting or suspending agents or for other purposes.
• Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)-sulfosuccinate; sorbitol est
• auxiliaries which can conventionally be used in pesticidal formulations include crystallization inhibitors, viscosity-modifyin substances, suspending agents, dyestuffs, antioxidants, foams, light absorption agents, mixing auxiliaries, defoamers, complexing agents, neutralizing or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, micronutrients, softeners, slip agents, lubricants, dispersing agents, thickeners, antifreezes, microbiocidal agents, and furthermore liquid and solid fertilizers.
• the formulations can also comprise additional active substances, e.g. further herbicides, plant growth regulators, fungicides or insecticides.
• the compositions according to the invention can furthermore comprise an additive comprising an oil of plant or animal origin, a mineral oil, alkyl esters of these oils or mixtures of these oils and oil derivatives.
• the application rates of oil additive in the composition according to the invention is as a rule between 0.01 and 10 %, based on the spray liquor.
• the oil additive can be added into the spray tank in the desired concentration after preparation of the spray liquor.
• Preferred oil additives comprise mineral oils or an oil of plant origin, such as, for example, rape oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rh ⁇ ne-Poulenc Canada Inc.), alkyl esters of oils of plant origin, such as, for example, the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
• a preferred additive substantially comprises e.g. as active components 80 wt.% of alkyl esters offish oils and 15 wt.% of methylated rape oil, as well as 5 wt.% of conventional emulsifiers and pH modifiers.
• Particularly preferred oil additives comprise alkyl esters of C 8 -C 22 fatty acids, the methyl derivatives of C ⁇ 2 -C 18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance in particular.
• These esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112- 62-9).
• a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH).
• These and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
• the application and the action of the oil additives can be improved still further by combination with surface-active substances, such as nonionic, anionic or cationic surfactants.
• surface-active substances such as nonionic, anionic or cationic surfactants.
• suitable anionic, nonionic and cationic surfactants are listed in WO 97/34485 on pages 7 and 8.
• Preferred surface-active substances are anionic surfactants of the dodecylbenzenesulfonate type, in particular the calcium salts thereof, and nonionic surfactants of the fatty alcohol ethoxylate type. Ethoxylated C ⁇ 2 -C 22 -fatty alcohols having a degree of ethoxylation of between 5 and 40 are particularly preferred.
• Examples of commercially obtainable surfactants are the Genapol types (Clariant AG).
• Silicone surfactants in particular polyalkyl oxide-modified heptamethyltrisiloxanes, which are commercially obtainable e.g. as Silwet L-77®, and perfluorinated surfactants are likewise preferred.
• concentration of the surface-active substances with respect to the total additive is in general between 1 and 30 wt.%.
• oil additives which comprise mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta Agro, CH) or Actipron® (BP Oil UK Limited, GB).
• the surface-active substances mentioned can optionally also be used in the formulations by themselves, i.e. without oil additives.
• an organic solvent may furthermore contribute towards an additional increase in the action.
• Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation).
• the concentration of such solvents can be from 10 to 80 wt.% of the total weight.
• Such oil additives which are in the form of a mixture with solvents are described, for example, in US-A-4,834,908.
• a commercially obtainable oil additive known from this is known by the name MERGE® (BASF Corporation).
• a further oil additive which is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
• formulations of alkylpyrrolidones e.g.
• Agrimax® may furthermore also be added to the spray liquor to increase the action of the compositions according to the invention.
• Formulations of synthetic lattices such as e.g. polyacrylamide, polyvinyl compounds or poly-l-p- menthene (e.g. Bond®, Courier® or Emerald®) can also be used for this.
• Solutions containing propionic acid, such as e.g. Eurogkem Pen-e-trate® can furthermore also be admixed to the spray liquor as action-increasing agents.
• the herbicidal formulations as a rule comprise 0.1 to 99 wt.%, in particular 0.1 to 95 wt.% of active compound mixture of the compound of the formula I with the compounds of the formula II, and 1 to 99.9 wt.% of a formulation auxiliary, which preferably comprises 0 to 25 wt.% of a surface-active substance. While concentrated compositions are conventionally preferred as commercial goods, the end user as a rule uses diluted compositions.
• Various methods and techniques are suitable for using safeners of the formula ⁇ or compositions containing them for protecting crop plants from the harmful actions of herbicides of the formula I, such as, for example, the following: i) Seed dressing a) Dressing of the seed with an active compound of the formula II formulated as a wettable powder by shaking in a vessel until uniform distribution over the seed surface is achieved (dry dressing). About 1 to 500 g of active compound of the formula S-I to S-X 5 (4 g to 2 kg of wettable powder) per 1 0 kg of seed are used here. b) Dressing of the seed with an emulsion concentrate of the active compound of the formula S-I to S-X by method a) (wet dressing). c) Dressing by immersing the seed in a liquor with 100-1,000 ppm of active compound of the formula S-I to S-X for 1 to 72 hours and optionally subsequent drying of the seed
• the dressing of the seed or the treatment of the sprouted seedling are of course the preferred methods of application, because the treatment with the active compound is directed entirely at the target crop.
• 1 to 1,000 g of antidote,, preferably 5 to 250 g of antidote are used per 100 kg of seed, it being possible to deviate upwards or
• Emulsifiable concentrates Active mixture of active compounds: 1 to 95 %, preferably 60 to 90 % Surface-active agent: 1 to 30 %, preferably 5 to 20 % Liquid carrier: 1 to 80 %, preferably 1 to 35 %
• Dusts Active mixture of active compounds: 0.1 to 10 %, preferably 0.1 to 5 % Solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
• Suspension concentrates Active mixture of active compounds: 5 to 75 %, preferably 10 to 50 % Water: 94 to 24 %, preferably 88 to 30 % Surface-active agent: 1 to 40 %, preferably 2 to 30 %
• Wettable powders Active mixture of active compounds: 0.5 to 90 %, preferably 1 to 80 %
• Surface-active agent 0.5 to 20 %, preferably 1 to 15 % Solid carrier material: 5 to 95 %, preferably 15 to 90 %
• Granules Active mixture of active compounds: 0.1 to 30 %, preferably 0.1 to 15 % Solid carrier: 99.5 to 70 %, preferably 97 to 85 %
• Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
• the solutions are suitable for use in the form of tiny drops.
• Active compound mixture 55 %% 2255 %% 5500%% 80%
• the active compound is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. Wettable powders which can be diluted with water to give suspensions of any desired concentration are obtained.
• Active compound mixture 0.1 % 5% 15%
• Active compound mixture 0.1 % 5% 15% Polyethylene glycol MW 200 1.0% 2% 3%
• Inorg. carrier material 98.0 % 92% 80%
• Finely ground active compound such as e.g. CaCO 3 or SiO 2
• the finely ground active compound is applied uniformly, in a mixer, to the carrier material moistened with polyethylene glycol. Dust-free coated granules are obtained in this manner.
• the active compound is mixed with the additives and the mixture is ground and moistened with water. This mixture is extruded and then dried in a stream of air. F7. Dusts . a) b) c)
• Ready-to-use dusts are obtained by mixing the active compound with the carrier substances and grinding the mixture in a suitable mill.
• Active compound mixture 3% 10% 25 % 50%
• the finely ground active compound is mixed intimately with the additives.
• a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water is obtained in this way. It is often more practical to formulate the active compound of the formula I and the mixing partner of the formula S-I to S-X individually and then to bring them together as a "tank mix" in water in the applicator in the desired mixing ratio shortly before application.
• the ability of the safeners of the formula S-I to S-X to protect crop plants from the phytotoxic action of herbicides of the formula I is illustrated in the following examples.

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