Indian Patents. 214354:HERBICIDAL COMPOSITION

Title of Invention	HERBICIDAL COMPOSITION
Abstract	Herbicidal composition comprising: a) a herbicidally effective amount of a compound of formula (I), wherein the substituents are as defined in claim 1; and b) an amount, effective for herbicide synergy, of mesosulfuron, mesotrione or flufenacet.

Full Text	HerbiC1dal composition The present invention relates to new herbiC1dal compositions for controlling grasses and weeds in C1ops of useful plants, espeC1ally in C1ops of maize and cereals, which compositions comprise a tetrahydropyrazolodione herbiC1de known from, for example, WO 99/47525, and a co-herbiC1de. The present invention relates to a herbiC1dal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbiC1dally effective amount of a compound of formula I wherein R1 and R3 are, each independently of the other, halogen, nitro, cyano, C1-C4alkyl, C2-C4-alkenyl, C2-C4alkynyl, C1-C4haloalkyl, C2-Cehaloalkenyl, C3-C6CycloalkyI, halo-substituted C8-C8cycloalkyl, C2-C8alkoxyalkyl, C2-C8alkylthioalkyl, hydroxy, mercapto, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, carbonyl, carboxyl, C1-C4alkylcarbonyl, C1-C4hydroxyalkyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkylamino or di(C1-C4alkyl)amino; R4 and R5 together are a group -C-R6(R7)-0-C-R6(R9)-C-R10(R11)-C-R,2(R,3)- (Z,), -C-R,4(R,5)-C-Ri6(Ru)-0-C-R,s(R,9)-C-R2o(R2i)- (Z2) or -C-R22(R23)-C-R24(R25)-C-R26(R27)-0-C-R28(R29)- (Z3), wherein R6, R7, Re, R9, R10 R11, R12. R13. R14. R15. R16. R17. R18. R19. R20. R21- R22- R23. R24. R25. R26. R27- R28 and R29 are, each independently of the others, hydrogen, halogen, C1-C4 alkyl or C1-C4haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the groups Z1, Z2 or Z3 contains from 2 to 6 carbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the carbon atoms of the groups Z,, Z2 or Z3, or that alkylene ring bridges at least one ring atom of the groups Z,, Z^ or Z3; G is hydrogen, -C(X,)-R3o, -CCX)-Xa-R3,, -C(X4)-N(R32)-R33, -SO2-R34, an alkali metal, alkaline earth metal, sulfonium or ammonium cation, or -P(X5)(R35)-R36 or -CH2-X6-R37; X,, X2, X3, X4, X5 and Xg are, each independently of the others, oxygen or sulfur; R30, Rsi, R32 and R33 are, each independently of the others, hydrogen, C1-C1oalkyl, C1-C10-haloalkyl, C,-C1ocyanoalkyl, C,-C1onitroalkyl, C1-C1oaminoalkyl, C1-C8alkylamino-C1C8alkyl, C2-C8dialkylamino-C1-C8alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C1oalkoxy-aIkyl, C4-C10-alkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, C2-C1oalkylthio-alkyI, C1-C8alkysulfoxyl-C1-C8alkyl, C1-C8alkylsulfonyl-C1-C8alkyj, C2-C8alkylideneamino-oxy-C1-C5alkyl, C1-C8aikylcarbonyl-C1-C8alkyl, C1-C8alkoxycarbonyl-C1-C3aikyl, C1-C8amino-carbonyl-C1-C3alkyl, C2-C8dialkyl-amino-carbonyl-C1-C3alkyl, C1C8alkylcarbonylamino-C1-C8alkyl, C2-C5alkylcarbonyl-{C1-C5-alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5a!kyl, phenyl-C1C8alkyl, heteroaryl-C1-C8alkyl, phenoxy-C1-C8alkyl, heteroaryloxy-C1-C8alkyl, C2-C8alkenyl, C2-C5haloalkenyl, Ca-C8Cyclo-alkyl, phenyl, or C1-CaalkyI-, C1-C3haloalkyl-, C1-Caalkoxy-, C1Cahaloalkoxy-, halo-, cyano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3-alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroaryl-amino, C1-C8alkyl-, C1-C8haloalkyI-, C1-C8alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1C3alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C8haloalkyl-, C1-C8alkoxy-, C1-Cahaioalkoxy-, halo-, cyano- or nitro-substituted diphenyl¬amino, C3-C7cycloalkylamino, C1-C3alkyl-, C1-C8haloalkyI-, C1-C3alkoxy-, C1C8haloalkoxy-, halo-, cyano- or nitro-substituted Ca-CTcycloalkylamino, di-C3-C7cycloaikylamino, C1-C3alkyl-, C1-Cahaloalky!-, C1-C3alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted di-C3-C7-cycloalkylamino, C3-C7cycloalkoxy or C1-C3alkyl-, C1-C8haloalkyl-, C1-C3a!koxy-, C1-C3halo-alkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkoxy; R34, R35 and R35 are, each independently of the others, hydrogen, C,-C1oalkyl, C1-C1ohalo-alkyl, C,-C1ocyanoalkyl, C1-C1onitroalkyl, C1C1oaminoalkylj C1-C8alkylamino-C1-C8alkyI, C2-C8dialkylamino-C1-C8alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C1oalkoxy-alkyl, C4-C10-alkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, C2-C1oalkylthio-alkyI, C1-C8alkysulfoxyl-C1C8alkyl, C1-C8alkylsulfonyl-C1-C8alkyl, C2-C8alkylideneamino-oxy-C1-C5alkyl, C1-C8alkylcarbonyl-C1-C3alkyl, C1-C8alkoxycarbonyl-C1-C3alkyl, C1-C8amino-carbonyl-C1-C8alkyI, C3-C8dialkyl-amino-carbonyl-C1-C8alkyl, d-C8alkylcarbonylamino-C1-C8alkyl, C2-C8alkylcarbonyl- (C1C8alkyO-aminoalkyI, C8-C8trialkylsilyl-C1-C8alkyl, phenyl-C1C8alkyI, heteroaryl-C,-C5alkyl, phenoxy-C1C8alkyl, heteroaryloxy-C1-C8alkyI, C2-C8alkenyl, C3-C8haloalkenyl, C8-C8cyclo-alkyl, phenyl, or d-C3alkyl-, C1CahaloalkyI-, C1-C3alkoxy-, C1C3haloalkoxy-. halo-, cyano- or nitro-substituted phenyl or heteroaryl or heteroarylamlno, C1-CaalkyI-, C1-C8haloalkyI-, C1-C3-alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroaryl-amino, C1-C8alkyl-, C1-CahaloalkyI-, C1C8alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C8alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C8haloalkyl-, C1-Caalkoxy-, C1Cahaloalkoxy-, halo-, cyano- or nitro-substituted diphenyl¬amino, Ca-CyCyC3oalkylamino, C1-CaaJkyl-, C1-C8haloalkyI-, C1-C8alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted C8-Cycycloalkylamino, di-C8-CyCycloalkylamino, C1-C3alkyl-, C1-Cahaloalkyl-, C1-C8alkoxy-, C1C8haloalkoxy-, halo-, cyano- or nitro-substituted di-C3-C7-cycloalkylamino, Ca-Cycycloalkoxy, C1Caalkyl-, C1CahaloalkyI-, C1-C3alkoxy-, C1-C8halo-alkoxy-, halo-, cyano- or nitro-substituted Ca-Cycycloalkoxy, C1-C1oalkoxy, C1-C1ohaloalkoxy, C1-C8alkylamino, C2-C8dialkylamino and benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by C1-C3alkyI, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, cyano, formyl, acetyl, propionyl, carboxyl, C1-C8alkoxy-carbonyl, methylthio, ethylthio or by nitro; and R37 is C1-C1oalkyl, C1-C1ohaloalkyl, C1-C,oCyanoalkyl, C1-C1onitroalkyl, C1-C1oaminoalkyl, C1-C8alkylamino-C1-C8alkyl, C2-Cedialkylamino-C1-C8alkyI, C3-C7cycloalkyl-C1-C5alkyl, C2-C,oalkoxy-alkyl, C4-C1oalkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, C2-C1oalkylthio-alkyI, C1-C8alkysulfoxyl-C1-C8alkyl, C1-C8alkylsulfonyl-C1-C8alkyI, C2-Caalkylideneamino-oxy-C1-C8alkyl, C1-C8alkylcarbonyl-C1-C8alkyI, C1C8alkoxycarbonyl-C1-C3alkyl, C1-C8amino-carbonyl-C1-C3alkyl, C2-C8dialkylamino-carbonyl-C1-C8alkyl, C1-C8alkylcarbonylamino-C1-C3-alkyl, C2-C8alkylcarbonyl-lC1-C8alkyO-aminoalkyI, Ca-Cetrialkyisilyi-C1-C8alkyl, phenyl-C,-C5-alkyl, heteroaryl-C1-C8alkyl, phenoxy-C1-C3alkyl, heteroaryloxy-C1-C8alkyI, C2-C5alkenyl, C2-C8haloalkenyl, Ca-C8cycloalkyl, pheny^"-^or C1-C3alkyl-. C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenyl or heteroaryl, or heteroarylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroarylamino, C1-CaalkyI-, C1-C3haloalkyl-, C,-C3alkoxy-, C1-Cahalo-aikoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1CaalkyI-, C1-CahaloalkyI-, C,-C3alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted phenyl- amino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyI-, C1-C8alkoxy-, C,-C3haloalkoxy-, halo-, cyano- or nitro-substituted diphenylamino, C8-Cycycloalkylamino, C1-C8alkyl-, C1Cahaloalkyl-, C1-C3alkoxy-, C1Cahaloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkylamino, di-Ca-C^cyC1oaikylamino, C1-CaalkyI-, C1Cahaloalkyl-, C1-Caalkoxy-, C1-C3haloaikoxy-, halo-, cyano- or nitro-substituted C1-C3-C7cycloalkylamino, C3-C7cycloalkoxy, C1-C3alkyI-, C,-C3-haloalkyl-, C1-C3alkoxy-, C,-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-Cycyclo-alkoxy or C1C1oalkylcarbonyl; and salts and diastereoisomers of the compounds of formula I, with the proviso that R, and R3 are not simultaneously methyl; and b) an amount, effective for herbiC1de synergy, of at least one herbiC1de selected from mesosulfuron, mesotrione and flufenacet. In the above definitions, halogen is to be understood as fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. The alkyl groups occurring in the substituent definitions are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, and the pentyl and hexyl isomers. Suitable cycloalkyi substituents contain from 3 to 6 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. They may be substituted one or more times by halogen, preferably fluorine, chlorine or bromine. Alkenyl is to be understood as, for example, vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl. HaloalkyI groups preferably have a chain length of from 1 to 4 carbon atoms. HaloalkyI is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, penta-fluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafIuoroethyl or 2,2,2-trichloroethyl, preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichloro-fluoromethyl. Suitable haloalkenyl radicals include alkenyl groups substituted one or more times by halogen, halogen being fluorine, chlorine, bromine or iodine and espeC1ally fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Among the C2-C6alkenyl groups substituted once, twice or three times by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms. Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or a pentyloxy or hexyloxy isomer, preferably methoxy or ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxy-carbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl. Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methyisulfinyl, ethyl-sulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methyisulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutyl-sulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or a butylamine isomer. Dialkylamino is, for example, dimethylamino, methylethylamino, diethyl-amino, n-propylmethylamino, dibutylamino or diisopropylamino. Alkoxyalkyl groups preferably have from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxy-methyl or isopropoxyethyl. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. Phenyl may be in substituted form, in which case the substituents may be in the ortho-, meta- and/or para-position. Preferred positions for the substituents are the ortho- and para-positions to the ring attachment point. Heteroaryl groups are usually aromatic heterocycles that contain preferably from 1 to 3 hetero atoms selected from nitrogen, oxygen and sulfur. Examples of suitable heterocycles and heteroaromatic compounds are: pyrrolidine, piperidine, pyran, dioxane, azetidine, oxetane, pyridine, pyrimidine, triazine, thiazole, thiadiazole, imidazole, oxazole, isoxazole and pyrazine, furan, morpholine, piperazine, pyrazole, benzoxazole, benzothiazole, quinoxaline and quinoline. Those heterocycles and heteroaromatic compounds may be further substituted, for example by halogen, alkyl, alkoxy, haloalkyi, haloalkoxy, nitro, cyano, thioalkyi, alkylamino or by phenyl. The C2-C10-alkenyl and -alkynyl groups R34 may be mono- or poly-unsaturated. They contain preferably from 2 to 12 carbon atoms, espeC1ally from 2 to 6 carbon atoms. Alkali metal, alkaline earth metal or ammonium cations for the substituent G are, for example, the cations of sodium, potassium, magnesium, calC1um and ammonium. Preferred sulfonium cations are espeC1ally trialkylsulfonium cations wherein the alkyl radicals each contain preferably from 1 to 4 carbon atoms. The left-hand free valence of the groups Z1, Z2 and Z3 is bound to the 1-position and the right-hand free valence to the 2-position of the pyrazoline ring. Compounds of formula I wherein It is possible for an alkylene ring, which together with the carbon atoms of the groups Z,, Z2 and Z3 contains from 2 to 6 carbon atoms, to be fused or spiro-bound to the groups Z,, Z2 and Z3 have, for example, the following structure: Compounds of formula I wherein in the groups Z,, Z2 or Z3 an alkylene ring bridges at least one ring atom of the groups Z,, Z2 or Z3, have, for example, the following structure: Flufenacet is known from The PestiC1de Manual, 12th Edition (BCPC) 2000, Entry No. 362; mesotrione is known from The PestiC1de Manual, 12th Edition (BCPC) 2000, Entry No. 500; mesosulfuron is desC1ibed, for example, in WO 00/3591 and WO 01/24633. In herbiC1des of formula I that are preferred for the compositions in accordance with the invention, R, and R3 are, each independently of the other, ethyl, haloethyl, ethynyl, C1-C2-alkoxy or C1-C3haloalkoxy. Preference is given also to those compositions in accordance with the invention wherein, in the herbiC1des of formula I, R4 and R5 together are a Z2 group -C-RH(R15)-C-R16(R17)-O-C-R18(R19)-C-R20(R21)- (Z2) WherC1H R,4, Ri5, R16, R,7, R,8. Ri9, R20 and R21 are espeC1ally preferably hydrogen. In a further preferred group of compositions according to the invention, in the herbiC1des of formula I R30, R31, R32 and R33 are, each independently of the others, hydrogen, C1-C8alkyl, C1-C8haloalkyl, C1-CeCyanoalkyl, C1-C8nitroalkyl, C1C8aminoalkyl, C3-C8alkenyl, C2-C5halo-alkenyl, Ca-Cecycloalkyi, C1-C8alkylamino-C1-C8alkyI, C2-CBdialkylamino-C1-C5alkyl, C3-C7-cycloalkyl-C1-C8alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6alkynyloxy-alkyl, C2-C4alkyithio-alkyl, C1-C4alkysulfinyl-C1-C2alkyl, C1C2Blkylsulfonyl-C1-C2alkyl, C2-C4alkyl-ideneamino-oxy-C1-C2aikyl, C1-C5alkylcarbonyl-C1-C2alkyl, C1-C8alkoxycarbonyl-C1-C2alkyl, C1-C5amino-carbonyl-C1-C2alkyl, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C8alkylcarbonyl-amino-C1-C2alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalky!, C3-C6trialkylsilyl-C1C5alkyl, phenyl-C1-C2aikyl, heteroaryl-C,-C2alkyl, phenoxy-C1C3alkyl, heteroaryloxy-C1-C2alkyl, phenyl or heteroaryl; R34, R35 and R36, are each independently of the others, hydrogen, C1Caalkyl, C1-C8haloalkyl, C1-C8cyanoalkyl, C1-C8nitroalkyl, C1-C8aminoalkyI, C2-C5aikenyl, C2-C5haloalkenyl, Ca-C8-cycloalkyl, C1-C8alkylamino-C1-C8alkyl, C2-C8Ctialkylamino-C1-C8alkyl, C3-C7cycloalkyl-C1-C3-alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6alkynyloxy-alkyl, C2-C4alkylthio-alkyl, C1-C4alkysuifinyl-C1-C2alkyl, C1-C2aikylsulfonyl-C,-C2alkyl, C2-C4alkylideneamino-oxy-C1-C2alkyi, C1-C8alkylcarbonyl-C1-C3alkyl, C1-C5alkoxycarbonyl-C1-C2alkyl, C1-C8amino-carbonyl-C1-C2alkyl, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C5alkylcarbonylamino-C1-C2-alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalkyl, Ca-Cfitrialkylsilyl-C1C8alkyl, phenyl-C1C3- alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl, phenyl or heteroaryl, benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl, C1-C5alkoxy-carbonyl or by C1- or C2-haloalkyI; and R37 is C1-C8alkyI, C1-C8haloalkyl, C1-C8cyanoalkyl, C1-C8nitroalkyl, C1-C8aminoalkyI, C2-C5-alkenyl, C2-C8haloalkenyl, C3-C8cycloalkyl, C1-C8alkylamino-C1-C8alkyl, C2-C8dialkylamino-C1-C3alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6-alkynyloxy-alkyl, C2-C4alkylthio-alkyl, C1-C4alkylsulfinyl-C1-C2alkyl, C1-C2alkylsulfonyl-C1-C2-alkyl, C2-C4alkylideneamino-oxy-C1-C2alkyl, C1-C5alkylcarbonyl-C1-C2alkyl, C1C8alkoxy-carbonyl-C1-C2alkyl, C1-C8amino-carbonyl-C1C2alkyI, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C8alkylcarbonylamino-C1-C2alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalkyl, Ca-Cetrialkyl-silyl-C1-C8alkyl, phenyl-C1-CaalkyI, heteroaryl-C1-C2alkyl, phenoxy-C1-C3alkyl, heteroaryloxy-C1-C3alkyl, phenyl or heteroaryl, benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl, C,-C2-alkoxycarbonyl or by C1- or C2-haloalkyI; or R37 is C1-C8alkylcarbonyl. SpeC1al preference is given to those compositions according to the invention wherein, in the herbiC1des of formula I, R30, R31, R32 and R33 are, each independently of the others, hydrogen, C1-C8alkyl, C1C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, Ca-C8CycloalkyI, C3-C7cycloalkyl-C1-C2alkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1C3alkyl, heteroaryl-C1C2alkyl. phenoxy-C1-C2alkyl, heteroaryloxy-C1-C3alkyl; R34, R35 and R36 are, each independently of the others, hydrogen, C1-C8alkyl, C1-CahaloalkyI, C2-C3alkenyl, C2-C5haloalkenyl, C3-C8Cycloalkyl, C3-C7 cycloalkyl-C1C2alkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1-C2alkyl, heteroaryl-C1-C3alkyl, phenoxy-d-C2alkyl, heteroaryloxy-C1-C2alkyI, C1-C8alkoxy, C1-C3alkylamino or di(C1-C3alkyl)amino; and R37 is C1-C8alkyl, GrCahaloalkyl, C2-Ggalkenyi, C2-C8haioalkenyl, C3-CeCycloalkyl, C3-C7-cycloalkyl-C1-C2alkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyI, heteroaryloxy-C1C2alkyI, C1-C8alkoxy. C1C3alkylamino, di-(C1-C3alkyl)-amino or C1-Cealkylcarbonyl. A further group of espeC1ally preferred compositions comprise as herbiC1des of formula I those wherein R1 and R3 are ethyl, R4 and R5 together are a group Z2 -C-R14(R,5)-C-R16(R17)-0-C-R,8(R19)-C-R20(R2,)-, wherein R,4, R,5, R,6, R,^, R,8, R19, R20 and R21 are hydrogen, and G is hydrogen or a radical of formula -C(X1)-R3o wherein X, is oxygen and R30 is hydrogen or C1-C8 alkyl, espeC1ally C4alkyl, preferably tert-butyl. The compositions according to the invention may also comprise salts that the compounds of formula I may form with aC1ds. Suitable aC1ds for the formation of aC1d addition salts are both organic and inorganic aC1ds. Examples of such aC1ds are hydrochloric aC1d, hydrobromic aC1d, nitric aC1d, phosphoric aC1ds, sulfuric aC1d, acetic aC1d, propionic aC1d, butyric aC1d, valeric aC1d, oxalic aC1d, malonic aC1d, fumaric aC1d, organic sulfonic aC1ds, lactic aC1d, tartaric aC1d, C1tric aC1d and salicylic aC1d. The salts of the compounds of formula I having aC1d hydrogen are also alkali metal salts, for example sodium and potassium salts; alkaline earth metal salts, for example calC1um and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, or are salts with other organic nitrogen bases. Suitable salt formers are accordingly alkali metal and alkaline earth metal hydroxides, espeC1ally the hydroxides of lithium, sodium, potassium, magnesium or calC1um, with those of sodium or potassium being given speC1al importance. Examples of suitable amines for ammonium salt formation that come into consideration are ammonia as well as primary, secondary and tertiary C1-C18 alkylamines, C1-C4hydroxyalkyl-amines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyi-heptylamine, hexyi-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl-ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethyl-amine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec- butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, N-methylmorpholine, thio-morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary aryl amines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylene-diamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but espeC1ally triethylamine, isopropylamine and diisopropylamine. If non-chiral starting materials are employed, the asymmetrically substituted compounds of formula I obtained in the processes desC1ibed in this Application are generally in the form of racemates. The stereoisomers can then be separated on the basis of their physicochemical properties according to known methods, such as, for example, fractional C1ystallisation following salt formation with optically pure bases, aC1ds or metal complexes, or by chromatographic procedures, such as, for example, high-pressure liquid chromatography (HPLC) on acetyl cellulose. In the present invention, "compounds of formula I" are to be understood as including both the concentrated and optically pure forms of the stereoisomers in question and the racemates and diastereoisomers. Where no speC1al mention is made of individual optical antipodes, the formula in question is to be understood as referring to the racemic mixtures that are obtained in the preparation process mentioned. When an aliphatic C=C double bond is present, geometric isomerism may also occur. The compounds of formula I may, also in dependence upon the nature of the substituents, occur as geometric and/or optical isomers and isomeric mixtures and as tautomers and tautomeric mixtures. For example, the compounds of formula I wherein the group G is hydrogen can occur in the following tautomeric equilibria: When G is other than hydrogen and Z is the group Z, or Z3, or when G is other than hydrogen and Z2 is asymmetrically substituted, fused or spiro-bound, the compound of formula I may occur as an isomer of formula Id Processes for the preparation of compounds that differ from the compounds of formula I according to the present invention in respect of the meanings of the substituents R4 and R5 are desC1ibed, for example, in WO 96/21652. The compounds of formula I according to the present invention can be prepared analogously to the processes desC1ibed in WO 99/47525 and WO 01/17351. Table 1: Compounds of fornnula la: (The substituents R4 and R5 in the compounds of formula I form a -C2H4-O-C2H4- radical in the compounds of formula la) The rates of application of herbiC1de are generally from 0.001 to 2 kg/ha, but preferably from 0.005 to 1 kg/ha. The ratio by weight of the compound of formula I to the second herbiC1de (mesosulfuron, mesotrione or fiufenacet) in the composition according to the invention is preferably from 1 : 100 to 1000: 1. The compositions according to the invention preferably contain in addition a safener and, optionally, an oil additive. The present invention accordingly relates also to herbiC1dal compositions that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprise as active ingredient a mixture of a) a herbiC1de of formula I, b) an amount, effective for herbiC1de synergy, of mesosulfuron, mesotrione or fiufenacet, c) an amount, effective for herbiC1de antagonism, of a safener selected from cloquintocet-mexyl and mefenpyr-diethyl; and, optionally, d) an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The safeners cloquintocet-mexyl and mefenpyr-diethyl can also be used in the form of their alkali metal, alkaline earth metal, sulfonium or ammonium salts. Examples thereof are desC1ibed, for example, in WO 02/34048. It is also possible to use hydrates of cloquintocet-mexyl, which are mentioned in WO 02/36566. Cultivated plants that can be protected against the harmful effect of the above-mentioned herbiC1de mixtures by means of such safeners are espeC1ally cereals, cotton, soybeans, sugar beet, sugar cane, plantation C1ops, rape, maize and rice, more espeC1ally cereals. C1ops are to be understood as including those that have been made tolerant to herbiC1des or classes of herbiC1des by means of conventional breeding or genetic engineering methods. The weeds to be controlled may be either dicotyledonous or, preferably, monocotyledonous weeds, for example the monocotyledonous weeds Avena, Agrostis, Phalaris, Lolium, Bromus, Alopecurus, Setaria, Digitaria, Brachiaria, Echinochloa, Panicum, Sorghum hal./bic, Rottboellia, Cyperus, Brachiaria, Echinochloa, SC1rpus, Monochoria and Sagittaria, and the dicotyledonous weeds Sinapis, Chenopodium, Stellaria, Galium, Viola, Veronica, Matricaria, Papaver, Solanum, Abutilon, Sida, Xanthium, Amaranthus, Ipomoea and Chrysanthemum. Areas of cultivation include the areas of ground on which cultivated plants are already growing or which have already been sown with the seeds of those cultivated plants, as well as ground intended for cultivation with such cultivated plants. Depending on the intended use, a safener according to the invention can be used to pre-treat the seed material of the cultivated plant (dressing the seed or the cuttings) or can be introduced into the soil before or after sowing. It can, however, also be applied, either alone or together with the herbiC1de mixture and the oil additive, after the emergence of the plants. The treatment of the plants or seed with the safener can therefore, in prinC1ple, be effected independently of the time at which the herbiC1de mixture is applied. The treatment of the plants can, however, also be carried out by applying herbiC1de, oil additive and safener simultaneously (for example in the form of a tank mixture). The rate of application of safener in relation to herbiC1de depends largely on the method of application. In the case of field treatment, which is effected either using a tank mixture comprising a combination of safener and herbiC1de mixture or by separate application of safener and herbiC1de mixture, the ratio of herbiC1des to safener is generally from 100:1 to 1:10, preferably from 20:1 to 1:1. In the case of field treatment, from 0.001 to 1.0 kg of safener/ha, preferably from 0.001 to 0.25 kg of safener/ha, is generally applied. In the composition according to the invention, the amounts of oil additive employed are generally from 0.01 to 2 %, based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin such as, for example, rapeseed oil, olive oil or sunflower oil, alkyl esters of oils of vegetable origin such as, for example, the methyl derivatives, or an oil of animal origin such as fish oil or beef tallow. EspeC1ally preferred oil additives comprise alkyl esters of higher fatty aC1ds (C8-C22), espeC1ally the methyl derivatives of C12-C18 fatty aC1ds, for example the methyl esters of laurlc aC1d, palmitic aC1d and oleic aC1d. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). The application and action of the oil additives can be improved by combining them with surface-active substances such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed In WO 97/34485 on pages 7 and 8. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, espeC1ally the calC1um salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. SpeC1al preference is given to ethoxylated C12-O22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commerC1ally available preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). The concentration of the surface-active substances based on the total additive is generally from 1 to 30 % by weight. Examples of oil additives consisting of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Emery 2231® (Henkel subsidiary company Cognis GmbH, Germany), Turbocharge® (Zeneca Agro, Stoney C1eek, Ontario, Canada) or, more espeC1ally, Actipron® (BP Oil UK Limited, GB). The addition of an organic solvent to the oil additive/surfactant mixture can, furthermore, bring about a further inC1ease in action. Suitable solvents are, for example Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation) types. The concentration of those solvents can be from 10 to 80 %, by weight, of the total weight. Such oil additives, which are also desC1ibed, for example, in US-A-4 834 908, are espeC1ally preferred for the composition according to the Invention. An espeC1ally preferred oil additive is known under the name MERGE®, can be obtained from the BASF Corporation and is basically desC1ibed, for example, in US-A-4 834 908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis C1op Protection Canada). In the composition according to the invention, the amounts of oil additive employed are generally from 0.01 to 2 %, based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared. The invention relates also to a method for the selective control of weeds and grasses in C1ops of useful plants, which method comprises treating the useful plants, seeds or cuttings thereof or the area of cultivation thereof with a herbiC1dal composition that comprises a mixture of a) a herbiC1dally effective amount of formula I, b) an amount, effective for herbiC1de synergy, of mesosulfuron, mesotrione or flufenacet, c) an amount, effective for herbiC1de antagonism, of a safener selected from cloquintocet-mexyl and mefenpyr-diethyl; and, optionally, d) an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The compositions according to the invention are suitable for all methods of application that are customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing. In the case of seed dressing, from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 6 g of safener/kg of seed, are generally applied. When the safener Is applied in liquid form shortly before sowing, with swelling of the seed, it is advantageous to use safener solutions that comprise the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 10 to 1000 ppm. For application, the safeners used according to the invention or combinations of those safeners with the herbiC1des and, optionally, the oil additives are processed, together with the adjuvants conventionally employed in formulation technology, into formulations, for example into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or miC1ocapsules. Such formulations are desC1ibed, for example, in WO 97/34485, on pages 9 to 13. The formulations are prepared in known manner, for example by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants, for example solvents or solid carriers. Furthermore, surface-active compounds (surfactants) may additionally be used in the preparation of the formulations. Solvents and solid carriers suitable for that purpose are mentioned, for example, in WO 97/34485 on page 6. Depending on the nature of the compound of formula I being formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8. Furthermore, the surfactants customarily employed in formulation technology, which are desC1ibed, inter alia, in "Mc Cutcheon"s Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll. Chemical Publishing Co., New York, 1980-81, are also suitable for preparation of the herbiC1dal compositions according to the invention. The herbiC1dal formulations generally comprise from 0.1 to 99 % by weight, espeC1ally from 0.1 to 95 % by weight, of active ingredient mixture comprising the compound of formula I, the second synergistically effective herbiC1de and, optionally, the safeners used in accordance with the invention, from 0 to 2 % by weight of the oil additive used in accordance with the invention, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, espeC1ally from 0.1 to 25 % by weight, of a surfactant. Whereas commerC1al products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further additives such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. There are various suitable methods and techniques for using the safeners or compositions comprising them for protecting cultivated plants against harmful effects of the herbiC1des; the following are examples: i) Seed dressing a) Dressing the seeds with a wettable powder formulation of safener active ingredient by shaking in a vessel until the formulation is uniformly distributed over the seed surface (dry dressing). Approximately from 1 to 500 g of safener active ingredient according to the invention (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed. b) Dressing the seeds with an emulsifiable concentrate of safener according to method a) (wet dressing). c) Dressing by immersing the seed in a liquid formulation comprising from 100 to 1000 ppm of safener for from 1 to 72 hours and, if desired, subsequently drying the seeds (immersion dressing). Dressing the seed or treating the germinated seedlings are naturally the preferred methods of application because the treatment with the active ingredient is directed wholly at the target C1op. Generally from 1 to 1000 g of antidote, preferably from 5 to 250 g of antidote, are used per 100 kg of seed, although, depending on the method employed, which also allows the addition of other active ingredients or miC1onutrients, amounts that exceed or fall short of the speC1fied concentration limits may be employed (repeat dressing). ii) Application in the form of a tank mixture A liquid formulation of a mixture of antidote and herbiC1de (ratio of the one to the other from 20:1 to 1:100) is used, the rate of application of herbiC1de being from 0.005 to 5.0 kg per hectare. The oil additive can be added to the tank mixture in an amount of, preferably, from 0.01 to 2 % by weight. Such tank mixtures are applied before or after sowing. iii) Application to the seed furrow The safener is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, a wettable powder or granules. After the seed furrow has been covered, the herbiC1de, optionally in combination with the oil additive, is applied pre-emergence in the normal manner. iv) Controlled release of the active ingredient The safener is applied in solution to granulated mineral carriers or polymerised granules (urea-formaldehyde) and dried. If desired, a coating may be applied (coated granules) which enables the active ingredient to be released in metered amounts over a predetermined period of time. Preferred formulations have espeC1ally the following compositions (% = percent by weight; "active ingredient mixture" denotes the mixture of compound of formula I with the synergistically effective second herbiC1de and, optionally, with the safeners and/or oil additives according to the invention. Emulsifiable concentrates: active ingredient mixture: from 1 to 90 %, preferably from 5 to 20 % surface-active agent: from 1 to 30 %, preferably from 10 to 20 % liquid carrier; from 5 to 94 %, preferably from 70 to 85 % Dusts: active ingredient mixture: from 0.1 to 10 %, preferably from 0.1 to 5 % solid carrier: from 99.9 to 90 %, preferably from 99.9 to 99 % Suspension concentrates: active ingredient mixture: from 5 to 75 %, preferably from 10 to 50 % water: from 94 to 24 %, preferably from 88 to 30 % surface-active agent: from 1 to 40 %, preferably from 2 to 30 % Wettable powders: active ingredient mixture: from 0.5 to 90 %, preferably from 1 to 80 % surface-active agent: from 0.5 to 20 %, preferably from 1 to 15 % solid carrier: from 5 to 95 %, preferably from 15 to 90 % Granules: active ingredient mixture: from 0.1 to 30 %, preferably from 0.1 to 15 % solid carrier: from 99.5 to 70 %, preferably from 97 to 85 % The Examples that follow illustrate the invention further. They do not limit the Invention. Formulation Examples for mixtures of herbiC1des and, optionally, safener and oil additive It is often more practical to formulate the herbiC1des (optionally in combination with the oil additive) and the safener separately and then, shortly before application, to bring them together in the applicator in the desired mixing ratio in the form of a "tank mixture" in water. The herbiC1des and the safener can also be formulated separately and, shortly before application, brought together in the applicator in the desired mixing ratio in the form of a "tank mixture" in water, with the oil additive being added thereafter. The herbiC1dally selective action of the compositions according to the invention is illustrated in the following Examples. Biological Examples Example B1: Post-emergence test: The test plants are grown in pots under greenhouse conditions until a post-application stage. A standard soil is used as cultivation substrate. At a post-emergence stage, the herbiC1des, both on their own and in admixture with safeners and/or oil additives, are applied to the test plants or to cultivated plants seed-dressed with safeners. The application is carried out using an emulsion (prepared from an emulsifiable concentrate (Example F1, c)) of the test substances. The rates of application depend on the optimum concentrations ascertained under field conditions or greenhouse conditions. The tests are evaluated after from 2 to 4 weeks (100 % action = complete destruction, 0 % action = no phytotoxic action). WE CLAIM: 1. A herbiC1dal composition that, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of a) a herbiC1dally effective amount of a compound of formula I wherein R1 and R3 are, each independently of the other, halogen, nitro, C7ano, C1-C4alkyl, C2-C4-aikenyl, C2-C4aikynyl, C1-C4haloalkyl, C2-C6 haioalkenyl, C3-C6 cycloalkyl, halo-substituted C3-C3C7cloalkyI, Cz-C3alkoxyalkyI, Cz-C3alkylthioalkyl, hydroxy, merC3pto, C1-C3alkoxy, C3-C3alkenyloxy, C3-Ceaikynyloxy, C3rbonyl, C3rboxyl, C1-C4alkylC3rbonyl, C,-C4hydroxyalkyl, C1-C4alkoxyC3rbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkyl-amino or di(C1-C4aIkyl)amino; R4 and R5 together are a group -C-R6(R7)-0-C-R8(R9)-C-Rio(R11)-C-R,2(R,3)- (Z1), -C-R14(R15)-C-R16(R17)-0-C-R18(R19)-C-R20(R21)- (Z2),or -C-R22(R23)-C-R24(R25)-C-R26(R27)-0-C-R28(R29)- (Z3), wherein R6, R7, R8, R9, R10, R11, R12. R13, R14. R15. R16. R17. R18. R19. R20. R21. R22. R23. R24. R25. R26- R27. R28 and R29 are, each independently of the others, hydrogen, halogen, C1-C4alkyl or C1-C4 haloalkyl, it being possible for an alkylene ring, which together with the C3rbon atoms of the groups Z1, Z2 or Z3 contains from 2 to 6 C3rbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the C3rbon atoms of the groups Z1, Z2 or Z3, or that alkylene ring bridges at least one ring atom of the groups Z,, Z2 or Z3; G is hydrogen, -C(Xi)-R3o, -C(X2)-X3-R3i, -C(X4)-N(R32)-R33, -SO2-R34, an alkali metal, alkaline earth metal, sulfonium or ammonium C3tion, or -P(X5)(R35)-R36 or -CH2-X6-R37; Xi, X2, X3, X4, X5 and Xfi are, each independently of the others, oxygen or sulfur; R30- R31- R32 and R33 are, each independently of the others, hydrogen, C1-C1oalkyl, C1-C10-haloalkyl, C1-C1oC7anoalkyl, C1-C1onitroalkyl, CrC1oaminoalkyl, C1-C3alkylamino-C1-C3alkyI, C2-C3dialkylamino-C1-C3alkyl, C3-C7C7cloalkyl-C1-C3alkyi, Cz-C1oalkoxy-alkyI, C4-C10-alkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, Cz-C1oalkylthio-alkyI, C1-C3alkysulfoxyl-C1-C3alkyI, C1-C3alkylsulfonyl-C1-C3alkyI, C3-C3alkylideneamino-oxy-C1-C3alkyl, C1-C3alkylC3rbonyl-C1-C3alkyl, C1-C3alkoxyC3rbonyl-C1-C3alkyl, C1-C3amino-C3rbonyl-C1-C3alkyl, C3-Cedialkyl-amino-C3rbonyl-C1-C3alkyl, C1-C3alkylC3rbonylamino-C1-C3alkyI, Cz-C3alkylC3rbonyl-(C1-C3alkyO-aminoalkyl, C3-C3trialkylsilyl-C1-C3alkyl, phenyl-C1-C3alkyl, heteroaryl-C1-C3alkyI, phenoxy-C1-C3alkyI, heteroaryloxy-C1-C3alkyl, C2-C3alkenyl, C2-C5haloalkenyl, C3-C3C7clo-alkyl, phenyl, or C1-C3alkyI-, CrC3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyI-, C1-C3haloalkyI-, C1-C3-alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted heteroarylamino, diheteroaryl-amino, C1-C3alkyI-, C1-C3haloalkyI-, C1-C3alkoxy-, C,-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diphenyl¬amino, C3-C7C7cloalkylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloaikoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkylamino, di-C3-C7C7cloalkylamino, CrC3alkyl-, C1-C3haloalkyI-, C1-C3alkoxy-, C,-C3haloalkoxy-, halo-, C7ano- or nitro-substituted di-C3-C7-C7cloaikyiamino, C3-C7C7cloalkoxy or C1-C3alkyl-, C1-C3haloalkyI-, C1-C3aikoxy-, C1-C3halo-alkoxy-, haio-, C7ano- or nitro-substituted C3-C7C7cloalkoxy; R34, R35 and R36 are, each independently of the others, hydrogen, C1-C1oalkyl, C,-C1ohalo-alkyl, C1-C1oC7anoalkyI, C1-C1onitroalkyl, C1-C1oaminoalkyl, C1-C3alkylamino-C1-C3alkyl, Cz-C3dialkyiamino-C1-C3alkyl, C3-C7C7cloalkyl-C1-C3alkyl, Cz-C1oalkoxy-alkyI, C4-C,o-alkenyioxy-alkyl, C4-C1oalkynyloxy-alkyl, Cz-C1oalkylthio-alkyI, C1-C3alkysulfoxyl-C1-C3alkyl, C1-C3alkylsuifonyl-C1-C3alkyl, Cz-C3alkylideneamino-oxy-C1-C3aikyi, CrC3aikylC3rbonyl-C1-C3aikyl, C1-C3alkoxyC3rbonyl-C1-C3alkyl, C1-C3amino-C3rbonyl-C1-C3aikyi, Cz-C3diaikyl-amino-C3rbonyl-C1-C3aikyl, C1-C3alkylC3rbonylamino-C1-C3alkyl, Cz-C3aikylC3rbonyl-(C1-C3aikyO-aminoalkyl, C3-C6triaikylsilyl-C1-C5alkyl, phenyl-CrC3alkyl, heteroaryl-C1-C3alkyl, phenoxy-C1-C3alkyi, heteroaryloxy-C1-C3alkyi, C3-C3alkenyl, Cz-C3haloalkenyl, C3-C8C7clo-alkyl, phenyl, or C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, CrC3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyl-, C1-C3haloalkyI-, C1-C3-alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted heteroarylamino, diheteroaryl- amino, C1-C3alkyl-, CrC3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyI-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substltuted phenylamino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diphenyl¬amino, C3-C7C7C1oalkylamino, C1-C3alkyi-, C1-C3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkylamino, dl-C3-C7C7cloalkylamino, C1-C3alkyl-, CrC3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted di-C3-C7-C7cloalkylamino, C3-C7C7cloalkoxy, C1-C3alkyl-, CrC3haloalkyl-, C1-C3alkoxy-, C,-C3halo-aikoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkoxy, CrC1oalkoxy, C1-C1ohaloalkoxy, C1-C3alkylamino, C3-C3dialkylamino and benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by C1-C3alkyI, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, C7ano, formyl, acetyl, propionyl, C3rboxyl, C1-C3alkoxy-C3rbonyl, methylthio, ethylthio or by nitro; and " R37 is C1-C1oalkyl, C1-C1ohaloalkyl, C1-C10C7anoalkyl, C1-C1onitroalkyl, C1-C1oaminoalkyl, C1-C3alkylamino-C1-C3alkyI, Cz-C3dialkylamino-C1-C3alkyI, C3-C7C7cloalkyl-CrC3alkyI, C2-C1oalkoxy-alkyl, C4-C1oalkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, Cz-C1oalkylthio-alkyI, C1-C3alkysulfoxyl-C1-C3alkyI, C1-C3alkylsulfonyl-C1-C3alkyI, Cz-Cealkylideneamino-oxy-C1-C3alkyl, C1-C3alkylC3rbonyl-C1-C3alkyl, CrC3alkoxyC3rbonyl-C1-C3aikyl, C1-C3amino-C3rbonyl-C1-C3alkyl, Cz-C3dialkylamino-C3rbonyl-C1-C3alkyl, C1-C3alkylC3rbonylamino-C1-C3-alkyl, Cz-C3alkylC3rbonyl-CC1-C3alkyO-aminoalkyl, C3-Cetrialkylsilyl-C1-C3alkyl, phenyl-C1-C3-alkyl, heteroaryl-C1-C3alkyl, phenoxy-C1-C3alkyl, heteroaryloxy-C1-C3alkyl, C3-C3alkenyl, Cz-C3haloalkenyl, C3-C3C7cloaikyl, phenyl, or C1-C3alkyl-, C1-C3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl or heteroaryl, or heteroarylamino, C1-C3alkyl-, C1-C3haioalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted heteroarylamino, diheteroarylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3halo-alkoxy-, halo-, C7ano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl-amino, diphenylamino, C1-C3alkyI-, C1-C3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diphenylamino, C3-C7C7cloaikylamino, C,-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkylamino, di-C3-C7C7cloalkylamino, C,-C3alkyl-, C1-C3haloalkyl-, CrC3alkoxy-, CrC3haloalkoxy-, halo-, C7ano- or nitro-substituted di-C3-C7C7cloalkylamino, C3-C7C7cloalkoxy, CrC3alkyl-, C,-C3- haloalkyi-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted C3-C7cyclo- alkoxy or C1-C10alkylcarbonyl; or a salt or diastereolsomer of a compound of formula I, with the proviso that R1 and R3 are not simultaneously methyl; and b) an amount, effective for herbiC1de synergy, of at least one herbiC1de selected from mesosulfuron, and flufenacet. 2. A composition according to claim 1, which comprises c) an amount, effective for herbiC1de antagonism, of a safener selected from cloquintocet-mexyl and mefenpyr-diethyl. 3. A composition according to claim 1, which comprises d) an additive comprising an oil of vegetable or animal origin, a mineral oil, alky! esters of such oils or mixtures of such oils and oil derivatives. 4. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a composition according to claim 1. 5. A method according to claim 4, wherein the crops of useful plants are cereals. 6. A herbiC1dal composition substantially as hereinabove described and exemplified. 7. A method for the selective control of weeds and grasses in crops of useful plants substantially as hereinabove described and exemplified.

Full Text

HerbiC1dal composition
The present invention relates to new herbiC1dal compositions for controlling grasses and weeds in C1ops of useful plants, espeC1ally in C1ops of maize and cereals, which compositions comprise a tetrahydropyrazolodione herbiC1de known from, for example, WO 99/47525, and a co-herbiC1de.
The present invention relates to a herbiC1dal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbiC1dally effective amount of a compound of formula I
wherein
R1 and R3 are, each independently of the other, halogen, nitro, cyano, C1-C4alkyl, C2-C4-alkenyl, C2-C4alkynyl, C1-C4haloalkyl, C2-Cehaloalkenyl, C3-C6CycloalkyI, halo-substituted C8-C8cycloalkyl, C2-C8alkoxyalkyl, C2-C8alkylthioalkyl, hydroxy, mercapto, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, carbonyl, carboxyl, C1-C4alkylcarbonyl, C1-C4hydroxyalkyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkylamino or di(C1-C4alkyl)amino; R4 and R5 together are a group
-C-R6(R7)-0-C-R6(R9)-C-R10(R11)-C-R,2(R,3)- (Z,),
-C-R,4(R,5)-C-Ri6(Ru)-0-C-R,s(R,9)-C-R2o(R2i)- (Z2) or
-C-R22(R23)-C-R24(R25)-C-R26(R27)-0-C-R28(R29)- (Z3),
wherein R6, R7, Re, R9, R10 R11, R12. R13. R14. R15. R16. R17. R18. R19. R20. R21- R22- R23. R24. R25. R26. R27- R28 and R29 are, each independently of the others, hydrogen, halogen, C1-C4 alkyl or C1-C4haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the groups Z1, Z2 or Z3 contains from 2 to 6 carbon atoms and which may be interrupted by

oxygen, to be either fused or spiro-bound to the carbon atoms of the groups Z,, Z2 or Z3, or that alkylene ring bridges at least one ring atom of the groups Z,, Z^ or Z3; G is hydrogen, -C(X,)-R3o, -CCX)-Xa-R3,, -C(X4)-N(R32)-R33, -SO2-R34, an alkali metal, alkaline earth metal, sulfonium or ammonium cation, or -P(X5)(R35)-R36 or -CH2-X6-R37; X,, X2, X3, X4, X5 and Xg are, each independently of the others, oxygen or sulfur; R30, Rsi, R32 and R33 are, each independently of the others, hydrogen, C1-C1oalkyl, C1-C10-haloalkyl, C,-C1ocyanoalkyl, C,-C1onitroalkyl, C1-C1oaminoalkyl, C1-C8alkylamino-C1C8alkyl, C2-C8dialkylamino-C1-C8alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C1oalkoxy-aIkyl, C4-C10-alkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, C2-C1oalkylthio-alkyI, C1-C8alkysulfoxyl-C1-C8alkyl, C1-C8alkylsulfonyl-C1-C8alkyj, C2-C8alkylideneamino-oxy-C1-C5alkyl, C1-C8aikylcarbonyl-C1-C8alkyl, C1-C8alkoxycarbonyl-C1-C3aikyl, C1-C8amino-carbonyl-C1-C3alkyl, C2-C8dialkyl-amino-carbonyl-C1-C3alkyl, C1C8alkylcarbonylamino-C1-C8alkyl, C2-C5alkylcarbonyl-{C1-C5-alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5a!kyl, phenyl-C1C8alkyl, heteroaryl-C1-C8alkyl, phenoxy-C1-C8alkyl, heteroaryloxy-C1-C8alkyl, C2-C8alkenyl, C2-C5haloalkenyl, Ca-C8Cyclo-alkyl, phenyl, or C1-CaalkyI-, C1-C3haloalkyl-, C1-Caalkoxy-, C1Cahaloalkoxy-, halo-, cyano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3-alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroaryl-amino, C1-C8alkyl-, C1-C8haloalkyI-, C1-C8alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1C3alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C8haloalkyl-, C1-C8alkoxy-, C1-Cahaioalkoxy-, halo-, cyano- or nitro-substituted diphenyl¬amino, C3-C7cycloalkylamino, C1-C3alkyl-, C1-C8haloalkyI-, C1-C3alkoxy-, C1C8haloalkoxy-, halo-, cyano- or nitro-substituted Ca-CTcycloalkylamino, di-C3-C7cycloaikylamino, C1-C3alkyl-, C1-Cahaloalky!-, C1-C3alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted di-C3-C7-cycloalkylamino, C3-C7cycloalkoxy or C1-C3alkyl-, C1-C8haloalkyl-, C1-C3a!koxy-, C1-C3halo-alkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkoxy;
R34, R35 and R35 are, each independently of the others, hydrogen, C,-C1oalkyl, C1-C1ohalo-alkyl, C,-C1ocyanoalkyl, C1-C1onitroalkyl, C1C1oaminoalkylj C1-C8alkylamino-C1-C8alkyI, C2-C8dialkylamino-C1-C8alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C1oalkoxy-alkyl, C4-C10-alkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, C2-C1oalkylthio-alkyI, C1-C8alkysulfoxyl-C1C8alkyl, C1-C8alkylsulfonyl-C1-C8alkyl, C2-C8alkylideneamino-oxy-C1-C5alkyl, C1-C8alkylcarbonyl-C1-C3alkyl, C1-C8alkoxycarbonyl-C1-C3alkyl, C1-C8amino-carbonyl-C1-C8alkyI, C3-C8dialkyl-amino-carbonyl-C1-C8alkyl, d-C8alkylcarbonylamino-C1-C8alkyl, C2-C8alkylcarbonyl-

(C1C8alkyO-aminoalkyI, C8-C8trialkylsilyl-C1-C8alkyl, phenyl-C1C8alkyI, heteroaryl-C,-C5alkyl, phenoxy-C1C8alkyl, heteroaryloxy-C1-C8alkyI, C2-C8alkenyl, C3-C8haloalkenyl, C8-C8cyclo-alkyl, phenyl, or d-C3alkyl-, C1CahaloalkyI-, C1-C3alkoxy-, C1C3haloalkoxy-. halo-, cyano- or nitro-substituted phenyl or heteroaryl or heteroarylamlno, C1-CaalkyI-, C1-C8haloalkyI-, C1-C3-alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroaryl-amino, C1-C8alkyl-, C1-CahaloalkyI-, C1C8alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C8alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C8haloalkyl-, C1-Caalkoxy-, C1Cahaloalkoxy-, halo-, cyano- or nitro-substituted diphenyl¬amino, Ca-CyCyC3oalkylamino, C1-CaaJkyl-, C1-C8haloalkyI-, C1-C8alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted C8-Cycycloalkylamino, di-C8-CyCycloalkylamino, C1-C3alkyl-, C1-Cahaloalkyl-, C1-C8alkoxy-, C1C8haloalkoxy-, halo-, cyano- or nitro-substituted di-C3-C7-cycloalkylamino, Ca-Cycycloalkoxy, C1Caalkyl-, C1CahaloalkyI-, C1-C3alkoxy-, C1-C8halo-alkoxy-, halo-, cyano- or nitro-substituted Ca-Cycycloalkoxy, C1-C1oalkoxy, C1-C1ohaloalkoxy, C1-C8alkylamino, C2-C8dialkylamino and benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by C1-C3alkyI, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, cyano, formyl, acetyl, propionyl, carboxyl, C1-C8alkoxy-carbonyl, methylthio, ethylthio or by nitro; and
R37 is C1-C1oalkyl, C1-C1ohaloalkyl, C1-C,oCyanoalkyl, C1-C1onitroalkyl, C1-C1oaminoalkyl, C1-C8alkylamino-C1-C8alkyl, C2-Cedialkylamino-C1-C8alkyI, C3-C7cycloalkyl-C1-C5alkyl, C2-C,oalkoxy-alkyl, C4-C1oalkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, C2-C1oalkylthio-alkyI, C1-C8alkysulfoxyl-C1-C8alkyl, C1-C8alkylsulfonyl-C1-C8alkyI, C2-Caalkylideneamino-oxy-C1-C8alkyl, C1-C8alkylcarbonyl-C1-C8alkyI, C1C8alkoxycarbonyl-C1-C3alkyl, C1-C8amino-carbonyl-C1-C3alkyl, C2-C8dialkylamino-carbonyl-C1-C8alkyl, C1-C8alkylcarbonylamino-C1-C3-alkyl, C2-C8alkylcarbonyl-lC1-C8alkyO-aminoalkyI, Ca-Cetrialkyisilyi-C1-C8alkyl, phenyl-C,-C5-alkyl, heteroaryl-C1-C8alkyl, phenoxy-C1-C3alkyl, heteroaryloxy-C1-C8alkyI, C2-C5alkenyl, C2-C8haloalkenyl, Ca-C8cycloalkyl, pheny^"-^or C1-C3alkyl-. C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenyl or heteroaryl, or heteroarylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3alkoxy-, C1-C8haloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroarylamino, C1-CaalkyI-, C1-C3haloalkyl-, C,-C3alkoxy-, C1-Cahalo-aikoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1CaalkyI-, C1-CahaloalkyI-, C,-C3alkoxy-, C1-Cahaloalkoxy-, halo-, cyano- or nitro-substituted phenyl-

amino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyI-, C1-C8alkoxy-, C,-C3haloalkoxy-, halo-, cyano- or nitro-substituted diphenylamino, C8-Cycycloalkylamino, C1-C8alkyl-, C1Cahaloalkyl-, C1-C3alkoxy-, C1Cahaloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkylamino, di-Ca-C^cyC1oaikylamino, C1-CaalkyI-, C1Cahaloalkyl-, C1-Caalkoxy-, C1-C3haloaikoxy-, halo-, cyano- or nitro-substituted C1-C3-C7cycloalkylamino, C3-C7cycloalkoxy, C1-C3alkyI-, C,-C3-haloalkyl-, C1-C3alkoxy-, C,-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-Cycyclo-alkoxy or C1C1oalkylcarbonyl; and salts and diastereoisomers of the compounds of formula I, with the proviso that R, and R3 are not simultaneously methyl; and b) an amount, effective for herbiC1de synergy, of at least one herbiC1de selected from mesosulfuron, mesotrione and flufenacet.
In the above definitions, halogen is to be understood as fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. The alkyl groups occurring in the substituent definitions are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, and the pentyl and hexyl isomers. Suitable cycloalkyi substituents contain from 3 to 6 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. They may be substituted one or more times by halogen, preferably fluorine, chlorine or bromine. Alkenyl is to be understood as, for example, vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl. HaloalkyI groups preferably have a chain length of from 1 to 4 carbon atoms. HaloalkyI is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, penta-fluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafIuoroethyl or 2,2,2-trichloroethyl, preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichloro-fluoromethyl. Suitable haloalkenyl radicals include alkenyl groups substituted one or more times by halogen, halogen being fluorine, chlorine, bromine or iodine and espeC1ally fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Among the C2-C6alkenyl groups substituted once, twice or three times by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms. Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or a pentyloxy or hexyloxy isomer, preferably methoxy or ethoxy. Alkylcarbonyl is preferably

acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxy-carbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl. Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methyisulfinyl, ethyl-sulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methyisulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutyl-sulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or a butylamine isomer. Dialkylamino is, for example, dimethylamino, methylethylamino, diethyl-amino, n-propylmethylamino, dibutylamino or diisopropylamino. Alkoxyalkyl groups preferably have from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxy-methyl or isopropoxyethyl. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. Phenyl may be in substituted form, in which case the substituents may be in the ortho-, meta- and/or para-position. Preferred positions for the substituents are the ortho- and para-positions to the ring attachment point. Heteroaryl groups are usually aromatic heterocycles that contain preferably from 1 to 3 hetero atoms selected from nitrogen, oxygen and sulfur. Examples of suitable heterocycles and heteroaromatic compounds are: pyrrolidine, piperidine, pyran, dioxane, azetidine, oxetane, pyridine, pyrimidine, triazine, thiazole, thiadiazole, imidazole, oxazole, isoxazole and pyrazine, furan, morpholine, piperazine, pyrazole, benzoxazole, benzothiazole, quinoxaline and quinoline. Those heterocycles and heteroaromatic compounds may be further substituted, for example by halogen, alkyl, alkoxy, haloalkyi, haloalkoxy, nitro, cyano, thioalkyi, alkylamino or by phenyl. The C2-C10-alkenyl and -alkynyl groups R34 may be mono- or poly-unsaturated. They contain preferably from 2 to 12 carbon atoms, espeC1ally from 2 to 6 carbon atoms.
Alkali metal, alkaline earth metal or ammonium cations for the substituent G are, for example, the cations of sodium, potassium, magnesium, calC1um and ammonium. Preferred

sulfonium cations are espeC1ally trialkylsulfonium cations wherein the alkyl radicals each contain preferably from 1 to 4 carbon atoms.
The left-hand free valence of the groups Z1, Z2 and Z3 is bound to the 1-position and the right-hand free valence to the 2-position of the pyrazoline ring.
Compounds of formula I wherein It is possible for an alkylene ring, which together with the carbon atoms of the groups Z,, Z2 and Z3 contains from 2 to 6 carbon atoms, to be fused or spiro-bound to the groups Z,, Z2 and Z3 have, for example, the following structure:

Compounds of formula I wherein in the groups Z,, Z2 or Z3 an alkylene ring bridges at least one ring atom of the groups Z,, Z2 or Z3, have, for example, the following structure:

Flufenacet is known from The PestiC1de Manual, 12th Edition (BCPC) 2000, Entry No. 362; mesotrione is known from The PestiC1de Manual, 12th Edition (BCPC) 2000, Entry No. 500; mesosulfuron is desC1ibed, for example, in WO 00/3591 and WO 01/24633.
In herbiC1des of formula I that are preferred for the compositions in accordance with the invention, R, and R3 are, each independently of the other, ethyl, haloethyl, ethynyl, C1-C2-alkoxy or C1-C3haloalkoxy.
Preference is given also to those compositions in accordance with the invention wherein, in the herbiC1des of formula I, R4 and R5 together are a Z2 group
-C-RH(R15)-C-R16(R17)-O-C-R18(R19)-C-R20(R21)- (Z2) WherC1H R,4, Ri5, R16, R,7, R,8. Ri9, R20
and R21 are espeC1ally preferably hydrogen.
In a further preferred group of compositions according to the invention, in the herbiC1des of formula I R30, R31, R32 and R33 are, each independently of the others, hydrogen, C1-C8alkyl, C1-C8haloalkyl, C1-CeCyanoalkyl, C1-C8nitroalkyl, C1C8aminoalkyl, C3-C8alkenyl, C2-C5halo-alkenyl, Ca-Cecycloalkyi, C1-C8alkylamino-C1-C8alkyI, C2-CBdialkylamino-C1-C5alkyl, C3-C7-cycloalkyl-C1-C8alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6alkynyloxy-alkyl, C2-C4alkyithio-alkyl, C1-C4alkysulfinyl-C1-C2alkyl, C1C2Blkylsulfonyl-C1-C2alkyl, C2-C4alkyl-ideneamino-oxy-C1-C2aikyl, C1-C5alkylcarbonyl-C1-C2alkyl, C1-C8alkoxycarbonyl-C1-C2alkyl, C1-C5amino-carbonyl-C1-C2alkyl, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C8alkylcarbonyl-amino-C1-C2alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalky!, C3-C6trialkylsilyl-C1C5alkyl, phenyl-C1-C2aikyl, heteroaryl-C,-C2alkyl, phenoxy-C1C3alkyl, heteroaryloxy-C1-C2alkyl, phenyl or heteroaryl;
R34, R35 and R36, are each independently of the others, hydrogen, C1Caalkyl, C1-C8haloalkyl, C1-C8cyanoalkyl, C1-C8nitroalkyl, C1-C8aminoalkyI, C2-C5aikenyl, C2-C5haloalkenyl, Ca-C8-cycloalkyl, C1-C8alkylamino-C1-C8alkyl, C2-C8Ctialkylamino-C1-C8alkyl, C3-C7cycloalkyl-C1-C3-alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6alkynyloxy-alkyl, C2-C4alkylthio-alkyl, C1-C4alkysuifinyl-C1-C2alkyl, C1-C2aikylsulfonyl-C,-C2alkyl, C2-C4alkylideneamino-oxy-C1-C2alkyi, C1-C8alkylcarbonyl-C1-C3alkyl, C1-C5alkoxycarbonyl-C1-C2alkyl, C1-C8amino-carbonyl-C1-C2alkyl, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C5alkylcarbonylamino-C1-C2-alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalkyl, Ca-Cfitrialkylsilyl-C1C8alkyl, phenyl-C1C3-

alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl, phenyl or heteroaryl, benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl, C1-C5alkoxy-carbonyl or by C1- or C2-haloalkyI; and
R37 is C1-C8alkyI, C1-C8haloalkyl, C1-C8cyanoalkyl, C1-C8nitroalkyl, C1-C8aminoalkyI, C2-C5-alkenyl, C2-C8haloalkenyl, C3-C8cycloalkyl, C1-C8alkylamino-C1-C8alkyl, C2-C8dialkylamino-C1-C3alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6-alkynyloxy-alkyl, C2-C4alkylthio-alkyl, C1-C4alkylsulfinyl-C1-C2alkyl, C1-C2alkylsulfonyl-C1-C2-alkyl, C2-C4alkylideneamino-oxy-C1-C2alkyl, C1-C5alkylcarbonyl-C1-C2alkyl, C1C8alkoxy-carbonyl-C1-C2alkyl, C1-C8amino-carbonyl-C1C2alkyI, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C8alkylcarbonylamino-C1-C2alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalkyl, Ca-Cetrialkyl-silyl-C1-C8alkyl, phenyl-C1-CaalkyI, heteroaryl-C1-C2alkyl, phenoxy-C1-C3alkyl, heteroaryloxy-C1-C3alkyl, phenyl or heteroaryl, benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl, C,-C2-alkoxycarbonyl or by C1- or C2-haloalkyI; or R37 is C1-C8alkylcarbonyl.
SpeC1al preference is given to those compositions according to the invention wherein, in the herbiC1des of formula I, R30, R31, R32 and R33 are, each independently of the others, hydrogen, C1-C8alkyl, C1C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, Ca-C8CycloalkyI, C3-C7cycloalkyl-C1-C2alkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1C3alkyl, heteroaryl-C1C2alkyl. phenoxy-C1-C2alkyl, heteroaryloxy-C1-C3alkyl;
R34, R35 and R36 are, each independently of the others, hydrogen, C1-C8alkyl, C1-CahaloalkyI, C2-C3alkenyl, C2-C5haloalkenyl, C3-C8Cycloalkyl, C3-C7 cycloalkyl-C1C2alkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1-C2alkyl, heteroaryl-C1-C3alkyl, phenoxy-d-C2alkyl, heteroaryloxy-C1-C2alkyI, C1-C8alkoxy, C1-C3alkylamino or di(C1-C3alkyl)amino; and R37 is C1-C8alkyl, GrCahaloalkyl, C2-Ggalkenyi, C2-C8haioalkenyl, C3-CeCycloalkyl, C3-C7-cycloalkyl-C1-C2alkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyI, heteroaryloxy-C1C2alkyI, C1-C8alkoxy. C1C3alkylamino, di-(C1-C3alkyl)-amino or C1-Cealkylcarbonyl.

A further group of espeC1ally preferred compositions comprise as herbiC1des of formula I those wherein R1 and R3 are ethyl, R4 and R5 together are a group Z2 -C-R14(R,5)-C-R16(R17)-0-C-R,8(R19)-C-R20(R2,)-, wherein R,4, R,5, R,6, R,^, R,8, R19, R20 and R21 are hydrogen, and G is hydrogen or a radical of formula -C(X1)-R3o wherein X, is oxygen and R30 is hydrogen or C1-C8 alkyl, espeC1ally C4alkyl, preferably tert-butyl.
The compositions according to the invention may also comprise salts that the compounds of formula I may form with aC1ds. Suitable aC1ds for the formation of aC1d addition salts are both organic and inorganic aC1ds. Examples of such aC1ds are hydrochloric aC1d, hydrobromic aC1d, nitric aC1d, phosphoric aC1ds, sulfuric aC1d, acetic aC1d, propionic aC1d, butyric aC1d, valeric aC1d, oxalic aC1d, malonic aC1d, fumaric aC1d, organic sulfonic aC1ds, lactic aC1d, tartaric aC1d, C1tric aC1d and salicylic aC1d. The salts of the compounds of formula I having aC1d hydrogen are also alkali metal salts, for example sodium and potassium salts; alkaline earth metal salts, for example calC1um and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, or are salts with other organic nitrogen bases. Suitable salt formers are accordingly alkali metal and alkaline earth metal hydroxides, espeC1ally the hydroxides of lithium, sodium, potassium, magnesium or calC1um, with those of sodium or potassium being given speC1al importance.
Examples of suitable amines for ammonium salt formation that come into consideration are ammonia as well as primary, secondary and tertiary C1-C18 alkylamines, C1-C4hydroxyalkyl-amines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyi-heptylamine, hexyi-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl-ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethyl-amine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-

butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, N-methylmorpholine, thio-morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary aryl amines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylene-diamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but espeC1ally triethylamine, isopropylamine and diisopropylamine.
If non-chiral starting materials are employed, the asymmetrically substituted compounds of formula I obtained in the processes desC1ibed in this Application are generally in the form of racemates. The stereoisomers can then be separated on the basis of their physicochemical properties according to known methods, such as, for example, fractional C1ystallisation following salt formation with optically pure bases, aC1ds or metal complexes, or by chromatographic procedures, such as, for example, high-pressure liquid chromatography (HPLC) on acetyl cellulose. In the present invention, "compounds of formula I" are to be understood as including both the concentrated and optically pure forms of the stereoisomers in question and the racemates and diastereoisomers. Where no speC1al mention is made of individual optical antipodes, the formula in question is to be understood as referring to the racemic mixtures that are obtained in the preparation process mentioned. When an aliphatic C=C double bond is present, geometric isomerism may also occur.
The compounds of formula I may, also in dependence upon the nature of the substituents, occur as geometric and/or optical isomers and isomeric mixtures and as tautomers and tautomeric mixtures. For example, the compounds of formula I wherein the group G is hydrogen can occur in the following tautomeric equilibria:

When G is other than hydrogen and Z is the group Z, or Z3, or when G is other than hydrogen and Z2 is asymmetrically substituted, fused or spiro-bound, the compound of formula I may occur as an isomer of formula Id

Processes for the preparation of compounds that differ from the compounds of formula I according to the present invention in respect of the meanings of the substituents R4 and R5 are desC1ibed, for example, in WO 96/21652. The compounds of formula I according to the present invention can be prepared analogously to the processes desC1ibed in WO 99/47525 and WO 01/17351.

Table 1: Compounds of fornnula la:
(The substituents R4 and R5 in the compounds of formula I form a -C2H4-O-C2H4- radical in
the compounds of formula la)

The rates of application of herbiC1de are generally from 0.001 to 2 kg/ha, but preferably from 0.005 to 1 kg/ha.
The ratio by weight of the compound of formula I to the second herbiC1de (mesosulfuron, mesotrione or fiufenacet) in the composition according to the invention is preferably from 1 : 100 to 1000: 1.
The compositions according to the invention preferably contain in addition a safener and, optionally, an oil additive. The present invention accordingly relates also to herbiC1dal compositions that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprise as active ingredient a mixture of
a) a herbiC1de of formula I,
b) an amount, effective for herbiC1de synergy, of mesosulfuron, mesotrione or fiufenacet,
c) an amount, effective for herbiC1de antagonism, of a safener selected from cloquintocet-mexyl and mefenpyr-diethyl; and, optionally,
d) an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of
such oils, or mixtures of such oils and oil derivatives.
The safeners cloquintocet-mexyl and mefenpyr-diethyl can also be used in the form of their alkali metal, alkaline earth metal, sulfonium or ammonium salts. Examples thereof are desC1ibed, for example, in WO 02/34048. It is also possible to use hydrates of cloquintocet-mexyl, which are mentioned in WO 02/36566.

Cultivated plants that can be protected against the harmful effect of the above-mentioned herbiC1de mixtures by means of such safeners are espeC1ally cereals, cotton, soybeans, sugar beet, sugar cane, plantation C1ops, rape, maize and rice, more espeC1ally cereals. C1ops are to be understood as including those that have been made tolerant to herbiC1des or classes of herbiC1des by means of conventional breeding or genetic engineering methods.
The weeds to be controlled may be either dicotyledonous or, preferably, monocotyledonous weeds, for example the monocotyledonous weeds Avena, Agrostis, Phalaris, Lolium, Bromus, Alopecurus, Setaria, Digitaria, Brachiaria, Echinochloa, Panicum, Sorghum hal./bic, Rottboellia, Cyperus, Brachiaria, Echinochloa, SC1rpus, Monochoria and Sagittaria, and the dicotyledonous weeds Sinapis, Chenopodium, Stellaria, Galium, Viola, Veronica, Matricaria, Papaver, Solanum, Abutilon, Sida, Xanthium, Amaranthus, Ipomoea and Chrysanthemum.
Areas of cultivation include the areas of ground on which cultivated plants are already growing or which have already been sown with the seeds of those cultivated plants, as well as ground intended for cultivation with such cultivated plants.
Depending on the intended use, a safener according to the invention can be used to pre-treat the seed material of the cultivated plant (dressing the seed or the cuttings) or can be introduced into the soil before or after sowing. It can, however, also be applied, either alone or together with the herbiC1de mixture and the oil additive, after the emergence of the plants. The treatment of the plants or seed with the safener can therefore, in prinC1ple, be effected independently of the time at which the herbiC1de mixture is applied. The treatment of the plants can, however, also be carried out by applying herbiC1de, oil additive and safener simultaneously (for example in the form of a tank mixture). The rate of application of safener in relation to herbiC1de depends largely on the method of application. In the case of field treatment, which is effected either using a tank mixture comprising a combination of safener and herbiC1de mixture or by separate application of safener and herbiC1de mixture, the ratio of herbiC1des to safener is generally from 100:1 to 1:10, preferably from 20:1 to 1:1. In the case of field treatment, from 0.001 to 1.0 kg of safener/ha, preferably from 0.001 to 0.25 kg of safener/ha, is generally applied.

In the composition according to the invention, the amounts of oil additive employed are generally from 0.01 to 2 %, based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared.
Preferred oil additives comprise mineral oils or an oil of vegetable origin such as, for example, rapeseed oil, olive oil or sunflower oil, alkyl esters of oils of vegetable origin such as, for example, the methyl derivatives, or an oil of animal origin such as fish oil or beef tallow.
EspeC1ally preferred oil additives comprise alkyl esters of higher fatty aC1ds (C8-C22), espeC1ally the methyl derivatives of C12-C18 fatty aC1ds, for example the methyl esters of laurlc aC1d, palmitic aC1d and oleic aC1d. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9).
The application and action of the oil additives can be improved by combining them with surface-active substances such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed In WO 97/34485 on pages 7 and 8.
Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate
type, espeC1ally the calC1um salts thereof, and also non-ionic surfactants of the fatty alcohol
ethoxylate type. SpeC1al preference is given to ethoxylated C12-O22 fatty alcohols having a
degree of ethoxylation of from 5 to 40. Examples of commerC1ally available preferred
surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland).
The concentration of the surface-active substances based on the total additive is generally
from 1 to 30 % by weight.
Examples of oil additives consisting of mixtures of oils or mineral oils or derivatives thereof
with surfactants are Edenor ME SU®, Emery 2231® (Henkel subsidiary company Cognis
GmbH, Germany), Turbocharge® (Zeneca Agro, Stoney C1eek, Ontario, Canada) or, more
espeC1ally, Actipron® (BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactant mixture can, furthermore, bring about a further inC1ease in action. Suitable solvents are, for example Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation) types. The concentration of those solvents can be from 10 to 80 %, by weight, of the total weight.
Such oil additives, which are also desC1ibed, for example, in US-A-4 834 908, are espeC1ally preferred for the composition according to the Invention. An espeC1ally preferred oil additive is known under the name MERGE®, can be obtained from the BASF Corporation and is basically desC1ibed, for example, in US-A-4 834 908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis C1op Protection Canada).
In the composition according to the invention, the amounts of oil additive employed are generally from 0.01 to 2 %, based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared.
The invention relates also to a method for the selective control of weeds and grasses in C1ops of useful plants, which method comprises treating the useful plants, seeds or cuttings thereof or the area of cultivation thereof with a herbiC1dal composition that comprises a mixture of
a) a herbiC1dally effective amount of formula I,
b) an amount, effective for herbiC1de synergy, of mesosulfuron, mesotrione or flufenacet,
c) an amount, effective for herbiC1de antagonism, of a safener selected from cloquintocet-mexyl and mefenpyr-diethyl; and, optionally,
d) an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives.
The compositions according to the invention are suitable for all methods of application that are customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing.

In the case of seed dressing, from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 6 g of safener/kg of seed, are generally applied. When the safener Is applied in liquid form shortly before sowing, with swelling of the seed, it is advantageous to use safener solutions that comprise the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 10 to 1000 ppm.
For application, the safeners used according to the invention or combinations of those safeners with the herbiC1des and, optionally, the oil additives are processed, together with the adjuvants conventionally employed in formulation technology, into formulations, for example into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or miC1ocapsules.
Such formulations are desC1ibed, for example, in WO 97/34485, on pages 9 to 13. The formulations are prepared in known manner, for example by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants, for example solvents or solid carriers. Furthermore, surface-active compounds (surfactants) may additionally be used in the preparation of the formulations. Solvents and solid carriers suitable for that purpose are mentioned, for example, in WO 97/34485 on page 6.
Depending on the nature of the compound of formula I being formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8. Furthermore, the surfactants customarily employed in formulation technology, which are desC1ibed, inter alia, in "Mc Cutcheon"s Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll. Chemical Publishing Co., New York, 1980-81, are also suitable for preparation of the herbiC1dal compositions according to the invention.
The herbiC1dal formulations generally comprise from 0.1 to 99 % by weight, espeC1ally from 0.1 to 95 % by weight, of active ingredient mixture comprising the compound of formula I, the

second synergistically effective herbiC1de and, optionally, the safeners used in accordance with the invention, from 0 to 2 % by weight of the oil additive used in accordance with the invention, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, espeC1ally from 0.1 to 25 % by weight, of a surfactant. Whereas commerC1al products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further additives such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. There are various suitable methods and techniques for using the safeners or compositions comprising them for protecting cultivated plants against harmful effects of the herbiC1des; the following are examples:
i) Seed dressing
a) Dressing the seeds with a wettable powder formulation of safener active ingredient by shaking in a vessel until the formulation is uniformly distributed over the seed surface (dry dressing). Approximately from 1 to 500 g of safener active ingredient according to the invention (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed.
b) Dressing the seeds with an emulsifiable concentrate of safener according to method a) (wet dressing).
c) Dressing by immersing the seed in a liquid formulation comprising from 100 to 1000 ppm of safener for from 1 to 72 hours and, if desired, subsequently drying the seeds (immersion dressing).
Dressing the seed or treating the germinated seedlings are naturally the preferred methods of application because the treatment with the active ingredient is directed wholly at the target C1op. Generally from 1 to 1000 g of antidote, preferably from 5 to 250 g of antidote, are used per 100 kg of seed, although, depending on the method employed, which also allows the addition of other active ingredients or miC1onutrients, amounts that exceed or fall short of the speC1fied concentration limits may be employed (repeat dressing).

ii) Application in the form of a tank mixture
A liquid formulation of a mixture of antidote and herbiC1de (ratio of the one to the other from 20:1 to 1:100) is used, the rate of application of herbiC1de being from 0.005 to 5.0 kg per hectare. The oil additive can be added to the tank mixture in an amount of, preferably, from 0.01 to 2 % by weight. Such tank mixtures are applied before or after sowing.
iii) Application to the seed furrow
The safener is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, a wettable powder or granules. After the seed furrow has been covered, the herbiC1de, optionally in combination with the oil additive, is applied pre-emergence in the normal manner.
iv) Controlled release of the active ingredient
The safener is applied in solution to granulated mineral carriers or polymerised granules (urea-formaldehyde) and dried. If desired, a coating may be applied (coated granules) which enables the active ingredient to be released in metered amounts over a predetermined period of time.
Preferred formulations have espeC1ally the following compositions (% = percent by weight; "active ingredient mixture" denotes the mixture of compound of formula I with the synergistically effective second herbiC1de and, optionally, with the safeners and/or oil additives according to the invention.
Emulsifiable concentrates:
active ingredient mixture: from 1 to 90 %, preferably from 5 to 20 %
surface-active agent: from 1 to 30 %, preferably from 10 to 20 %
liquid carrier; from 5 to 94 %, preferably from 70 to 85 %
Dusts:
active ingredient mixture: from 0.1 to 10 %, preferably from 0.1 to 5 %
solid carrier: from 99.9 to 90 %, preferably from 99.9 to 99 %

Suspension concentrates:
active ingredient mixture: from 5 to 75 %, preferably from 10 to 50 %
water: from 94 to 24 %, preferably from 88 to 30 %
surface-active agent: from 1 to 40 %, preferably from 2 to 30 %
Wettable powders:
active ingredient mixture: from 0.5 to 90 %, preferably from 1 to 80 %
surface-active agent: from 0.5 to 20 %, preferably from 1 to 15 %
solid carrier: from 5 to 95 %, preferably from 15 to 90 %
Granules:
active ingredient mixture: from 0.1 to 30 %, preferably from 0.1 to 15 %
solid carrier: from 99.5 to 70 %, preferably from 97 to 85 %
The Examples that follow illustrate the invention further. They do not limit the Invention.
Formulation Examples for mixtures of herbiC1des and, optionally, safener and oil additive

It is often more practical to formulate the herbiC1des (optionally in combination with the oil additive) and the safener separately and then, shortly before application, to bring them together in the applicator in the desired mixing ratio in the form of a "tank mixture" in water. The herbiC1des and the safener can also be formulated separately and, shortly before application, brought together in the applicator in the desired mixing ratio in the form of a "tank mixture" in water, with the oil additive being added thereafter.

The herbiC1dally selective action of the compositions according to the invention is illustrated in the following Examples.
Biological Examples
Example B1: Post-emergence test:
The test plants are grown in pots under greenhouse conditions until a post-application stage. A standard soil is used as cultivation substrate. At a post-emergence stage, the herbiC1des, both on their own and in admixture with safeners and/or oil additives, are applied to the test plants or to cultivated plants seed-dressed with safeners. The application is carried out using an emulsion (prepared from an emulsifiable concentrate (Example F1, c)) of the test substances. The rates of application depend on the optimum concentrations ascertained under field conditions or greenhouse conditions. The tests are evaluated after from 2 to 4 weeks (100 % action = complete destruction, 0 % action = no phytotoxic action).

WE CLAIM:
1. A herbiC1dal composition that, in addition to comprising customary inert formulation
adjuvants, comprises as active ingredient a mixture of
a) a herbiC1dally effective amount of a compound of formula I
wherein
R1 and R3 are, each independently of the other, halogen, nitro, C7ano, C1-C4alkyl, C2-C4-aikenyl, C2-C4aikynyl, C1-C4haloalkyl, C2-C6 haioalkenyl, C3-C6 cycloalkyl, halo-substituted C3-C3C7cloalkyI, Cz-C3alkoxyalkyI, Cz-C3alkylthioalkyl, hydroxy, merC3pto, C1-C3alkoxy, C3-C3alkenyloxy, C3-Ceaikynyloxy, C3rbonyl, C3rboxyl, C1-C4alkylC3rbonyl, C,-C4hydroxyalkyl, C1-C4alkoxyC3rbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkyl-amino or di(C1-C4aIkyl)amino; R4 and R5 together are a group
-C-R6(R7)-0-C-R8(R9)-C-Rio(R11)-C-R,2(R,3)- (Z1),
-C-R14(R15)-C-R16(R17)-0-C-R18(R19)-C-R20(R21)- (Z2),or
-C-R22(R23)-C-R24(R25)-C-R26(R27)-0-C-R28(R29)- (Z3),
wherein R6, R7, R8, R9, R10, R11, R12. R13, R14. R15. R16. R17. R18. R19. R20. R21. R22. R23. R24. R25. R26- R27. R28 and R29 are, each independently of the others, hydrogen, halogen, C1-C4alkyl or C1-C4 haloalkyl, it being possible for an alkylene ring, which together with the C3rbon atoms of the groups Z1, Z2 or Z3 contains from 2 to 6 C3rbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the C3rbon atoms of the groups Z1, Z2 or Z3, or that alkylene ring bridges at least one ring atom of the groups Z,, Z2 or Z3; G is hydrogen, -C(Xi)-R3o, -C(X2)-X3-R3i, -C(X4)-N(R32)-R33, -SO2-R34, an alkali metal, alkaline earth metal, sulfonium or ammonium C3tion, or -P(X5)(R35)-R36 or -CH2-X6-R37; Xi, X2, X3, X4, X5 and Xfi are, each independently of the others, oxygen or sulfur;

R30- R31- R32 and R33 are, each independently of the others, hydrogen, C1-C1oalkyl, C1-C10-haloalkyl, C1-C1oC7anoalkyl, C1-C1onitroalkyl, CrC1oaminoalkyl, C1-C3alkylamino-C1-C3alkyI, C2-C3dialkylamino-C1-C3alkyl, C3-C7C7cloalkyl-C1-C3alkyi, Cz-C1oalkoxy-alkyI, C4-C10-alkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, Cz-C1oalkylthio-alkyI, C1-C3alkysulfoxyl-C1-C3alkyI, C1-C3alkylsulfonyl-C1-C3alkyI, C3-C3alkylideneamino-oxy-C1-C3alkyl, C1-C3alkylC3rbonyl-C1-C3alkyl, C1-C3alkoxyC3rbonyl-C1-C3alkyl, C1-C3amino-C3rbonyl-C1-C3alkyl, C3-Cedialkyl-amino-C3rbonyl-C1-C3alkyl, C1-C3alkylC3rbonylamino-C1-C3alkyI, Cz-C3alkylC3rbonyl-(C1-C3alkyO-aminoalkyl, C3-C3trialkylsilyl-C1-C3alkyl, phenyl-C1-C3alkyl, heteroaryl-C1-C3alkyI, phenoxy-C1-C3alkyI, heteroaryloxy-C1-C3alkyl, C2-C3alkenyl, C2-C5haloalkenyl, C3-C3C7clo-alkyl, phenyl, or C1-C3alkyI-, CrC3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyI-, C1-C3haloalkyI-, C1-C3-alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted heteroarylamino, diheteroaryl-amino, C1-C3alkyI-, C1-C3haloalkyI-, C1-C3alkoxy-, C,-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diphenyl¬amino, C3-C7C7cloalkylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloaikoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkylamino, di-C3-C7C7cloalkylamino, CrC3alkyl-, C1-C3haloalkyI-, C1-C3alkoxy-, C,-C3haloalkoxy-, halo-, C7ano- or nitro-substituted di-C3-C7-C7cloaikyiamino, C3-C7C7cloalkoxy or C1-C3alkyl-, C1-C3haloalkyI-, C1-C3aikoxy-, C1-C3halo-alkoxy-, haio-, C7ano- or nitro-substituted C3-C7C7cloalkoxy;
R34, R35 and R36 are, each independently of the others, hydrogen, C1-C1oalkyl, C,-C1ohalo-alkyl, C1-C1oC7anoalkyI, C1-C1onitroalkyl, C1-C1oaminoalkyl, C1-C3alkylamino-C1-C3alkyl, Cz-C3dialkyiamino-C1-C3alkyl, C3-C7C7cloalkyl-C1-C3alkyl, Cz-C1oalkoxy-alkyI, C4-C,o-alkenyioxy-alkyl, C4-C1oalkynyloxy-alkyl, Cz-C1oalkylthio-alkyI, C1-C3alkysulfoxyl-C1-C3alkyl, C1-C3alkylsuifonyl-C1-C3alkyl, Cz-C3alkylideneamino-oxy-C1-C3aikyi, CrC3aikylC3rbonyl-C1-C3aikyl, C1-C3alkoxyC3rbonyl-C1-C3alkyl, C1-C3amino-C3rbonyl-C1-C3aikyi, Cz-C3diaikyl-amino-C3rbonyl-C1-C3aikyl, C1-C3alkylC3rbonylamino-C1-C3alkyl, Cz-C3aikylC3rbonyl-(C1-C3aikyO-aminoalkyl, C3-C6triaikylsilyl-C1-C5alkyl, phenyl-CrC3alkyl, heteroaryl-C1-C3alkyl, phenoxy-C1-C3alkyi, heteroaryloxy-C1-C3alkyi, C3-C3alkenyl, Cz-C3haloalkenyl, C3-C8C7clo-alkyl, phenyl, or C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, CrC3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyl-, C1-C3haloalkyI-, C1-C3-alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted heteroarylamino, diheteroaryl-

amino, C1-C3alkyl-, CrC3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyI-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substltuted phenylamino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diphenyl¬amino, C3-C7C7C1oalkylamino, C1-C3alkyi-, C1-C3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkylamino, dl-C3-C7C7cloalkylamino, C1-C3alkyl-, CrC3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted di-C3-C7-C7cloalkylamino, C3-C7C7cloalkoxy, C1-C3alkyl-, CrC3haloalkyl-, C1-C3alkoxy-, C,-C3halo-aikoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkoxy, CrC1oalkoxy, C1-C1ohaloalkoxy, C1-C3alkylamino, C3-C3dialkylamino and benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by C1-C3alkyI, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, C7ano, formyl, acetyl, propionyl, C3rboxyl, C1-C3alkoxy-C3rbonyl, methylthio, ethylthio or by nitro;
and "
R37 is C1-C1oalkyl, C1-C1ohaloalkyl, C1-C10C7anoalkyl, C1-C1onitroalkyl, C1-C1oaminoalkyl, C1-C3alkylamino-C1-C3alkyI, Cz-C3dialkylamino-C1-C3alkyI, C3-C7C7cloalkyl-CrC3alkyI, C2-C1oalkoxy-alkyl, C4-C1oalkenyloxy-alkyl, C4-C1oalkynyloxy-alkyl, Cz-C1oalkylthio-alkyI, C1-C3alkysulfoxyl-C1-C3alkyI, C1-C3alkylsulfonyl-C1-C3alkyI, Cz-Cealkylideneamino-oxy-C1-C3alkyl, C1-C3alkylC3rbonyl-C1-C3alkyl, CrC3alkoxyC3rbonyl-C1-C3aikyl, C1-C3amino-C3rbonyl-C1-C3alkyl, Cz-C3dialkylamino-C3rbonyl-C1-C3alkyl, C1-C3alkylC3rbonylamino-C1-C3-alkyl, Cz-C3alkylC3rbonyl-CC1-C3alkyO-aminoalkyl, C3-Cetrialkylsilyl-C1-C3alkyl, phenyl-C1-C3-alkyl, heteroaryl-C1-C3alkyl, phenoxy-C1-C3alkyl, heteroaryloxy-C1-C3alkyl, C3-C3alkenyl, Cz-C3haloalkenyl, C3-C3C7cloaikyl, phenyl, or C1-C3alkyl-, C1-C3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl or heteroaryl, or heteroarylamino, C1-C3alkyl-, C1-C3haioalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted heteroarylamino, diheteroarylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3halo-alkoxy-, halo-, C7ano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C,-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted phenyl-amino, diphenylamino, C1-C3alkyI-, C1-C3haloalkyI-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted diphenylamino, C3-C7C7cloaikylamino, C,-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted C3-C7C7cloalkylamino, di-C3-C7C7cloalkylamino, C,-C3alkyl-, C1-C3haloalkyl-, CrC3alkoxy-, CrC3haloalkoxy-, halo-, C7ano- or nitro-substituted di-C3-C7C7cloalkylamino, C3-C7C7cloalkoxy, CrC3alkyl-, C,-C3-

haloalkyi-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, C7ano- or nitro-substituted C3-C7cyclo-
alkoxy or C1-C10alkylcarbonyl; or a salt or diastereolsomer of a compound of formula I, with
the proviso that R1 and R3 are not simultaneously methyl; and
b) an amount, effective for herbiC1de synergy, of at least one herbiC1de selected from
mesosulfuron, and flufenacet.
2. A composition according to claim 1, which comprises c) an amount, effective for herbiC1de antagonism, of a safener selected from cloquintocet-mexyl and mefenpyr-diethyl.
3. A composition according to claim 1, which comprises d) an additive comprising an oil of vegetable or animal origin, a mineral oil, alky! esters of such oils or mixtures of such oils and oil derivatives.
4. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a composition according to claim 1.
5. A method according to claim 4, wherein the crops of useful plants are cereals.

6. A herbiC1dal composition substantially as hereinabove described
and exemplified.
7. A method for the selective control of weeds and grasses in crops of
useful plants substantially as hereinabove described and
exemplified.

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Patent Number

214354

Indian Patent Application Number

619/CHENP/2004

PG Journal Number

13/2008

Publication Date

31-Mar-2008

Grant Date

11-Feb-2008

Date of Filing

25-Mar-2004

Name of Patentee

SYNGENTA PARTICIPATIONS AG

Applicant Address

Schwarzwaldallee 215, CH-4058 Basel,

Inventors:

#	Inventor's Name	Inventor's Address
1	HOFER, Urs	Syngenta Crop Protection AG, Schwarzwaldallee 215, 4058 Basel,

PCT International Classification Number

A01N 43/90

PCT International Application Number

PCT/EP2002/010829

PCT International Filing date

2002-09-26

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	1781/01	2001-09-27	Switzerland